Studies in Surface Science and Catalysis 65

CATALYSIS AND ADSORPTION BY ZEOLITES

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Studies in Surface Science and Catalysis

Advisory Editors: 6. Delmon and J.T. Yates

Vol. .65

CATALYSIS AND
ADSORPTION BY
ZEOLITES
Proceedings of ZEOCAT 90, Leipzig, August 20-23, 1990

Editors

G. Ohlmann
Zenrralinsrirur fur Physikalische Chemie, Rudower Chaussee 5,
Berlin Adlershof, 0- 1 7 99 FRG

H. Pfeifer
Universirar Leipzig, Sekrion Physik, Linnhstrasse 5, Leipzig, 0-70 10 FRG

and

I?.Fricke
Zenrralinstirur fur Physikalische Chemie, Rudo wer Chaussee 5,
Berlin Adlershof, 0- 1 199 FRG

ELSEVIER Amsterdam - Oxford - New York - Tokyo 1991

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 V

CONTENTS

Preface.........................................................XI
International Scientific Committee, National Organizing
Committee, Sponsors ........................................... XI11

INVITED LECTURES

Catalysis on ZSM-5 zeolites modified by phosphorus

G. Ohlmann, H.-G. Jerschkewitz, G. Lischke, R. Eckelt,
B. Parlitz, E. Schreier, B. Zibrowius, E.Lijffler...........l
New directions in zeolite catalysis
J. Weitkamp ............................................... 21

Zeolites as catalysts for alkane oxidations

R.F. Parton, D.R.C. Huybrechts, Ph. Buskens, P . A . Jacobs..47
Sorption and separation of binary mixtures of CH4, N, and COz in
zeolites
L.V.C. Rees...............................................61
Use of ZSM zeolites in the liquid phase separation of alcohols
R. Schollner, W.-D. Einicke.......................... .....75
Basic principles and recent results of 'H magic-angle-spinning
and pulsed field gradient nuclear magnetic resonance studies
on zeolites
H. Pfeifer, D. Freude, J. Karger .......................... 89

Spectral study of lewis acidity of zeolites and of its role in

catalysis
V.B. Kazansky........ ....................................
~ 1 7

Comparative measurements on acidity of zeolites

H.G. Karge. .............................................. 133

Acidity and basicity in zeolites

D. Barthomeuf.............................................l57
Matrix vs zeolite contributions to the acidity of fluid
cracking catalysts
R. v. Ballmoos, C.-M.T. Hayward .......................... 171
VI

ZEOSORB HS-30 - a template-free synthesized pentasil-type

zeolite
K.-H. Bergk, W. Schwieger, H. Furtig, U. Hadicke.. ....... 185
Selective conversion of syngas to hydrocarbons by zeolites
H. Tominaga, K. Fujimoto, T. Tatsumi........... ..........203

'"Xe NMR of adsorbed xenon for the determination of void spaces

Q. Chen, M.A. Springuel-Huet, J. Fraissard... ............
219

Diffusion of hydrocarbons in A and X zeolites and silicalite

D.M. Ruthven, M. Eic, Z. Xu..............................233

Atlas of zeolite structure types: Past - Present - Future

W.M. Meier.... ........................................... 247

Zeolites as membranes: The role of the gas-crystal interface

R.M. Barrer..............................................257
The roles of metal and organic cations in zeolite synthesis
D.E.W. Vaughan.. ......................................... 275

Temperature dependence of nucleation of zeolites in alkaline

aluminosilicate gels in hydrothermal crystallization conditions
S.P. Zhdanov, N.N. Feoktistova, L.M. Vtjurina ............
287

SUBMITTED PAPERS
Catalvsis

Synthesis of piperazine and triethylenediamine using ZSM-5-type

zeolite catalysts
J. Weitkamp, S . Ernst, H.-J. Buysch, D. Lindner..........297
Diffusion effects on the kinetics of toluene methylation and
xylene isomerization on HZSM-5 zeolites
F. Bauer, J. Dermietzel, W. Jockisch...... ............... 305
Iron-containing ZSM-5 type zeolites used in the coupled
methanol-hydrocarbon cracking (CMHC)
A. Martin, S. Nowak, B. Lucke, W. Wieker, B. Fahlke......315
Dispersion dependent selectivities of syngas conversion on
faujasite encapsulated Pt, Pd or Ir
N.I. Jaeger, G. Schulz-Ekloff, A . Svensson...............327
 VII

Contribution of 13C N M R spectroscopy to the analysis of surface

compounds formed in the transformation of acetone on zeolites
V. BosaEek, L. Kubelkova, J. Novakova....................337
Isopropylation of benzene over large pore zeolites
A.R. Pradhan, B.S. Rao, V.P. Shiralkar ...................347
EXAFS study of local structure of Pt-Cr clusters in pentasils
in relation with their reactivity in lower alkanes
aromatization
E.S. Shpiro, R.W. Joyner, G.J. Tuleuova, A.V.
Preobrazhensky, O.P. Tkachenko, T.V. Vasina, O.V. Bragin,
Kh.M. Minachev ...........................................
357

Splitting of methane into the elements over nickel containing

ZSM-5 catalysts
J. Hoffmann, R. Bauermeister, B. Hunger, K. Hantel,
G. Ullmann, K.-H. Steinberg, H. Siege1 ...................367
Sulfur tolerant Ni-Mo-Y-zeolite catalysts for water-gas shift
reaction
M. Zianiecki, W. Zmierczak........................... .....377
The influence of cations on the alkylation of toluene with
ethylene over modified ZSM-5 zeolites
J. Eejka, B. Wichterlova, G.L. Raurell................... 387
Multinuclear MAS NMR studies on coked zeolites H-ZSM-5
H. Ernst, D. Freude, M. Hunger, H. Pfeifer...............397
Coke oxidation in HZSM-5 zeolites. Intermediates, final
products and reformation of OH groups and void volumes
J. Novakova, L. Kubelkova................................405
Influence of the conditions of dealumination and the effect of
partial extraction of non-framework aluminium on the catalytic
properties of ZSM-5 catalysts
G . Ohlmann, H.-G. Jerschkewitz, G . Lischke, R. Eckelt,
T. Gross, B. Parlitz, I. Schulz, K. Wehner, D. Timm... ...415
Spectroscopic and catalytic investigations of hydrothermally
dealuminated ZSM-5
E. Loffler, L.M. Kustov, V.L. Zholobenko, Ch. Peuker,
U. Lohse, V.B. Kazansky, G. Ohlmann......................425
VIII

Sorption and diffusion

Computer modelling of p-xylene sorption in ZSM-S/silicalite-l

K.-P. Schroder ........................................... 435

Microdynamics of guest molecules in zeolites studied by

quasi-elastic neutron scattering and NMR pulsed field gradient
technique
H. Jobic, M. Bee, J. Caro, M. Bulow, J. Karger,
H. Pfeifer ...............................................
445
Permeability studies on a silicalite single crystal membrane
model
E.R. Geus, A.E. Jansen, J.C. Jansen, J. Schoonman,
H. van Bekkum....... ..................................... 457
The adsorptive and the catalytic diffusion of 2,3-dimethyl-
butane in large crystals of (aluminated) silicalite
P. Voogd, H. van B e k k u m . . . . . . . . . . . . . . . . . . . . . . . . . ......... 467
Transport phenomena and reactions in 13X type zeolites
M. Biilow, W. Hilgert, G. Emig ............................ 479

Svnthesis and structure

The effect of various physical and chemical parameters on the

synthesis of ZSM-5 for propene oligomerization
C.T. O'Connor, S. Schwartz, M. Kojima .................... 491
On controlled growth of SAPO-5 molecular sieve crystals of
different sizes and shapes
G. Finger, J. Kornatowski, J. Richter-Mendau,
K. Jancke, M. Bulow, M. Rozwadowski......................501
Approximate assignment of vibrational frequencies of the NaX
framework
E. Geidel, H. Bohlig, Ch. Peuker, W. Pilz................511
The topological structure representation of zeolites
B. Muller................................................521
Studies of secondary synthesis on modified pentasil zeolites
W. Reschetilowski, W.-D. Einicke, B. Meier, E. Brunner,
H. Ernst........................... ...................... 529
 IX

Incorporation of silicon into the framework of SAPO-5 studied

by N M R and IR spectroscopy
B. Zibrowius, E. Loffler, G. Finger, E. Sonntag,
M. Hunger, J. Kornatowski ................................ 537
On the synthesis and structure of A1P04-14
B. Zibrowius, U. Lohse, K. Szulzewsky, H. Fichtner-
Schmittler, W. Pritzkow, J. Richter-Mendau....... ........549
Y-zeolite treated with Sicl, vapour. Structure and properties
G.M. Telbiz, A.I. Prilipko, I.V. Mishin..................563
Characterization and nucleation of Na,TPA-ZSM-5 zeolite with
different aluminium content
G. Golemme, A. Nastro, J.B. Nagy, B. Subotic, F. Crea,
R. Aiello................................................573
New molecular sieve - vanadium silicalite ms-5
J. Kornatowski, M. Sychev, V. Goncharuk, W.H. Baur.......581
Multinuclear NMR study of the crystallization of SAPO-37
N. Dumont, T. Ito, J.B. Nagy, Z. Gabelica,
E.G. Derouane...................... ...................... 591

Metastability of zeolites in tetraethylammonium media

F. di Renzo, A. Albizane, M.-A. Nicolle, F. Fajula,
F. Figueras, Th. des Courieres...........................603
Synthesis of ferrierites with high gallium content
M.A. Camblor, J.A. Martens, P.J. Grobet, P . A . Jacobs.....613
Synthesis of artificial zeolite-like mountainite
M.K. Babayev, D.M. Ganbarov, D.B. Tagiyev ................ 623
The distribution of iron in ZSM-5 type iron containing zeolites
and ferrisilicates: acidic and catalytic properties
G. Vorbeck, M. Richter, R. Fricke, B. Parlitz,
E. Schreier, K. Szulzewsky, B. Zibrowius.................631
Zeolite ZSM-57: Synthesis, characterization and shape selective
properties
S . Ernst, J. Weitkamp ....................................
645
X

Aciditv

New data on the structure and properties of acidic sites in

HZSM-5 zeolites: IR-spectroscopic studies and non-empirical
quantum chemical calculations
I.N. Senchenya, V.Yu. Borovkov... ........................ 653

FTIR in-situ investigation of zeolite activation

R. Salzer, B. Ehrhardt, J. Dressler, K.-H. Steinberg,
P. Klaeboe....... ........................................ 663

IR spectra of CO adsorbed at low temperature (77 K) on titanium-

silicalite, H.-ZSM5 and silicalite
A. Zecchina, G. Spoto, S . Bordiga, M. Padovan,
G. Leofanti, G. P e t r i n i . . . . . . . . . . . . . . . . . . . . . . . . . . ........671
The properties of boralites of various boron contents
J. Datka, A. Cichocki, Z. Piwowarska................. ....681
An electrostatic model to predict the infra red characteristics
of zeolite hydroxyl groups after adsorption of aromatics
P.J. O'Malley ............................................
6ag

The influence of the acidity of zeolites on the formation of

unsaturated carbenium ions
I. Kiricsi, H. Forster, G . Tasi, P. Fejes ................ 697
Author Index................. .................................. 707
Subject Index............. ..................................... 711
Studies in Surface Science and Catalysis (Other volumes in the
series) ........................................................
715
 XI

PREFACE

There is a permanently growing interest, worldwide, in zeolite

science and technology. Especially in Europe it has become an
established tradition to hold specialized zeolite meetings which
occur sandwiched in between the large International Zeolites
Conferences. The ZEOCAT 90 Conference held in Leipzig, is the latest
in a series of successful European zeolite conferences which have
been held previously in Wurzburg, Nieuwpoort, Siofok, Prague and
Bremen.
The range of synthesized zeolites and zeolite-related molecular
sieve materials is constantly expanding. The variety of structures
comprises high- and low-silica zeolites, micro-porous metallo-
silicates, alumino-phosphates and crystalline silica polymorphs.
These newly developed, modified or improved zeolites and other
molecular sieves have opened up new horizons by their application as
shape-selective catalysts and adsorbents, as cation exchangers or as
high-tech materials. Current topics of interest are the newly
developed catalytic applications of zeolites in the synthesis of fine
chemicals, the use of zeolites as a new material for sensors or solid
electrolytes and the setting up of sophisticated zeolite-based
separation processes including molecular sieve membranes. In order
to master the promising potential offered by the new zeolites, the
links between the various fields of molecular sieve research are
growing closer. This is especially true for merging synthesis and
characterization by such powerful methods as solid state NMR and X-
ray or neutron diffraction, as well as for adsorption, diffusion and
catalytic studies. A new trend is the growing interest in the use of
computational and theoretical approaches to explain synthesis,
sorption, diffusion and catalytic data.
ZEOCAT 90 was comprised of the many different and diverse aspects
of the rapidly expanding field of zeolite science and technology. The
invited plenary lectures of this conference summarize our current
knowledge and address topical areas of zeolite research. New
interesting findings produced by fundamental research have led to new
industrial applications and these developments have, in their turn,
inspired new directions for fundamental research.
The deliberate control of crystallization processes has led to the
production of many zeolites which do not occur naturally. Chemically
XI1

and physically controlled treatments have been used to tailor shape-

selective zeolite catalysts and adsorbents for industrial use. Newly
developed physical and chemical spectroscopic and diffraction methods
have given us new insights into the exciting world of molecular
interactions of solid surfaces.
The editors are convinced that ZEOCAT 9 0 contributed, like its
European predecessors, to the successful interdisciplinary
exploration of zeolites and to finding new pathways for their
application in science and technology.

G. dhlmann, H. Pfeifer, R. Fricke (Editors)

 XI11

ZEOCAT 90 - Leipzig

International Scientific Committee

R.M. Barrer, London
D. Barthomeuf, Paris
H.K. Beyer , Budapest
H. Bremer, Berlin
P. Fejes, Szeged
J.P. Fraissard, Paris
J. Haber, Krakow
P.A. Jacobs, Heverlee
H.G. Karge, Berlin
V.B. Kazansky, Moscow
W.M. Meier, Zurich
W.J. Mortier, Heverlee
C. Naccache, Villeurbanne
L.V.C. Rees, London
W. Schirmer, Berlin
G. Schulz-Ekloff, Bremen
J. Weitkamp, Stuttgart
B. Wichterlova, Prague
S.P. Zhdanov, Leningrad

National Orsanizina Committee

Chairmen: G. Ohlmann, H. Pfeifer
Secretary: H. Miessner, B. Staudte

H. Bremer, Berlin W. Schirmer, Berlin

M. Bulow, Berlin R. Schollner, Leipzig
D. Freude, Leipzig H. Stach, Berlin
R. Fricke, Berlin K.-H. Steinberg, Leipzig
J. Karger, Leipzig J. Volter, Berlin
H. Lieske, Berlin

SI)onsors
AKZO Chemicals B.V.
BASF AG
BAYER AG
Chemie AG Wolfen-Bitterfeld
Degussa AG
Deutsche Shell AG
EXXON Chemical Holland-BCT
Hoechst AG
Intern. Zeolite Ass. (IZA)
Leuna-Werke AG
PCK AG Schwedt
PQ Corp.
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 G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 1
0 1991 Elsevier Science Publishers B.V.. Amsterdam

G OHLMANN, H.-b.JtHSCHKEWlIL, b.LlSCHKt, H.ECKtLT, b.PARLIIL,

t S C H R k l E R . B / I K R O W i I I S . 6 InFFLER

CentraJ I n s t i t u t e o t P h v s i c a l Chemistry o f t h e Academy o f Sciences

R:idower u m i s s e p 5 . 11'JY M R L IN-ADLtRSHOF

AbS1 R A L !

M o d i r v i n s (J teinplcite-tree s y n t h e s i z e d and h y d r o t h e r m a l l y dealu-

minuted LSIY-5 t v o e z e o l i t e w i t h o r t h o p h o s D h o r i c a c i d v i e l d s c a t a -
l y s t s t o r t h e h i g h - t e m p e r a t u r e MIO-reaction which a r e s u p e r i o r t o
t h e n i e i ' e l y aealuniiiiot t'cl z e o l i t e s i n r e s p e c t o f Cz-Cd-olef i n s e l e c -
t i v i . t i e c nncl d e a c t i v a t i o n t i m e s . F o r m a t i o n o f methane, a r o m a t i c s
ond coke i s : ; t i - o n y I v suppressed. I h e mechanism o f t h e P-modificn-
r t o n 3 5 char;ic,teriz;ld by on n t l e n s t partially r e v e r s i b l e c h e m i c a l
i n t e i - i l i . t i u i 1 o i p h l i s E t j o i ' l c a c i d w i t h t h e sti-onq a c i d s i t e s and by n
c t ~ i i : y e i.11 ; . o n c e n t r u t i n n and n a t u r e o t weak a c i d s i t e s which a l s o
contrtbute f o c a t a l y s i s . A f t e r P-modification, dealumination of
t h e z e o l i t e tramework by steoiaing i s i n h i b i t e d .

';inre t h e work n t Kciedinq and R u t t e r ( 1 ) who f i r s t hnvp shown

t h e p o s i t i v e e t f r c t o f t h e PhosDhOrus m o d i t i c a t i o n o f ZSM-5 c a t a -
l v r t s on t h e i r r r r : a l v t i c p r o p e r t i e s i n t h e MIO-process and sonie-
what l a t e r on t i l e P o c o - s e l e c t i v e a l k y i a t i o n o t t o l u e n e w i t h metho-
no1 ( L ) , numeruus s t u d i e s have been aevoted t o t h e problem o t t h e
niec;huiiisin o t ttiis i a o d i r i c a t i o n ( 3 - 11).
KUt?dillg uiicl B u t t e 1 pruposed i n t h e i r Paper bonding o t PhosPhorLls
t o the z e o l i t e framework t h r o u g h oxygen what f o r m a l l y i s equiva-
l e n t t o t h e reoiacpinent o f t h e h r i d g e d h y d r o x y l groups hv a HZP04-
QI'OUD bv means o t I P D mensuremmts o f NHs t h e y tound a s i g n i f i -
r a n t l v i n r r e a s f t l number o f a c i d s i t e s . which a r e weaker i n
s t r e n u t h compared t i l t h those i n t h e unmodi t i e d z e o l i t e .
Vedrine e t a 1 ( 4 ) s t z t e d t h a t Phosphorus n e u t r a l i z e s a c i d s l t e s
p r i m a r i l v u t t n e e n t r a n t - e a t t h e LSM-5 channels whereas t h e s t r o n -
aest n c i a s i t e s o r e n o t m o d i i i e d . Consequentlv t o r e x p l a n a t i o n o t
t h e observed i n c r e n s e n f C2-C4-.nlefin selectivities. o slight
aocl; : i r . a t i n n i n chnnnel r;ize und i n c r e a s e d t u r t u o s i t v due t o phos-
~ h o i ~ i i : ;comooirnd i s p r e f e r e d , compared t o changes i n a c i d s t r e n g t h .
U e r e w i n s k i und Haber (6) found by NHZ-lPD t h a t m o d i f i c a t i o n w i t h
r I. inie t n y 1piio 5 uii i t e ond d iilmmon i umhyd r agenp hos p ha t e e 1i m i n a t es t h e
Hrrjn:;ted acirl s i . t e s and a l s o s i ~ n I f I c a n t decreases l~ the content
u r W C ~ C I K C ~ Iricic'l
. S I tes
B~isecl on P~IISC~I~~I~Y experiments w i t h q u i n o l i n e and t r i m e t h y l p h o s -
p l i i t e Nunoil et o i ( L , j r;ont:liirierl, t h a t t h e most i m p o r t a n t e f f e c t o f
u n o s ~ h ~ ~I:;r ~ ~r h; t : ooir,oning n t t h e s t r n n g ocirf site:, o n t h e e x t e r -
r i o l :;urtnr.f r i t t h e i ' . r , v s t a l s .
K:IIl. Maiiit~c~arid Yii;hinio ( i i J ) s t u d i e d t h e shupe s e l e c t i v e a l k y l u t i o n

n t ethvlhenzene W I tll e t h a n o l or1 P - m o d i f i e d ZSM-5 c a t a l v s t s and

claim t h n t t h e S L I P P ~ ~ S S I O o~ i Para-di.ethvlbenzene L s o m e r i z a t i o n i s
achieved by I'eduLing t h e amount o t s t r o n s a c i d s i t e s r a t h e r t n a n
tiy r e ~ ~ u c i nthe a e t t e c t i v e pnre diameter o f LSM-5.
S h i u e r u I k ( i 1 et r i l . ( 1 2 ) orepnred a c a t a l y s t f o r methanol conver-
sion (;oIir;i?,t i n u ot H'-LSM-5 oel l e t i z e d and m o d i t i e d w i t h
onrl HPU4&- A c c o r d i n g t o t h e i r c o n c l u s i o n t h e b i n d e r
reduces t h e a c i d s i t e s an t h e e x t e r n a l s i i r t u c e CJt t h e
serves 0s a source o f g r a d u a l s u p p l y o f HPUqA-, which
ocirl s i t e s arid r e t a r d s d e a l u m i n a t i o n . Most comprehen-
problein o f t h e mechanism o f P - m o d i f i c a t i o n has been
the wnrks n t l e r c h e r e t n l ( 7 . 8 . 1 4 , 1 5 ) . I n t h e i r w r -
I :FI- w,i; 1, ( 8 ) tl;ev hnd develooed a concept o f c o n t r o l l e d decrease
. * ;;i- -i,.; .?,i:-~r,ath hv c n n v e r s i n n o f s t r o n g a c i d s i t e s i n t o weakely
L i .

i i ( i d oiler,. u i t l l o i i i alteration n t t h e OVel-all acid-base P r o p e r t i e s .

111 t t i , L: i;r:est p u b l i c a t i o n s they come t o t h e c o n c l u s i o n , t h u t
t i e u ( i n e : i ~ o i t i l e zeolite w i t h H3PU4 and t r i i n e t h u l p h a s p h i t e decrea-
~ e ! tire, CcjiiLenti'ution O T s t r o t i s a c i u s i t e s e s s e i i t i u i l y by dealunii-
r x i T i n i i , I n t h e case n t t r i m e t h y l p h o s p h i n e as t h e m o d i f y i n g agent
thev rniiiid ( 1 5 ) ('I hl.ocking o f s t r o n q a c i d s i t e s up t o u r e a c t i o n
teinc;t?rotiir~C i t 0 O O n C . Ahc,ve t h i s t e m p e r a t u r e t h e phosphine i s de-
?,rjrtji?<j. i r ? q c i i e r o I 1 . i ~t h e o r i g i n a l a c i d i c p r o p e r t j . e s o f H I - L S M - 5 .

Lumniar-iziriy t h i s o v e r v i e w i t may be s t a t e d , t h a t decreuse o t

;troriy i l i i i l i t y atiJ i ' t ' a u c t i o n o f p o r e d i a m e t e r a r e i n o s t l y d i s c u s s e d
i n ui'tJei tc, e x p l a i n t h e e t i e c t o t phosphorus m o d i f i c a t i o n . the
I e i c l i ~ v t ' 1 l l l I J l J I ~ t ~ i l oL r~ these r o c t o r s is a i t r e r e n t l y e v a l u a t e d and
rfww-ids G I I t h e s t t i d i e d r e a c t i o n . C o n t r a d i c t o r y a r e t h e views o f
v n r i o i i s nilthrbrs on t h e wov. i.n which s t r o n g a c i d s i t e s a r e decren-
 3

sed, by i n t e r a c t i o n w i t h t h e b r i d g e d h y d r o x y l groups, o r by u a r -
t i a l deaiumination.
i n t h i s paper we d e s c r i b e t h e combined e f f e c t o f h y d r o t h e r m a l
d e a l u m i n a t i o n and phosphorus m o d i f i c a t i o n on t h e s e l e c t i v i t i e s and
d e a c t i v a t i o n rimes i n t h e high-temperature MTO-reaction. F o r a l l
experiments t h e ZSM-5 type. template-free synthesized z e o l i t e
HS-30 o f Chemie AG B i t t e r f e l d , has been used. TPD o f ammonia, I R -
and :*1P--.27AI-MAS-NMR soectroscopy were employed t o g e t deeper
i n s i g h t i n t o t h e mechanism o f t h e z e o l i t e m o d i f i c a t i o n by o r t h o -
ptiosplioric a c i a . l h e work was p a r t o f a c o o p e r a t i o n w i t h t h e
Researcn and Uevelopment D i v i s i o n o f Leuna-Werke-AG.

f r e P a r o r i o n v t soimles
P e n t a s i l t y p e LSM-5 z e o l i t e (HS-30, Si/Al=19, Chemie AG B i t t e r -
t e l d ) i s c o n v e r t e d I n t o t h e H*-form by a f o u r t i m e s r e p e a t e d
t r e a t m e n t w i t h a 0 . 2 N so1.ution o f HN03 i n a s i m u l e b a t c h Proce-
d i i r e . For d e u l u s i n a t i o n . samples o f t h e H+-form a r e exposed t o a
stream o t a i r and steam (pwater.=90 kPa) a t 400, 410 and 700°C.
Framework aluminiirm ( A h ) i s determined u s i n g t h e ammonium exchon-
ge method. For p a r t i a l e x t r a c t i o n o f non-framework aluminium
t A 1 1 . i ~ ) torined d u r i n g deUlUminatiOn, samples a r e t r e a t e d w i t h 2 N
HN03 a t 105°C f o r t w o h o u r s . E x t r a c t e d aluminium was d e t e r m i n e d
o n a l y t i c a l l v i n the s o l u t i o n o f t h e e x t r a c t i n g agent. C a t a l y s t
p a r t i c l e s were oreoared by m i x i n q t h e HS-30 samples w i t h Aero-
sil-ZGO and water and subsequent e x t r u d i n g , t h e ready made e x t r u -
d a t e s (d = 1 t o 2 mm) c o n t a i n i n g 6 5 % by w e i g h t o t z e o l i t e . P-modi-
r i c a t i o n was c a r r i e d o u t by i m p r e g n a t i o n w i t h aqueous p h o s p h o r i c
a c i d . i h e c o n t e n t o f phosphorus f o r c a t a l y s t s based upon e x t r a c t e d
HS-30 was h e l a somewhat lower t a k i n g i n t o c o n s i d e r a t i o n t h e i r
di.minished c o n t e n t s o f t o t a l . alilminium. F i n a l l y c a t a l y s t samples
were c o n d i t i o n e d b y steaming a t 700°C f o r 1 h o u r .

Ammonium exchange
l h e H I - i o n s o t LSM-5 z e o l i t e s a r e exchanged by NH4*-ions by
treatment w i t h an aqueous s o l u t i o n o f an ammonium s a l t . F o r t h i s
Purpose t h e sample i s p l a c e d on a 64 s l a s t r i t (approx. 4s) and
exposed t o CI tiow o f 50u m l o t an aqueous 0,2 N NH4(CHaCOO) s o l u -
t i o n t o r b Iluurs a t /c) t o 80°C. A t t e r c a r e f u l washing, t h e c o n t e n t
4

o f ammonium i s d e t e r m i n e d by t h e K j e l d a h l method.

D e t e r m i n a t i o n o f ahasphorus i n o w ous s o l u t i o n s
Ihe suiiif d e v i c e a s i n t h e ammonium exchanse i s used t o a n a l y z e
phosphorus removed from P-modified samples by e l u t i o n w i t h h o t
w a t e r . Q u a n t i t a t i v e d e t e r m i n a t i o n o f t h e e x t r a c t e d Phosphorus i s
based on t h e p h o t o m e t r i c molvbdo-vanada-phosphoric a c i d method.

Temper a t w r o g r a m m e d des o r p t i o n o f am0n i a (NH 3-TPD)

A t t e r - c l e a n i n g z e o l i t e samples by h e a t i n g t o 500°C i n an He 9ns
stream ( v = 3 m l / s ) f o r one hoirr, ammonio i s odsarbed a t 120°C
from a He gas stream c o n t a i n i n g 3 Vo1.-I o f N H 3 . A f t e r f l t r s h i n g by
p u r e He a t 120°C f o r two ho:irs, d e s o r p t i o n o f ammonia up t o 500°C
1 s s t a r t e d crlow f a t e o f h e l i u m : 1 ml/s; heat r a t e l P C / m i n ) . I h e
c o n c e n t r a t i o n o t NH3 i n t h e e x i t gas i s d e t e r m i n e d u s i n g a thernio-
c o n d u c r i v i t y c e l l . I h e c u r v e o f t h e desorptogram is r e c o r d e d DY a
c o n v e n t i o n o l d e v i c e . A d d i t i o n a l l y ammonia i s absorbed from t h e
e x i t acts stream SY on 0 . 1 N HaS04 s o l u t i o n . I t s t o t a l amount i s
determined by back t j t r a t i o n o f excess s u l f u r i c o c i c l .

T R Soectroscooy
LSM-5 z r o l i t e samples a r e compacted t o t h i n s e l f s u p p o r t i n g
waTe1-s tiouohlu 7 mg/cmz) and p l a c e d i n a q u a r t z 1 R c e l l . The
worers o r e c u r c i n e a a t 400°C i n vacuo. A f t e r c o o l i n g t o 200°C,
p y r i o i n e vapour i s uailiitted i n t o t h e system f o r 30 m i n u t e s . A f t e r -
w u r ~ t s , t l i e c e l l 1 s degusbecl and evacuated t o e l i m i n u t e p h v s i s o r b e d
P v r i d l nf
Transmission s p e c t r a a r e r e c o r d e d i n t h e range from 4000 t o
3300 cm-' b o t h h e t o r e and a f t e r p y r i d i n e n d s o r p t i n n . u s i n g o
SDecord M 85 spectrometer o f C a r l Z e i s s Jena w i t h a 4 c m - l r e s o l u -
t ion.
Diffuse r e t l e c t a n c e s p e c t r a a r e r e c o r d e d w i t h t h e t - T - 1 H t e c h n i q u e
u s i n g u s p e c i a l aevice, t h e r e s o l u t i o n o f which i s 4 cm-I. The
z e o l i t e Powdei i s p r e t r e a t e d f o r t o u r h o u r s a t 450°C and a t
10- ' Po

L 7 A l- and P-MAS-NMK--measurement s
I h e NMK s p e c t r a were o b t a i n e d on a BRUCKER MSL4OO m u l t i n u c l e a r
spectronieter o p e r a t i n g a t u f i e l d o t 9 , 4 r w i t h a s t a n d a r d BRUCKER
d o u b l e - b e a r i n g MAS p r o b e , I h e z i r k o n i u o x i d e r o t o r s were spun near
 5

5 kHz w i r h a r y n i t r o g e n as d r i v i n g gas. About 200 my o f sample

m a t e r i a l a r e f i l l e d i n t h e i n n e r r o t o r volume o f about 0 . 3 5 cm:’.
T y p i c a l l y , 1500 t o 1800 f r e e i n d u c t i o n decays ( F I D ’ s ) were ac-
cumulated p e r sample f o r b o t h n u c l e i . The p u l s e w i d t h s were 3 . 9 11s
(n/U-pulse) w i t h r e p e t i t i o n times between 5 t o 30 s and 0.6 11s
(n/l2-puise) w i t h a r e p e t i t i o n time o f 1 s f o r a t 362 MH7 and
f o r 2 7 A l a t 104 MHz, r e s p e c t i v e l y . The c h e m i c a l s h i f t s a r e g i v e n
on t h e d s c a l e w i t h a maximum u n c e r t a i n t y o f fl Ppm.
I n o r d e r t o o b t a i n r e l i a b l e q u a n t i t a t i v e r e s u l t s by t h e L’7Al-MAS;-
NMR measurements, t h e samples were h y a r a t e d i n an e x s i c c a t o r i n an
atmosphere s a t u r a t e d wi.th water f o r more t h a n 20 h o u r s . Ihct ah-
s o l u t e i n t e n s j t v mode (AI-mode o f t h e DISMSL-software package) was
used t o r e x p e r i m e n t a l d a t a a n a l y s i s .

La t a l v s i s
C a t a l y t i c experiments were c a r r i e d o u t i n a t u b u l a r f i x e d bed
r e a c t o r (6 = 12 mm) u s i n g a m i x t u r e o f methanol/Nz ( m o l e c u l a r
r a t i o = 1 : l ) as r e a c t i o n feea ( c o n d i t i o n s o f r e a c t i o n see t a b l e 1 ) .
Products were analyzed DY an o n - l i n e o p e r a t e d guscnromotogrophic
device C a l c u l a t i o n o f t h e c o n c e n t r n t i n n from a n a l v t i c a l d a t a i s
based on i n d i v i d u a l c a l i b r a t i o n o f t h e components

lABLE I : Parameters o f r e a c t i o n
- ~ _ _ ~

t enipe r a t u r e : 560°C
c o n c e n t r a t i o n o t methanol: 50 Val-%
c a t a l y s t volume: 12 m l
c a t a l y s t mass ( a v e r a g e ) : 5.b 9
teed t-are ( i n i x r u r e ) : 4 . 0 m l / s (Sir)
charge
GHSV ( m i x t u r e ) . 1200 m l / m l c a t I vs t *h
LHSV(methano1): 1 m 1/ml a t I I. *h

I h e t i m e on stream when methanol f i r s t appears i n the e x i t gas o f

t h e r e a c t o r i s clenGted as t 1 m e o t d e a c t i v a t i o n
C a t a l y s t s a r e named a c c o r d i n g t o t h e g e n e r a l formula D X P v . x
d e n o t i n g the b i / A l ~ r a t i o and Y t h e c o n t e n t o t pnosphorus us
weight p e r c e n t .
6

RESUL LS .MRDILSCUSSIQN

R e c e n t l y we have shown ( 2 0 ) , t h a t d e a l u r n i n a t i o n o f z e o l i t e
HS-30, used as c a t a l y s t i n t h e M'10-reaction a l t e r s t h e s e l e c t i v i -
t i e s o f l i g h t o l e f i n s and o f a r o m a t i c s i n a s i m i l a r way as was
found by Chans e t a 1 . ( 1 9 ) f o r ZSM-5 c a t a l y s t s s y n t h e s i z e d w i t h
v a r i o u s S ~ / A I F r a t i o s . f o r t h e r e a c t i o n c o n d i t i o n s chosen i n t h i s
worK t n e e t t e c t o t w r y i n g c a t a l y s t S i / A l F r o t i o on t h e s e l e c t i v i -
t i e s o t cZ-c4- o i e T i n s , L 6 - b - U r o l n a t i c s and methone as w e l l a s on
t h e d e a c t i v a t i o n t i m e i s demonstrated i n F i g . 1 . S e l e c t i v i t i e s o f
l i g h t o l e t i n s i n c r e a s e UD t o almost 70% wh,ile t h e f o r m a t i o n o f
a r o m a t i c s ond methane i s d i s t i n c t l v decreased UP t o c a t a l ~ s t
S i / A l F o r 2 6 8 . lhese changes a r e accompanied by ii inarked ~ r o l o i i ~ a -
t i o n o i t h e d e a c t i v a t i o n t i m e . As d e s c r i b e d i n a s e p a r a t e paper
( 7 0 ) a remarkable i n c r e a s e o f t h e d e a c t i v a t i o n t i m e may be n t t a i -
ilea by e x t r a c t i o n o t t h e non-tramework aluminium u t t e r s u i t i c i e n t -
IY l o n g d e a l u m i n a t i o n a t mediuin t e m p e r a t u r e s . F u r t h e r dealumina-
t i n n , however, does n o t r e s u l t i n a b e t t e r c a t a l v s t . O l e f i n s e l e c -
t i v i t i e s t e n d t o decrease a g a i n , t h e some h o l d s t r i i e o f t h e dent:--
t i v a t i . o n t i m e . W h i l e t h e s e l e c t i v i t i e s a t a r o m a t i c s a r e n o t sn

I0

6C

50
m
\

40
Y
r(
c
Y
r(

10
m
9
#

! 20
L

k
10

,so
'61 '9 6 268 102 1.25

1 -,immntics 0 -time o r dcactiv.

F i g . l . E t t e c t o f d e a l u m i n a t i o n on p r o d u c t s e 1 e c : i v r t i e s and
O e a c t i v a t i o n t i m e compured w i t h u d d i t i o n a l phosphorus
inod1 t i c a t i o n
 7

mucn affected, a significant growtn o f methane - in particular on

the catalyst with S i / A l F 480 - is observed. lhus maxima o f olefin
selectivity and a t deactivation time, attainable by dealumination.
seem to exist. Concerning the deactivation time this behaviour is
to be expected since the concentration of strong acid sites heco-
mes very sma 1. lhe behaviour of the oiefins, however, is less
plausible. lhe Turtner decrease of strong acid sites should result
in a further loss ot catal.ytic activity and consequently favour
the accumulat on of the lower olefins as the primory products in
the reaction sequence. Under the severe reaction conditions the
light olefins - ethene in particular - are partly formed a l s o by
crackina of higher olefins. A strong suppression of these cracking
reactions by the decrease of strong acid sites as compared with
tne diminished rate of the overall reaction may therefore contri-
bute to the changes in olefin selectivity. Indeed. the portion of
ethene in the c 2 - c 4 olefin fraction decreases from 30% for D 2 6 8 to
around 18% for 0 4 8 0 . B e s i w s , one has to taKe into consideration,
thflt Si/AlF ratios above 270 can be obtained with reasonable times
o f hydrothermal treatment only at temperatures o f 700 - 750 " C .
Nevertheless no loss of cristallinity could be detected by X-ray
diffraction tor the sainples treated at this severe conditions.
However, they undergo a phose transformation from orthorhombic to
monoclinic. As wns reported ( 2 1 ) this phase transition is indeed
aependent on sl/ulF ond temperature. It i s not clear, however,
wtietner this i s ot importance for the observed reversed olefin
selectivities or not.
For further improving the selectivity of light olefins. suppres-
sing the tormation o t aromatics and increasing the deactivation
time, the modirication with phosphorus, f i r s t used by Sutter and
Kaeding ( 1 ) with non-dealuminated LSM-5, was chosen. Ihe results
achieved arter systematical study are examplitied by the catalyst
b 2 6 8 f 1 . 2 5 in k i g . 1 .

i n order to rina tile conditions Tor preparing catalysts with opti-

mum activity, maximum light oletin selectivity and deactivation
time. the influence o f qrowing amounts o f phosphorus at different
degrees of dealumination on the product distributlon of methanol
coilversion had to be studied. As shown in Fig.2 UP t o 2% phos-
phorus the selectivities O T L 2 - i 4 oieTins grow on a level which i s
the higher the greater the Si/AiF ratio, except for very hign
S i I A 1 ( 1 ) 3 0 0 ) . Aocive 2% i.' the octivities 01 the catalysts drop,
dimetnvlether appears right from the beginning o f the reaction and
the selectivities o f the CZ-C4 olefins ore drastically decreased.
8

ring only hydrocarbons as reoc- sz

\
t i o n p r o d u c t s . Quite t h e o p p o s i t e Bo

b e h o v i o u r show t h e s e l e c t i v i t i e s
o f t h e a r o m a t i c s . They f a l l w i t h
g r o w i n g c o n t e n t o t phosphorus,
but agoin the catalysts with
7 0 . I yp!
\
67*57 ! I

d i T r e r e n t S i / A l F r a t i o s have d i f -
ferent levels o f s e l e c t i v i t i e s ,
M,
/,P$y
/
/. ,./
1'
ea

*/.,' ,/'
t h e lowest t o r
w i t h the highest
the c o t o l ~ s t s
degree o f de- 50.
.--__-.J
m-

-. ..
!'
I,'; . I

a l u m i n a t i o n . Here t h e samples
w i t h S i / A l i - = 3 3 0 e x h i b i t no exc:ep-
'i-330

I
\. I
\
40.
t i o n a l behoviour. [he suwr'es- I

S %
'
10 .
9 -

8 .

1 -

6 -

5 -

4 -

J -

2 .

1 -

I .'
0:5 i.0 1.5 2:O 2.5 IP 0.5 1.0 1,5 2.0 2.5 3.0 S P

k i g . 5 , t t i e c t o t Phosphorus k l Q . 4 . tlrei1 O T P1105PtlOfU5

s e l e c t i v i t y O T aroinotics on s e l e c t i v i t y 0 1 inetnune
l o r various S i / A l F r a t i o s for varioiis S i / A l t . rfltins
 9

p u r t i c u l n r i n the r e g i o n sx 4
between 1 . 5 and 2 . 0 % P .
i t i s g e n e r a l l y acceated ,,,- i4,
now. t h a t t h e higher *,
I
‘... ..__,
\

Si/A1=107
o l e t i n s a r e formed main- 1
’ -l

l v hv n l k v l n t i o n o f t h e
l o w e r ones w i t h m e t h a n o l
”-
rO‘
./’
I’
;.-*-. -__a
,/a
x Ethene
c) Propene
Butene
o r d i n i e t h ~ l e t h e r and t o 20. .”
P /d 0 C,-aliphatics
wme degree a l s o hv yi\x II
t h e i r o l i g o m c r i z a t i on.
tthene i s the primary
p r o d u c t o f t i r s t C-C-
lo- ---*--‘
\ ,!

bond toi-tnation, b u t un- *

10

ably also for crackinn. while catalyst ability for the alkvlation
o f oiefins by methanol is evidently less affected. lhis conclusion
i s supported by an experimerit with cofeeding of Propene to the
methanol stream durjng the MTO reaction. A higly dealuminated
cotalyst sample with very small concentration of strong acid Bran-
sted s i t e s , additionallv modified with 0.5% phosphorus was chosen
for this purpose. The most striking effect of cofeeded propene. as
f o l l o w s troin table 2, i s the distinct increase of methanol conver-

WHSVIh- I ) Methanol 1,55 1,55

WHLV(h-') Prnoene 0.00 0,46
Methanol conversion ( X I 90.3 98,7 +8.4

Products (% V o l . )

Methane 1,65 0.81 -0,84

E.f ha tie 0,05 0,05 0,oo

Prooane 0.31 0,49 +0,18
I -Butane 0.35 0.54 +o. 19
N- Hu tflne 0.14 0,zo + O . 06

La-Aliphatics 0,81 0,96 +0,15

senzene 0,oo 0,04 +0,04

I oluene 0,lO 0,16 +0,06
Xylenes 0,3Y 0,38 -0,Ol
Cs-Aromatics 0,075 0,06 -0,015

sion, which most likely may be explained as the result of its

consumption in the alkylation of added propene. Indeed the
concentrations of all Ca+-products. except for Cs+-aromatics. are
 11

increusecl. I n e t a c t , t n a t t h i s i s v a l i d a l s o f o r t h e c o n c e n t r a t i o n
o f ethene i s i n d i c a t i v e o f t h e a t l e a s t p a r t l y m a i n t a i n e d c r a c k i n g
a c t i v i t y o t the catalyst.
To g e t deeper i n s i g h t i n t o t h e mechanism o f m o d i f i c a t i o n by
phosphorus t h e i n t l u e n c e
of growing amounts o f
phosphorus on t h e con- '*O

c e n t r a t i o n o f weaK and
0-3
strong a c i d s i t e s was A

s t u d i e d by NHS-TPD. I h e 7mC.6
IPD t r a c e s o f ammonia de- ,+
s o r p t i o n show characte-
r i s t i c a l l y o f ZSM-5 ( 2 2 )
8 OB:

two maxima, one f o r weak 'D!

z
acid sites of ditferent
n a t u r e a t about 240°C and '0 '1#5 '
0 '1.5 Po '1.0
'0.5 '2.5 '0.5 p ~ , 2 ~ '0.5 '2.5
a h j g h temperature peak
-ti2*- -&"-
0"
-3,07-
o t 420°C r e f l e c t i n the
strong Bronsted acid F i g . 6 . E f t e c t o t P on weak and s t r o n g
sites (bridged hydro- (hatched p a r t ) a c i d i t y f o r
x v l groups zSi.-p--Al=). various Si/AlF of the z e o l i t e
il
i h e i r c o n c e n t r a t i o n c o u l d De determined q u a n t i t a t i v e l y f o r SUtTl-
c i e n t l v , separated peaks by t h e i r peak a r e a s . Otherwise, t n e
amount o t s t r o n g a c i d si.tcts was determined s e p n r a t e l y from s p e c i a l
exaeriments a f t e r NH3 a d s o r p t i o n a t 2500C. The r e s u l t s a r e demon-
s t r a t e d i n F i g . 6 . The f i r s t column o f each group ( P O ) r e p r e s e n t s
the data f o r the unmoditied c a t a l y s t s . Obviously both type o f
s i t e s decrease w i t n d e a l u m i n a t i o n , a t l e a s t . above S j / A 1 ~ = 2 8 . A f -
t e r m o d i f i c a t i o n w i t h g r o w i n g amounts o f phosphorus, t h e concen-
t r a t i o n o f s t r o n g Bronstea a c i d s i t e s i s d r a s t i c a l l y d i m i n i s h e d by
a f a c t o r o f 10 t o 5 depending on S i / A l F r a t i o t h e most pronounced
e f f e c t b e i n g ochi.eved w i t h 0 . 5 % phosphorus. a l r e a d y . F u r t h e r i n -
crease o f P-content r e s c i l t s i n p r a c t i c o l l v no change o f t h e i r con-
c e n t r a t i o n , which, i f any. l i e s w i t h i n t h e margins o f e x p e r i m e n t a l
e r r o r ( * 0 . 0 0 5 mmol/g N H 3 ) . T h i s i s i n p a r t i c u l a r v a l i d f o r t h e
c a t a l y s t s based on 068 and 0107. I-he c o n c e n t r a t i o n o f weak a c i d
s i t e s i s reduced d i f f e r e n t l y , dePendinQ on t h e P-content and on
the s l / U l F r a t i o 0s w e l l . t a c h o r t h e samples oased on D2e and D ~ H
seem t o have a maximum c o n c e n t r a t i o n a t 1 . 5 % P w h i l e f o r t h e ca-
tfllvsts DlOiP0.s-2.5 t h e l o w e s t c o n c e n t r a t i o n o f weak a c i d s i t e s
i s o b t a i n e d w i t h 0 . 5 % P . I n t h i s case f u r t h e r i n c r e a s e o f P-con-
12

t e n t i s accompanied bv a c o n t i n u o u s i n c r e n s e o f t h e c o n c e n t r a t i o n
o f weak a c i d s i t e s . r e a c h i n g w i t h 2 . 5 % P an even h j q h e r v a l u e t h a n
w i t h o u t phosphorus. l h i s complex dependency is a c l e a r i n d i c a t i o n
o t a change i n t h e n a t u r e o f weak a c i d s i t e s w i t h P - m o d i f i c a t i o n .
some o f them h e i n s removed, o t h e r s newlv c r e a t e d .
I h e f a c t t h a t P-content above 1 - 1 . 5 % t o r a l l S ~ / A I Fr a t i o s p r a c -
t i c a l l y t h e same c o n c e n t r u c i o n o f s t r o n g a c i d s i t e s is observeo
l e a d s t o t h e c o n c l u s i o n , t h a t t h e d i s t i n c t d i f i e r e n c e s i n Product
s e l e c t i v i t i e s . o b t a i n e d i n t h j s ranqe o f P - c o n t e n t s . s h o u l d he
due, a t l e a s t p a r t l y . t n t h e d i f f e r e n c e s i n n n t l r r e and c a n c e n t r a -
t i o n o f t h e w e a k a c i d s i t e s . rhus. weak a c i d s ' i t e s n t t h i s
high-temperature c o n d i t i o n s a r e l j k e l v t o p a r t i c i p o t e i n c a t a l v -
sis. O f course, an a d d i t i o n a l shape s e l e c t i v i t y e f f e c t caused bv
t n e growing amount o t P-compounds d e p o s i t e d i n s i d e t h e channels
cannot iie r u i e u o u t .
l h e q u e s t i o n i s now. how t h e decrease o f s t r o n g nnd weok a c i d
s i t e s caused by phosphorus m o d i f i c a t i o n can he e x o l a i n e d As n l -
ready mentioned. t h i s problem i s s t i l l d i s D u t e d . h u t t h e n i i t h n r s
OT most r e c e n t p u b l i c a t i o n s i n t e r o r e t t h i s e t f e c t e s s e n t i n l l v hv
d e a l u m i n a t i o n o t t h e z e o l i t e . I n case or a c n e m i c a l i n t e r a c t i o n
o f p h o s p h o r i c n c i d w i t h t h e b r i d g e d h v d r o x v l 4roiIPs as t h e a l t e r -
n a t i v e t o d e a l u m i n a t i o n , one would expect a c e r t n i n degree o r
reversibility. i n Fig./. t n e columns r e p r e s e n t a g a i n t h e sulil of
wenk and strong acid
s i t e s o f a non-dealuminn-
t e d z e o l i t e sample.
ThF! m o d i f i c a t i o n o f t h i s
sample w i t h 2 . 5 % P onrl
treatment for 1 hour
i n a He- stream n t 500 O L
causes a d i s t i n c t decrea-
se o t s t r o n q nc;.tl sites.
A T t e r e x t r a c r i o n o i phos-
p n o r i c a c i d w i t t i water u t
80 C'C t o r b h o u r s , now-
ever, t n e former concen-
t r a t i o n o f strong uciu
Fig.7.Changes o f a c i a s i t e s c o n c e n t r a - sites i s fully restorea.
t i o n of a P-modified s a m p l e ( D ~ ~ P ~ . o ConseqitPnt1.v) the rlis-
a f t e r various treatments (hatched onpearence o f s t r o n a a c i d
p a r t o t columns: c o n c e n t r a t i o n o f s i t e s has t o be under-
strong acid s i t e s ) . s t o o d as t h e r e s u l t o f
 13

reversible chemicnl i n t e r a c t i o n o f p h o s p h o r i c a c i d w i t h t h e b r i g -
df*d h y d r o x v l q r o i t p s and cannot be due t o d e a l u m i n a t i o n o f t h e zeo-
. I i , t e . I f t h e P - m o d i f i e d sample p r i o r t o e x t r a c t i o n i s steamed f o r
4 hours o t 40u "i r e s p . t o r 0 , 5 hours a t 700 "C a f u r t h e r decrease
o r s t r o n g and weak a c i d s i t e s occurs (see F i g . 7 ) . The same e x t r a c -
t i o n pi-i.rr.edure, employed t o t h i s samples, a g a i n r e s t o r e s t h e aci.d
s i t e s b u t the o r i g i n o l c o n c e n t r a t i o n o f t h e s t r o n g a c i d s i t e s i s
nnt n t t n i n e r l l r r e v e r s i b l e changes. o b v i o u s l . . ~d e a l u m i n a t i o n , have
token olnce. I t tins t o b e noted, however, t h a t a f t e r steaminq i n
c o n t r a s t t o t h e i n e r e l y thermal o r e t r e a t m e n t i n He a t 500 " C . phos-
p h o r i c u c i a c o u l d be e x t r a c t e d o n l y by 89% and 60% r e s p e c t i v e l y .
l h e c ~ u e s t i o n o r i s e s us t o whether the Presence o t t h e p h o s p h o r i c
nLi.d 1.n the z e o l i i e channels i a v o u r s t h e process o f d e a l u m i n a t i o n
o r n o t . i h e ciiogront i n t-19.8. shows t h e c o n c e n t r a t i o n o t weak
and s t r o n g a c i d s i t e s o f
t w o HS-30 samples one un-
1.1

1.0
m o d i f i e d and t h e other
0.9 modified w i t h 2,5% P o f -
t e r steaming a t eqiinl.
- 0.8

c 0.7 condi t i o n s and subsealtent

'b 0.6
e x t r n c t i o n o f ohosohorus
.+ 0.5
gE 0.4 from t h e m o d i f i e d sample.
v 0.3 The concentrations o f
$0.2 strong acid s i t e s d i f f e r
z 0.1 by a f a c t o r o f t w o i n t a -
vour o f t h e P-inoditied
i i ~ . 8 . A c i u i 1cnuiiges
~ O T unmoditied sample. Consequently t h e
U i i i l i'-InOC)iTieCI Hb-50 ( Z , 5 X P ) o t t e r modification o f strong
steominu und e x t r a c t j o n o t P . a c i d B r o n s t e d s i t e s by
phosphoric a c i d excerts a
p r o t e c t i n n e t t e c t on t h e A1F-atoms r a t h e r t h e n f a v o u r i n s t h e j r
exvu1:ion t r o m t h e Traniework. I h o t e x t r a c t i o n o f phosphorus l e a d s
t o i u t u l y s t s w i t h p r u p e r t i e s approaching a g a i n t h o s e o f u n m o d i f i e d
i ; u t a l y s t s i s cleinonstratecl i n F i g . 9 . I h i s h o l d s t r u e a l t h o u g h , due
t u 11io1-2sever-e steuiiiiriy o t t h i s sample, o n l y about 16% o i pnospho-
r u s c o u l d be removed. A complete r e s t o r a t i o n o f t h e o r i g i n a l p r a -
a e r t i e r , o t IJnmOditied somples t h e r e f o r e c o u l d n o t be expected.
Neverthelexr, t h e t o c t o t r e o p p r o a c h i n g t h e former p r o p e r t i e s i n d i -
c o t e ! : t h a t t h e v e r v molecules o t p h o s p h o r i c a c i d which hove i n t e r -
n c t e d w i t h t h e s t r o n a o c i d si.tes can e a s i l y be removed by e x t r a c -
~ 1 0 1 1 . i h e gi.eiitt:r p o r t o f phosphoric a c i d m o l e c u l e s must e x i s t i n -
s i d e t h e channels i n a c l i t f e r e n t s t a t e , o b v i o u s l y c h e m i c a i l y
14

70

30

20

10

k1g.Y. Product s e l P c r i v i t i e s a f t e r P - e x t r a c t i o n compared w i t h [in-

m o d i t i e d nnd m o d i t i e d samDles

bonded w i t h t h e non-framework a l i i m i n i u m
k u r t n e r s u p p o r t and a d d i t i o n a l i n f o r m a t i o n on t h e mechanism o f P-
m o d i t i c . a t l o n wete o b t a i n e d by means o f 1R- ond MAS-NMR-spectrosco-
PV I h e T i r s f two s p e c t r a i n F i g 10 a r r a n g e d one upon a n o t h e r ,
i l l u n t r n t e t h e e f f e c t o t P - m o d i f i c a t i o n ( 2 5% P, w i t h o u t steamiiiq)

3610
I

k i s . i U . I K - l r a n s l n i s s i o n s p e c t r a o f HS-30 samples o t t e r d i f f e r e n t
o r e t r e a t m e n t s . Kegion o t O H - s t r e t c h i n g f r e q u e n c i e s .
 15

nn t h e i n t e n s i t v ,if t h e s t r o n a hand o t 3610cm-i which is g e n e r a t e d

bv t h e b r i d g e d OH-arnilos i n t h e 7 e o l i . t e . 1-he d r a s t i c decrease o f
t h i s hnnd i s riuoarent. The next two s p e c t r a demonstrate how t h e
i n t e n s i t i e s and t h e n a t u r e o f OH-groups a r e changed by steaming
and SIJbSeClUent e x t r a c t i o n o f phosphorus.
besides t h e d i s t i n c t l y aecreased band a t 3610 cm-I, t h e appearance
n f n new hand nt 3 6 6 5 c m - I , which hos been assigned t o A1-OH
groups o f non-framewnrk aluminium (23). i s r e g i s t e r e d . Consequent-
I v . steomina f o r 5 hours a t 400°C causes a o a r t i a l d e a l u m i n a t i o n .
Ihe l a s t two s p e c t r a show. what happens w i t h t h e u n m o d i f i e d samole
a f t e r t h e sume steaming p r e t r e a t m e n t compared w i t h t h e P - m o d i f i e d
one ( t h e t o p s p e c t r u m ) . l h e decrease o f t h e s t r o n g B r o n s t e d s i t e s
is s z g n i r i c a n t i y g r e ( l l e r , d e a l u m i n a t i o n proceeded t o a l a r g e r
degree. I h u s . t h e p r o t e c t i n g e f f e c t o f phosphorus i s c o n f i r m e d
a l s o bV t h e IR-dfltfl.
lhe i n t e r a c t i o n a t ohosohoric a c i d w i t h non-framework aluminium i s
shown i n F 1 9 . 1 1 . M o d i r y i n g a deaJuminated sample w i t h P p r a c t i -
c n i l v r e s u l t s i n the disauuearance o f t h e band a t 3 6 6 5 cm-I , which
reappears, however. a r t e r severe steaming a t 7OO0C, a p p a r e n t l y as
u consequence o t f u r t h e r d e a l u m i n a t i o n and d e f i c i e n c y o f phospho-
r u s t o r c o i w l e r e oonding t h e newly c r e a t e d non-framework alum].-

3740
P
at 120°C
37iC

/ :::5

-b-------L-
3900 3800 3700 3600 3500 3600
-- -'
I +steamed
lh at 700°C
?/Em

k i 8 Il.trrect OT P on 1 R - Fig.lZ.IR-dittuse reflectance spectra

hnnu i n t e n s i t i e s a t o f dealuminated HS-30 b e f o r e ( f u l l
5 b 6 3 and 5610 cm-' l i n e ) and a f t e r P - m o d i f i c a t i o n
16

niiim. l h e i n t e n s e i n t e r a c t i o n w i t h t h e s t r o n g a c i d s i t e s and t h e
OH-QroUPS o r non-TrameworK a l u m i n i i l m can be concluded a l s o from
the d i f t u s e r e t t e c t a n c e IR-spectra presented i n F i g . 1 2 . A dealu-
minuted sample h l z , r u l l l i n e spectrum) shows t h e t y p i c a l bands
Tor o i l o b s e r v e a b l e OH-groups as a s s i g n e d b e f o r e . A f t e r m o d i f i c o -
t i o n w i t h 1 . 5 % P t h e c h a r a c t e r i s t i c bands o f t h e s t r o n g a c i d s i -
t?-, (361.0 cm-l) rind t h e A ~ N F - O H groitos ( 3 3 6 5 cm-') a r e s i q n i f i -
c n n t i v reduced. l n t e r e s t i n s l v t h i s spectrum r e v e a l s a s h o u l d e r o f
rJ twitid a t 3670 cm-' - a frequency r e g i o n , where P-OH-groups show
absorption. i h i s muy be c o n s i d e r e d as an i n d i c a t i o n o f t h e i r p r e -
sence.
Wh;le i t i s c l e a r trom t h e s e d a t a , t h a t p h o s p h o r i c a c i d r e a c t s
w i t h t h e b r i d a e u h v d r o x v l groups and t h e non-tramework a l u m i n i u n i
CIS w e l l . t h e i n t o r m a t i o n about t h e n n t u r e o f t h e p r o d u c t o f t h i s
i n t e r a c t i o i i remains r a t h e r D o o r . l h e r e f o r e t h e P - m o d i f i e d sarnolea
o d d i t i o n o l l v :;tiidie!d hv :I1P- and "'Al-MAS-NMR spectroscopv.
I h e :"P-MAS-NMR spectrum o f a d e a l u m i n a t e d P-modified sample
(spectram A i.n k i q . 1 3 ) e x h i b i t s a t l e a s t t h r e e d i f f e r e n t resonance
i i n e s . one o t them ( a t =1 ppm) corresponds t o t h e o r i g i n a l o r t h o -
ohosphorlr: o c i d . t h e second a t - 1 5 ppm r e p r e s e n t s c h e m i c a l s h i f t s
u s u a l l y o b t a i n e d t o r s h o r t c h a i n polyphasphates (241, and t h e r e -
inoinina l i . n e n t nboitt -;."-I opm corresoonds t o t h e range c h a r a c t e r i -
:;tic o f ~;IiiminiUr;i ahos- 3 r p - NMR ~ ~ -,
phiites ( 2 5 ) . Residues u l A

o r t h o u n o s p h o r i c o c i u and D95p1,6

A-A
dried a t 120% Y.:traotion (80.C)
snort c h a i n Doiyuhos-
phate s ~ e ~ i e fart? , remo-
vea by e x t r u c t i o r i w i t t i

spzctt'uin ils L ii n
wuter s k Shown
i g . 1 5 by
111 l h 100%
at eteame: ax'raction (80.C)

which t t i e col-I-esPunuinY - ,"

s i g t i a l s a r e absent .
u n i y t n e i i n e cnuroc-
teristic ot alumiilluni- 0 0 -0 -10 0 3 -0 -rG

pnosphates, t h e pr'ouuct 71

0: i n t e r a c r i o n o r phos- k i q 13.="P-MAS-NMR s p e c t r a o t P - m o d i t l e d .
u h o r i c a c i d w i t h non- dealurninated samples o t t e r v a r l o t i r
f I ninework oluminium pretrmtments
r emoins
ITt h e sample i s steamed t o r 1 hour a t 100 " C (spectrum b) t h e
s i ~ n a i s a t 1 cliiu - 1 5 ppin d i s a p p e u r and new l i n e s a t -3Y and
-4b pplli appear U b v l o u s l y t h e p h o s p h o r i c anu POlyPhOSPhOt~lC a c i d
 17

species undergo f u r t h e r condensation r e a c t i o n s , s i n c e t h e new li-

nes may be i n t e r p r e t e d as caused by h i g h l y condensed p o l y ~ h o s h a t e
species ( 2 6 ) . A chemical s h i f t a t -46 ppm is known f o r t h e bran-
c h i n g groups i n P 4 h O ( 2 4 ) . These s p e c i e s can be removed by h o t
water e x t r a c t i o n as is r e f l e c t e d by spectrum D, i n which t h e
c o r r e s p o n d i n g l i n e s almost c o m p l e t e l y v a n i s h . Unchanged remains
t n e s i g n a l a t -30 ppni c h a r a c t e r i s t i c or aluminium phosphate.
Inus, d i r e c t evidence i s g i v e n f o r t h e i n t e r a c t i o n p r o d u c t o f
pnosphoric a c i d w i t h non-framework aluminium. U n f o r t u n a t e l y . from
these d a t a t h e e x i s t e n c e of an i n t e r a c t i o n o r o d u c t o t p h o s p h o r i c
a c i d w i t h b r i d g e d hvdroxv.1 groups cannot be concluded. However.
t n e "'Al-MAS-NMR p r o v i d e s o d d i t i o n a l i n d i r e c t evidence t o r t h e
e x i s t e n c e O T such a p r o d u c t . The spectrum on t o p of F i g . 1 4 shows
t h e c h a r a c t e r i s t i c l i n e o f A ~ Fa t 5 5 ppm and a s m a l i amount o f
o c t a h e d r o l l y c o o r d i n a t e d A I N F a t -1 ppm. P - m o d i T i c a t i o n o f t h i s
sample and steaming T o r 3 hours s i g n i f i c a n t l y l o w e r s t h e i n t e n s i t y
o f t h e A l l . s i g n a l . The s i g n a l a t about -10 ppm i s c h a r a c t e r i s t i c
o t o c t a h e d r a l l y c o o r d i n a t e d aluminium ( 2 7 ) I n aluminophosphates,
which r e s u l t from t h e r e a c t l o n o f orthoDhosPhoric a c i d w i t h A ~ N F .
I h e secona new s i g n a l a t 40 PPm stems from t e t r a h e d r a l l y c o o r d i n a -
t e d A ~ N F a l s o p r e s e n t as alulninophosphutes. Other t e t r a h e d r a l l y
c o o r d i n a t e d A ~ N F species can c o n t r i b u t e o n l y t o a s m a l l e x t e n t . dy
means o f n u t a t i o n NMR spectroscopy (28, t h e quadrupoie i n t e r -
action o t the nuclei g i v i n g r i s e t o
t h i s l i n e was shown t n be s m a l l .
l h e soectrum a t t h e bottom o f F i g . 1 4
demonstrates. t h a t e x t r a c t i o n of
phosphoric a c i d i n c r e a s e s c o n s i d e r -
ably the i n t e n s i t v of the Ah-signal
a t 5 5 w i n . A s r e u i u i n i n a t i o n a t these I . . . . ,. . _I.. . . . I . .

c o n d i t i o n s is u n l i k e l y t o occur,
D22P1 , 6 (>h/7W°C)
t n i s pnenonienoii i s i n u i c a t i v e TOI- o
very close i n t e r a c t i o n o r r w i t h A
AIP, causing a diStOrtiOn O T i t s , . . . . , . . . . I . . . . ,

Syininetry, Which i s e i i m i n a r e c l DY t h e D2*P,,(, eluted

removal of P . so, t n e i n t e n s i t y p t
t h e A1F-signal i s a t l e a s t p a r t l y
reduced by t h i s i n t e r a c t i o n .
F i n a l l y a few words concerni.ng t h e $00 50 0 - -50 ppo

n a t u r e o f weak a c i d s j . t e s . I t has F i g 14.z7A1-NMH s p e c t r a o f

been P o i n t e d o u t a l r e a d y . t h a t P- DzzHS-30 b e f o r e ana n f t e r P -
m o d i f i c o t i o n changes n o t o n l y t h e i r m o d i t i c a t i o n and - e x t r a c t i o n
18

c o n c e n t r a t i o n b u t a l s o t h e i r n a t u r e . Some i n c l i c a t i o n as t o t h i s
p o i n t was o b t a i n e d trom t h e temperature-programmed d e c o m p o s i t i o n
o f t h e NH-~*-exchanaed, P - m o d i f i e d samples.

c
h

,.
?

d
I

2M

F i n . l 5 . T e m p e r a t u r e - ~ r o g r a m m e d d e c o m p o s i t i o n o f an NH4+-exchanged
u n m o d i f i e d ( l e f t ) and P - m o d i f i e d somple.

From F i a . 1 5 i t appears, t n a t i n d i s t i n c t i o n t o t h e u n m o d i f i e d sam-

p l e , t h e P-modified sample b e s i d e s t h e h i g h - t e m p e r a t u r e PeaK exni-
b i t s a second one w i t h a maximum a t about 280 " C . l h i s peok may be
assigned t o a c i d s i t e s w i t h medium s t r e n g t h . [ h e i r p r o p e r t y t o he
ion-exchangeable f a v o u r s t n e i r i n t e r p r e t a t i o n us f i r o n s t e d a c i d
s i t e s . Whether t h e i r e x i s t e n c e i s due t o t h e i n t e r o c t i o n p r o d u c t
of phosphorlc acid w i t h b r i d g e d h v d r o x y l groups o r w i t h
non-framework oluminium i s d i f f i c u l t t o d e c i d e w i t h o u t f u r t h e r
experimental data.

D e a l u r i n a t i o n oT LSPI-5 t y p e HS-30 z e o l i t e bv h y d r o t h e r m a l t r e a t -
ment decreases t h e s t r o n g a c i d S i t e s and - c o n s e q u e n t l y i s osso-
c i a t e d w i t h a d i m i n i s h i n g o t c o t u l y t i c a c t i v i t y . C o n s e c u t i v e oro-
d u c t s o f t h e o l e f i n s a r e suppressed and t h e Cz-C4-olefin s e l e c t i -
v i t y i s r a i s e d . I t s v a l u e seems t o he l i m i t e d . however. t o about
b 5 X . M o d i t i c a t i o n of P r e v i o u s l y d e a l u m i n a t e d samoles w i t h o r t h o -
phosphoric a c i d i n c r e a s e s t h e s e l e c t i v i t y o t cZ-c4 o l e t i n s UP to
80%, s u p p r e s s i n g t o r m a t i o n o f o r o m o t i c s and coking. D e a c t i v a t i o n
times a r e s i g n i t i c a n t l v Prolonged (UP t o 1 0 0 h ) . A l l c a t a i y t i c
 19

parameters depend bn t h e o r i g i n a l degree O T d e a l u m i n a t i o n and UP

t o a c e r t a i n l e v e l at S i / A l = 250-300 t h e y a r e improved.
M o d i f i c a t i o n w i t h o r t h o p h o s p h o r i c a c i d causes a f u r t h e r decrease
o f s t r o n g a c i d s i t e s by i t s r e v e r s i b l e i n t e r a c t i o n w i t h t h e s e
s i t e s . This i n t e r a c t i o n seems t o p r o t e c t AlF-atoms from b e i n g
expulsed trom t h e framework under h y d r o t h e r m a l c o n d i t i o n s . The
observed t u r t h e r d e a l u m i n a t i o n o f P - m o d i f i e d samples a f t e r severe
hvdrotherinal t r e a t m e n t a p p a r e n t l y i n v o l v e s P r e f e r e n t i a l l y unpro-
tected Ah-atoms. C o n c o m i t a n t l y w i t h t h e decrease o f s t r o n g a c i d
s i t e s t h e c o n c e n t r a t i o n o f weak a c i d s i t e s i s changed and t h e
s i t e s a r e a l t e r e d i n t h e i r n a t u r e . A new. ion-exchanseoble a c i d
s i t e w i t h medium a c i d i c s t r e n g t h has been d e t e c t e d . These chnnaes
a r e p r e d o m i n a n t l y due t o an i n t e r a c t i o n o f t h e p h o s p h o r i c a c i d
w i t h t h e non-framework aluminium, which r e s u l t s i n a k i n d o f a l u -
minium phosphate.
Ihe v e r y slnail diTTerences o t t h e c o n c e n c r a t i o n o i s t r o II g
a c i d s i t e s above 1%P a l o n e h a r d l y e x p i o i n t n e Uependence 0 1 se-
l e c t i v i t y on t h e o r i g i n a l degree o t d e a l u m i n a t i o n . The more oro-
nounced d i f f e r e n c e s i n t h e c o n c e n t r a t i o n o f w e a k a c i d sites
favour t h e i d e a o f t h e i r p a r t i c i p a t i o n i n c a t a l y s i s a t these cnn-
d i t i o n s . An a d d i t i o n a l shape s e l e c t i v i t y e t r e c t , can n o t be e x c l u -
ded and seems t o be even l i k e l y f o r coke t o r m a t i o n .

I'he a u t h o r s express t h e i r g r a t i t u d e t o Leuna-Werke-AG t o r fun-

d i n g P a r t s o f t h i s w o r k . They a r e i n p a r t i c u l a r i n d e p t e d t o Or-.
K.Wehner and D r . D 3 i m m f o r t h e i r Permanent i n t e r e s t i n th1.s work
and s t i m u l a t i n g d i s c u s s i o n s . The a u t h o r s thank M r s I n a Schulz t o r
t h e d e t e r m i n a t i o n o f coke on spent c a t a l v s t s .

REF LRENCtS
1 W . W Kaedinq Und S 8 . B u t t e r . J . C o t a 1 . b l . 155(1Y80)
2 W.W.Kaeding, C.Lhu; L B.Youna. B . W e l n s t e l n , anu s . A . d u t t e r , J
Cata1.67, 159(1981)
5 L.6.Young, S . U . B u t t e r . and W.W.Kaeuing, J . ~ u t a l . / b . 41811Y8L)
4 J.C.Vedrine, A Auroux, P . D e j a i f r e , V Oucarme, H.Hoser. s Lnou.
J . C a t a l . / 3 . 14/(1982)
5 J Nunan. J C r o n i n . and J.Cunningham, J . C a t a 1 . 8 7 . I7(1984)
20

6 M . D e r e w i n s k i . J . Haber, J . P t a s z y n s k i , V . P . S h i r a l k a r , and
S . U z w i g a j . S t u d . S u r t . S c i . C a t a l . 1 8 , 209(1984)
1 J . A . L e r c h e r , ti. Rumplmayr, H . N o l l e r , A c t a Phys .Chem. 3 1 , 7 1 (1985)
8 J . A . L e r c t i e r , 6 . Rumplmavr, UPPI. C a t u l . 2 S , 215(1986)
9 A.Hahman, G.LemaY, A.Adnot, S . K a l i a s u i n e , J . C a t a 1 . 1 1 2 . 4 5 3 ( 1 9 8 8 )
10 J.H.Kim, S.Namba. l-.Yasnima, Bull.Chem.Soc.Japan 61, l O S l ( 1 9 8 8 )
11 F . L o n v l , J.Enge1hardt and D . K a l l o ; P . A . J a c o b s nnd R . A . v a n
S a n t e n ( t d i t o r s ) , Z e o l i t e s : F-acts, F i g u r e s . F u t u r e 1988 t l s e v i e r
Pub. B . V . Amsterdam. 1 3 5 /
1%S . 1 k a i , and M . Okamo t o , H .N i s h i o k a , r . Mivainoto, K . Mat s u z a k i ,
K . S u z u k i , Y.Kivazumi, T.Sano, S.Shin, A ~ p l . C a t a l . 4 9 , 143(1989)
1 5 H . V i n e k , G . Rumplmavr, ana J . A . L e r c h e r , J . C a t a l , 1 1 5 , 2 Y 1( 198Y)
14 A , J e n t y s , ci. Huiiwimavr, and J . A . L e r c h e r , A p p l . C a t o l . 5 5 , 2 9 9 ( 1 9 8 9 )
1 5 G.Ruinplmavr. ~ . A . ~ e r c n e rL,e a l i t e s , l O . 283(1990)
36 G . S e o . R.Rvoo, J . C a t a 1 . 1 2 4 , 224(1990)
1/ M . Ko j ima , F . 1.et ebvre, flnd Y . Ben Taa r it , J . Chem . Soc . Fnrad . 1 r a i l s .
86(4), /5/(1YYO)
18 G.ohlmann, H . - G . J e r s c h k e w i t z , G . L i s c h k e . B . P a r l i t z , R. t c k e l t ,
M . R i c h t e r , L . ~ . L n e n i i e28, 5 , l b l ( 1 9 8 8 )
1 9 c.D.Chans, C . T.--W.Chu, and R . F . Socha. .I . i o t a l . 8 6 . % 8 9 (1984)
20 li.ohlinann, H.-G.Jerschkewitz, G . i i s c h k e , R . k c k e l t , r . G r o s s ,
b . P a r i i t z , I . S c h u l z , K.Wehner, and D . l i m m , t h i s e d i t i o n O T
Stud.Surf.Sci.Cata1.
2 1 . I . R .Anderson. K . Fnqer, T.Mole, and R . A . R n j a d h v a k s h i , . I . C a t n l . S 8
118 (1919)
2 5 t.LotTler, Ch.Peuker. H . - G . J e r s c h k e w i t z . C a t a l . lodclv 3 .
415(1988)
24 A . -R . Grimmer and U . HaUDeIlrel S s e r , i hein. P h v s . Ler t . Y 9 . 48 / ( 19 8 S )
i 3 U . f ” l u i i e r , t .Junn, b . ~ a O w and
i ~ U.Hauoenreisser, C n e m . r h y s . L t ? t t .
lU5, 55L(1984)
Zb 1 .M.Duiican and D.C.Doualass. Chern.Phys.8/. 5 ? 9 ( 1 9 8 4 )
Z/ D . M u l l e r , 1 .Grilnze. t . H o l l a s and G.Ladwig. 7 . a n o r q . f l l l ~ . C . h e m .
500. 80(1985)
28 6 . L i t ) r o w i u s nnd W.Storek, u n p u b l i s h e d r e s u l t s .
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 21
0 1991 Elsevier Science Publishers B.V., Amsterdam

New Directions in Zeolite Catalysis

Jens Weitkamp
Institute of Chemical Technology I, University of Stuttgart, Pfaffenwaldring 55,
D-7000 Stuttgart 80 (Federal Republic of Germany)

Summary
It is likely that the catalytic performance of a much broader variety of zeolites and related
microporous materials will be routinely scrutinized in the nineties. In shape selective catalysis,
reactions of lar er molecules will play an increasing role. Even in petroleum refining and the
manufacture o f commodity petrochemicals, there is room for novel a plications of zeolite
P
catalysts. Two examples, viz. dewaxing by isomerization and isobutane butene alkylation are
discussed in some detail. The use of zeolite catalysts for the synthesis o organic intermediates
and fine chemicals continues to be a thrust area. It is desirable that synthetic organic chemists
routinely employ molecular sieve catalysts. Stereoselective catalysis in zeolites is still an
underdeveloped field. The same holds for base catalysis in zeolites, especially shape selective
base catalysis, but new approaches can be perceived in this area. Coupling of the exothermic
MTO process and the endothermic hydrocarbon cracking on ZSM-5 type catalysts allows an
almost thermoneutral production of lower olefins. The role of zeolites as hosts for a variety of
guests is recognized by an ever increasing number of researchers. Ship-in-the-bottle catalysts
or shape selective photochemistry are just a few examples for host/guest chemistry in zeolites,

Introduction and scope

About thirty years after its first industrial application, catalysis on zeolites continues to be
a most dynamic and promising field of research. The advantages of microporous crystalline
materials over more conventional solid catalysts are nowadays recognized by an ever
increasing number of scientists. Among these advantages are (i) the strictly regular pore size
and pore architecture; (ii) pore widths of molecular dimensions which enable shape or size
selective catalysis; (iii) acid surface properties with the possibility to tune the nature
(Br6nsted versus Lewis acidity), density, strength (or strength distribution) and location (e. g.,
inside the pores or at the external surface) of the acid sites within certain ranges; (iv) the high
thermal stability; (v) the possibility to regenerate deactivated catalysts, e. g., by burning off
carbonaceous deposits; (VI)the capability of zeolites to act as hosts for a variety of guests with
catalytically attractive properties, such as transition metal ions, small metal clusters or highly
selective transition metal complexes or chelates. Indeed, through host/guest chemistry, zeolite
science has many features in common with the modern supramolecular chemistry.
Although nowadays, an impressive number of industrial processes are operated with
zeolite catalysts, the riunzber of strLictiiru//y different zeolites accepted as commercial catalysts
has remained surpri.ying/y.mu//:To our knowledge, the zeolites utilized so far as industrial
catalysts are restricted to faujasite, mordenite, ZSM-5 and, probably, erionite.
The domain of zeolite Y is petroleum refining where it has been used on a very large
scale in fluid catalytic cracking (FCC) [l-41and hydrocracking [5-9].-Mordenite is applied in
22

the isomerization of light alkanes for octane enhancement of gasoline [5,8-101. Zeolite ZSM-S
is the prototype of shape selective catalysts. Its realm is the manufacture of commodity
petrochemicals, such as ethylbenzene or para-xylene [ 11-13]. Moreover, ZSM-5 based
catalysts are applied i n the production of gasoline from methanol [13-151, in the M-Forming
process [16,17] for octane improvement of reformer gasoline and in dewaxing of middle
distillates and lubricating oils [12,13]. For the latter process, mordenite based catalysts have
;iIso been employed [ lS,l9]. Finally, ZSM-S is used as an additive in some F C C catalysts for
octane enhancement of the gasoline produced [20,21]. The titanium containing analogue of
ZSM-5, named TS-1 [22,23], is employed for the hydroxylation of phenol to hydro-
quinone/catechol mixtures. Erionite was the catalyst in the old Selectoforming process [24,2S]
and is reported to be used again, in an improved form, i n the German Democratic Republic
for octane enhancement of reformate [26].
Until several years ago, most fundamental studies on zeolite catalysis, too, were restricted
to ;I very small number of structural types, again mostly faujasites, mordenite and ZSM-S.
Lately, this situation has changed significantly: The catalytic behavior of an ever increasing
number of alumosilicates and related microporous materials is being scrutinized, which stems,
in part, from the remarkable progress in hydrothermal synthesis and structure determination.
Likewise, the recent progress in post-synthesis modification techniques has a strong impact on
catalysis. It is another most important trend that zeolite catalysis spreads into almost all
branches of chemistry with a remarkable boom in the manufacture of organic intermediates
and fine chemicals. The present review paper is intended to describe some selected
developments in zeolite catalysis which, in the author’s opinion, deserve particular attention
in the nineties.

Hroader variety of microporous materials

More and more groups which have been traditionally active in zeolite catalysis are
adopting the techniques of hydrothermal synthesis with the benefit that they now dispose of a
broad assortment of zeolitic materials, in addition to the few ones which are commercially
available. In our opinion the alumosilicate zeolites listed in ‘Table 1 will receive particular
attention in catalysis over the coming decade. Even today, materials like Beta [27-311,
Omega [32-35], L [35-371, offretite [3 1,351, EU-1 [38-401, ZSM-12 (35,411, ZSM-22 [38,42-441,
E M - 2 3 [38,42,43] and ZSM-48 [35,38,45] are known to possess attractive catalytic properties
for many applications. It is likely that, in the nineties, several other alumosilicates with eight-,
ten- o r twelve-membered ring or even larger pores have to be added to this list. One example
could be ZSM-18 with its unique pore system consisting of pseudo-unidimensional, puckered
12-membered ring channels with side pockets capped by 7-membered rings [46].
The zeolites enumerated in Table 1 cover a n appreciable range of pore widths from ca.
0.5 to 0.8 nm which is the relevant range for most shape selective conversions. As a relative
nie:isure for the effective pore width of microporous materials, indices derived from certain
cat:ilytic test reactions have been found to be very useful. The oldest and best known example
is Mobil’s Constraint Index [47]. Other useful indices for this purpose are the Refined or
 23

TABLE 1
Aluniosilicate zeolites with particular potential in catalytic research. (The dotted line
separates zeolites with 10- and 12membered*ring pores. CI denotes the Constraint Index [47],
the* data for CI were taken from [48]; CI is the Refined Constraint Index [49,50], the
CI data were taken from [51]; SI stands for the Spaciousness Index [52,53], the SI data were
taken from [53]).

ZEOLITE IZA RELATED STRUCTURES CI CI* SI

CODE

Theta-1 TON ZSM-22, ISI-I, KZ-2, Nu-10 7.3 14.4 w l

ZSM-23 M7T EU-13, ISI-4, KZ-1 9.1 10.8 -1
Ferrierite FER ZSM-35, ISI-6, NU-23,FU-9 4.5 10.3 w 1
ZSMJ MF1 Silicalite 1, Nu-4, Nu-5 6- 8.3 6.8 w l
ZSM-48 EU-2, EU-11, ZBM-30 3.5 5.2 Fa1
ZSM-11 MEL Silicalite 2 5 - 8.7 2.7 u l
_____. . . . . . . . . . . . . . . . . . . . . . . . . . . ____
ZSM-12 MTW CZH-5, Nu-13, Theta-3 2.3 2.2 3
EU-1 EUO ZSM-50, TPZ-3 2.1 5
Offre tite OFF 3.7 1.8 5.5
Mordenite MOR 0.4 1.8 7.5
Omega MAZ Mazzite, ZSM-4 0.5 1.2
L LTL 1.0 16.5
Beta NU-2 0.6- 2.0 1.4 13- 19
ZSM-20 Intergrowth of BSS1) and FAU 0.5 20
Y FAU Faujasite, X 0.4- 0.5 1.3 21

1)Code for Breck’s Structure Six

Modified Constraint Index which was defined by Jacobs et al. [49,50] and the Spaciousness
Index which was introduced by Weitkamp et al. [52,53]. Wherever available, these three
indices are given for the zeolites listed in Table 1. From top to bottom, i. e., with increasing
effective pore width, both the Constraint Index and the Refined Constraint Index decrease
whereas the Spaciousness Index increases.
A number of elements other than silicon and aluminum can occur on tetrahedral sites in
the crystal lattice of microporous solids [54]. This way, a huge number of materials result, part
of which possess structures known from the alumosilicates. An example is titanium silicalite,
TS-I, with the crystal structure of ZSMd and very interesting catalytic properties in selective
oxidation reactions [22,23,55-571. Other members from this familiy of materials possess
completely new structures. This is particularly true for certain alumophosphates (AIPOds),
silicoalumophosphates (SAPOs) and the microporous solids derived from them by
24

incorporation of additional elements, such as titanium, manganese, cobalt or iron into the
lattice [58,59]. The potential of alumophosphate based molecular sieves in catalysis has
rcccntly been reviewed by Rabo et al. [60].

I ( c a . 0.8nm I lea. 1.2 nm 1

Fig. 1. Structures of AIP04-11, AIP04-5 and VPI-5.

Within the frimily of AIP04s, very large and super-large pore molecular sieves have
recently been identified. Davis et al. recognized that V P I J is a material with unidimensional
channels formed from 18-membered rings with an approximate diameter of 1.2 nm [61-631.
The structure of VPI-5 is shown in Fig. 1 along with the related structures of A1P04-5, a
material with unidimensional 12-membered ring pores, and AIP04-l 1, a material with
unidimensional 10-membered ring pores. It is seen that the cross section of the pores in
AIP04-I 1 is strongly elliptic which renders the material particularly interesting for shape
selective catalysis. The discovery of the existence of super-large pore molecular sieves might
be a landmark in zeolite catalysis. Such materials are of great interest for the catalytic
conversion of feedstocks containing large molecules as, e. g., petroleum residues. AIPO,s,
however, possess very little o r n o acidity. As soon as silicoalumophosphates or zeolitic
:ilumosilicates with super-large pores can be synthesized this will have a tremendous impact
o n catalysis. Another material, named MCM-9 [64,65a], does contain Si-VPI-5 but it is
apparently not a pure phase. A third molecular sieve material with very large pores, i. e.,
channels formed by more than 12 tetrahedra, is AIPO4-8 [65a] the structure of which has been
determined very recently [6Sb]. A1P04-8 possesses unidimensional channels formed from
14-membered rings with the approximate dimensions 0.79 x 0.87 nm [65b].

Shape selective catalysis: Towards larger molecules

Shape selectivity effects can occur if the pore width of the catalyst is in the same order as
the dimensions of reactant molecules, transition states, intermediates and/or product
molecules. The principles of shape selective catalysis in zeolites have been discussed in much
detail in prior review articles, e. g. [66, 671. In the past, almost all shape selectivity effects were
 25

related to the conversion of aliphatic compounds or inononuclear aromatics [68] in ten-

membered ring zeolites, typically HZSM-5. We perceive more and more attempts to make
use of shape selective catalysis for the production of larger molecules, e.g., valuable
derivatives of biphenyl or naphthalene. 4,4’-Diisopropylbiphenylwhich is an intermediate for
liquid crystals could be produced from propene and biphenyl in high yields on dealuminated
H-mordenite [69]. Other 12-membered ring zeolites like HY, H L or H-offretite which were
tested for comparison gave very poor results. So did the original mordenite sample with an
Si/AI ratio of 5. Upon massive dealumination up to an Si/AI ratio of 1300 mesopores were
created. It was one of the authors’ conclusions that the mesopores are important for an
efficient mass transport of the bulky molecules and that dealumination, i. e., dilution of the
active sites, slows down both coke formation and undesired alkylations, e. g. in para-meta
positions.
2-Methylnaphthalene which is an intermediate in the synthesis of vitamin K can be formed
by isomerization of 1-methylnaphthalene on acid catalysts. Usually, however, the
isomerization is accompanied by undesired side reactions, especially by transalkylation and
coking, and this was found to be particularly true for zeolite H Y [70]. In HZSM-5, on the
other hand, the isomerization turned out to be severely hampered by diffusional limitations.
As shown in Fig. 2, certain zeolites with an intermediate pore width, characterized by
Spaciousness Indices from 3 to ca. 16, gave excellent results: Initially, the equilibrium

6\” 100 I I 100 I I

HZSM-12 (SI = 3) . H-EU-1 (SI = 5) -
>: 75- Si/AI = 35 - 75 - Si/AI = 20 -
- \m: O S 1
- ; 05
-I
w
25- - 25- -
P I I 1 I

X
- 100 I
H-Mordenite
I

(SI = 7)
1001 I

H-Beta
I

(SI = 16)
Si/Al = 6.7-

O ,,-x, -
y,*,
A y,,
--
n - 1 I

STREAM, h

Fig. 2. Isomerization of I-methylnaphthalene in acid zeolites with intermediate pore widths at

300 “C after [70] (SI: Spaciousness Index; Tr: Transalkylation products).
26

conversion of ca. 70 % was achieved. The bimolecular transalkylation into naphthalene and
dimethylnaphthalenes which requires a very bulky transition state and/or intermediate, was
almost completely suppressed. With HZSM-12, H-EU-1 and H-Beta the deactivation was
moderate. Only with H-mordenite, there was a rapid deactivation due to coke formation
which has probably to do with the relatively high aluminum content rather than with the
unidimensional pore system; otherwise one would expect the same rapid deactivation for
HZSM-12 which has unidimensional pores as well.
2,6-Dimethylnaphthalene is a particularly valuable compound. It can easily be oxidized
into naphthalene-2,6-dicarboxylicacid which is a starting material for high quality polyesters,
polyamides and liquid crystals. The problem in its synthesis is that it is usually formed
together with 9 other isomers which are difficult to separate. In principle, zeolite catalysis
offers the possibility of enhanced selectivities for the 2,6-isomer, since its molecular
dimensions are smaller than those of most other isomers. Indeed, Matsuda et al. [71,72] found
that the disproportionation of 2-methylnaphthalene in H Z S M J leads to a dimethyl-
naphthalene fraction which contains the 2,6-isomer (and the 2,7-isomer which has the same
molecular dimensions) in excess of thermodynamic equilibrium. The yields, however, were
very small, presumably due to diffusional limitations. By dealumination of the external surface
with (NH&SiF6 it was shown that the shape selective disproportionation occurs inside the
ZSM-5 pores [73].
Another way to 2,6-dimethylnaphthalene is the shape selective alkylation of naphthalene
or 2-methylnaphthalene with methanol. Fraenkel et al. [74] did observe such enhanced
selectivities for 2,6- and 2,7-dimethylnaphthalene on HZSM-5, but not on H-mordenite or
HY. These authors proposed [75,76] that the shape selective conversion of naphthalene
derivatives occurs uf the cxternul surjiuce of zeolite ZSM-5, in so-called "half-cavities". This
concept which was generalized by Derouane et al. [77,78] has, however, been questioned
severely [70,79]. It is more likely that the shape selective alkylation of naphthalene or
2-methylnaphthalene on HZSM-5 occurs inside the pores and is slowed down by diffusional
limitations.
So far, most shape selectivity effects were observed in zeolite Z S M J . It is clear from the
origin of these effects [66,67] that with bulkier reactant and/or product molecules, shape
selectivity can occur in zeolites with 12-membered ring pores as well. An example is the
suppression of transalkylation of methylnaphthalenes in HZSM-12, H-EU-I, H-mordenite or
H-Beta, as shown in Fig. 2. Even in the very open and spacious pore system of zeolite Y shape
selectivity effects were observed, e. g. during the competitive hydrogenation of cyclohexene
and cyclododecene in Rh/NaY [go], hydrocracking of hydropyrenes in NiW/ultrastable Y [81]
or catalytic cracking of cis-decalin/trans-decalinmixtures in ultrastable Y [82].

Petroleum refining and commodity petrochemicals

The application of zeolite catalysts in petroleum refining and the manufacture of
commodity petrochemicals is sometimes considered as a mature technology. Even in these
fields, however, there is room for improvements and new developments. Large efforts are
being undertaken by the industry to develop FCC catalysts which yield gasoline with enhanced
octane numbers, especially motor octane numbers. Once the petroleum prices rise again all
problems associated with catalytic cracking of residues will receive renewed attention,
especially the resistance of the zeolite in FCC catalysts towards vanadium and nickel.
Possibly, new zeolite based hydrocracking catalysts will be developed. For example, Idemitsu
Kosan Co. claims a novel iron on Y-type zeolite catalyst for residue hydrocracking [83]. For
the isomerization of light alkanes, zeolite catalysts with higher acid strength and hence higher
activity are desirable, so that lower process temperatures can be applied, where the
equilibrium is more favorable for the high-octane isomers. Making aromatics from liquefied
petroleum gas (LPG) by BP/UOP's Cyclar [85] or Mobil's M2-Forming process [86] is ready
for commercial application and the same is probably true for the production of distillates
from light olefins by the MOGD process [87]. Acid pentads could have advantages [88] over
the conventional organic cation exchange resins which are used as industrial catalysts for the
production of methyl tert.-butyl ether. Another process which offers a large potential for
zeolite catalysts is the manufacture of cumene from benzene and propene.

Dewaxing by isomerization
The cold flow properties, e. g. the pour point and cloud point, of petroleum fractions are
largely determined by their content of normal paraffins. One method for the removal of these
disturbing waxes is shape selective hydrocracking on ZSMd based catalysts [13]. In this
process, the undesired paraffins in the boiling range of the middle distillate or lubricating oil
feedstock are converted into gasoline and C, + C4 (LPG) hydrocarbons. Another approach is
to transform the waxy paraffins into branched isomers which have considerably better cold
flow properties. This way, the yield loss necessarily associated with dewaxing by selective
hydrocracking could be avoided.
The isomerization of long chain n-alkanes can indeed be achieved on bifunctional zeolite
catalysts with a strong hydrogenation component, e. g., Pt/CaY or Pd/LaY in the presence of
hydrogen [89,90]. Under these conditions, skeletal isomerization takes place at the acid sites
via carbenium ions. These carbenium ions, however, can also undergo 0-scission, then the
overall reaction is hydrocracking. Since skeletal rearrangement and 0-scission are consecutive
reactions, the selectivity for long chain iso-paraffins is high at low conversions, but as the
conversion is increased, hydrocracking becomes more and more severe. In other words, the
yield of the desired iso-paraffins in dependence of the conversion of long chain n-paraffins
passes through a maximum. Even with the best catalysts based on zeolite Y, this maximum
yield of long chain iso-alkanes amounted to ca. 60 % (891.
Significantly higher yields of long chain iso-alkanes can be attained on certain other
zeolites, especially on bifunctional forms of Beta [91,92], ZSM-22 [43] and ZSM-23 [43]. Two
examples are shown in Fig. 3: The maximum yields of iso-decanes from n-CloHzz or iso-
tetradecanes from n-CI4H30 on Pd/H-Beta are above 70 %.
In the future, the fundamentals of dewaxing by isomerization need further clarification.
Presumably, the mechanistic reasons for the unusually high yields of iso-alkanes are different
28

for zeolite Beta on the one hand and medium pore zeolites such as ZSM-22 or ZSM-23 on the
other hand. It has been argued [43] that in the latter zeolites, B-scission is slowed down
because the highly branched precursors for the most favorable type of 13-scission (so-called
type A O-scission) cannot form due to spatial constraints. No explanation for the interesting
behavior of zeolite Beta has been proposed so far. Apparently, not all samples of zeolite Beta
do give the high yields of long chain iso-alkanes [27]. It is particularly desirable to find out the
key property of zeolite Beta which governs its catalytic performance in isomerization of
n-alkanes. Furthermore, isomerization experiments with mixtures of homologous n-alkanes
on bifunctional Beta catalysts are needed in the future.

100

-
n Decane n-Tetradecane
WIF = 570g.hImol WIF = 6LOg-hlmol
$ 60
0 Xn-De 0 Xn-Te
> Ylso
A Ycr.
0, 60
tl!
>
Ili
0
10
X

z
0
v)
OL 20
W
2
0
V

210 220 230 210 250 260 270 280 190 200 210 220 230 210 250 260 270

TEMPERATURE , ' C

Fig. 3. Isomerization and hydrocracking of long chain n-alkanes on 0.27 wt.-% Pd/H-Beta
after [92]. (The hydrogen partial pressure was 2 MPa).

Isobutane/butene alkylation
This refinery process converts the C4 by-product from catalytic crackers into high quality
gasoline. Today, alkylation is carried out either with concentrated sulfuric acid or anhydrous
hydrogen fluoride as catalysts. There is a very large incentive for replacing these processes by
a new technology which is environmentally more acceptable and safer.
In the sixties and seventies, the potential of acid faujasite catalysts in isobutane/alkene
alkylation has been explored by several groups [93-1011. Typical results are depicted in Fig. 4
and Fig. 5: 011fliefiesh zeolite, the olefin is totally converted (Fig. 4), and a perfect alkylate is
formed (Fig. 5 ) which consists fully of iso-alkanes. After a certain time on stream, however,
the olefin conversion drops and the product quality deteriorates drastically: More and more
C8-alkenes form and eventually, the zeolite no longer alkylates isobutane; rather, the butene
 29

+a
- 100

0 80
I-

z
60
u)
U
W
5 40
0
0

TIME ON STREAM, rnin

Fig. 4. Conversion of isobutane with 1-butene (11:l) at 80 "C in the liquid phase on CeY-98
zeolite after [loo].

bp

I
W

I I I I

Fig. 5. Reaction of isobutane with I-butene on CeY-98 at 80 "C. Composition of the Cg

product fraction after [loo].

oligomerizes. This dramatic loss of catalyst performance is due to the build-up of low
temperature coke from the olefin. Concomitantly, the zeolite looses its hydrogen tranfer
activity.
The yields of alkylate which could be achieved on faujasite catalysts were much too low for
an industrial application. If one arbitrarily considers the product as an alkylate as long as it
contains 90 mol-% or more alkanes in the C,-fraction, then one can define an integrated yield
30

of alkylate (total mass of alkylate formed/mass of catalyst) for a given catalyst and set of
reaction conditions. Typically, these yields were in the order of SO to SO0 mg/g [loo]. Zeolite
HZSM-S was reported to be inactive in isobutane/butene alkylation a t temperatures up to
100 "C and this was attributed to the narrow pores [102]. In the meantime, a much broader
variety of zeolitic materials and techniques for their manipulation are known. Given the high
incentive for replacing the H$04 and HF catalysts we foresee a renewed interest in the use
of zeolite catalysts for isobutane/butene alkylation.

Organic intermediates and fine chemicals

Although so far, the industrial application of zeolite catalysts has been essentially
restricted to hydrocarbon chemistry, their potential in the synthesis of organic intermediates,
especially of oxygen and nitrogen containing compounds, was recognized by several research
groups as early as in the sixties. This early work was reviewed by Venuto and Landis [103].
With the advent of the modern molecular sieve materials, novel modification techniques
and a better understanding of shape selective catalysis, a renewed interest arose in the
utilization of zeolite catalysts for organic syntheses from about 1980 onward. O n e result was
the introduction of at least one new commercial process, viz. the hydroxylation of phenol to
hydroquinone/catechol mixtures on titanium silicalite by EN1 [22,23]. A few others, such as
the conversion of methanol with ammonia with enhanced yields of methylamine and
dimethylamine at the expense of the less valuable trimethylarnine on narrow pore zeolites like
Rho or ZK-5 [104-1091 are considered to be ready for commercialization. In recent years, the
potential of zeolite catalysts was explored in numerous organic reactions, both in the gas and
in the liquid phase. Essential parts of this modern work have been discussed and evaluated in
a number of excellent review articles [110-1141. The application of zeolite catalysts in the
manufacture of organic intermediates and fine chemicals will continue to be a thrust area in
the nineties. In the following paragraphs a few selected reactions will be addressed which,
from the author's viewpoint, are examples for the specific behavior and versatility of
molecular sieve catalysts.
Gallezot et al. [ 1151 investigated the selective hydrogenation of cinnamaldehyde in the
liquid phase at 60 "C under a hydrogen pressure of 40 bar. The first hydrogenation step can
lead to either 3-phenylpropanal or cinnamyl alcohol (Fig. 6), depending on whether hydrogen
adds to the carbon-carbon double bond or the carbonyl group. Ultimately, 3-phenyl-
propanol is formed. Two samples of Pt/Y zeolite were prepared by ion exchange of NaY with
Pt(NH3)4?+ and subsequent decomposition of the ammine complex under different, but well
defined conditions. The Pt loadings were 11 and 14 wt.-%, respectively. Transmission electron
microscopy revealed that, in the first sample, the noble metal was homogeneously distributed
inside the zeolite with a particle diameter of 1 to 2 nm. In the second sample, the platinum
was still inside the zeolite pores. However, it formed much larger agglomerates with an
average diameter of 5 nm, and these metal particles were preferentially located in a shell near
the external surface.
 31

clnnamsldehyde
(CAL)
a cn = CH - C H ~ O H

clnnemyl alcohol (COU

Catalyst

11 wt.-% PtlY (1-2 nm. insidel

14 wt.-% PtlY (5 nm, inside] 97 %

"Liquid phase, T = 6OoC. pnz = 40 bar

After P. Gallerot el at.. Catal. Letters2 169 11990)

Fig. 6. Selective hydrogenation of cinnamaldehyde to cinnamyl alcohol on platinum clusters

encapsulated in zeolite Y after [ 1151.

The results summarized in Fig. 6 show that hydrogenation on platinum in Zeolite Y gave
much better selectivities for cinnamyl alcohol than on a non-zeolitic reference catalyst like
platinum on charcoal. This was interpreted by a special shape selectivity effect: Inside the
faujasite pores, the cinnamaldehyde molecule can adsorb on the platinum clusters, sitting in
the supercages, only in an end-on mode, i. e., via its carbonyl group, through the twelve-
membered ring window. By contrast, the adsorption and activation of the carbon-carbon
double bond in the center of the molecule is considered to be strongly hindered, but only as
long as the supercage is completely filled with platinum; a small cluster of six or less metal
atoms would leave enough space for cinnamaldehyde molecules to enter the supercage and
adsorb laterally, i. e., via the carbon-carbon double bond, so that hydrogenation leads to
3-phenylpropanal. This is how the authors explain that on Pt/Y with the 1 to 2 nrn clusters
the undesired hydrogenation of the carbon-carbon double bond occurs to a certain extent.
Adamantane has been found to form readily by rearrangement of tetrahydro-
dicyclopentadiene (tricycIo[5.2.1.O2b]decane, see Fig. 7) which, in turn, is easily accessible
from the Diels-Alder dimer of cyclopentadiene. Suitable catalysts for this interesting
reaction are acid or bifunctional forms of zeolite Y, such as rare earth Y (REY),
Pt-Re/REY or H Y [116,117]. For example, at temperatures around 250 "C, adamantane
selectivities between 40 and 50 % could be achieved at conversions above 50 %. Likewise,
mixtures of 1- and 2-methyladamantane were obtained on the same catalysts from tricyclo-
[6.2.1.0.2>7]undecane [ 1171. One of the conclusions from these studies was that the faujasite
structure, due to the existence of almost spherical cages, is in general a promising catalyst for
the formation of spherical molecules, and adamantane or its homologues might be just
examples for spherical molecules which can be advantageously synthesized inside the cages of
zeolites.
 L

a) K. Honna et al.. ldemllsu Koaan Co., since 1985

b) G.C. Leu and W.F. Maler. LanOmulr 1987

endo- exo- Adamantane

Trlcyclo [5.2.1.0"] decsne

Fig. 7. Formation of adamantane from tetrahydrodicyclopentadiene in zeolite Y after

[116,117].

A more recent article [ 1181 reports on the formation of adamantane and its homologues
from a simple alkene, viz. 1-hexene, at 240 "C in SAPO-34, a silicoalumophosphate with the
chabazite structure. However, unlike in the above-mentioned studies with zeolite Y, the
adamantanes did not appear in the gaseous effluent from the reactor; rather, they were built
up and entrapped inside the chabazite cages (see Fig. 8), presumably again via tetra-
hydrodicyclopentadienes as intermediates. The adamantanes are, of course, too bulky to
escape through the eigth-membered ring windows of the chabazite cage. The only way to
detect them is the dissolution of the used molecular sieve, e. g., in hydrogen fluoride, followed
by extraction with an appropriate solvent, e. g., CH,Cl,. It has been again concluded from
these results [118] that the microporous catalyst with its cages of molecular dimensions can be
considered as an ideal host for transition state guests which lead to spherical, polynuclear
products. At higher reaction temperatures around 400 "C, naphthalene and its methyl
derivatives were preferentially formed inside the cages (cf. Fig. 8) of SAPO-34, probably in
related chemical pathways via dicyclopentadienes.
It is too early to judge upon the general validity of these concepts. If zeolite cages act
indeed as hosts which favor the formation of spherical products, then one could imagine a
completely new direction of zeolite catalysis: A zeolite with cages of appropriate size and
geometry could act as u templute which directs a chemical reaction towards the desired
product, which may or may not have a spherical shape. If this product is of sufficiently high
value (and/or the molecular sieve used as a reaction template sufficiently cheap) then it could
even be economical to dissolve the zeolite so that the product becomes accessible through
extraction. In the precise sense, the zeolite would then no longer play the role of a catalyst
(with a high number of closed catalytic cycles or turnovers) but simply act as a selectivity
directing reaction vessel with uppropriute moleculur dinzensions.
 33

After J.R. Anderson el. al.. J. Catal. 124.

259 (1990)
Flow reactor, I-hexene in N, dissolution of used catalyst
in HF. extraction with CH,CI,, analysis by G C l M S

b-
Adamantane

1-Hexene - '2400c Methyladamantane

Dimethyladamantane
Ethyladamantane
1 =4OO0C

Naphthalene
Methylnaphthalenes
Dimethylnaphthalenes

Fig. 8. Formation of polycyclic hydrocarbons entrapped inside the chabazite-like cages of

SAPO-34 from 1-hexene after [118].

An example for such a reaction which one could envisage in a very speculative manner is
the synthesis of compounds with the dodecahedrane (C,,H,,, see Fig. 9) skeleton. Such
compounds which strongly resemble a sphere became accessible in the eighties by multi-step
syntheses, usually via precursors with the pagodane structure [ 119-1241. To our knowledge, no
systematic and professional attempt has been undertaken so far, to utilize molecular sieves for

L H . Paquette et al., alnce ce. 1981

H. Prinzbach e l al., since ca. 1985

Fig. 9. A speculative example for the use of molecular sieves as reaction templates:
Pagodanes to dodecahedranes.

dodecahedrane synthesis. The reasons are obvious: Modern synthetic organic chemistry and
professional zeolite chemistry are dealt with in different laboratories and separated from each
other. It is a managerial challenge to bring inorganic host/guest chemistry and synthetic
organic chemistry together.
34

Stereoselective catalysis
Enantioselective catalysis in zeolites is often looked upon as one of the ultimate goals. It
requires chiral centers next to the catalytically active sites. In principle, different methods can
be used to induce chiral properties.
According to Dessau [125], chiral hydrogenating catalysts result if a n acid zeolite loaded
with a hydrogenation metal, e. g., Pt/HZSM-5, is neutralized with an optically active
amine, such as S-(-)- a-methylbenzylamine (Fig. 10). O n such a catalyst, the hydrogenation of

2-Phenylbutene y 5 2-Phenylbutane

Pt/(CH 3 - C x - N H , ) Z S M - 5
I
H H

C,H,- C - CH,
I1
0
b- C,H,- k-
OH
CH,
+H2
Acetophenone 1-Phenylethanol

Afler R.M. Dessau. US Patent 4 554 262, Mobil Oil Corp.. 1985

Fig. 10. Enantioselective hydrogenation of prochiral compounds after [ 1251.

prochiral compounds, e. g., 2-phenylbutene or acetophenone, is claimed to give 2-phenyl-

butdne or 1-phenylethanol, respectively, in a n optically active form, i. e. with an excess of one
cnantiomer. It is astonishing that, since the appearance of Dessau’s patent [ 1251, his approach
has not heen dealt with more comprehensively in the scientific literature.
Zeolite Beta, as it can be synthesized today, is an intergrown hybrid of two closely related
structures [120,127]. One of these end members, the so-called polymorph A, forms an
enantioniorphic pair while polymorph B is achiral. Since the structure of zeolite Beta has
been determined, large efforts are being undertaken to develop synthesis procedures for its
pure polymorph A. If, at the end, these endeavors will be successful and methods for the
separation of the enantiomorphic pair will be available, then the old dream of
enantioselective catalysis i n zeolites could become reality.

Base catalysis
Base catalysis in zeolites is still an underdeveloped field of science and technology,
especially in comparison with acid catalysis. In the literature, essentially three approaches to
create basic sites in zeolites can be discerned. Interestingly, these attempts were almost
completely restricted to faujasites.
It was recognized early [ 1281 that faujasites exchanged with large alkali cations, especially
CsX and RbX, catalyze the side chain alkylation of toluene with methanol or formaldehyde,
rather than ring alkylation to xylenes which occurs on acid zeolites. Later, side chain
alkylation to styrene/ethylbenzene mixtures on faujasites exchanged with alkali cations has
 35

been studied in detail by several groups [129-1351. It has been generally concluded that this is
a base catalyzed reaction via carbanions, although the nature of the basic sites under reaction
conditions remained a matter of debate [136,137].
Clusters from sodium metal can be generated in the pores of faujasites using various
techniques. According to Jacobs et al. [138-1411 the preferred method from the viewpoint of
catalysis is the impregnation of the dehydrated zeolite with NaN, followed by the thermal
decomposition of sodium azide under carefully controlled conditions. In faujasites modified
by this procedure, three types of sodium particles can be distinguished by ESR spectroscopy:
Na43+ clusters located inside the sodalite cages, neutral Na, clusters inside the pore system
and neutral Nay particles at the external surface. Basic framework oxygen anions next to
intracrystalline Na, clusters seem to be the active sites [141] for base catalyzed reactions such
as the isomerization of cis-2-butene [ 139,1401, the side chain alkylation in toluene,
ethylbenzene or cumene with ethene [ 1411 or regioselective ring opening in unsymmetrical
epoxides [142]. While basic zeolites prepared via the azide method appear to be very active
catalysts, it remains to be seen how stable they are against potential poisons, such as water
formed in many reactions or sulfur compounds present in traces in many feedstocks.
The third method, introduced by Hathaway and Davis [143,144], consists of impregnating
a faujasite, e. g. CsNaY, with cesium acetate followed by decomposition of the acetate at
450 "C in air or helium. It appears that the active site in such catalysts is cesium oxide rather
than metallic cesium, cesium carbonate or cesium hydroxide [ 1451. These modified faujasites
were tested in various base catalyzed reactions, such as the dehydrogenation of isopropanol to
acetone [ 144-1461 and the alkylation of methane, ethane, acetone or toluene with methanol
[146]. It will be interesting to observe whether this new method is accepted by other groups. If

Si 0,

0 0 0 0 0 0 0 0 0 0 0 0

A l PO1
Al

0 0 0 0 0 0 0 0 0 0 0 0

Zeolite H'B He H@
IAcid 1
o \ i / V S /o\;
i /VSi /o\si /O\$/O

/ \ / \ I \ / \ / \ / \
0 0 0 0 0 0 0 0 0 0 0 0

OH8 OH8 OH 0
Sip0 ? 0
(Base 1
/ \
i ' o i ' o o/\o d'o o/\o 0 0

Fig. 11. Neutral, acid and hypothetical basic molecular sieves.

36

so, this could foster base catalysis in zeolites including, perhaps, shape selective base catalysis
with its huge potential in the manufacture of organic intermediates and fine chemicals.
A hypothetical approach towards a new generation of molecular sieve Briinsted bases
might be seen in the preparation of microporous silicophosphates, either by direct synthesis or
post-synthesis modification. As shown schematically in Fig. 11, and for obvious reasons, a
molecular sieve S i 0 2 , such as silicalite 1 or 2, has no lattice charge. The same is true for the
overuff lattice in AIP04s due to the strictly alternating arrangement of @lo4)- and (PO4)+
tetrahedra. Alumosilicate zeolites are cation exchangers and, in their H + forms, strong
Briinsted acids. By mere analogy and in a formal manner a porous silicophosphate would be
expected to be an anion exchanger and, in its OH- form, a Briinsted base.
In a triangular compositional diagram (Fig. 12), the alumosilicate zeolites and the
hypothetical silicophosphates are just limiting cases which are represented by positions on the
Si02-A102' and SO2-PO2+ connecting lines, respectively. There exist a whole field of cation
exchangers, embracing both the SAPOs and alumosilicate zeolites, and a whole field of

A Electroneutrality

Field of anion
/e xc ha ng e rs ?
.....................

AI02-/ 0.5 SiO,

-
Field of cation :. Al- high :
exchangers : rich silica :
).

ZEOLITES

Fig. 12. Schematic representation of the possible compositions of molecular sieve materials in
the Si02/A102/P02 system, adapted from Flanigen et al. [%I.
 37

hypothetical anion exchangers, and these two fields are separated from each other by the
electroneutrality line which connects the AIPO4s and SiO2.
It has, in fact, been reported [147] that the overall framework charge in a zeolite can be
changed from negative to positive if a synthetic zeolite is treated with a melt of ammonium
dihydrogen phosphate at 230 "C. For the resulting materials with anion exchanger properties
the name phosphated aluminosilicates or PASOs [147] was coined. It remains to be seen
whether the new procedure is reliably applicable to other zeolites and by other groups. If so,
the door to a new class of microporous Bronsted bases would be open.
It is sometimes difficult to distinguish unambiguously between acid and base catalysis
on molecular sieve materials. Recently, Dessau [ 148,1491 proposed the conversion of

HZSM-5
(SIIAI = 35)
HC CH
T = 225OC I X=25%

CHS-C-CH,-CH,-C-CH, 2,5-Dlmethyl-
I1 I1 luran
0 0
Acetonylacetone
-C /C%
-.,A- H,C
I
H,C, /CH
II X=51%
S=95%
NaZSM-5
$
(SI/Al = 13 000) 0
(Na/AI = 300) 3-Methylcyclo-
T = 300% pentenone

After R.M. Dessau, Zeolites -

10, 205 (1990)

Fig. 13. Conversion of acetonylacetone as a valuable test reaction for distinguishing between
acid and base catalysis in zeolites after [149].

2,5-hexanedione (acetonylacetone) as a test reaction which, from the products formed, allows
a safe discrimination (Fig. 13). On acid zeolites, e. g. HZSM-5, 2,s-dimethylfuran is formed
almost exclusively at medium conversions; base catalysis, on the other hand leads to 3-methyl-
cyclopentenone, again in a very high selectivity a t conversions above 50 %. A broader
application of this test reaction could be very helpful in future research on base catalysis in
zeolites.

Engineering aspects: Coupling of exothermic and endothermic reactions

Lower alkenes, i. e., mainly ethene and propene along with some butenes, are currently
produced on an industrial scale by steam cracking of petroleum or natural gas derived
hydrocarbon fractions, such as light naphtha. Steam cracking is a non-catalytic pyrolysis at
high temperatures around 850 "C in the presence of steam. The process is highly endothermic.
An alternative route to lower alkenes is the methanol-to-olefin (MTO) process [13].
Ultimately, this process relies on coal or natural gas as raw materials from which methanol
38

Alter S. Nowak el .I.. since 1983

Fig. 14. Production of lower alkenes by coupled methanol/hydrocarbon cracking (CMHC)

after [150-152]. X is the conversion and Y denotes product yields.

can readily be manufactured via gasification to CO and H, followed by methanol synthesis.

MTO is a catalytic process: Methanol is dehydrated on Z S M J type catalysts under such
conditions that the yield of C,- to C,-alkenes is maximized. This is usually the case at
temperatures in the order of 400 "C. MTO which is not yet a commercial process, is strongly
exothermic.
Nowak et al. [150-1521 advanced the idea to combine the exothermic MTO reaction and
the endothermic hydrocarbon cracking with such a feed ratio that the overall process is nearly
thermoneutral (Fig. 14). This is favorable from an engineering point of view since the
problems associated with heat removal in MTO and heat generation in steam cracking are
avoided. One problem in the coupled rnethunol/liyrlrocurbon cracking (CMHC) is to find an
appropriate reaction temperature which is not excessively high for MTO, yet sufficiently high
for hydrocarbon cracking. Since the latter reaction which in the non-catalytic steam cracking
process proceeds via radicals, is now catalyzed by an acid zeolite (presumably with a
mechanism via carbocations), much lower temperatures in the range of 600 to 700 "C seem to
suffice. Typical conversions and product yields achieved in CMHC with methanol and
n-butane are given in Fig. 14. For the most part, zeolite HZSM-5 was used as catalyst, recent
studies [152] revealed, however, that molecular sieves with a lower acid strength, such as iron
containing ZSM-5, might offer advantages in CMHC, especially a lower coking and
deactivation rate.

Zeolites: Hosts for a variety of guests; ship-in-the-bottle catalysts

It is evident that in the channels or cages of zeolite molecular sieves, a broad variety of
guests with catalytically attractive properties can be accommodated or encapsulated. Indeed,
host/guest chemistry is playing an ever increasing role in the preparation of sophisticated
 39

zeolite catalysts. Zeolite host/guest chemistry which is, at this time still at its infancy, can be
expected to become a thrust area in the nineties. In a few review articles [113,153,154], the
potential of zeolite host/guest chemistry for catalysis has been outlined and the different
approaches were described.
In complete analogy with a ship-in-the-bottle, transition metal complexes which are too
bulky to escape through the twelve-membered ring window of faujasite, can be synthesized in
its supercages from sufficiently small building blocks which do have access to the cages.
The best known examples are phthalocyanine complexes of cobalt, nickel, copper and iron
[ 155-1591. For their preparation, the transition metal ion is first exchanged into the zeolite
whereupon the complex is synthesized by reaction with 1,2-dicyanobenzene at temperatures
around 300 "C. Usually, part of the phthalocyanine complexes are formed at the external
surface, but this part can be selectively removed by Soxhlet extraction. Iron phthalocyanine in
NaY has also been synthesized from [HFe3(CO),,]- which was first oxidized and then reduced
under controlled conditions whereupon 12-dicyanobenzene was admitted [ 1601. Metal
phthalocyanines immobilized in zeolite Y have been described to exhibit interesting catalytic
properties, e. g., in oxidation reactions with iodosobenzene [ 158,1591: Reactant shape
selectivity occurred with cyclohexane/cyclododecane mixtures, n-octane was oxidized in a
regioselective manner and stereoselective oxidation of methylcyclohexane and norbornane
took place. Recently, an electron donor/acceptor complex (Na+)4 (FePc)@/NaY was
prepared from iron phthalocyanine (FePc) encapsulated in NaY by reaction with sodium
naphthalene, Na+ (CloH8)-, and this complex gave unusually high ratios of trans-2-butene/
cis-2-butene in the selective hydrogenation of butadiene [ 1601.
Another guest which has been synthesized in zeolite Y as a host is cobalt salen [161].
About one Co2+ per two supercages was exchanged into NaY followed by sublimation of the
free ligand salen [1,6-bis(2-hydroxyphenyl)-2,5-diaza-l,5-hexadiene]into the zeolite voids.
Cobalt salen, a tetradentate chelate has dimensions greater than the window diameter of
zeolite Y, hence it is a true ship-in-the bottle. The complex and its pyridine adduct were found
to form adducts with dioxygen and can be considered as hemoglobin mimic [161].
Metal clusters entrapped in the intracrystalline voids are of utmost importance in zeolite
catalysis. Since the pioneering work of Gallezot et al. [162,163] it is known that the size and
location of such clusters depend, to a large extent, on the preparation conditions. The metal
can be introduced by ion exchange with its cation or a cationic complex, especially an ammine
complex, followed by a controlled thermal treatment including reduction. Metals which are
difficult to introduce by ion exchange in aqueous suspension, such as molybdenum, vanadium
and others, can often be easily incorporated by solid state ion exchange which has recently
found much interest [ 164-1661. An alternative method for preparing highly dispersed metal
clusters in molecular sieves is the adsorption and controlled decomposition of volatile metal
compounds, mostly carbonyls [167]. In all these methods, metal atoms or small metal
oligomers are probably formed as intermediates which migrate rapidly through the zeolite
pores and coalesce to form larger agglomerates. Once these particles are larger than the
windows of the cages the metal agglomerates find themselves entrapped, e. g., in a supercage
40

of faujasite. In other words, it is the ship-in-the-bottle principle which enables the preparation
of highly dispersed metals in zeolites.
Similarly, the encapsulation af metal carbonyls in zeolites has found considerable interest
because many carbonyls can act as selective catalysts. An example is the ship-in-the-bottle
formation of Pd,,(CO), clusters in NaY [168].
While, in the eighties, the potential role of zeolites as hosts for a variety of guests has
clearly been recognized, host/guest chemistry has been essentially confined to faujasites. It is
likely that, in the nineties, host/guest chemistry will be systematically extended to additional
microporous materials, such as AlPO,-8, VPI-5 or the hexagonal counterpart of faujasite,
Breck's Structure Six,which can now be synthesized in a pure form using a crown-ether based
supramolecule, viz. 18-crown-6,as template [ 1691.

Photochemical transformations of guest molecules in zeolites as hosts

It is an attractive idea to combine the host/guest principle with photochemistry. Indeed,
one can expect that the selectivities of certain photochemical reactions can be altered if they
are carried out under the spatial constraints inside the pores of an appropriate zeolite.
Examples for shape selective photochemical reactions have already been described in the
literature, and one example is summarized in Fig. 15.

it;
Norrish Type II Reaction: C6H5

C6H5

R H H
L

~~~~~ ~ ~~~~

E/C In: Benzene NaX CBX NaZSM-5 NaZSM-11 Na-Beta

R= C,H, 1.9 1.5 1.9 >>lo0 >>I00 0.62

R= C,,H2, 2.7 2.7 6.8 >> 100 >> 100 0.48

Alter V. Aemamurlhv el 01.. J. Cham. SOC, Chsm. Commun. 1213 (1989)

Fig. 15. Shape selective photolysis of alkanophenone guests in zeolites as hosts after [170].

The Norrish type I1 reaction, i. e., the photochemical decomposition of alkanophenones

was studied in non-acidic forms of zeolites X, ZSM-5, ZSM-11 and Beta [170]. The interme-
diate 1,4-biradical can stabilize into two directions, viz. by cyclization (C) to a cyclobutanol or
elimination (E) to acetophenone and an olefin. In a liquid solvent like benzene, E/C amounts
to 1.9 for octanophenone and 2.7 for octadecanophenone, i. e., the elimination is slightly
preferred. Essentially the same E/C ratios are observed in zeolite X with its spacious pore
system. In the pentads, by contrast, the cyclization was almost completely suppressed, and
 41

this was attributed to the restriction of the rotational motion of the central u bond in the
1,4-biradical. In other words and in the language of the zeolite community, this is a
photochemical example for restricted transition state shape selectivity [66,67]. Interestingly,
zeolite Beta with its intermediate pore width clearly favors cyclization, especially for
octadecanophenone with its long alkyl chain, which is not yet understood.
Similar photochemical studies with molecules adsorbed in zeolites were carried out by
Turro et al. [171,172] and Zimmermann and Zuraw [173]. It has been found, for example,
that the photochlorination of n-alkanes in pentad zeolites proceeds with a high selectivity for
monochlorination at terminal methyl groups [172].

Conclusion: Zeolites and host/guest chemistry

Shape selective photochemistry, in a rigorous sense, is beyond the scope of a review on
zeolite catalysis. Nevertheless, the topic was briefly addressed because it clearly demonstrates
that through host/guest chemistry, zeolites begin to spread into various new branches of
science. Indeed, we foresee an ever increasing importance of the host/guest principle in
zeolite chemistry and catalysis. Given the role of zeolites as inorganic hosts, the zeolite
community is adviced to watch the current progress in tailor-made organic host molecules,
i. e., suprari~olecitlrrr chetnistty [ 174-1801. Enzyme mimics in zeolites, ship-in-the-bottle
catalysts and shape selective photochemistry in zeolites are just a few examples which show
that zeolite chemistry and supramolecular chemistry are growing together.

Acknowledgements
The author expresses his gratitude to the following funding institutions which have
sponsored his research on catalysis in zeolites: Deutsche Forschungsgemeinschaft,
Bundesministerium fur Forschung und Technologie, Fonds der Chemischen Industrie and
Max Buchner-Forschungsstiftung.

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G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 47
0 1991 Elsevier Science Publishers B.V., Amsterdam

ZEOLITES AS CATALYSTS FOR ALKANE OXIDATIONS

R.F. P art on, D.R.C. Huybrechts, Ph. Buskens and P.A. Jacobs
K.U. Leuven, Dept. B i o t e c h n i s c h e Wetenschappen, Laborat orium voor
Oppervlaktechemie, K a r d i n a a l M e r c i e r l a a n 92, 8-3030 Heverlee (Leuven),
Belgium

SUMMARY
The o x i d a t i o n o f u n a c t i v a t e d alkanes was s t u d i e d on z e o l i t e encaged
p h t h a l l o c y a n i n e s w i t h t e r t i a r y b u t y l hydroperoxide and on t i t a n i u m
s i l i c a l i t e w i t h aqueous hydrogen p e r o x i d e as o x i d a n t . On b o t h t y p e s o f
c a t a l y s t s secondary and/or t e r t i a r y a l c o h o l s and ketones a r e formed. The
o x y f u n c t i o n a l i z a t i o n occurs i n a r e g i o s e l e c t i v e way on t h e o u t e r carbon
atoms o f t h e hydrocarbon c h a i n , t h u s r e f l e c t i n g t h e shape s e l e c t i v e
properties o f the catalysts.

INTRODUCTION
The ma jo r industrial applications of zeolites in refinery and
pet roc hemic a l o p e r a t i o n s a r e r e l a t e d t o r e a c t i o n s where t h e z e o l i t e i s used
as an acid or bifunctional catalyst, e.g. cracking, hydrocracking,
isomerization, alkylation, etc. [l].
Th eref ore, up t o now most o f t h e
fundamental work i n t h e f i e l d o f z e o l i t e s has been c o n c e n t r a t e d on t h e i r
a c i d o r metal s t a b i l i z i n g p r o p e r t i e s . On t h e c o n t r a r y , relatively l i t t l e
e f f o r t s have been done t o e x p l o i t t h e u n i q ue f e a t u r e s o f z e o l i t e c a t a l y s t s ,
such as shape s e l e c t i v i t y , i n o t h e r t y p e s o f r e a c t i o n s [ 3-51. One o f t h e
l e a s t studied z e o l i t e catalyzed reactions i s t h e o x y f u n c t i o n a l i z a t i o n o f
alkanes i n t h e l i q u i d phase. N e v e r t h e l e s s , t h e g r e a t abundance o f alkanes
makes them t o one o f t h e g r e a t e s t r e s o u rces f o r t h e energy and f o r t h e
chemical industry. The extreme low r e a c t i v i t y o f alkanes makes their
a c t i v a t i o n and f u n c t i o n a l i z a t i o n a c h a l l e n g e f o r many chemical s c i e n t i s t s .
D u r i n g t h e l a s t 10 y e a r s many e f f o r t s have been done i n t h i s area u s i n g
homogeneous c a t a l y s t s [ Z ] . Therefore, m a j or c o n t r i b u t i o n s o f r e s e a r c h e r s i n
the f i e l d o f z e o l i t e catalyzed reactions f o r t h e f u n c t i o n a l i z a t i o n of
alkanes cannot h o l d o f f . I n t h i s work a l k a nes a r e o x i d i z e d by a p e r o x i d i c
oxygen source (ROOH) to the c o r r e s p o n ding alcohols and ketones with
maintenance o f t h e carbon c h a i n s t r u c t u r e , according t o t h e f o l l o w i n g
genera l r e a c t i o n scheme:

CnH(2n+2) + ROOH - ROH + H20 + CnH(2,,+qOH ( + CnHZnO)

48

The behav i o r o f two new t y p e s o f c a t a l y s t w i l l be discussed, namely

p h t h a l l o c y a n i n e c o n t a i n i n g l a r g e - p o r e z e o l i t e s and t i t a n i u m s i l i c a l i t e 1
(TS-1). The f o r m e r one uses t - b u t y l h y d r o p e r o x i d e as o x i d a n t , whereas
aqueous hydrogen p e r o x i d e i s t h e oxygen s o urce f o r t h e l a t t e r one.

ALKANE OXIDATIONS ON ZEOLITE ENCAGED PHTHALLOCYANINES

Introduction
M e t a l l o - p o r p h y r i n e s and p h t h a l l o c y a n i n e s a r e a c t i v e c a t a l y s t s f o r t h e
s e l e c t i v e e p o x i d a t i o n o f alkenes and h y d r o x y l a t i o n o f alkanes and many
o t h e r o x i d a t i o n r e a c t i o n s [6-81. They r e p r e s e n t models f o r t h e a c t i v e s i t e
o f cytochrome P-450. However, t h e y l a c k a p r o p e r mimic o f t h e p r o t e i n
function.
Metallo-phthallocyanines encaged i n z e o l i t e s Y have been proposed as
complete enzyme mimics [9-131. Z e o l i t e s can r e p l a c e t h e p r o t e i n p o r t i o n o f
n a t u r a l enzymes and m o d i f y t h e r e a c t i v i t y i n t h e same way as enzymes do by
imposing s t e r i c c o n s t r a i n t s on t h e environment o f t h e a c t i v e complex.
I n t h e p r e s e n t work, t h e c o n s t r u c t i o n o f a mimic o f cytochrome P-450
is at t emp t e d by in situ synthesis of iron-phthallocyanines in the
supercages o f zeolite Y and i n t h e channels o f VPI-5. I t s catalytic
a c t i v i t y and s e l e c t i v i t y i s t e s t e d i n t h e o x y f u n c t i o n a l i z a t i o n o f n-a1 kanes
w i t h t e r t i a r y b u t y l hydroperoxide.

ExDerimental
Materials
A sample o f NaY w i t h a Si/A1 r a t i o o f 2.46 was purchased f r o m Ventron.
VPI-5 was s y n t h e s i z e d a c c o r d i n g t o a r e c e n t l i t e r a t u r e procedure [14]. 1,2-
Dicyanobenzene (DCB) (+98%), f e r r o c e n e (FeCp2) (+98%), t e r t i a i r y butyl
hy dro pero x ide (t.BHP) (70% i n w a t e r ) , acetone, dichloromet hane (CH2C12), n -
hexane, n-heptane, n-octane, n-nonane and n-decane (all +99%) were
purchased f rom A l d r i c h . H e - p h t h a l l o c y a n i n e (H2Pc) (+98%) was purchased f rom
A l d r i c h and F e - p h t h a l l o c y a n i n e (FePc) (+98%) f r o m Strem Chemicals.
F erric enium - Y i s p r e p a r e d by adding 5 g o f a i r - d r y NaY t o 50 m l o f a
s o l u t i o n o f f e r r o c e n e i n acetone c o n t a i n i n g 84 mg (=1 complex p e r u n i t
c e l l ) o f FeCp2, f o l l o w e d b y a i r d r y i n g a t 343 K. The l a t t e r s o l i d i s mixed
w i t h 5 g o f DCB and h e a t e d under He atmosphere a t 423 K f o r 4 hours. T h i s
khaki -coloured sol i d is succesively soxhlet extracted with acetone,
p y r i d i n e and a g a i n w i t h acetone, u n t i l a c o l o u r l e s s e x t r a c t i s obt ained.
The f i n a l c a t a l y s t i s a i r d r i e d a t 343 K. FePcVPI-5 i s s y n t h e s i z e d a t 523
i n s t e a d o f 423 K a c c o r d i n g t o t h e same procedure.
 49

Characteri sat i o n
I.R. c h a r a c t e r i s a t i o n o f t h e samples i s c a r r i e d o u t u s i n g t h e K6r
t ec hnique. U.V. spectroscopy was used for the semi-quantitative
d e t e r m i n a t i o n o f t h e amount o f i n t r a c r y s t a l l i n e p h t h a l l o c y a n i n e s , after
d i s s o l u t i o n o f t h e z e o l i t e i n c o n c e n t r a t e d s u l f u r i c a c i d (0.1 g o f c a t a l y s t
i n 10 m l o f c on c e n t r a t e d H2S04 f o r 4 h ) . The i r o n c o n t e n t o f t h e samples i s
determined by chemical a n a l y s i s . X - r a y powder d i f f r a c t i o n i s used t o ensure
good c r y s t a l l i n i t y o f t h e z e o l i t e a f t e r t h e s y n t h e s i s and p u r i f i c a t i o n
procedures.

R eac t io n Drocedure
O x y f u n c t i o n a l i z a t i o n r e a c t i o n s o f n - a lkanes a r e c a r r i e d o u t a t room
temperature and atmospheric p r e s s u r e w i t h t.BHP as oxidans and acetone as
s o l v e n t . Product a n a l y s i s was done w i t h GC on a 50 m CP S i l - 8 6 c a p i l l a r y
column f rom Chrompack.

R e s u l t s and d i s c u s s i o n
C h a r a c t e r i s a t i o n o f encaqed FePc
I n spite o f d i f f e r e n t conditions, such as t h e r e s p e c t i v e s y n t h e s i s
c o n d i t i o n s mentioned above, a r e a p p l i e d f o r FePc and FeCp2 impregnat ion on
NaY and VPI-5 is the application o f the st andard s o x h l e t extraction
procedure s t i l l s u f f i c i e n t t o remove a l l i r o n f rom t h e s o l i d s . When i n s i t u
synthesis of FePc is made in both molecular sieve structures, the
e x t r a c t i o n procedure removes o n l y p a r t o f t h e i r o n . Thus a l l r e s i d u a l i r o n
p r e s e n t i s ' a s s o c i a t e d w i t h encaged FePc. Indeed, after extraction the
c h a r a c t e r i s t i c l i n e s o f Cp2 (814 c m - l ) and DC6 (965 c m - l ) a r e absent as
shown by I . R . d a t a [ 1 5 ] .
Chemical a n a l y s i s combined w i t h U.V. spectroscopy o f samples d i s s o l v e d
i n c onc ent rat e d s u l f u r i c a c i d a l l o w t o d et ermine t h e amount o f FePc and
H2Pc pre s ent i n t h e molecular sieves. The NaY samples used f o r the
c a t a l y t i c experiments have about 1 FePc f o r e v e r y 77 supercages. I n case o f
VPI-5 samples t h e amount o f i n t r a c r y s t a l l i n e FePc corresponds t o 0.021 f o r
each u n i t c e l l .
M o l e c u l a r g r a p h i c s a n a l y s i s o f FePc l o c a t e d i n t h e supercages o f NaY
z e o l i t e s shows a s a d d l e - t y p e d e f o r m a t i o n o f t h e p l a n a r FePc molecule which
det e rmines t h e f r e e a p e r t u r e s t o t h e a c t i v e s i t e [15]. I t c o n t r a s t s w i t h
FePc encaged i n VPI-5 where no d e f o r m a t i o n o f t h e c h e l a t e occurs.

C a t a l y t i c a c t i v i t v w i t h FePcY
Zeolite-enclosed FePc are suitable catalysts for the selective
o x i d a t i o n o f p a r a f f i n e s t o ketones and a l c o h o l s a t ambient t emperat ure and
pre s s ure w i t h t.BHP as oxygen atom donor. O x i d a t i o n r e a c t i o n s a r e performed
50

b o t h i n a i r and i n n i t r o g e n atmosphere w i t h o u t s i g n i f i c a n t changes i n

c o n v e r s i o n and p r o d u c t d i s t r i b u t i o n . Fe3+-Y, ferricenium-Y, f errocenium-Y
as w e l l as H2Pc impregnated on NaY a r e i n a c t i v e , i n d i c a t i n g t h a t t h e low
amounts o f FePc p r e s e n t i n t h e m o l e c u l a r s i e v e s a r e t h e a c t i v e s i t e s .
F i g . 1 shows t h e c o n v e r s i o n o f a s e r i e s o f n - a l k a n e s w i t h d i f f e r e n t
c h a i n l e n g t h on FePcY and FePcVPI-5 c a t a l y s t s a t a c o n s t a n t r a t e o f t.BHP
addition. I n FePcY initial conversions approach the limit imposed by
reaction stoichiometry. Upon f u r t h e r a d d i t i o n o f oxidans t h e c o n v e r s i o n
curve g r a d u a l l y deviates from t h e t h e o r e t i c a l l i n e , pointing t o catalyst
d e a c t i v a t i o n . Turnover numbers (N) p e r FePc molecule amount t o 6,000 and
exceed t h o s e o f homogeneous FePc (N r a n g i n g f rom 20 t o 30) [15] as w e l l as
t h o s e r e p o r t e d i n t h e l i t e r a t u r e on FePcY c a t a l y s t s w i t h iodosobenzene as
ox idans (N=5.6) [9, 121. Because o f t h e l o w a c t i v t y o f FePc, d i s s o l v e d i n
dichloromethane, it is not shown in Fig. 1. Initial activities are
presumably h i g h on homogeneous FePc c a t a l y s t s b u t t h e complexes a r e r a p i d l y
d e s t r o y e d as shown by b l e a c h i n g o f t h e s o l u t i o n . FePcY t u r n s y e l l o w - b r o w n
a f t e r r e l a t i v e h i g h t u r n o v e r numbers i n c o n t r a s t w i t h FePcVPI-5 which
remains a c t i v e even a f t e r t u r n o v e r numbers over 2,000. The l a t t e r c a t a l y s t
does n o t undergo any c o l o u r change a t a l l and can be reused. O bviously, t h e
stability and t h e r e f o r e the overall conversion is improved when the
complexes a r e encaged i n t h e m o l e c u l a r s i e v e s . It i s c l e a r t h a t t h e z e o l i t e
p r o t e c t s t h e p h t h a l l o c y a n i n e s t r u c t u r e a g a i n s t o x i d a t i o n compared t o t h e
homogeneous case, j u s t as t h e p r o t e i n m a n t l e does i n t h e enzyme cytochrome
P-450. However, even a f t e r correction f o r differences i n experimental
c o n d i t i o n s , FePcVPI-5 remains l e s s a c t i v e t han FePcY. I n t h e f o r m e r system,
f r e e t.BHP accumulates g r a d u a l l y w h i l e w i t h FePcY a l l t.BHP added i s
consumed a t once. The l i n e a r i n c r e a s e i n c o n v e r s i o n observed w i t h FePcVPI-
5, suggests t h e absence o f c a t a l y s t d e a c t i v a t i o n , a t l e a s t up t o t u r n o v e r
numbers o f 2,000.
A t t h i s st a g e o f t h e work, t w o p o s s i b l e e x p l a n a t i o n s can be advanced
t o r a t i o n a l i z e t h e h i g h e r a c t i v i t y o f FePcY and t h e s u p e r i o r s t a b i l i t y o f
FePcVPI-5. As a r e s u l t o f t h e t u b u l a r n a t u r e o f t h e pores o f VPI-5 and
ev ent u al d i f f u s i o n l i m i t a t i o n s o f t h e r e a c t i o n , o n l y t h e FePc complexes a t
the external r i m o f the crystals are active i n i t i a l l y but are gradually
consumed d u r i n g r e a c t i o n . Consequently, FePc complexes 1 ocat ed more towards
t h e c e n t r e o f t h e c r y s t a l s become a c t i v e . Secondly, i t can be s p e c u l a t e d
that the s ad d l e - c o n f o r m a t i o n of FePc in NaY changes the electronic
environment o f t h e a c t i v e i r o n , thus increasing not o n l y i t s c a t a l y t i c
a c t i v i t y b u t a l s o i t s v u l n e r a b i l i t y towards s e l f - o x i d a t i o n .
The y i e l d o f a l c o h o l s and ketones on p e r o x i d e b a s i s on FePcY and
FePcVPI-5, r e s p e c t i v e l y t h e FePc c a t a l y s t s i s 75% and l e s s t han lo%,
 51

r e s p e c t i v e l y . The m a j o r s i d e r e a c t i o n i s t h e decomposition o f t h e o r g a n i c
peroxide t o molecul a r oxygen and t. b u t a n o l .
F i g . 1 a l s o shows a f a s t e r d e a c t i v a t i o n r e a c t i o n f o r an alkane when
t h e c h a i n l e n g t h i n c r e a s e s f r o m 6 t o 10 carbon atoms. The reason f o r t h i s
behav iour i s n o t c l e a r .

15
5, .~

h
FePcY
v
3 0 octane
10 FePcY
C
0
.I u decane
rA
h FePcY
w
b ~ 1 0 0 % ketone
C formation
0 5
u octane
FePcVPI- 5

0
0.0 0.5 1 .o 1.5
Ratio of t.BHP
to alkane (mol/mol)

F i g . 1. O x i d a t i o n c o n v e r s i o n o f n - a l k a nes w i t h t . B H P t o ketones and

a l c o h o l s a t 298 K and 0 . 1 MPa. Wi t h FePcY 0 . 5 g o f c a t a l y s t (lFePc/77
supercages), 200 mmol o f n-alkane, 100 m l o f acetone and a t.BHP i n j e c t i o n
r a t e o f 21.9 mmo1.h-' i s used. W i t h FePcVPI-5 0.1 g o f c a t a l y s t (0.021 p e r
u n i t c e l l ) , 50 mmol o f n-C8, 50 m l o f acetone and a t.BHP i n j e c t i o n r a t e o f
8.76 mmo1.h-l i s used. The s t r a i g h t l i n e r e p r e s e n t s t h e maximum p o s s i b l e
c onv ers io n when o n l y ketones a r e formed and t.BHP c o n v e r s i o n i s complete.

Fig. 2A shows f o r n - o c t a n e o x i d a t i o n on FePcY, FePcVPI-5 and FePc

c a t a l y s t s t h e d i s t r i b u t i o n o f ketones and a l c o h o l s . A l l t hese c a t a l y s t s
e x h i b i t a h i g h s e l e c t i v i t y towards t h e f o r m a t i o n o f ketones. Encaged FePc
complexes a r e more s e l e c t i v e f o r ketones t han t h e homogenous ones. S i m i l a r
behav ior i s a l s o e s t a b l i s h e d by Herron e t a1 [ 9 ] and t h e y a t t r i b u t e i t t o
d i f f u s i o n e f f e c t s i n t h e m o l e c u l a r s i e v e s. The ketone t o a l c o h o l r a t i o
which ranges f r o m about 4 t o 9, i s t y p i c a l f o r f r e e r a d i c a l c h a i n o x i d a t i o n
r e a c t i o n s and s i m i l a r t o what i s r e p o r t e d by Fontecave and Mansuy [ 16] f o r
t h e system MnTPP(C1 )/02/ascorbate. They a t t r i b u t e t h e f o r m a t i o n o f ketones
t o t h e involvement o f f r e e r a d i c a l s . A l s o t h e oxygen f o r m a t i o n i n d i c a t e s
that r e a c t i o n s o f r a d i c a l a r n a t u r e a r e i n v o l v e d i n t h e mechanism. It
suggests t h a t t h e a c t i v e s i t e i s n o t an "oxenoi'd" species as i n enzymes
[17] and t h e i r mimics [6-81, b u t t h a t t h e r e a c t i o n r a t h e r occurs v i a a f r e e
r a d i c a l c h a i n mechanism. T h i s c h a i n mechanism seems t o be d i s t u r b e d by t h e
z e o l i t e framework where t h e r e a c t i o n y i e l d on a p e r o x i d e b a s i s exceeds t h a t
52

o f f r e e FePc by a f a c t o r of 10. However, Haber e t a l . [ 18] using the

oxidation of cyclohexane with hydrogen peroxide over c h l oro-
tetratolylporphyrinatochromium( 111), o b t a i n e d under comparable c o n d i t i o n s
k et o ne t o a l c o h o l r a t i o s between 1.4 and 4, and claimed t h a t t h e r e a c t i o n s
were n o t r a d i c a l a r i n n a t u r e . Another e x p l a n a t i o n i s t h a t d i f f e r e n t k i n d o f
r e a c t i o n s a r e i n v o l v e d i n t h e f o r m a t i o n o f p r o d u c t s . Indeed, i t i s shown
[19] t h a t t h e i r o n - c a t a l y z e d t.BHP o x i d a t i o n o f cyclohexane proceeds w i t h
different parallel r e a c t i o n pathways. However, the total lack o f the
formation o f t.butoxy s u b s t i t u e n t s on t h e a l k y l chain’, i n our results,
c o n t r a s t s w i t h a f r e e r a d i c a l mechanism.

A
ketone alcohol C2lC3 C2IC4
100, I

FePcY FcPcVPI- 5 FePc FcPcY PePcVPI- 5 PCPC

Catalyst Catalyst

2. S e l e c t i v i t y f o r k e t o n e and a l c o h o l formation (A) and

r e g i o s e l e c t i v i t y (B) ;n t h e o x i d a t i o n o f n-oct ane a t l o w c o n v e r s i o n s o v e r
FePcY, FePcVPI-5 and FePc c a t a l y s t s . C o n d i t i o n s a r e t h o s e o f F i g . 1.

On homogeneous FePc no r e g i o s e l e c t i v i t y i s observed as t h e C2/C3 and

C2/(C4tC5) r a t i o s a r e a l l around 1. F i g . 28 i n d i c a t e s t h a t r e g i o s e l e c t i v i t y
e x i s t s f o r b o t h m o l e c u l a r s i e v e s , p o s s i b l y due t o t h e encaged n a t u r e o f t h e
complex. However, l o w e r v a l u e s o f t h e C2/C3 and C2/C4 r a t i o s a r e o b t a i n e d
i n VPI-5 compared t o z e o l i t e Y, p o i n t i n g t o t h e e x i s t e n c e o f shape
s e l e c t i v i t y . The m o l e c u l a r g r a p h i c s a n a l y s i s enables q u a n t i f i c a t i o n o f t h e
f r e e pore a p e r t u r e s , which f o r b o t h m o l e c u l a r s i e v e s a r e about 0.6 nm [ 15] .
I t shows t h a t t h e d i f f e r e n c e i n s e l e c t i v i t y can h a r d l y be caused by
d i f f e r e n c e s i n t h e z e o l i t i c environment. The enhanced c o n s t r a i n t observed
f o r FePcY s hou l d t h e n be r e l a t e d t o t h e s a d d l e - t y p e d e f o r m a t i o n o f t h e
complex. R e g i o s e l e c t i v i t y i n t h e a l c o h o l f r a c t i o n i s i n s i g n i f i c a n t .
 53

TABLE 1
R e g i o s e l e c t i v i t y i n t h e ketone f r a c t i o n f o r t h e o x i d a t i o n o f C6 t o C10 n -
a1 kanes on FePcY c a t a l y s t a expressed as s t a n d a r i z e d molar r a t i o s b o f C2/C3
and C2/ (C4tC5) .
Substrate Regi osel e c t i v i t y C
Ketone f r a c t i o n
C2/C3 C2/(C4tC5)
n - hexane 0.92
n - heptane 1.15 1.51
n -o c t a ne 1.29 1.95
n-nonane 1.38 2.80
n-decane 1.56 2.59

a; R eac t io n c o n d i t i o n s : i n a m i c r o r e a c t o r o f 3 m l w i t h 2.4 mmol o f t.BHP,

6 mmol o f p a r a f f i n , 0.1 g o f FePcY and 1.5 m l o f acetone and a t 298 K,
0.1 MPa, 5 % c o n v e r s i o n .
b; C o r r e c t i o n s a r e made so as t o have an equal number o f C2 and (C4+C5)
p o s i t i o n s i n t h e n-alkane chain, i r r e s p e c t i v e o f i t s chain length.
c; R a t i o o f o x y g e n a t i o n a t C p o s i t i o n 2 over oxygenat ion a t i n n e r C
positions.

T a ble 1 shows t h a t f o r n-hexane as s u b s t r a t e no r e g i o s e l e c t i v i t y i s

observed. However, f o r l o n g e r c h a i n s t h e z e o l i t e enclosed FePc e x e r t s a
shape s e l e c t i v e e f f e c t o f i n c r e a s i n g i n t e n s i t y on t h e i n s e r t i o n o f oxygen.
Carbon atoms a t p o s i t i o n 0 - 1 a r e p r e f e r e n t i a l l y o x i d i z e d o v e r carbon atoms
a t p o s i t i o n w-2, which i n t u r n a r e o x i d i z e d f a s t e r t h a n t h o s e a t p o s i t i o n 4
and 5. Thus t h e r e g i o s e l e c t i v i t y i n c r e a s es w i t h c h a i n l e n g t h , o b v i o u s l y ,
because l o n g e r a l k y l c h a i n s a r e more l i a b l e t o s t e r i c c o n s t r a i n t s e x e r t e d
by t h e z e o l i t e framework a t t h e l e v e l o f t h e a c t i v e s i t e .

Conclusions
I r o n - p h t h a l l o c y a n i n e s a r e encaged i n m o l e c u l a r s i e v e s by an i n s i t u
s y n t h e s i s f rom ferrocenium-Y and f e r r i c e n i u m-VPI -5. The a c t i v i t y o f i r o n -
p h t h a l l o c y a n i n e s i n z e o l i t e Y i s h i g h e r t h a n i n t h e VPI-5 c a t a l y s t which i n
t u r n exceeds t h o s e o f t h e f r e e complexes as shown by t u r n o v e r numbers o f
respectively, 6,000, 2,000 and 25. However, iron-phthallocyanine-VPI-5 i s
more s t a b l e t h a n t h e i r o n - p h t h a l l o c y a n i n e - Y c a t a l y s t , which t u r n s i n a c t i v e
a f t e r t u r n o v e r numbers h i g h e r t h a n 6,000, and t h e f r e e complex s u f f e r s f rom
v e r y f a s t o x i d a t i v e d e s t r u c t i o n . Shape s e l e c t i v i t y i n t h e r e g i o s e l e c t i v e
o x i d a t i o n o f alkanes i s h i g h e r on FePcY t h a n on FePcVPI-5, which i n t u r n i s
higher t h an on the non-selective homogeneous catalyst. This can be
explained by a combined e f f e c t of steric constraint imposed by the
framework of the molecular sieve and the deformation of the
phthallocyanine. The shape s e l e c t i v e o x i d a t i o n o f t h e secondary carbon
atoms o f normal alkanes i n c r e a s e s w i t h t h e c h a i n l e n g t h .
54

ALKANE OXIDATIONS ON TITANIUM SILICALITE

Introduction
T i t a n i u m s i l i c a l i t e - 1 o r TS-1 i s a t i t a n i u m c o n t a i n i n g d e r i v a t i v e o f
s i l i c a l i t e - 1 , w h i c h i n a s e l e c t i v e way c a t a l y z e s t h e o x i d a t i o n o f o r g a n i c
s u b s t r a t e s w i t h d i l u t e d hydrogen p e r o x i d e as o x i d a n t [20-231. The r e a c t i o n s
described i n t h e p a t e n t 1 i t e r a t u r e i n c l u d e t h e (mono)epoxidat ion o f
( d i ) o l e f i n s [24-251, t h e c o n v e r s i o n o f o l e f i n s t o g l y c o l monomethyl e t h e r s
i n t h e presence o f methanol [26], t h e h y d r o x y l a t i o n o f aromat ics [27], t h e
o x i d a t i o n o f p r i m a r y o r secondary a l c o h o l s t o aldehydes o r ket ones [28],
t h e ammoxidation o f ketones i n t h e presence o f NH3 [29], and t h e c o n v e r s i o n
o f v in y lbenz ene s t o 8 - p h e n y l aldehydes [30]. Very r e c e n t l y , t h e o x i d a t i o n
o f u n a c t i v a t e d a l k a n e s on TS-1 was d e s c r i b e d i n d e p e n d e n t l y b y Tatsumi e t
a l . [31] and by us [32].

ExDerimental
TS-1 was p r e p a r e d by t h e h y d r o t h e r m a l procedure d e s c r i b e d i n example 2
o f US 4,410,501. I t s i n f r a r e d spectrum i s c h a r a c t e r i z e d by an I R band a t
960 cm-l, as r e p o r t e d f o r T S - 1 [20-211, and no e x t r a z e o l i t i c c r y s t a l l i n e o r
amorphous phases c o u l d be d e t e c t e d by XRD o r SEM.
The o x i d a t i o n r e a c t i o n s were conducted a t 373K under v i g o r o u s s t i r r i n g
i n a s t a i n l e s s s t e e l b a t c h r e a c t o r p r e v i o u s l y f l u s h e d w i t h N2. A f t e r
c o m p l e t i o n o f t h e r e a c t i o n , t h e two l i q u i d phases (H202 and alkane) were
homogenized w i t h an excess o f acetone. The o x i d a t i o n p r o d u c t s were analyzed
by GC on a 50 m CP S i l - 8 8 c a p i l l a r y column f rom Chrompack, u s i n g t o l u e n e as
internal s t a nd a r d . W i t h i n t h e accuracy o f t h e GC a n a l y s i s , yields of
a l c o h o l s and ketones add up t o 100% on a carbon b a s i s . H202 conversions
were det e rmined by c e r i m e t r i c t i t r a t i o n [33].

R e s u l t s and d i s c u s s i o n
F i g . 3 shows t h e o x i d a t i o n p r o d u c t s o b t a i n e d i n t h e o x i d a t i o n o f n -
hexane w i t h 35% aqueous H202 as a f u n c t i o n o f r e a c t i o n t i m e .
The o x i d a t i o n p r o d u c t s a r e d e r i v e d f r o m n-hexane by o x i d a t i o n a t t h e
secondary carbon p o s i t i o n s , w h i l e o x i d a t i o n o f p r i m a r y C - H bonds i s below
d e t e c t i o n 1 i m i t s . Wi t h i n c r e a s i n g n-hexane conversion, t h e s e l e c t i v i t y f o r
ketones i n c r e a s e s a t t h e expense o f t h a t f o r a l c o h o l s , i n d i c a t i n g t h a t t h e
o x i d a t i o n oc c u r s i n two c o n s e c u t i v e s t e p s, i.e. hexane i s o x i d i z e d t o a
m i x t u r e o f 2- and 3-hexanols, w h i c h i s t h e n f u r t h e r o x i d i z e d t o 2- and 3 -
hexanones. The absence o f i s o m e r i s a t i o n o f t h e p r o d u c t s was c o n f i r m e d by
t h e f o r m a t i o n o f o n l y 2-hexanone o r 3-hexanone when r e s p e c t i v e l y 2-hexanol
o r 3-hexanol were used as s u b s t r a t e s . Theref ore, t h e o v e r a l l r e a c t i o n
scheme f o r n-hexane o x i d a t i o n on TS-1 can be r e p r e s e n t e d as f o l l o w s :
 55

H202
2-hexanol 1 2-hexanone
H202
n-hexane , H202
3-hexanol 1 3-hexanone

I r I
3-hexanone
/
/
/ lZ@#2-hexanone

EB 2-hexanol
total

-
n
0 0.5 1 2 3

Reaction time (h)

F i g . 3. n-Hexane o x i d a t i o n by H202 on TS-1 as a f u n c t i o n o f r e a c t i o n t i m e .
R eac t io n c o n d i t i o n s : 500 mg o f TS-1, 115 mmoles o f n-hexane, 240 mmoles o f
H202 (35% i n H20), 45 m l o f acetone; 373K, 700 RPM s t i r r i n g r a t e .

T a ble 2 shows t h e H202 y i e l d and s e l e c t i v i t i e s i n t h e o x i d a t i o n o f

d i f f e r e n t n-alkanes and hexane isomers by 35% aqueous H202 [31].

TABLE 2
Alkane o x i d a t i o n s by H202 on TS - l a

Substrate H202 y i e l d b Regiosel e c t i v i t y C

(%I Total products Ketone f r a c t i o n
C2/C3 C2/(C4tC5) C2/C3 C2/(C4tC5)
n-pentane 68 2.12 2.45
n - hexane 70 1.13 1.78
n -o c t a ne 65 1 1.17 2.77 3.59
n-decane 56 1.12 0.60 3.28 2.56
2-methylpentane 59 5.67 2.70
3-methyl pentane 58 0.78 >loo
2,2-dimethylbutane 50 OD

a; R eac t io n c o n d i t i o n s : 400 mg o f TS-1, 310 mmoles o f alkane, 210 mmoles

o f H202 (35% i n H20), 60 m l o f acetone, 3 hours a t 373K and 1000 RPM.
b; H202 y i e l d = f r a c t i o n o f H202 used f o r alkane o x i d a t i o n on t o t a l H202
c onv ers io n ; H202 c o n v e r s i o n s a r e h i g h e r t han 90% i n a l l r e a c t i o n s .
c; R a t i o o f o x y g e n a t i o n a t C p o s i t i o n 2 over oxygenat ion a t i n n e r C
positions.
56

F o r t h e d i f f e r e n t n - a l k a n e s as w e l l as o f t h e f o u r hexane isomers t h e
e f f i c i e n c y o f H202 use f o r o x i d a t i o n i s h i g h on TS-1, b u t decreases as t h e
dimensions of the substrate increase. The t o t a l amount of oxygenated
p r o d u c t s i s almost statistically d i s t r i b u t e d over t h e d i f f e r e n t carbon
p o s i t i o n s , w i t h o n l y a s l i g h t s e l e c t i v i t y f o r o x i d a t i o n a t t h e w-1 p o s i t i o n
o f t h e carbon c h a i n . W i t h i n t h e ketone f r a c t i o n however, a v e r y pronounced
s e l e c t i v i t y f o r 2-ketones i s observed. T h i s means t h a t t h e f i r s t o x i d a t i o n
step, i.e. the formation o f alcohols, i s only l i t t l e regioselective,
whereas i n t h e second o x i d a t i o n s t e p , t h e 2 - i s o m e r s o f t h e a l c o h o l m i x t u r e
a r e s e l e c t i v e l y f u r t h e r o x i d i z e d t o 2 - k e t o n e s . T h i s s e l e c t i v i t y i s imposed
by t h e shape s e l e c t i v e p r o p e r t i e s o f TS-1. Furthermore, i t i s seen t h a t f o r
branched a1 kanes, tertiary C-H bonds are selectively oxidized over
secondary ones. The a l k a n e o x i d a t i o n on TS-1 t h u s f o l l o w s t h e ' n o r m a l '
r e a c t i v i t y o r d e r : t e r t i a r y C-H > secondary C-H >>> p r i m a r y C-H.
Furthermore the H202 yield decrease with increasing substrate
dimensions. T h i s o f f e r s s t r o n g e v i d e n c e f o r an i n t r a c r y s t a l l i n e r e a c t i o n .
Indeed, because o f t h e g e o m e t r i c a l c o n s t r a i n t s imposed by t h e p o r e geometry
of TS-1 on the catalyzed reactions, the oxidation rate of organic
s u b s t r a t e s decreases as t h e i r dimensions i n c r e a s e , and t h e r e f o r e t h e main
side reaction, i.e. t h e r m a l and c a t a l y t i c d e c o m p o s i t i o n o f H202 t o 02,
becomes more c o m p e t i t i v e .
F i g . 4 shows t h e dependance o f t h e TS-1 c a t a l y z e d n-hexane o x i d a t i o n
on t h e amount o f s o l v e n t i n t h e r e a c t i o n m i x t u r e .

100

3-hexanone
80
be
W
@%%l
2-hexanone
3-hexanol
.-
v1
60

h 2-bexanol
2 40
C 0 total
0

20

0
0 10 20 30 45 60 90

Acetone (ml)
F i g . 4 . n-Hexane o x i d a t i o n by H202 on TS-1 as a f u n c t i o n o f acetone
c o n c e n t r a t i o n . R e a c t i o n c o n d i t i o n s : 500 mg o f TS-1, 115 mmoles o f n-hexane,
240 mmoles o f H202 (35% i n H20), I h r a t 373K and 700 RPM.

F i g . 4 shows t h a t t h e hexane c o n v e r s i o n e x h i b i t s an optimum a g a i n s t

t h e acetone c o n c e n t r a t i o n . I n absence o r a t v e r y l o w c o n c e n t r a t i o n s o f
 57

acetone, t h e s o l u b i l i t y o f t h e o r g a n i c s u b s t r a t e i n t h e aqueous H202 phase,

and t h e r e f o r e t h e d r i v i n g f o r c e f o r d i f f u s i o n o f t h e s u b s t r a t e t o t h i s
phase i s v e r y l o w . As a r e s u l t t h e r e a c t i o n r a t e may become d i f f u s i o n
l i m i t e d . When t h e amount o f acetone i s increased, b o t h t h e hexane
s o l u b i l i t y and t h u s t h e d r i v i n g f o r c e f o r d i f f u s i o n increase, which ' r e s u l t s
i n an in c re as e d r e a c t i o n r a t e . When t h e acetone c o n c e n t r a t i o n i s s t i l l
f u r t h e r inc re as e d however, b o t h H 2 0 2 and n-hexane become more d i l u t e d i n
the reaction solution, t h u s c a u s i n g a decrease i n r e a c t i o n r a t e . The
compromise between h i g h hexane s o l u b i l i t i e s and d i f f u s i o n r a t e s and l o w
d i l u t i o n s e x p l a i n s t h e optimum o f t h e acetone c o n c e n t r a t i o n . The t r a n s i t i o n
of a diffusionally t o a chemically controlled system w i t h increasing
s o l v e n t c o n c e n t r a t i o n , i s c o n f i r m e d by t h e r e s u l t s shown i n F i g . 5, f o r n-
hexane o x i d a t i o n as a f u n c t i o n o f c a t a l y s t c o n c e n t r a t i o n b o t h i n t h e
presence and i n t h e absence o f acetone. I n t h e presence o f acetone t h e
hexane c onv ersi o n increases in a proportional way with the catalyst
c o n c e n t r a t i o n up t o conversions o f about 60%. I n t h e absence o f a p o l a r
solvent deviations of this linearity are already observed at low
c onv ers io ns , indicating that the reaction is no longer chemically
c o n t r o l 1ed.
100

80 0
m
h

ae
W d
0

60 0
C 0,' U
0
.I
vl .' 0 O
2-bexanol
L, 40
a2
P
El
$ 20 0

0 ++1
0 . 2 5 . 5 0 .75 1.00 0 . 2 5 . 5 0 .75 1.00

TS-1 (g)

F i g . 5. n-Hexane o x i d a t i o n by H20 as a f u n c t i o n o f TS-1 c o n c e n t r a t i o n .

R eac t io n c o n d i t i o n s : 115 mmoles 03
n-hexane, 2 4 0 mmoles o f H 2 0 2 (35% i n
H 2 0 ) , 1 h r a t 373K and 700 RPM, a; 4 5 m l acetone added, b; no s o l v e n t
added.

As i s seen i n F i g . 4 , t h e acetone c o n c e n t r a t i o n a l s o s t r o n g l y a f f e c t s
the k et o ne/ a lc o h o l ratio of the oxidation product s. The decreasing
s e l e c t i v i t y f o r ketones w i t h i n c r e a s i n g acetone c o n c e n t r a t i o n i s p r o b a b l y
p a r t l y connected w i t h t h e v a r i a t i o n o f t h e conversion, b u t i s a l s o caused
by t h e v a r i a t i o n o f hexane c o n c e n t r a t i o n i n t h e aqueous H202 phase. Indeed,
58

a t l o w acetone c o n c e n t r a t i o n s , t h e hexane s o l u b i l i t y and t h u s t h e s u b s t r a t e

concentration i s low, and t h e r e f o r e a hexanol m o l e c u l e w h i c h has been
formed on t h e c a t a l y s t w i l l be e a s i l y c o n v e r t e d t o t h e k e t o n e . A t h i g h e r
acetone c o n e n t r a t i o n s and h i g h e r hexane s o l u b i l i t i e s however, c o m p e t i t i o n
between hexane and hexanol f o r o x i d a t i o n w i l l become s i g n i f i c a n t , and o n l y
a f r a c t i o n o f t h e hexanol m i x t u r e , m a i n l y 2-hexanols, will be f u r t h e r
oxidized.
A l t h o u g h no e x t e n s i v e m e c h a n i s t i c s t u d y o f t h e a l k a n e o x i d a t i o n on
titanium silicalite has been made, it is believed that the reaction
proceeds v i a t h e a c t i v a t i o n o f H202 on t h e t i t a n i u m s i t e s w i t h f o r m a t i o n o f
T i - p e r o x o s p e c i e s , which a r e t h e a c t u a l oxygen donors. The f o r m a t i o n o f
such species was shown by adsorption of H202 on Ti-silicalite and
subsequent vacuum drying [32,34]. This treatment results in the
disappearance o f t h e 960 cm-’ I R band, ascribed t o t h e surface t i t a n y l
(Ti=O) group [26], and t h e f o r m a t i o n o f a 425 nm a b s o r p t i o n band i n t h e
v i s i b l e spectrum. The l a t t e r a b s o r p t i o n i s c h a r a c t e r i s t i c f o r T i complexes
w i t h peroxo l i g a n d s [31]. H e a t i n g o f t h e H202 t r e a t e d t i t a n i u m s i l i c a l i t e
l e a d s t o t h e disappearance o f t h e 425 nm and t h e reappearance o f t h e 960
c m - l a b s o r p t i o n bands i n t h e V I S and I R s p e c t r a , due t o d e c o m p o s i t i o n o f
the Ti peroxo complexes with reformation of the titanyl group. The
f o r m a t i o n o f hydroxyhydroperoxo o r peroxo complexes by r e a c t i o n o f hydrogen
p e r o x i d e w i t h t i t a n y l groups on TS-1 i s r e p r e s e n t e d i n scheme 1.

0
II
Ti
H202 OH
\ /
Ti
OOH
- 0-0
\
Ti
< + H20

Scheme 1: F o r m a t i o n o f s u r f a c e peroxo s p e c i e s by r e a c t i o n o f T i - s i l i c a l i t e
w i t h H202.

C o n s i d e r i n g t h e i n e r t n e s s o f s a t u r a t e d hydrocarbons, t h e i r oxidation
p r o b a b l y r e q u i r e s a h o m o l y t i c mechanism, involving radical intermediates.
Furthermore, i t was shown above t h a t t h e p r i m a r y o x i d a t i o n p r o d u c t s a r e
alcohols, ketones b e i n g formed i n a c o n s e c u t i v e o x i d a t i o n . A tentative
mechanism f o r a l k a n e h y d r o x y l a t i o n on TS-1 i s r e p r e s e n t e d i n Scheme 2, in
analogy with the mechanism proposed for the stoichiometric alkane
o x i d a t i o n s by V-peroxocomplexes [ 3 1 ] .

-0
\ /
Ti
d
-0*
\
Ti
H-C-
-
/

\
\
0-0-H
Ti
* /
C-
\
- 0
II
Ti
HO-C-
/
\

Scheme 2: Hydroxylation o f a l k a n e s by surface peroxo species on T i -

s i 1 i c a l it e .
 59

I n this scheme, an open d i r a d i c a l f orm o f t h e T i peroxo complex

a b s t r a c t s a hydrogen f r o m t h e alkane t o g i v e a carbon r a d i c a l . The a l c o h o l
i s formed by r e c o m b i n a t i o n o f t h e carbon r a d i c a l w i t h t h e h y d r o x y l r a d i c a l
coming f rom Ti-0-OH, w i t h r e f o r m a t i o n o f t h e t i t a n y l group.

Conclusions
T i t a n i u m s i l i c a l i t e can be used as a selective catalyst for the
o x i d a t i o n o f u n a c t i v a t e d a1 kanes by aqueous hydrogen p e r o x i d e . Secondary
and/or t e r t i a r y a l c o h o l s a r e t h e p r i m a r y o x i d a t i o n product s, t h e f ormer
ones a r e f u r t h e r o x i d i z e d t o ketones i n a c o n s e c u t i v e r e a c t i o n . The shape
s e l e c t i v i t e p r o p e r t i e s o f t h e c a t a l y s t favour a r e g i o s e l e c t i v e o x i d a t i o n a t
t h e 0-1 p o s i t i o n o f t h e carbon c h a i n which i s most pronounced i n t h e
f o r m a t i o n o f ketones. A d d i t i o n o f a p o l a r s o l v e n t t o t h e r e a c t i o n system
improves t h e mutual s o l u b i l i t y o f t h e aqueous H202 phase and t h e alkane
phase, and r e s u l t s i n an i n c r e a s e o f t h e r e a c t i o n r a t e and a decrease o f
t h e k et o ne/ a lc o h o l r a t i o o f t h e p r o d u c t s. A homolyt ic, non-free r a d i c a l
c h a i n r e a c t i o n mechanism, i n v o l v i n g T i peroxo compounds i s proposed.

GENERAL CONCLUSIONS

Iron-phthallocyanines encaged i n zeolite Y o r VPI-5 and t i t a n i u m

s i l i c a l i t e were used as c a t a l y s t s f o r t h e o x i d a t i o n o f alkanes w i t h t - b u t y l
hy dro pero x ide o r aqueous hydrogen p e r o x i d e b e i n g used i n t h e f ormer and t h e
l a t t e r case, r e s p e c t i v e l y . Both t y p e s o f c a t a l y s t c a t a l y z e t h e f o r m a t i o n o f
a m i x t u r e o f secondary and/or t e r t i a r y a l c o h o l s and ketones. However, a
controlled free radical chain r e a c t i o n mechanism i s proposed f o r the
p h t h a l l o c y a n i n e based c a t a l y s t s , w h i l e a c o n s e c u t i v e h o m o l y t i c , b u t n o t
f r e e r a d i c a l c h a i n mechanism i s p r o b a b l y i n v o l v e d i n t h e t i t a n i u m
s i l i c a l i t e c a t a l y z e d r e a c t i o n . A l t h o u g h t h e t h r e e c a t a l y s t s have d i f f e r e n t
p ore systems, v e r y s i m i l a r shape s e l e c t i v e e f f e c t s , r e s u l t i n g i n t h e
r e g i o s e l e c t i v e o x i d a t i o n a t t h e o u t e r p o s i t i o n s o f t h e carbon chain, a r e
observed. T h i s suggests t h a t t h e s t e r i c c o n t r o l a t t h e a c t i v e s i t e i t s e l f
i s comparable i n t h e t h r e e cases.

ACKNOWLEDGMENTS
RFP and DRCH acknowledge a f e l l o w s h i p f rom t h e B e l g i a n Fund o f
S c i e n t i f i c Research.

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4. H. van Bekkum and H.W. Kouwenhoven, Recl. Trav. Chim. Pays-Bas, 108
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G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeotes 61
0 1991 Elsevier Science Publishers B.V., Amsterdam

SORPTlON AND SEPARATION OF BINARY MIXTURES OF CH4, N2 AND COz I N

ZEOLITES

LOVAT V.C. REES

Imperial College of Science. Technology & Medicine, London. SW7 2AY, U.K.

SUMMARY
The sorption of methane, nitrogen and carbon dioxide and their binary
mixtures has been studied i n both silicalite-1 and Na-Y zeolites. The above
sorbates have increasing polarity and the effect of change of polarity on
their sorption behaviour in the uncharged silicalite and highly charged Na-Y
frameworks has been determined. Separation factors calculated from the
initial slopes of the single component isotherms are compared with those
obtained by experiment for both sorbents. Three isotherm models have
been tested for their ability to predict the sorption of nitrogedmethane
mixtures in Na-Y.

1NTRODUCTION
The separation of gas mixtures by pressure swing adsorption (PSA) is
becoming more widely used as the cost of energy increases. The design and
optimisation of PSA separation units requires a detailed knowledge of
equilibrium adsorbate mixture data over the temperature and pressure
range likely to be used in such units. There is also a need to select the
adsorbent with the optimum properties for the specific adsorbate mixtures
to be separated. This paper describes some interesting results which
compare the sorptions of binary mixtures of CH4, N2 and COz in two zeolites
with completely different surfaces. The first is silicalite-1, which is the pure
s’ilica end member of the zeolite ZSM-5, and Na-Y a more open, highly
charged zeolite containing a high concentration of aluminium atoms in the
framework and sodium ions to neutralize the negative charge introduced in
the framework by the substitution of Si by Al atoms.

EXPERIMENTAL
The sorption of the single components and their binary mixtures was
measured in a modified version of the isosteric method developed by Bulow
et a1(1,2) and is fully described in a previous paper(3) The important
feature of this method in the case of mixtures, is the constant composition of
the sorbed phase over the temperature range scanned.
62

The silicalite sample, supplied by Laporte Inorganics (Widnes, UK),

consisted of clean. elongated slabs 15-25 p m in length containing less than
0.01 % of aluminium. The zeolite was calcined in air at 550°C to remove the
organic template and outgassed at all other times at 350°C.
The Na-Y zeolite was also supplied by Laporte Inorganics and had the
unit cell formula Nas6[(A10~)~6(Si0~)136].250Hz0. No detectable amorphous
material was present in the sample. 27Al magic angle spinning NMR
confirmed that no dealumination of the sample occurred whilst activating
the sample at 100°C to remove most of the zeolitic water followed by
heating to 350'C for 14 hours. The 29Si MAS NMR spectrum was
deconvoluted to give a Si/AI ratio of 2.5 f 0.2 confirming the chemical
analysis above.

RESULTS AND DISCUSSION

The quality of the isosteres obtained by the isosteric method are
clearly demonstrated in Fig. 1 and 2 for the sorption of nitrogen in silicalite-
1 and Na-Y respectively. Isosteres of similar quality were obtained for
methane and carbon dioxide sorbed in these two zeolites. The temperature
range covered by the silicalite-l isosteres is 273-343K and the Na-Y
isosteres is 110-250K for nitrogen and methane and 210-270K for the
carbon dioxide.
The isosteric apparatus was designed specifically to cope with
mixtures and in Fig.3 the quality of the isosteres obtained with a mixture of
75 mole % N2 and 25 mole % COz sorbed in Na-Y is shown to be equal to that
obtained with single component sorbates.
The isotherms obtained from the isosteres in Fig.1-3 are shown in
Fig.4-6 respectively and, once again, clearly show the quality of the single
component and binary mixture data which can be obtained from the
isosteric method. In Fig. 7 isotherms for the sorption of methane, nitrogen
and carbon dioxide in silicalite-1 and Na-Y at 273K may be compared.
Carbon dioxide is very strongly sorbed in Na-Y compared with silicalite-1
demonstrating the strong interaction of the large electric fields in Na-Y with
the large quadrupole moment of carbon dioxide. Nitrogen has a much
smaller quadrupole moment than that of carbon dioxide. Although the small
quadrupole moment of nitrogen does lead to its enhanced sorption in the
highly charged Na-Y supercages over the uncharged silicalite-l pores this
enhancement is only -16% compared with the 50 fold enhancement found
with carbon dioxide. It is interesting to note that the non-polar methane
molecule is more strongly sorbed by some 75% in silicalite-1 than in Na-Y
 63

12

11

10

.
I

no
-n
5 9

7 ~.
3.0 3.1 3.2 3.3 3.4 3.5 3.6 I
low1

Fig. I Pure nitrogen silicalite- 1 isosteres. P,=l Pa.

Sorbate loadings (in mmol/g): (a) 0.012: (b) 0.047; (c) 0.069; (d) 0.097:
(e) 0.139; (f) 0.157: (8) 0.195.

14

12

10

D
3.0 4.0 5.0 6.0 7.0 E.0
lOC/T

Fig. 2 Pure nitrogen Na-Y isosteres. P,=lPa.

Sorbate loadings (in mmol/g): (a) 0.0702: (b) 0.121: (c) 0.237; (d) 0.449 ;
(e) 0.762: (f) 0.925; (g) 1.449; (h) 4.522; (i) 7.633.
64

Fig. 3 75 mol% N2/25 mol% C02 Na-Y isosteres. P,=lPa.

Sorbate loadings (in mmol/g): (a) 0.0265; (b) 0.125; (c) 0.235; (d) 0.416;

Fig.4

Nz-silicalite- 1
isot heriris

Fig.5

N 2 - N a Y i sot her 111s

 65

1.4

1.2

1.0 Fig.6

.
2
P
b
0.n

0.6
75 mol% N2/25 mol% C 0 2
- NaY isotherms

0.4

0.2

0.0
0 20 40 60 80 100 120 140 160 1

e.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

0.0
I

Pressure/kPe Pressure/kPe

Fig. 7 Comparison of the sorption of CH4, N2 and C02 at 27313 in silicalite-1

and NaY zeolites
I-7
30

25 I Fig.8

Isosteric heat of
sorption. qT. of C02/N2
mixtures in silicalite- I
as a function of mole
fraction, Yco?.of C 0 2 in
gas phase.
5
0.0 0.2 0.4 0.6 0.9
I
1.0

ycor
66

demonstrating the enhanced repulsion-dispersion interaction of this sorbate

in the snialler channels and intersections of silicalite-1 compared with the
corresponding interaction in the much larger supercages of Na-Y.
The Henry's Law constants, KH. have been determined from the initial
slopes of the sorption isotherms of methane, nitrogen and carbon dioxide in
silicalite-l and Na-Y and these constants are listed in Tables 1 and 2
respectively. These tables also include the separation factors
a;,? = K H ( I ) / K H ( ~ )for gases ( 1 ) and ( 2 ) calculated from these constants and
the corresponding experimentally determined separation factors
al,? = (Xl/Y,) (Y?/X?) where Xi and Yi are the mole fractions of component i
i n the sorbed and gas phases respectively. Good agreement between these
a' and a separation factors can be seen.

TABLE 1
Henry's Law Constants. K H and Separation Factors a' and a for Sorption of
CO?. N: and CHJ in Silicalite.
Temp I
KH/( 10-6mol.kg.'.Pa-' a' a I
(K) I CQ N? CHj CO:/N2 COI/CH4 C H 4 / N 2 IC@/N2 C02/CHj CHJ/N2
273 I 85.0 4.97 17.0 17.04 4.99 3.43 I -20 3.5 3.5
13.29 4.38 3.04 3.0 2.8
9.44 3.69 2.69 2.7 2.7
5.65 2.81 2.01 2.5 2.2
10.3 2.54 4.31 4.04 2.38 1.69 -4 2.0

TABLE 2
Henry's Law Constants, KH and Separation Factors a' and a for Sorption of
CO,, N2 and CHJ in Na-Y Zeolites
Temp1 a' a

1 50 2 . 5 9 ~10-3 4 . 0 7 10-3
~ I .57
200 0.363 8.37~10-~ 1 . 3 6 ~ 1 0 - ~ 4337 2657 1.63 1.52
247 1 . 9 9 ~ 1 0 - ~1 . 5 0 ~ 1 0 - ~ 2 . 5 0 ~ 1 0 - ~ 1327 795 1.67
270 3.95~ 5.79~ 9.75~ 693 405 1.68

The experimentally determined a factors for C02/N2 and C O ~ / C H J

mixtures sorbed in Na-Y are not given in Table 2. Because of the very
strong sorption o f carbon dioxide in Na-Y at 2 0 0 - 2 7 0 K the concentrations of
carbon dioxide in the gas phase at equilibrium were too small to be
measured by the on-line mass-spectrometer and the a factors could not,
therefore. be calculated. These low concentrations of carbon dioxide are
fully consistent with the very large a' separation factors in Table 2
calculated from the KH constants.
 67

The separation factors in Table I for silicalite indicate that this

sorbent would be an excellent sorbent to use for PSA separations of binary
mixtures of carbon dioxide, nitrogen and methane. Na-Y could be used to
separate methanehitrogen mixtures but the large separation factors when
carbon dioxide is one component of the mixture would lead to desorption
problems if the PSA separation was carried out in room temperature. Na-Y
could be used for such separations but the temperature would need to be
raised well above 300K.
From the slopes of the isosteres the isosteric heat of sorption, q, can be
calculated by the Clausius-Clapeyron equation: d(lnP)/d( 1/T) = -q/R. The
initial values of q at low coverages were found to be 15.3, 7.6 and 23.6
kJ/mol for methane, nitrogen and carbon dioxide in silicalite-l and 18.1,
16.9 and 34.4 kJ/mol for these sorbates respectively in Na-Y. The small
difference in q for methane in the two zeolites reflects the non-polar nature
of the sorbate. The heat of sorption of methane in Na-Y will contain a
polarization energy contribution from the high concentration of sodium
cations present in the supercages which will tend to be balanced by an
additional dispersion-repulsion contribution to q from the closer fit of the
methane molecule in the smaller channels of silicalite-I. The 9.3 and 10.8
W/mol difference in q for nitrogen and carbon dioxide respectively in the
two zeolites arise mainly from the additional quadrupole moment/electric
field gradient contribution to q for these two sorbates in Nay.

Heats of sorption of mixtures

The isosteric heat of sorption of mixtures, q,, in silicalite-1 were found
to be controlled by the composition of the gas phase i.e. q, = Y,q, +Y2q2
where q is the isosteric heat of sorption of the pure component, Y the gas
phase mole fraction and subscripts 1 and 2 represent the two components of
the mixture. Fig. 8 shows the linear variation of q, with Yco2 for
nitrogedcarbon dioxide mixtures in silicalite-I. Thus the heat of sorption,
q,, is not controlled by the composition of the sorbed phase but by the gas
phase composition.
The above equation for q, was found to be invalid for the ionic zeolite
Na-Y. The isosteric heats of sorption, q,, of nitrogen/carbon dioxide and
methane/carbon dioxide mixtures do not fall between the heats qN20r
qcQnd 9C O , respectively as would be the case if the above equation was
valid. Because of the very large separation factors involved the gas phase
for these systems is virtually pure nitrogen or methane respectively and the
isosteric heats of the mixtures should. therefore, be that of nitrogen or
68

methane i.e. - 17kJ/mol. Although the heat of sorption of nitrogen/carbon

dioxide mixtures is initially - 16kJ/mol this heat decreases with increasing
coverage to 13kJ/mol indicating that the carbon dioxide molecules are not
only preferentially sorbed on the high energy sites but that they contribute
an additional repulsion contribution to the heat of sorption of the nitrogen
molecules because the heat of sorption of pure nitrogen is never found to
decrease below 17kJ/mol. Carbon dioxide molecules similarly affect the
heat of sorption of methane i n methanelcarbon dioxide mixtures. The value
of qT decreases to -14kJ/mol at higher loadings and is thus less than the
minimum value of 16kl/m0l found for the sorption of pure methane in
Na-Y.
The isotherms and isosteric heat of sorption of nitrogen and methane
in Na-Y are very similar. The isosteric heat for nitrogedmethane mixtures,
qT, was found to be controlled by the component present in excess in the
sorbed phase. Because of the small differences in q and qCH, it was
N2
difficult to really test the relationship between qT and the isosteric heats of
the pure single components.

Model Dredictions of mixture sorDtion in Na-Y

The object of much of this work is to develop theoretical models which
are capable of predicting the sorption behaviour of binary mixtures from
knowledge only of the single component sorption data. In a previous paper
(3) the Ideal Adsorbed Solution (IAS) theory was used to make such
predictions of the sorption behaviour of nitrogedcarbon dioxide mixtures in
silicalite-1. The calculated isotherms were found to be in close agreement
with the experimental isotherms for three different binary mixture
compositions. The root mean square deviations, [ ~ ( v ~ . ,-, ~ , , ~ ~ ~ ) ~ / n ] ” ’
where n is the number of experimental points, between the experimental.
v,,, and predicted, vpred.amounts sorbed were found to be of the order of 5%.
Thus the IAS model is capable of accurate predictions for this specific
system.
In Fig. 9-11 the isotherms predicted by the I A S theory for three
different nitrogen/carbon dioxide mixture compositions in the sorbed phase
of Na-Y may be compared with the experimentally determined isotherms.
Isotherm temperatures of 220, 250 and 270 K were covered for each
mixtures to indicate the effect of temperature on the predictions. The IAS
theory predicts a) too large amounts sorbed at high nitrogen compositions of
the sorbed phase b) smaller amounts sorbed than found experimentally
when the sorbed phase contained equal amounts of the two components and
 69

40

+ experimental
3 5 .

-- IAS Theory

25 M 75 100 125 150 175 200

Ressurc/kPa

Fig. 9 Isotherms for 75 mol% N2/25 mol% C02 sorbed in Na-Y

30

+ experimental
- 20

.-, - IAS Theory

: 10
u

Fig. 10 Isotherms for 50 mol% N2/50 mol% C02 sorbed in Na-Y

Fig. 1 1 Isotherms for 25 mol% N2/75 mol% C02 sorbed in Na-Y

40

30 + experimental
-
.
= 20
-- IAS Theory

0
10

0
70

c) very much smaller amounts sorbed than found experimentally at high

carbon dioxide compositions of the sorbed phase. These differences were
the same at all three temperatures studied. Although the agreement was
poor between experiment and IAS theory predictions at the three different
sorbed phase compositions studied the agreement was best for the sorbed
phase containing equal quantities of the two components. The root mean
square (rms) deviations calculated for these IAS predictions were -7, 5 and
28 molecules per unit cell for the 75%N2, 50%N2 and 25%N2 sorbed phase
compositions respectively.
The IAS theory was similarly unable to predict the sorption behaviour
of methanelcarbon dioxide mixtures in Na-Y over the same composition and
temperature ranges covered for the above nitrogenlcarbon dioxide
mixtures. However, the IAS predictions were found to be reasonably
accurate for a sorbed phase containing equal amounts of methane and
carbon dioxide at 220 and 250K. The root mean square deviations
calculated for these two isotherms were found to be less than 1 molecule
per unit cell at 220 and 250K respectively.
The isotherms obtained with mixtures of nitrogen and methane are
similar to the pure nitrogen and pure methane isotherms at the same
temperature. The mixture isotherms were less curved when the sorbed
phase contained excess nitrogen consistent with the less curved nature of
the pure nitrogen isotherms compared to the pure methane isotherms. Na-Y
showed a small, but reasonable selectivity for methane. This selectivity is
clearly shown in the McCabe-Thiele diagram in Fig.12 over the whole range
of sorbed phase compositions. This diagram also clearly demonstrates the
increasing selectivity towards methane as the temperature increases. The
corresponding McCabe-Thiele diagram for nitrogenlcarbon dioxide mixtures
in silicalite-1(3) showed the opposite temperature effect. As the
temperature was raised the selectivity towards carbon dioxide decreased.
The mixture data obtained for the sorption of nitrogenhethane
mixtures in Na-Y were suitable for testing three different predictive models
( i ) IAS (ii) Competitive Langmuir(4) and (iii) Ruthven's(5) Statistical
Thermodynamical Model. These three models were tested for three sorbed
phase mixture compositions of 75%/25%, 50%/50% and 25%/75%
nitrogenhethane and at three different sorption temperatures of 150, 200
and 250K. Fig.13-15 compare the predictions of the three models against
the experimental data for these three sorbed phase mixture compositions at
the most sensitive temperature of 150K. The Competitive Langmuir model
is clearly seen to give the best fit to the experimental data. At the higher
 71

1.0

-
- 0.6
Ne
0
a
0.6 -
n
I?)

2
Y
0.4 -
a

CH,

0.0
0.0 0.2 0.4 0.6 0.8 1
M o l e Fraction Sorbed Phase (X)

Fig. 12 McCabe-Thiele diagram for N2/CH4 mixtures sorbed in NaY

loo
90 f

10
2o
0
0
i
4
40 80 120 160 2 I0
Pressure/kPa

Fig. 13 Isotherms for 75 mol% N2/25 mol% CH4 sorbed at 150K in NaY
(+) experimental versus predictions by Competitive Langmuir, TAS and
Ruthven's Statistical Thermodynamical models.
72

.................................
90 - .... .... t Langmuir

-
80
.+ IAS

0
0 40 80 120 160 0
Pressure/kPa

Fig. 14 Isotherms for 50 mol% N2/50 mol% CH4 sorbed at 150K in NaY
(+) experimental versus predictions by Competitive Langmuir, IAS and
Ruthven's Statistical Thermodynamical models.

100 , .'; . . . . . . . . . . . . . . .L.a n.g.m.u .i r . . . . . . .

90 -

;cF
.'
80 -
f'
70 - :

-;
\ 50
60
-
\ - - - - - _ _ _ _ _ _ _ _
m
m 40 - Ru t h u e n
PI

9 30
-
c
20 -

0 4 .~
0 40 80 120 160 200
Pressure/kPa

Fig. 15 Isotherms for 25 mol% N2/75 mol% CH4 sorbed at 150K in NaY
(+) experimental versus predictions by Competitive Langmuir, IAS and
Ruthven's Statistical Thermodynamical models.
 73

temperatures the IAS and the Competitive Langmuir model were both
equally good at predicting the experimental isotherms. The root mean
square deviations calculated for all three models for all three sorbed phase
compositions and for all three temperatures are summarized i n
Table 3.
In this Table the very poor predictive ability of the Statistical
Mechanical model compared with the other two models can be clearly seen.
However, this is not surprising since this model is not really designed to
cope with the large number of molecules sorbed per supercage in these
mixtures. In order to cope with the large number of molecules sorbed per
unit cell the unit cells were divided into smaller volumes which contain only
4 molecules at saturation. The model then assumes that there is little
transference from one sub-volume to another and this is a gross
simplification of the actual experimental situation.

TABLE 3
Comparison of the predictive models for nitrogenlmethane mixtures sorbed
Na-Y ________~ - ~~~

Sorhed Phase Temperature Root Mean Square Deviation*

Composition K Statistical Competitive Ideal Adsorhed
mole %NZ
Thermodynamic Langmuir Solution
mole %CH4
1 so 22.0 4.7 12.7
75/25 200 23.7 2.3 2.9
2so 24.7 2.1 1.4

150 19.7 3.2 12.2

50150 200 15.0 2.1 2.9
250 11.2 1 .o 0.3

150 18.1 8.4 3.1

25/75 200 18.3 4.0 2.0
250 9.2 1.6 1.2

t RMS deviations are in molecules per unit cell

74

REFERENCES

1 M. Bulow and P. Lorenz, Fundamentals of Adsorption 11: A. Liapus (Ed),

Engineering Foundations. New York. USA, 1987, pl19.
2 M. Bulow and P. Lorenz in preparation
3 P. Graham, A.D. Hughes and L.V.C. Rees, Gas Sep. Purif. 3 (1989) 56.
4 E.C. Markham and A.F. Benton. J. Amer. Chem. SOC. 5 3 (1931) 497
5 D.M. Ruthven, K.F. Loughlin and K.A. Holbrow Chem. Eng. Sci., 28
(1973) 701
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 75
0 1991 Elsevier Science Publishers B.V., Amsterdam

USE OF ZSM ZEOLITES IN THE LIQUID PHASE SEPARATION OF ALCOHOLS

R. SCHOLLNER and W.-D. EINICKE

Department of Chemistry, Karl M a r x University, Talstr. 35, 7010
Leipzig, German Democratic Republic

SUMMARY
A study was made on the adsorption of alcohol-water mixtures
on hydrophobic siliceous molecular sieves. The aim of this paper
is to show the concept from the selection of the most effective
structure types over the influence of the Si/Al ratios of the ad-
sorbent.~from template synthesis and the dealumination of Penta-
sils from the “inorganic way’, the selection of a hydrophobic bin-
der to the use of the zeolites in innovative processes.

INTRODUCTION
The novel h l g h silica molecular sieves with distinct hydropho-
bic properties synthesized during recent years make a selective
separation of organic compounds from aqueous solutions possible
(ref. 1). As polnted out by several authors, an industrial poten-
tial is the adsorptive separation of alcohols from ethanol (ref.
2) and butanol-isopropanol (ref. 3) fermentation. I t seems that
adsorption processes are alternative methods for the energy consu-
ming conventional three stage process : strlpplng-rectification-
vacuum rectlfication (ref. 4). The aim of this paper 1s to examine
the thermodynamics of ethanol-water mixtures on hydrophobic sill-
ceous adsorbents for an optimization of the adsorbents properties.
The analysis of the excess isotherms was carried out by the ther-
modynamics of energetically homogeneous and heterogeneous adsor-
bents. Further investigations deal with the selection of suitable
binders for hydrophobic molecular sieves, the characterization of
the desorption step of ethanol from the adsorbents and the use of
the molecular sieve pellets in innovative processes.

THEORY
To describe the liquid phase adsorption of blnary alcohol-wa-
ter mixtures the adsorption excess was used (ref. 5) :
r2e= n2e/ rn = no ( x20- x21 / m (1)
0
The adsorption excess can bedetermined experimentally, when n
76

molecules of a mixture of known composition were contacted with

the mass m of the adsorbens and the mole fraction of the solution
changes from x20 to the equilibrium mole fraction x21. The repre-
sentation of the adsorption excess versus the equilibrium mole
fraction gives the so-called adsorption excess Isotherm, classi-
fied by Schay and NagY (ref. 6).
For the thermodynamical description of the excess isotherms two
main approaches exist (ref. 7). From the technological point of
view one disadvantage of the method of excess functions of Gibbs
(ref. 8 ) 1s that there is no information concerning the content
and the distribution of the two components inside a porous adsor-
bent. For this reason the model of the adsorbed phase (ref. 9) was
used, where in the case of the zeolites the free adsorption volume
corresponds to the space of the adsorbed phase.
From the analysis of the adsorption excess isotherms the limi-
ting value of adsorption n2,0s, the equilibrium diagram x2' vs.
x 2 1 , the individual isotherms n i S , the differences of the interac-
tion energies o t both components including their distribution and
the activity coefficients of the adsorbed phase are available.
The limiting values of adsorption determined by the extrapola-
tion method of schay (ref. lo), the isopiestical uptake from the
gas phase and the pyknometric method of Dubinln (ref. 11) are very
similar and demonstrate that the ethanol molecules can occupy the
whole free adsorption volume of the adsorbents.
The composition of the adsorbed phase x2' was determined accor-
ding to :
S r x21 + r2
X2S = "2,o
"210 r + 1-r I r2e
where r is the ratio of the limiting values of adsorption of both
components r = "1,o S '"2,o S '
The equilibrium constant for the exchange process between the
bulk and the adsorbed phase is given by :

where y, are the activity coefficients of the components in the

adsorbed and the bulk phase respectivily. The activity coeffi-
cients of the bulk phase were calculated by UNIFAC (ref. 12). The
value K connected with the free standard enthalpy of the exchange
and the difference of the interfacial enthalpies can determined by
 77

the integration of the Gibbs adsorption equation

1

with the upper integration boundary x2l=l.

Taking into account the energetical heterogeneity, the follo-
wing equation for the overall adsorption isotherm was used (ref.
13) :

X F(UZ1) d U21 (5)

‘21,min

where x 2 S (x21,U21) is the local isotherm, U21 the difference of

the interaction energies of both components and F(UZ1) their dis-
tribution. The functlon F(UZ1) was calculated by a numerical regu-
larization method on the basis of a singular value decompositlon
(ref. 14) without any assumption concerning the shape of the dis-
tribution function. For comparison for all systems the same regu-
larization parameters were used.

EXPERIMENTAL
The molecular sieves were calcinated to remove organic com-
pounds, exchanged with 0.1 M aqueous NaN03 solution and washed be-
fore use.
For the determination of the adsorption excess about 0 . 2 g ac-
tivated adsorbens was contacted with about 1 ml of alcohol-water
mixture of known composition. The equilibrium mole fractlon was
determined refractometrically after 48 hrs.
The DTG measurements were carried by means of a microbalance
(Setaram, Lyon) with a controlled linear heating rate of 10 K/ min
and a dried argon stream a t a flow rate of 3 l/h.

RESULTS AND DISCUSSION

The efficiency of selective separation of alcohol-water mixtu-
res on pentasil zeolites is shown in Fig. 1 by the equilibrium
diagrams on NaZSM-5 (Si/A1=19) at 293 K. The alcohols were prefe-
rentially adsorbed in the whole concentration range, which is due
to the dominance of the nonspecific disperslon interaction.
78

Fig. 1 Equilibrium dia-

grams in wt-% for etha-
nol , 1-propanol 0 and
1-butanol-water mix-
tures on NaZSM-5 (Si/Al=
19) at 293 K
25 5.0 7.5
weight fractiodo/0)

In the technologically interesting concentration range ethanol

was concentrated from 10 t o 90 percent by weight.
The equilibrium constant K is increasing linearly with a higher
carbon number of alcohol. The limiting values of adsorption are
independent of the carbon number of the alcohol with about 130 mg/
g. In comparison with other hydrophobic adsorbents (charcoals, co-
polymers, dealuminated Y-zeolites) the low capacities of the pen-
tasils seems to be a disadvantage of these zeolites.
For this reason we investigated other siliceous molecular sie-
ves with distinct hydrophobic properties to get information about
the influence of the growth and the geometry of the channels and
the cavities of the adsorbents on the liquid phase adsorption of
ethanol-water mixtures. The characterization of the sodium forms
of the molecular sieves is given in Table 1.

TABLE 1
Characterization of the hydrophobic adsorbents used
~~

Zeolite Pore System Chemical composition mg EtOH/g

ZSM-5 small channels Na4. (AloZ) 4. (sio2)91. 128.5

Mordenite channelstcavities Na2m5(A102) 2.5(si02)40.0 100.0
US-EX cav 1 ties Na4. 8 (A102) 4.8 (' i02) 158.9 235.4
Hectorite "large channels* Na0,7Mg5, 3 ~ i o . 7 ~ i 8 0 2 0 ( ~130.2
~)
 79

The excess isotherms for the adsorption of ethanol-water mix-

tures on the adsorbents at 293 K are demonstrated in Fig. 2.

Fig. 2 Excess isotherms for

the adsorbents 0 ZSM-5, 0
mordenl te, us-Ex and A hec-
torite at 293 K

It can be seen that the shape of the excess isotherms is quite

different. While the isotherm for the zeolite NaZSM-5 is of t y p
1 1 1 of the Schay-Nagy classificationl the other adsorbents show
type V behaviour which is connected with an adsorption azeotrope
in the low ethanol region.
The equilibrium diagrams calculated by eqn. (2) are illustrated
in Flg. 3. It seems that the larger the pores of the adsorbens the
lower the efficiency of the ethanol-water separation.
From our expierences we would expect that similar Si/Al ratios
and respectivily similar ratios of the nonspecific and specific
adsorption interaction leads to the same excess isotherm type.
Therefore the differences only can be caused by the behaviour of
the adsorbed phase.
In the bulk phase the water molecules are associated in cla-
thrates (ref. 15). The first ethanol molecules of the mixture can
OCCUPY the cavities of the clathrate structure. A f t e r saturation
of the clathrate cavities a pseudo two phase system exists with
filled clathrates and a random ethanol-water mixture. With regard
to the high ethanol region, the degree of association increases is
due to the decreasing number of hydroxyl groups.
80

Fig. 3 Equllibrium dia-

grams for the systems
mentioned in fig. 2

mole fraction x i

In contrast the small channels of the ZSM-5 zeolite with a dia-

meter of about 0.6 nm do not allow the formation of the clathrate
structures. As reported earlier (ref. 16)I the activity coeffi-
cients show in contrast to the bulk phase negative deviations from
Raoults law. Therefore the hydrophobic Part of the ethanol mole-
cule should be adsorbed on the oxygen walls of the channels and
the OH-group of the molecules can interact with water and/or etha-
nol on the basis of hydrogen bonding.
In the case of the zeolites mordenlte and US-Ex and the layer
silicate the activity coefficients are similar to the bulk phase.
This behaviour confirms the possibility of the formation of cla-
thrate structures in the adsorbed phase. For all adsorbents with
large channels or cavities the water clathrates and the sil con-
dioxid framework compete with the first ethanol molecules in the
adsorbed phase. That means that hydrophobicity is an essentia but
not a sufficient condition for an effective adsorptive ethanol-wa-
ter separation. Because the zeolites with small channels are the
most effective ones, the considerations below only deal with the
pentasil zeolites.
As pointed out by several authors (refs. 17, 18), the hydropho-
bicity depends strongly on the aluminium content of the unit cell
of the pentasil zeolites. Therefore we investigated a series of
zeolites from template synthesis with different Si/Al-ratios given
in Table 2.
 81
TABLE 2
Characterization of the NaZSM-5 zeolites investigated

Si/Al chemical composition adsorbed mg g-l zeolite

ethanol water

85 117.0 32.1
Nal. 1 (A102)1.1 (‘‘O2) 94.5
50 112.8 33.5
Nal. 9 (A’02) 1.9 (s102) 94.1
40 115.6 33.1
Na2. 3 (A102)2. 3 (si02)93. 7
19 128.4 36.5
Na4,8 (A102) 4.8 (“O2) 91.2
13.5 Nag.6(Alo2)6.6(Si02)8g,4 132.2 42.0

The systems are of interest for an analysis in terms of the

thermodynamics of adsorption from solution on energetically hete-
rogeneous adsorbents. The idealized aluminium-free end member of
the pentasils, the so-called silicalite, can only interact with
the molecules of the mixture on the basis of dispersion forces.
W i t h the installation of aluminium into framework positions the
possibility of specific interaction occurs and the adsorbents be-
come more energetically heterogeneous. The distribution functions
of the adsorption energy differences are shown in Fig. 4.

c 02
Si IAI.13

-10 0 10
mMa
-10
Kl:
Si/AI=19

0 10
-
.
Si/AI= 40

U/kJmol”
Si/Al= 50

10 0 10
SilAI.85

-10 0 10
0.1

Fig. 4 Distribution functions for the energy differences (from

left to right increasing Si/Al-ratio)

The numerical calculations demonstrate, that the greater the

aluminium content of the adsorbent the higher the peak of the low
energy difference. This fact led us to the conclusion that this
peak corresponds to the difference of the interactions of both mo-
lecules with the field of the dipoles (A104)-- Na+ The position .
and the height of the other peak is almost independent of the Si/
A1 ratio. Therefore this peak was assigned to the difference of
the London-type interactions of the molecules with the zeolitic
82

framework. It is interesting to note that in dependence on the ad-

sorbate-adsorbate interaction the peaks shift toward higher or
lower U21 values. For Fig. 4 the calculations of the interaction
within the adsorbed phase were carried out by the Ising model in
the Bragg-William approximation (ref. 19) with the assumption that
the interaction based on hydrogen bonding and a coordination num-
ber c=3.
Accordingly with the model of an energetically homogeneous ad-
sorbens i t becomes clear that the lower the aluminium content of
the pentasils the higher the separation efficiency for ethanol-
water mixtures.
The demand for the use of silicalite in the adsorptive ethanol
separation was also underlined by the desorption experiments (ref.
20). While in the DTG curve for the ethanol saturated silicalite
only one desorption effect at 380 K appears, the curves for the
aluminium containing samples show two maxima. The area of the high
temperature effect (510-590 K) increases with increasing alum nium
content. That means that an economic thermal regeneration of the
adsorbens after the adsorption step is only possible for si 1ca-
te.
Two disadvantages of the pentasils from template synthesis are
the high production costs and the problems of air pollution during
the burning of the pentasils to remove all organic compounds.
Therefore several authors investigated the dealurnination of
pentasil zeolites synthetisized with Si/A1 ratios varying from 13
to 20 by the inorganic way without template (ref. 21). For the
dealumination of zeolites the acid extraction, the modification
with C0Cl2, SiC14 and (NH4)2SiF6 and the hydrothermal treatment
were proposed (ref. 22). To obtain pentasils with higher Si/A1 ra-
tios we used the hydrothermal dealumination of the parent pentasil
HS 30 at water steam pressures of 4, 1 3 , 40 and 80 kPa (ref. 23).
As suggested by Breck (ref. 24) the nonframework aluminium species
built during the dealumination exist in a cationic form.
The dealuminated samples were modified by three procedures :
A : cation exchange with 0.1 M aqueous Nacl at 350 K
8 : cation exchange with 0.1 M aqueous NaOH at 350 K
C: extraction with 0.1 M aqueous HC1 and recationization with 0.1
M aqueous NaOH at 350 K
The framework Si/A1 ratios of the pentasils are shown in Table
3. It can be seen that the dealumination of the strongly steamed
samples can be partially reversed by treatment with NaOH. A fur-
 83

TABLE 3
(Si/A1IF ratios after modification determined by 27Al MAS NMR

(S i /All
water pressure/kPa
A B C

0 15 15 15
4 20 21 18
13 25 24 26
40 53 27 36
80 64 25 46

ther effect of the NaOH modification is the decrease of the micro-

pore volume of the pentasils which Is due to the partial dissolu-
tion of the zeolitic framework.
The formation of a secondary pore system was detected by nitro-
gen adsorption at 77 K as shown in Fig. 5.

tI
20 40 60 80
p(kPa1

Fig. 5 Nitrogen adsorption (open symbols) and desorption ( filled

symbols) isotherms for the samples modified by procedure B
by water steam pressures 0 0 , V 4, 0 13, A 40 and 0 8 0 kPa

From the hysteresis between adsorption and desorption isotherms

the following micropore and secondary pore volumes (Table 4) were
calculated by the "t-method" of de Boer (ref. 25).
In the case of the acid treated dealuminated pentasils i t can
be seen from Table 3 that the extraction of the non-framework alu-
minium was incomplete. During the following recationization with
NaOH, a part of these species was reinserted into framework posi-
tions. It is interesting to note that the modification with HC1
84

TABLE 4
characterization of the Pore volume of the pentasiles modified by
procedure B

water pressure "micro "sec "sum surf.

k Pa cm 3 g-l cm 3 g-l cm3 9-1 m 2 g-l

0 0.166 0.060 0,226 70

4 0.154 0,081 0.235 115
13 0.154 0 101
m 0.255 140
40 0.146 0.122 0.268 145
80 0.129 0.194 0.323 230

must lead to a reconstruction of the dealuminated framework be-

cause the realumination is not connected with the formation of the
secondary pore system.
The adsorption behaviour of all modified samples in the etha-
nol-water separation is shown by the equilibrium constants in Fig.
6. For comparison the values for the template synthesis products
(ref. 26) are also given.

Flg. 6 Equilibrium con-

stants of the dealumina-
ted pentasils in compa-
rison t o the products
from template synthesis
( OHS 3 0 , A A e A B , AC

and 0 (ref. 26))

I : : ; : : :
1 2 3F4 5 6
Aluminium per unit cell

For the NaCl recationized samples i t can be seen from F i g . 6

that the equilibrium constants do not achieve the values of the
template synthesis. The differences must be assigned to the influ-
 85

ence of the non-framework aluminium which prefers water adsorp-

tion. The extraction of these species with HC1 leads to higher
equilibrium constants. But the formation of SiOH groups detected
by 1H NMR (ref. 27) as adsorption centres for specific interac-
tions prevent a better separation of the ethanol-water mixture.
In the case of the NaOH treated pentasils the formation of the
secondary pore system gives no contribution to a higher concentra-
tion of ethanol. I t seems that association of the water molecules
in the secondary pore system is the main reason for the decrease
of the equilibrium constants.
The evidence compares well with the results of the DTG investi-
gations on the same samples. The portion of ethanol desorbed at
higher temperatures increases in comparison with the template syn-
thesis products with the same Si/Al ratio (ref. 20).
Therefore the use of the dealuminated and modified pentasils
produced with our procedure seems to be doubtful for ethanol-water
separation .
The use of the pentasil zeolites in the industrial scale-up
makes i t nessesary to find a suitable binder f o r pelletizatlon.
The information concerning a hydrophobic binder in the literature
is limited. Several authors used Si02 (ref. 28) and especially for
catalytic investigations A1203 (ref. 2 9 ) . Both binders detoriat
the efficiency of the ethanol-water separation. Therefore we used
hydrophobic cellulosic triacetate. For comparison zeolite NaZSM-5

Fig. 7 Adsorption ex-

cess isotherms for etha-
nol-water mixtures on 0
NaZSM-5, pelletized with
Vsio2, A ~ 1 and~ O C0 A ~
86

(Si/Al=19) was pelletized with 30 Per cent by weight of Si02,

A1203 and cellulosic acetate (CA). The excess isotherms for etha-
nol-water mixtures are shown in Fig. 7.
According to the Schay-Nagy isotherm classification the system
sthanol-water-NaZSM-5+A1203 belongs to the type I V , which is con-
nected with an adsorption azeotrop.
From the excess isotherms the equilibrium constants, the limi-
ting values of adsorption and the ethanol enrichment (E) in the
adsorbed phase from solutions of 10 percent by weight were deter-
mined and are given in Table 5.

TABLE 5
Adsorption characteristics of the pelletized pentasil

adsorbens ns/mmole g-l K E/Wt -%

NaZSM-5 powder 3.34 28.7 90

NaZSM-S+CA 2.30 27.8 90
NaZSM- 5+S i O2 3.37 13.8 50
Na Z SM- 5+A1 2O 4.16 5.2 30

I t can be seen that the zeolite NaZSM-5 pelletlzied with

A1203
shows the highest capacity for ethanol-water mixtures, followed by
the zeolite Powder and the NaZSM-5+Sio2 system. The CA containing
pellets give the lowest limiting value of adsorption. In compari-
son with the powder, the capacity was decreased during the pelle-
tization by about 31 percent. That means that the binder is inert
concerning the adsorption of ethanol-water mixtures.
From the equilibrium constants and the ethanol enrichment in
the adsorbed phase i t becomes clear that the cellulosic acetate
maintalnes the hydrophobicity of the zeolite. In the case of the
binder Si02 the silanol groups and the possibility of associate
formation in the mesopore system of the binder decrease the hydro-
phoblcity of the system. Also A1203 decreases the efflclency of
the ethanol-water separation considerably. Additionally the asso-
ciate formation a migration of aluminium species from the binder
into framework positions during the calcination was detected (ref.
30).
However, i t seems that cellulosic acetate is a suitable binder
for hydrophobic siliceous molecular sieves in the adsorptive etha-
nol-water separation. The binder content can be reduced to about 5
 87

percent by weight.
The hydrophobic Pellets were sucessfully applicated in the
- removal of ethanol from the gas and the aqueous phase
- separation of alcohols from ethanol and butanol fermentation
- in-situ fermentation of ethanol
- dealcoholization of beer and wine

ACKNOWLEDGEMENTS
The authors are indebted to Dr. W. Reschetilowski for helpful con-
tributions and the group of Prof. Br%uer for numerical calcula-
tions.

REFERENCES
1 E.M. Flanigen, J.M. Bennett, R.W. Grose, J.P. cohen, R.L.
Patton, R.M. Kirchner and J.V.C. Smith, Nature (London), 271
(1978) 512
2 N.B. Milestone, Report NO. C.D. 2355, Methods of Separating
and Concentrating of Ethanol and Other Alcohols, New Zealand,
March 1985
3 I.S. Maddox, Biotechnol. Lett.. 4 (1982) 23
4 A. Serra, M. Poch and C. Sola, Rev. Agroquim. Tecnol. Ali-
ment, 27 (1987) 372 and 508
5 D.H. Everett, Trans. Faraday Sac. 61 (1965) 2478
6 L.G. Nagy and G. Schay, Magyar Kem. Foliorat. 68 (1960) 31
7 A.A. Lopatkin, Pure Appl. Chem. 61 (1989) 1981
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London, Toronto 1928
9 A.I. Rusanov, Fazovye ravnovesija i poverkhnostnye yavlenia,
Khimia, Moscow 1967, p. 13
10 0. Foti, L.G. Nagy and G. Schay, Acta chim. Aced. Sci. Hung.
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Serpinski, Adsorption of Hydrocarbons on Zeolites, Berlin
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12 A. Fredenslund, J. Gmehling and P. Rasmussen, Vapor-Liquid
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Ernst, Positron Annhilation, (Ed. P.C.Jainl R.M.Singru and
K.P. Gopinethan), world Sci. Pub. Co., Singapore 1985, P.
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sci. 122 (1988) 280
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1956
20 W.-D. Einicke, W . Reschetilowski, H. siegel, J. BBhm and
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v.Szombathely, M. Jusek, H.-R. Poosch, P. Brluer, W.
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23 E. Brunner, H. Ernst, D. Freude, M . Hunger, C.B. Krause, D.
Prager, W. Reschetilowski, W. schwieger and K.-H. Bergk,
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Katzer,Ed.) ACS SYmP. ser. 40, Washington D.C., 1978,
I

p. 271
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2 6 W.-D. Einicke, M. Heuchel, M. v.szombathely, P. Brtluer, R.
SchBllner and 0. Rademacher, J. Chem. Soc., Farad. Trans. I
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G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 89
0 1991 Elsevier Science Publishers B.V., Amsterdam

BASIC PRINCIPLES AND RECENT RESULTS OF 'A MAGIC-ANGLE-SPINNING

AND PULSED FIELD GRADIENT NUCLEAR MAGNETIC RESONANCE STUDIES
ON ZEOLITES

H. PFEIFER, D. FREUDE AND J. m G E R

Sektion Physik der Karl-Marx-Universitat Leipzig, LinnkstraBe 5,
DDR-7010 Leipzig

ABSTRACT
In the first part it is shown both experimentally and
theoretically that the H' NMR chemical shift of surface hydroxyl
groups as measured for strongly dehydrated zeolites by the MAS
technique is a suitable parameter to characterize their strength
of acidity. Moreover, this method allows a direct and unambiguous
determination of the concentration and accessibility of the
various OH groups. In contrast, for hydrated zeolites a
superposition of several effects (e.g. Plank's mechanism,
formation of hydroxonium ions, adsorption of water molecules on
Lewis acid sites) may occur which requires a more detailed
analysis of the spectra and additional information for an
unambiguous interpretation.
In the second part recent results of pulsed field gradient
(PFG) NMR studies of self-diffusion in zeolites are presented
which include xenon self-diffusion, the anisotropy of diffusion
in zeolites, NMR tracer exchange experiments and a critical
comparison of PFG NMR diffusivities with results of other
techniques.

H' MAS NMR STUDIES ON DEHYDRATED ZEOLITES

The elementary step of catalysis by Bronsted acidic sites is
the proton transfer from the surface hydroxyl group ZOH to the
adsorbed molecule M:
ZOH + M = zo- + MH+ (1)

Hence, the catalytic activity of a catalyst will be determined by

at least three independent parameters for each sort of surface
hydroxyl groups (Bronsted acidic sites):

(i) The strength of acidity as defined by the rate constant

of the proton transfer to the adsorbed molecule,
(ii) the concentration and
(iii) the accessibility of the acidic sites.
90

Strenuth of Bronsted Aciditv

According to eq. (1) the rate constant of the proton transfer
depends both on the properties of the acidic site ZOH and of the
particular molecule M. In order to define a parameter which
characterizes the protonating ability of the ZOH group but does
not depend on the particular molecule we decompose reaction (1)
into two processes:

ZOH = 20- + H+
H+ +M = MH+

which leads to the definition of the strengths of gas phase

acidity and basicity as the standard Gibbs free energy change of
processes (2) and ( 3 ) , respectively (ref. 1).
In the following we shall use "strength of acidity" as a
synonym for the standard Gibbs free energy change of process
(2) since it is exactly this parameter which describes
quantitatively the protonating ability of the Bronsted acidic
site. To compare the strength of acidity with the deprotonation
energy of the ZOH group h E D P l a quantity which follows from
quantum chemical calculations, one must take into consideration
that the standard Gibbs free energy hGDpo is the sum of the
deprotonation energy A EDp, of the zero-point energy change AEDpo
and of the Gibbs free energy change b GDPtherm which results from
the conversion of the three vibrational degrees of freedom of the
proton as part of the ZOH group into its three translational
degrees of freedom after leaving this group. Assuming that the
zero-point energy change AEDpo is a constant and that the
contribution of b GDptherm is negligible (ref. 2) , the
deprotonation energy &EDPI i.e. the energy difference of 20-
and ZOH, can be taken as a suitable measure for the strength of
acidity.
With regard to the position of the H ' MAS NMR signal of the
ZOH group which is generally described by the so-called chemical
shift i.e. the shift of the resonance relative to a standard
(tetramethylsilane) in ppm, the following qualitative argument
may be taken as a hint, that there is a direct relation between
J H and the strength of acidity: A higher value of 6H corresponds
per definition to a reduced shielding of the external magnetic
field and hence to a larger value for the net atomic charge of
the hydrogen. On the other hand an enhancement of the net atomic
 91

charge will lead to a reduction of the deprotonation energy. In

agreement with this suggestion experimental values for 6H and for
the absolute gas phase acidities aGDPo measured for hydroxyl
groups of various organic compounds in the gaseous state which
are plotted in Fig. 1 show in fact a good correlation (cf. ref.
3) -
I

PhOH

Fig. 1. Dependence of the

chemical shift JH for the OH
$’PPm proton of various molecules
2 on the absolute gas phase
acidities A G in the
gaseous statef)’The 6 values
1
were taken from ref.H;2, the
AGDpo-values were measured by
Lias, Bartmess et al. and are
0 presented in ref. 73.
1550 1500 1450 1400

Another experimental proof of our suggestion that 6H is a

suitable and sensitive measure for the strength of acidity is
given by Fig. 2. In this figure Sanderson‘s intermediate
electronegativity Sm, computed for zeolites of composition
HA102(Si02)n according to the equation
sm = (SH S A ~So 2n+2 SSi)1/ (3n+4) (4)

with SH = 3.55; SA1 = 2.22; So = 5.21; Ssi = 2.84 (cf. ref. 4),
is plotted together with experimental values of 6H in dependence
on the silicon-to-aluminium ratio n. The nearly identical
functional dependence of both quantities provides ample evidence
for the usefulness of JH as a measure for the strength of
acidity. In this connection it should be mentioned that due to
the use of CH4 as an inner standard (ref. 3 ) the absolute values
of 6H plotted in Fig. 2 are reduced by about 0.3 ppm with respect
to ref. 5 and that the accuracy of the absolute values of JH has
been enhanced considerably so that the present error does not
exceed ? 0.05 ppm. Moreover it was possible to show by a thorough
investigation that the residual linewidths which limit the
accuracy for a determination of the values of 6H for bridging OH
groups on zeolites are not controlled by artefacts or
imperfections rather than by the distribution width of the
strength of acidity (ref. 6).
92

n-
Fig. 2. Values for the intermediate electronegativity Sm and
the chemical shift bH of the (accessible) bridging OH groups
in dependence on the silicon-to-aluminium ratio n for various
zeolites (HX: zeolite H-X; HY: zeolite H-Y; HM: mordenite;
HE: erionite; HZ: H-ZSM-5).

For bridging OH groups of a zeolite H-Y with a silicon-to-

aluminium ratio n = 2.6 the residual linewidth which can be
reduced in the MAS NMR spectra after partial deuteration of the
sample or by using multiple pulse sequences to reduce the
dipolar proton proton interaction is of the order of 0.3 ppm
(ref. 7). Taking into consideration the empirical formula
(ref. 3 )
f1cm-l = 3906 - 74.5 GH/ppm (5)

which connects GH with the stretching vibration frequency f of

the OH groups, the residual MAS NMR linewidth of 0.3 ppm cor-
responds to a residual linewidth of the IR band of the bridging
OH groups of ca. 20 cm-l. This value agrees quite well with
experimental results published recently in literature (ref. 8 ) .
A s a third argument which supports our suggestion that bH can
serve as a measure for the strength of acidity we refer to non-
empirical quantum chemical calculations (ref. 2) although due to
the approximations inherent in such a treatment it is not such a
conclusive proof as the above mentioned experimental results.
In Fig. 3 calculated shielding constants uH (connected to the
chemical shifts SH by the equation uH = Gbare proton - GH) taken
from ref. 2 are plotted in dependence on calculated deprotonation
energies hEDp. Once more one observes a good correlation between
both quantities.
 93

20 -
+
"iO

A E D ~ /kJrnd-' -
Fig. 3 . Dependence of calculated values for the chemical
shielding aH on calculated values for the deprotonation energy
(ref. 2 ) .

Summarized, Figs. 1-3 demonstrate clearly that bH is a

suitable and sensitive spectroscopic quantity to measure the
strength of acidity as defined by eq. ( 2 ) . In principle however,
one should take into account that in these figures isolated
hydroxyls of similar type are compared so that it is not clear
whether there exists a generally valid correlation between 6H and
EDp. Further experiments and calculations are necessary to
answer this question which is of basic interest.
In the H' MAS NMR spectra of dehydrated zeolites containing
only oxygen, silicon and aluminium in the framework, in general
five lines can be separated which have been denoted (refs. 3 and
9) as a, b, c, d, and e:

Line a at 1.8 to 2.3 ppm is caused by non-acidic (silanol) OH

groups. In the case of carefully dehydrated (200 OC, 10 K/h,
lo-' Pa, 2 4 h) silica this line appears at somewhat lower values
(1.65 ppm for aerosil 200/Degussa). A distinction between single
and geminal OH groups however is not possible since from the
single line shown in Fig. 4 (dehydrated sample) we must conclude
I 6Hsing1e - 6 Hgeminall 5 0.1 ppm (6)

which is in agreement with infrared studies

lfsingle - fgeminall (7)

but at variance with a former interpretation of Lippmaa et al.

(ref. 10).
94

on air
Si

1.65 ppm
3.0ppm 2.0ppm

10 5 0 -5 10 5 0 -5
-61 H ppm -61 H ppm
Fig. 4. H' MAS NMR spectra of carefully dehydrated (200 O C , 10
K/h, lo-' Pa, 24 h) silica (aerosil 200 1 Degussa) and after
keeping it 30 s on air (ref. 11).

The adsorption of water which interacts with SiOH groups gives

rise to a shift of ca. 0.4 ppm to higher values of JH as can be
seen from Fig. 4 (ref. 11). The H' MAS NMR signal of silanol
groups in molecular sieves of SAPO-type may also appear at lower
values of JH (cf. Fig. 5 ) .

S A PO-511 S A PO-512
f b)

'HMAS NMR H
Si O A I
Ibl

SiOH

Fig. 5. H' MAS NMR

(Bruker MSL 300) and
infrared stretching
vibration spectra
(Digilab FTS-20) of two
differently synthesized
specimens of SAPO-5 (ref.
13).

3630
f/rm-'L- t/cm-1 -
3630
 95

Line b at 3.8 to 4.4 ppm is ascribed to acidic O H groups which

are known to be of bridging type (SiOHA1). The value of JH
increases with increasing silicon-to-aluminium ratio of the
zeolite (cf. Fig. 2).
Line c at 4.8 to 5.6 ppm is also ascribed to acidic OH groups of
the bridging type but influenced by an additional electrostatic
interaction of the hydroxyl proton presumably with neighbouring
oxygen atoms of the six-membered ring (corresponding to the shift
of the so-called LF-band in infrared spectroscopy). The fact that
for the bridging OH groups pointing into the large cavities (HF-
band) and into the small cavities (LF-band) separate lines appear
in the 'H MAS NMR spectra (lines b and c, respectively) excludes
the possibility of a fast proton exchange among the four oxygens
around an aluminium atom of the zeolite framework.
Line d at 6.5 to 7.0 ppm is due to residual ammonium ions.
Line e at 2.5 to 3.6 ppm represents hydroxyl groups associated
with extra-framework aluminium species. Due to the limited space
available for these OH groups their JH-value will be determined
at least to a certain degree by an additional electrostatic
interaction of the hydroxyl proton with other oxygen atoms. In
accordance with this suggestion, for isolated AlOH groups the
chemical shift is much lower and in the interval -0.5 ppm 5 bH 5
1 ppm (cf. Fig. 5 and ref. 12).
For P O H groups the value of 6H is between 1.5 ppm and 4 ppm
depending among others on interactions mentioned for line c.

Concentration of Bronsted Acidic Sites

With respect to a measurement of the concentration of hydroxyl
groups (Bronsted acidic and non-acidic sites) nuclear magnetic
resonance spectroscopy has an extremely important advantage
compared with infrared spectroscopy since the area of an H' MAS
NMR signal is directly proportional to the concentration of the
hydrogen nuclei contributing to this signal irrespective of their
bonding state so that any compound with a known concentration of
hydrogen atoms can be used as a reference (mostly water). In
Fig. 5 H' MAS NMR (Bruker MSL 300) and infrared stretching
vibration spectra (Digilab FTS-20) are shown for two differently
synthesized specimens of SAPO-5 (ref. 13). While the positions of
the various signals in the NMR and IR spectra correspond to each
other quite well and are in agreement with IR results published
recently (ref. 14), there are dramatic differences in the
96

relative intensities. Hence, even the relative intensity of an

OH stretching vibration band cannot be taken as a measure for the
concentration of the respective hydroxyl group in contrast to the
NMR signal.

Accessibilitv of Bronsted Acidic Sites

The accessibility of hydroxyl groups can be easily determined
through a study of the 'H MAS NMR spectra after loading the
adsorbent with a suitable molecule which however must be fully
deuterated in order to avoid an unwanted additional H ' NMR
signal. Using deuterated pyridine the concentrations of
accessible and non-accessible silanol groups of silica could be
determined (ref. 15). With the same probe molecule it was also
possible to show unambiguously that line (b) in the H' MAS NMR
spectra of zeolites H-Y is due to OH groups which are easily
accessible to pyridine (ref. 16) and that line (c) is caused by
OH groups pointing into the small cavities (LF-band in infrared
spectroscopy). Through this direct method it was possible to
correct the formerly (ref. 17) postulated wrong correlation (LF-
band and line (b)). In Fig. 6 results are shown for a shallow-bed
(400 OC) pretreated SAPO-5 unloaded, and after keeping it loaded
with deuterated n-hexane for 1 hour at 5 0 O C . There is no doubt
that the 3.9 ppm signal is caused by bridging OH groups which are
easily accessible to n-hexane in contrast to the 4 . 9 ppm signal.

' MAS NMR spectra of a shallow-bed ( 4 0 0 OC) pretreated

Fig. 6. H
SAPO-5. a) unloaded, (b) after keeping the sample loaded with
deuterated n-hexane for 1 hour at 50 O C .
 97

So the higher value of JH must be due to the above mentioned

additional electrostatic interaction and we ascribe the signals
at 4 . 9 ppm and 3.9 ppm to bridging OH groups located in the 6-
and 12-membered rings of the SAP0 - 5 structure.

H' NMR STUDIES ON HYDRATED ZEOLITES

MAS
H' MAS N M R studies of hydrated zeolites may be complicated by
a superposition of three effects:
(i) Plank's mechanism, i.e. the adsorption and dissociation of
water molecules on extra-framework multivalent cations like Ca2+
with a formation of bridging OH groups. The H' MAS NMR signal of the
latter hydroxyls appears at JH values of ca. 0 ppm and 2 . 8 ppm
for calcium ions in the large and small cavities of zeolites Y,
respectively (ref. 18). It seems to be noteworthy that for these
OH groups eq. ( 5 ) is not fulfilled and that a simple
interpretation cannot be given at present for this experimental
finding.
(ii) Formation of hydroxonium ions at Bronsted acid sites which,
however, take part in a fast proton exchange with physically
adsorbed water molecules and OH groups. In general, it should be
necessary to include in this exchange also water molecules
hydrogen-bonded to Bronsted acid sites. These species for which
the chemical shift JH is unknown could not be observed in the
infrared spectra of rehydrated zeolites (ref. 19). It is possible
to determine quantitatively the concentration of hydroxonium ions
from the position of the H' NMR signal. In shallow-bed (400 OC)
treated zeolites H-Y the probability to find a water molecule in
-
the state of a hydroxonium ion is ca. 0 . 2 0.3 for a rehydration
corresponding to one water molecule per bridging OH group (ref.
20).
(iii) Adsorption of water molecules on Lewis acidic sites giving
rise to a narrow line at JH = 6 , 5 ppm. In the case of
hydrothermally pretreated zeolites H-Y (540 OC, 20 h, 4 kPa water
vapour pressure) a concentration of (2 ? 0.5) Lewis acid sites of
this type per unit cell could be found. Surprisingly the MAS
sideband pattern of the signal at 6.5 ppm could only be explained
quantitatively if these Lewis acid sites are not connected with
extra-framework aluminium ions. Therefore, we assume that the signal
at 6.5 ppm is caused by water molecules adsorbed on threefold
coordinated and positively charged silicon atoms of the zeolite
framework (ref. 20), i.e. on sites which where proposed by
98

Kazansky (ref. 21) in order to explain an infrared band at

4035 cm-’ for H2 adsorbed on a zeolite H-Y activated at 400 O C
under deep-bed conditions. Further experimental and theoretical
work seems necessary to prove whether threefold coordinated and
positively charged silicon atoms in the zeolite framework really
exist.

PULSED FIELD GRADIENT (PFG) NMR SELF-DIFFUSION STUDIES

Xenon Self-Diffusion
In the last few years, xenon has turned out to be an efficient
adsorbate for probing the pore structure and the internal surface
of adsorbents by means of NMR spectroscopy (refs. 22-24). The
advantage of xenon in comparison to other adsorbates is brought
about by the large chemical shifts of ‘”Xe NMR as a consequence
of the large electron shell, and by the fact that xenon as a
noble gas leaves the adsorbent structure essentially unaffected.
In particular, in zeolite research I2’Xe NMR has been
successfully applied for probing pore and channel dimensions
(ref. 25), cation distributions (ref. 26), reaction sites (ref.
27) and structural peculiarities (ref. 28). Following the
pioneering work of J. Fraissard and coworkers, it is now applied
in various laboratories (refs. 29-31).
The advent of 12’Xe NMR in zeolite research has been
accompanied by some controversy in the interpretation of the
obtained spectra. In particular, on observing separate lines in
the NMR spectra and attributing them to certain states or regions
of the xenon atoms within the adsorbate-adsorbent systems, one
has to imply that the rate of exchange between these states or
regions is less than the difference in the Larmor frequencies of
these lines (ref. 32). If the spatial separation of the
respective regions is known, an estimate of the diffusivities of
the xenon atoms within the sample becomes possible (ref. 33). It
is obvious that in such cases the validity of the interpretation
of the 12’Xe NMR spectra would be substantially supported if the
diffusivities could be measured directly.
As yet, owing to their large gyromagnetic ratios, pulsed field
gradient NMR (PFG NMR) self-diffusion measurements of adsorbed
molecules have been exclusively carried out with ‘H and ‘’F
nuclei. However, experimental progress in the PFG NMR technique
(ref. 34) recently enabled the application of 12’Xe NMR to a
direct measurement of xenon self-diffusion in zeolites (ref. 35).
 99

P1 Fig. 7 . Mean squ re

250 . displacements <r9 ( A ) > of

Fig. 7 provides an example of the measurement of the mean

square displacements <r2(&)> of the xenon atoms in the three
different zeolite types NaX, NaCaA and ZSM-5 in dependence on the
observation timeA. For comparison, the data for methane in ZSM-5
are included. According to Einstein’s relation

each of the observed linear relations yields a value for the

self-diffusion coefficient D. Fig. 8a shows the results of I2’Xe
measurements in a representation of the thus determined self-
diffusion coefficients in dependence on the sorbate
concentrations. The sorbate concentrations are given in atoms per
24 Si(A1)-atoms, corresponding to one channel intersection in the
case of ZSM-5 and to one large cavity in the case of the X and A
type zeolites. The error bars indicate the uncertainty in the
self-diffusion coefficients resulting from the scattering of the
experimental data of the mean square displacements. A comparison
of the diffusivities of xenon and of methane presented in Figs.
8a and 8b, respectively, shows similar tendencies: For both
adsorbates, the mobility in zeolite NaX is found to be higher

i
100

than in the other adsorbents. This corresponds to the fact that

the diameters of the windows between the large cavities in the X-
type structure (0.75 nm) are considerably larger than the
corresponding diameters in zeolite NaCaA (0.4 ...
0 . 5 nm) or the
channel diameters in zeolite ZSM-5 (0.55 nm).

1
0 1 2 3 4 atoms per
24 si (A1 )atoms

0
I . .
2
. .
4
. .
6
. .
8
-
molecules per
24 Si ( A l l atoms

Fig. 8 . Concentration dependence of the intracrystalline self-

diffusion coefficient D. of xenon (Fig. 8a) and methane (Fig. 8b)
in zeolite NaX (I),Na6$%CaA ( 0 ) , Na45%CaA ( 0 ) and ZSM-5 ( x ) at
293 K.

In zeolite A , the degree of calcium exchange determines the

relative number of Ilopenll windows, i.e. the number of windows
unblocked by cations, which thus are easily penetrable for the
adsorbate molecules (refs. 36, 37). A numeric calculation given
in ref. 36 yields that a reduction of the calcium content from
63% to 45% should reduce the diffusivity by a factor of about 2.
 101

The experimental results collected in Table 1 (3rd and 6th

column) are in satisfactory agreement with this prediction.
Considering the concentration dependence of the diffusivities,
for xenon and methane again identical tendencies are observed:
While in zeolites NaX and ZSM-5 the diffusivities are found to
decrease monotonously with increasing concentration, for zeolite
NaCaA the diffusivities either remain constant or increase
slightly with increasing concentration. It has been demonstrated
in ref. 3 8 that concentration dependences of the first type are
due to a reduction of the jump length (in NaX) or of the jump
rate (in ZSM-5), while the latter behaviour results if mass
transfer is controlled by the passage through an llactivatedll
state as represented by the windows in the A type structure.
Obviously, the similar size and shape of xenon and methane lead
to coinciding dependences.

Probinu Surface Barriers by 12’Xe PFG NMR

Besides the possibility of a direct comparison with the
llconventionalllI2’Xe NMR line shift analysis of the same system,
the application of xenon in NMR diffusion studies may offer
promising prospects in providing a more sensitive tool for
probing the existence of surface barriers. These prospects are
based on the expectation that (i) due to their larger kinetic
diameter (ca. 0.49 nm, ref. 39) in comparison to methane (ca.
0.41 nm, ref. 39) the xenon atoms should be more affected by any
narrowing in the zeolite pore systems, and that (ii) the reduced
magnetic interaction of 12’Xe with the environment should allow a
significant enhancement of the observation time.
Fig. 9 represents typical plots of the signal intensity (spin
echo amplitude) versus the width of the gradient pulses as
observed in 12’Xe NMR pulsed field gradient experiments (ref.
40). Obviously, for zeolites NaX and ZSM-5 the obtained NMR data
may be satisfactorily represented by the relation (ref. 34)

with Y denoting the attenuation of the NMR signal (spin echo

attenuation) under the influence of the field gradient pulses of
intensity g, width 6 and separationA.
102

a I 55 ms b
0.2 1
I ’ . ’ ’ ’ . ’ -6,,mSI
0 OD4 a2 0

L o zeolites NaX (Fig. 9a,

‘60 ms crystallite diameter ca.
(1 50 pm), ZSM-5 (Fig. 9b,
02 ’ crystallit5 dimensions 100 x
30 x 30 pm ) , and Na45%CaA

<r2(A)> stands for the mean square displacement of the molecules

during A , and T i s the gyromagnetic ratio of the considered
nuclei. Thus, for the self-diffusion measurements of xenon in
zeolites NaX and ZSM-5, the complete information turned out to be
contained in the mean square displacements. In Figs. 10a and lob,
these mean square displacements are represented in dependence on
the observation time b .
For the A-type zeolites, the observed echo attenuations
(cf. Fig. 9c) turned out to be represented by a superposition of
two exponentials. One has to conclude, therefore, that the xenon
atoms contributing to the NMR signal may be subdivided into two
groups having different transport properties.
 103

b I .
0 20 40 60 80 Alms

Fig. 10. Dependence of

the mean square
displacement <r2( A ) >
according to eq. !9) on
the observation time A
for xenon in NaX (Fig.
10a) and ZSM-5 (Fig.
C lo%), and and of
<r ( A ) >i, according to
eq. (10) for xenon i
NaCaA (Fig. lOc, Ca5+
content as indicated in
Table 1).

Following the conception of the NMR tracer desorption technique

(ref. 34), these two subgroups result very easily by
distinguishing between those diffusants which remain in the
interior of the individual crystallites over the whole
observation time (i = intracrystalline diffusion) and those which
may leave their crystallites and which are able, therefore, to
cover large diffusion paths through the intercrystalline space
(1.r. = long range diffusion). The echo attenuation is given
therefore by
104

with <r2 (A)>i and <r2 (4) >l.r. representing the mean square
displacements of the two subgroups, respectively, and with r(A)
denoting the relative amount of the latter subgroup, i.e. the
relative amount of atoms leaving the individual crystallites
during the observation timed. For a discussion of the transport
properties of the zeolite crystallites, an echo attenuation of
the form of eq. (10) contains two types of information: the mean
square displacement <r2 ( A ) >i of the atoms in the intracrystalline
space as obtained from the slope of the second, slower decaying
part of the 1n"f-vs.- J2 plot, and the quantity r ( h ) , resulting
from the relative contributions of the two constituents. Both
quantities are represented in Figs.10~and 11, respectively, in
dependence on the observation time. It is obvious, that the
function r(A) contains the same information as a conventional
tracer desorption curve (ref. 3 4 ) . In previous NMR self-diffusion
studies with methane, in general echo attenuations of the type of
Fig. 9c have been observed (ref. 34). Such a behaviour has again
been found on investigating the methane diffusivities in the
zeolite specimens applied in this study.

Fig. 11. Relative amount r(A)

of xenon atoms which have
r [A] left their crystallites
during the observation time A
1.0- ("NMR tracer desorption
curves11)for z olite NaCaA at
293 K, with Gas+ content as
indicated in Table 1. The
l3Pm magnitude of r ( 0 ) is
determined by analysing the
In y -vs- J~ plots as
presented in Fig. 9c
o 20 LO 60 eo A,ms according to eq. (10):
Extrapolating the second,
less steeply decaying part to
the ordinate yields the
quantity 1-r( A ) .
For a comparison of the NMR tracer desorption curves with each
other as well as with other transport related properties it is
useful to introduce a mean intracrystalline life time

This definition coincides with that of the first statistical

moment of an uptake curve (ref. 41). If the tracer exchange is
controlled by intracrystalline diffusion it can be shown that
 105

for crystallites of spherical shape ri is equal to

with cR2> and Di denoting the mean square radius of the

crystallites and the intracrystalline self-diffusion coefficient,
respectively (refs. 34, 41). Numerical values of the relation
between Di and 7 7 for crystallites with the shape of
parallelepipeds are given in ref. 53.
According to Einstein's relation (eq. ( 8 ) ) which is valid for
self-diffusion in homogeneous systems, the intracrystalline self-
diffusion coefficient Di may be easily determined from the slope
of the representation of the mean square displacement versus the
observation time A , provided that the mean square displacements
cr2(b)> are still smaller than the mean square radii of the
crystallites.

TABLE 1
Values for the intracrystalline self-diffusion coefficients Di
and the intracrystalline mean life time ri of xenon and methane
in various specimens of zeolites NaCaA, NaX and ZSM-5 at 293 K
and a sorbate concentration of about 3 methane molecules or xenon
atoms per 24 Si(A1) atoms.

Adsorbents and the Xeno%

mean c r y s t a l l i t e D. T.
diameters i n lun
Ims /ms

Y c o n t .
45 X 13 1.0t0.3 3.0tl.0 80t2O 1.0t0.3 3.0tl .O 6t2
63 X 20 1.5t0.4 4.0t1.0 45t10 1.5t0.4 4.0tl .O 4t2
80 x 5 1.5t0.4 0.4t0.2 252 8 1.520.4 0.4t0.2 lt0.5
Wax 50 5.0t1.5 8.0t2.O 15t10 20t5 2tl 5tl
20 5.0t1.5 1.5t0.5 5t3 20t5 0.4t0.2 2t1
ZSM-S(a) 25 * O.Pt0.3 11t3 ,40 4tl 3tl 4t1
ZSM-5(b ) 100~30x30 0.Pt0.3 160t40 >70 4t1 45t10 ~ 3 0
mean c r y s t a l l i t e dimension

Table 1 gives a summary of the self-diffusion coefficients

thus determined for sufficiently short observation times from the
106

presentations of Fig. 10 and from corresponding results for

methane. Furthermore included are values for the intracrystalline
mean life time ri and the quantity riD calculated from Di and
< ~ 2 >via eq. (12).
For those adsorbents (ZSM-5 and NaX) which did not reveal a
two-phase behaviour in the In Y -vs- 62 plots, the values for the
intracrystalline mean life time were estimated by realizing that
the rms displacements can only exceed the mean crystallite radii
by a noticeable value if during the observation time h a
substantial part of the adsorbate molecules or atoms have left
their crystallites, i.e. if the observation time A is at least of
the order of the magnitude of the intracrystalline mean life time
r i . Thus, for NaX the intracrystalline mean life times have been
put equal to those observation times, for which the mean square
displacements coincided with the mean square radii. For both ZSM-
5 specimens even for the largest observation times the mean
square displacements remained smaller than the crystallite
dimensions, so that ri must be assumed to be larger than the
maximum observation time A ,

Direct information about the existence of surface barriers is

provided by a comparison between the values for the
intracrystalline mean life time ri and the quantity riD which
represents the minimum possible life time calculated via eq.
(12) from the intracrystalline diffusivities. Table 1 shows that
for methane these two quantities are in reasonable agreement. One
has to conclude therefore that molecular exchange is mainly
controlled by intracrystalline diffusion and that, consequently,
possible surface barriers can only be of minor importance. This
result is in agreement with the finding of previous studies (ref.
3 3 ) that on applying methane as a probe molecule, in zeolite
NaCaA surface barriers do only occur after coking or hydrothermal
pretreatment. It appears from Table 1, that xenon reveals a
completely different situation: In all NaCaA specimens as well as
in the considered ZSM-5 specimen with the smaller crystallites,
xenon desorption is significantly retarded by influences
different from intracrystalline diffusion, i.e. by an additional
transport resistance on the external surfaces or in a surface
layer of the crystallites. This result may be related to the
larger kinetic diameter of the xenon atoms, making them suitable
for probing the surface permeability of adsorbents with limiting
 107

free diameters of this order of magnitude (0.4 ... 0.5 nm for

NaCaA, ca. 0.55 nm for ZSM-5). It is not unexpected that for
zeolite NaX, also with xenon no surface resistances are observed,
since the increase of the diameter of the probe particle in
comparison to methane is still insignificant compared with the
limiting free diameters of NaX (ca. 0.75 nm). The experimental
finding that the existence of a surface barrier may depend on the
sort of the diffusing particles reflects an essential feature of
the surface barrier: Though being determined by structural or
energetic peculiarities at the crystallite surface (cf. ref. 43),
the surface barrier can only be defined in connection with a
certain probe molecule. This statement becomes self-evident on
considering the reciprocal of the surface barrier, the surface
permeability which - as the diffusity - must be a function of the
diffusant. It is possible that the low literature data for
intracrystalline diffusion of xenon in zeolite NaCaA deduced from
uptake measurements (lXlO-I4 m2/s (ref. 44), 1.2x10-'' m2/s (ref.
4 5 ) or 8x10-'I m2/s (ref. 46), determined for a loading of about 1
atom per cavity and at temperatures of about 300 K) are caused by
the significant surface barriers for this system.

Diffusion Anisotrovv
Among the problems connected with new zeolite structures, a
possible anisotropy of self-diffusion deserves special
consideration. Since the PFG NMR method allows the observation of
molecular migration with respect to the direction of the applied
field gradient (ref. 3 4 ) which may be easily changed by applying
suitable gradient coil arrangements, favourable conditions exist
for the investigation of diffusion anisotropy. Literature
provides various examples of such diffusion studies with liquid
crystals and membranes where molecular diffusion proceeds in a
well oriented sample of macroscopic dimensions.
A completely different situation exists if one considers
molecular diffusion in crystalline catalysts and adsorbents.
Being of the order of a few micrometers, the diameters of the
individual crystallites are too small to allow the conventional
method of studying diffusion anisotropy. However, also in this
case PFG NMR may provide information about the extent of
diffusion anisotropy. This information is contained in the shape
of the N M R spin echo attenuation versus the gradient intensity,
which in the case of isotropic diffusion yields a simple
108

exponential dependence (cf. eq. (9)), but which in the case of

anisotropic diffusion may be shown to obey the relation (refs.
34, 47)

~ ( c3,,Y)= exp {-C(D,~ cos2y sin’> + D sin’ 7 sin2nt

+ DZZcos2a ) 1 ,

where the quantities DXX, Dyy and D,, denote the principal
values of the diffusion tensor. The orientation of the field
gradient with respect to the principal axes system is represented
by the angles &and Y .
The quantity

is determined by the parameters of the pulse sequence, explained

in connection with eq. (9).
In the case of powder samples, i.e. of randomly oriented
crystals, averaging over all possible directions leads to the
expression

c Y(C)> = -
1 J1exp{- c
471 -1
with
I ( J ) = J2;xp{-c sin22
0

As an example, Fig. 1 2 shows the result of a numerical

calculation of eq. (15) for an axial symmetric diffusion tensor
(ref. 47). It s obvious, that for D,,>D,, the sensitivity of the
PFG NMR method with respect to deviations from isotropic
diffusion is h gher than in the reverse case.
Fig. 13 compares the echo attenuation obtained in PFG NMR
measurements of methane diffusion in ZSM-5 (ref. 47) with the
theoretical dependence calculated from eq. (15) with the tensor
elements DXX (= 1.22 lo-’ m’s-l), Dyy (= 14.9 10-9m2s-1) and D,,
(= 1.22 10-9m2~-1) as determined in recent Molecular Dynamics
calculations (ref. 48). It turns out that the calculated pattern
is already beyond the range compatible with the experimental
behaviour, so that one has to conclude that the influence of
anisotropy is overestimated in the Molecular Dynamics
calculations.
 109

Fig. 12. Spin echo attenuation due to anisotropic diffusion in

randomly oriented crystallites with axial symmetry for D , , > , D L
and D , , c DL as a function of the product of the field gradient
intensity parameter C defined by eq. (14) and the quantity
<D>=(Dxx+Dyy+Dzz)/3.

Fig. 13. Spin echo attenuation of the proton NMR signal of

methane adsorbed in an assembly of ZSM-5 crystallites at 23 OC
eq. 5 -7
( 0 ) I and comparison with the theoretical curve- b ai ed from
(15) with bhs tfnsor elements Dxx = 3 59x10 8m s ,
D = 14.9~10-m s- and D,, = 1.22x10-9m2s-1 (ref. 48) ( - - - I I

rxgpectively.

Limits of ADwlication
The versatility of the PFG NMR method to study diffusion
processes in zeolites and its successful application to numerous
problems in zeolite science and technology (cf. ref. 42) implies
the temptation to apply it also under such conditions where
110

extreme caution is recommended. This is in particular true for

heterogeneous or, in general, multi-phase systems, where the
contribution of the various phases to the spin echo is controlled
by their nuclear magnetic relaxation properties (ref. 52) or,
with other words, where with increasing observation time A the
contribution of the phases with the largest relaxation times will
become more and more dominant. So it may happen that by formally
applying the PFG NMR method one determines the diffusivity of a
trifling amount of very mobile molecules (occurring e.g. in
tracks within the zeolite crystallites or on their outer
surfaces) rather than that of the phase represented by most of
the adsorbed molecules. It is most likely that the surprisingly
high values for the diffusivity of benzene in silicalite which
were recently determined using PFG NMR (ref. 49) are due to this
effect.
In order to exclude the possibility of such artifacts in NMR
self-diffusion measurements, a modification of the traditional rf
pulse sequence has been proposed (ref. 50). It allows an
unambiguous check whether the obtained diffusivities are in fact
unaffected by the influence of a trifling amount of very mobile
molecules.

NMR Tracer Exchanse

The lowest diffusivities accessible by PFG NMR in zeolites are
of the order of m2s-' (refs. 34, 42). However, for
systems with diffusivities below this limit an alternative NMR
method for studying mass transfer may be applied (ref. 52). Under
such conditions and for crystallite diameters k l 0 pm, the rates
of molecular adsorption or desorption become small enough so that
it is possible to study these processes by an analysis of the
intensity of the NMR signal. As an example, Fig. 14 shows the
arrangement of such an experiment for the investigation of the
rate of molecular exchange for benzene in H-ZSM-5 with the
surrounding atmosphere (refs. 52, 53). The exchange experiment is
started by crushing the glass vial using the glass cylinder as a
striker: The hydrogen form of benzene initially adsorbed on the
zeolite will then be exchanged by the deuterated compound
stemming from the gas phase.
 111

gaseous C6D6
adsorption vessel
granulated NaX +C6D6

20 mm

glass vial
H - Z S M - 5 .CgH(

-
-

Fig. 14. Experimental arrangement for the NMR tracer exchange

measurements.

D
Fig. 15. Comparison
of the self-diffusion
coefficients obtained
\ from NMR tracer
\ exchange measurements
\
( 0 293 K; A 386 K)

i\ f\
\
with values
calculated from
sorption uptake
experiments ( o 303
K; 0 363 K; A 393
K) using eq. (17).
Both experimental
f
10Eo 1.0
series have been
carried out with the
same silicalite
specimens.
Loading I molecules per 0.25 U.C.
This exchange process may be directly recorded via the intensity
of the H' NMR signal. It is shown in Fig. 15 that the self-
diffusivities determined from these experiments are in
satisfactory agreement with the results of uptake experiments,
when the relation between the coefficient of diffusion (Dd) which
112

follows from the uptake experiment and the coefficient of self-

diffusion (D) is assumed to be (ref. 54)

with c(p) denoting the sorbate concentration in equilibrium with

the sorbate pressure p. Clearly, the experimental arrangement as
shown in Fig. 14 may be easily modified to allow both adsorption
or desorption experiments (in this case, the sorbate pressure in
the surrounding atmosphere must be much greater or much less than
over the adsorbent within the glass vial) and counter diffusion
experiments. Taking advantage of high resolution NMR spectroscopy
(ref. 5 5 ) , such experiments (e.g. the observation of the exchange
between aliphatic and aromatic compounds) may even be carried out
without the necessity of applying deuterated compounds.

TABLE 2
Comparison of PFG NMR diffusivities with the results of quasi-
elastic neutron scattering and Molecular Dynamics simulations as
well as with the results of macroscopic non-equilibrium measure-
ments (uptake, zero length column, permeation). Data refer to the
limit of small sorbate concentrations, the unit is m2s-'.

Adsorbent NaCaA NaX H-ZSM-5

nethane ethane ethylene benzene methane xenon

Tewperature/K 300 250 300 458 250 293

los9 6 ~ 1 0 . ~ 1~. ~ X I D 8x1D-10

-~ ~ x I O -4~~ 1 0 . ~
ef. 37 r e f . 37 r e f . 61 r e f . 63 r e f . 67 r e f . 35

Neutron Scattering 5x10-" 3xlO-l' 7xlO-l' S X ~ O - ~

r e f . 59 r e f . 62 r e f . 64 r e f . 68

Molecular Dynamics =5x10-9 2x10-9

r e f . 48 ref.-$O
4x10
r e f . 71

Uptake 3xlO-l' 8~10-l~

r e f . 65 r e f . 46

Zero length colum 3 . ~ 1 0 ~ ~ ~ 8 ~ 1 0 ~ ' ~

r e f . 40 r e f . 66

Permeation 10.10
334 K
r e f . 69
 113

ComDarison of PFG NMR Diffusivities with the Results of other

Technisues
The comparison of the diffusivities determined in PFG NMFt
measurements with the results of other techniques has concerned
zeolite workers over more than a decade (refs. 56, 57). While
there is still some controversy whether in general the results of
uptake (i.e. of non-equilibrium) measurements after applying eq.
(17) should or should not agree with the NMR self-diffusivities
(cf. ref. 52), in the last few years by other microscopic
techniques (neutron scattering, 2H NMF2) as well as by Molecular
Dynamics calculations a large amount of diffusivity data has been
provided which are in remarkable agreement with the results of
PFG NMR measurements. Some of these results are compared in
Table 2.

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This Page Intentionally Left Blank
G . Ohlrnann et al. (Editors),Catalysis and Adsorption by Zeolites 117
0 1991 Elsevier Science PublishersB.V., Amsterdam

SPECTRAL STUDY OF LEWIS ACIDITY OF ZEOLITES AND OF ITS ROLE IN CATALYSIS

V .B .KAZANSKY
N.D.Zelinsky Institute of Organic Chemistry, Moscow, USSR

SUMMARY
The Lewis acidity of cationic forms of zeolites and of those modified by
mild steaming or by Zn and Ga ions was studied using molecular hydrogen and
light paraffins as molecular probes. The extent of their perturbation was con-
trolled by IR diffuse reflectance spectroscopy. It was concluded, that Lewis
sites should be considered not as low coordinated cations, but rather as
acid-base pairs in which the neighboring basic oxygen is equally important.
The role of extra lattice aluminum or modifying Zn and Ga ions in cracking of
paraffins or their aromatization is discussed.

INTRODUCTION
The catalytic properties of zeolites are mainly connected with their aci-
dity. Therefore the central problem of catalysis on zeolites is the nature of
their acid active sites.
The recent information on the Broensted acidity of zeolites is rather com-
plete, since it could be easily followed by such direct spectroscopic methods
as IR or high resolution solid state NMR. On the contrary the knowledge of the
nature and the properties of Lewis acid sites is quite not as full. This is
because they could be investigated only by indirect way by means of molecular
probes with spectral control of perturbation of adsorbed molecules.
For this purpose most often ammonia or pyridine adsorption is used. These
molecules have however very little in common with hydrocarbons, whose cata-
lytic transformations on zeolites are of the greatest interest. In other
words, if adsorbed ammonia is protonated by a Broensted acid site or is stron-
gly bonded by a Lewis site, this does not yet mean, that the adsorbed hydro-
carbons would behave in the similar way.
Another, more principal difference between strong bases and hydrocarbons
consists in the chemical nature of their interaction with Lewis acid sites. In
the case of hydrocarbons or hydrogen the elementary step, which is most often
discussed, is the heterolytic dissociation:

6- 6 +
H--H H- H+
-Me--0- + H --.c -Me--O- ----L -Me--O- (1)
2
Unlike this ammonia or pyridine adsorption results in coordinative binding:
118

(2)
Y3
-Me--0- + NH3 c_) -Me--0-
Thus, the strong bases are the tests only for Lewis sites, whereas the mo-
lecu- lar hydrogen is rather the test for the acid-base ion pairs. Therefore
the conclusions on the nature, the strength and the number of Lewis sites ob-
tained from adsorption of strong bases could not be so simply transferred to
adsorption of hydrocarbons.
Of course the best molecular probes for Lewis acidity are the reactants
themselves. Therefore in the previous studies of aluminum oxide and H-zeo-
lites we used the adsorption of light paraffins or the low temperature adsorp-
tion of molecular hydrogen (refs. 1.2). Below the application of the similar
approach for the investigation of Lewis acidity of zeolites modified by vari-
ous methods is reported.

CATIONIC FORMS OF ZEOLITES

Zodlurn-Errns
The univalent cations or multivalent cations introduced by ion exchange re-
present the simplest examples of Lewis acid sites in zeolites. Therefore al-
ready in the very first papers on their catalytic application the probable ro-
le of such active sites was postulated and discussed (ref.3).
According to these works the cations could activate adsorbed molecules due
to their electrostatic polarization. The strength of electric field created by
cations and of the degree of such polarization have been however never estima-
ted experimentally. Some ideas on this point could be drawn out from our re-
sults on low temperature molecular hydrogen adsorption (ref.2,4).
IR spectra of molecular hydrogen adsorbed at 77 K and the pressure of 2-5
Torr on sodium forms of different zeolites are presented in Fig.1. They show,
that low temperature adsorption of hydrogen results in the appearance of se-
veral bands in the region of H-H bond stretching vibrations. This indicates
the existence of various types of adsorption sites, which seem to be sodium
ions in different positions of the zeolite framework. They are able to polari-
ze adsorbed hydrogen molecules in various extent, resulting in the appearance
of several absorption bands.
When the spectra of adsorbed hydrogen contain more than one line, then the
decrease of hydrogen pressure or evacuation at 77 K result in the following
change of their relative Intensities: the high frequency bands at w =
4120-
-1
4150 cm-l disappear , whereas those at lower frequencies of w = 4080-4110 cm
remain unchanged. This could be explained by the different strength of hydro-
 119

gen binding by cations located in various positions of the zeolite framework.

It correlates with the values of low frequency shifts of the H-H stretching
vibrations.

Fig.1 Diffuse reflectance IR spectra of molecular hydrogen adsorbed on sodium

forms of zeolites at 77 K at various pressures. P=5 Torr:(b)-NaM,(c)-NaZSM-5,
(e)-NaA, (f)-NaX, (g)-NaY. P=100 Torr: (a)-NaM, (d)-NaA, (h)-NaY.
At low pressure the spectra of pentasils and mordenites are the simplest
(Fig.1. spectra (a)-(c) 1. For mordenite they consist of a single band at 4108
-1
cm , which is shifted by 55 cm-l towards lower frequencies as compared with
the stretching vibrations of free hydrogen in gas phase at 4163 cm-l. This is
consistent with conclusion of ref. 5, that in mordenite Na cations are prefe-
rentially located at one main type of sites at the centers of eight membered
rings. At higher pressure of 100 Torr (spectrum (a) 1 an additional shoulder
-1
of lower intensity appears near 4120 cm . It may be connected with sodium ca-
tions distributed among other available sites of localization.
For NaZSM-5 zeolite there is no published data on Na cations distribution.
Our results show, that there is only one type of sodium in its framework
(Fig.1, spectrum (c) 1. The corresponding stretching frequency shift of hydro-
gen is very close to that of hydrogen adsorbed by mordenite. Therefore it is
highly probable, that in NaZSM-5 the sodium ions are also localized at the
similar positions.
According to X-ray analysis, in NaA 8 of the overall number of 12 sodium
ions are located near the centers of the six membered rings, which form the
sodalite cages. The 3 of remaining 4 Na cations are situated near the centers
of 8-rings and one is statistically located over 12 fold equipoints (ref.6).
120

This is also consistent with the spectra (d) and (el of Fig.1, which show,
that the majority of Na ions bind hydrogen more strongly and exhibit the lar-
ger low frequency shifts of H-H stretching vibrations, while the rest of sodi-
um ions could hold and perturb molecular hydrogen only at higher pressures.
The spectra of hydrogen adsorbed on sodium forms of faujasites are more
complicated (Fig.1, spectra (f)-(h) 1. According to our results (ref.4) they
could be ascribed to H molecules perturbed by sodium ions located in SI; SI,
2
and in SIIpositions. Thus, low temperature molecular hydrogen adsorption
allows to follow both the different sites of sodium ions localization in the
zeolite frameworks and the distribution of ions among these sites.
The important feature of IR spectra of hydrogen adsorbed by sodium forms of
zeolites is the dependence of the line shifts on the type of zeolite frame-
works. In this respect hydrogen behaves quite differently from adsorbed carbon
monoxide (ref.7) which for the same cations exhibits very close shifts for
different frameworks. Thus, the perturbation of adsorbed hydrogen depends not
only on the nature of cations, but also on the type of the zeolite crystal
lattice. This is in consistence with the by-point adsorption of molecular hyd-
rogen, which was earlier supported by quantum chemical calculations for alumi-
num oxide (ref.8).
If this conclusion is also correct for zeolites, then for their sodium
forms the shifts should be dependent on the basic properties of oxygen. This
is really observed experimentally. Indeed, the least basic oxygen is that one
in high silica zeolites, which contain the lowest amount of aluminum in their
framework. This results in the smallest low frequency shifts of H2 stretching
vibrations. On the contrary the largest shifts were observed for NaA zeolite,
which contains the most basic oxygen. However, even in this case the value of
the low frequency shift is only 90 cm-l i.e. is about twice less, than that
for hydrogen adsorbed by acid-base pairs of aluminum oxide (ref.1). Thus,
sodium ions are rather weak perturbing sites of adsorbed hydrogen. This is
consistent with the fact, that contrary to aluminum oxide we never observed
dissociative hydrogen adsorption on sodium forms of zeolites.

Bllralent-catlonlr-~orms_oy_qeoliteq
The IR spectra of hydrogen, adsorbed at 77 K on alkaline earth forms of
mordenite are presented in Fig.2. They contain two bands for Mg and Ca
exchanged samples, but only single bands for the samples exchanged with Sr and
Ba ions.
Such difference could be easily explained by various hydrolysis extent of
these cations.
 121

d
Fig.2. IR diffuse reflectance spectra of molecular hydrogen adsorbed at 77 K
on alkaline earth forms of mordenite dehydrated at 720 K. (a)-MgNaM, (bl-
CaNaM,(c)-SrNaM,(d)-BaNaM. The degree of cationic exchange is about 60 %.
Hydrogen pressure is 30 Torr.

Indeed,the second dissociation constants of (MgOHl' and (CaOH)' ions are

rather low (3'10-3 and 4'10-2 respectively). On the contrary for (SrOH)' and
(BaOH)' cations they are much higher ( about 0.15-0.21. Therefore after dehy-
dration at elevated temperature magnesium and calcium ions exist in the zeoli-
te framework in two forms: as bivalent Me2' cations and as hydrolyzed MeOH'
species. On the contrary Sr and Ba cations are completely dehydroxylated
resulting in doubly charged ions.
Such an interpretation is supported by IR spectra of these samples in OH
stretching region. For dehydrated Mg and Ca forms they contain both the bands
from structural OH groups and those from basic hydroxyls of MeOH' fragments.
+2
On the contrary removal of water from S
r
'
2 and Ba containing samples results
in complete dehydration and only the bands of silanol groups are observed.
The comparison of results on hydrogen adsorption on sodium and alkaline
earth forms of mordenite shows, that for Na' and MeOH'cations the shifts are
very close. This also supports the above interpretation based on hydrolysis of
M
g
'
2 and Ca'2 cations, which behave in hydrolyzed form similar to univalent
ions. More surprising are the small shifts exhibited by nonhydrolyzed bivalent
Sr" and Ba" cations, which are only slightly larger, than for sodium. In our
opinion, this is consistent with the above idea of bypoint adsorption of
122

hydrogen.
If it is really of the bypoint nature, then the charge and the polarizing
ability of lattice oxygen is also important. In other words the charges of ca-
tions and their dimensions are not the only factors affecting polarization of
adsorbed hydrogen. In addition, for bivalent cationic forms the higher positi-
ve charge results in the partial electron density transfer from basic oxygen
to cations. This decreases both positive charges of cations and those of oxy-
gen in ion pairs and results in smaller shifts of stretching vibrations of ad-
sorbed molecular hydrogen in comparison with which one could expect from the
formal electric charges.

DEHYDROXYLATED HYDROGEN FORMS OF ZEOLITES

Historically, one of the first mechanisms of dehydroxylation of H-faujasi-
tes was suggested by Uytterhoeven, Crystner and Hall (ref. 91. They postulated
the formation of trigonally coordinated A1 and Si atoms, when two hydroxyl
groups are removed from the zeolite framework:

H -
0 0
\ / \ / \ + / \ / \ /
2 Si A1 d Si A1 + Si A1 (31
/ \ / \ / \ / \ / \ / \

Later this mechanism was found to be incorrect, since according to the nu-
merous solid state high resolution NMR data the dehydroxylation of hydrogen
forms of faujasites results instead of formation of lattice Lewis sites in de-
alumination (ref.101. Nevertheless our experimental results on low temperature
molecular hydrogen adsorptioii clearly show, that f o r high silica containing
zeolites dehydroxylation still could occur according to scheme (31 (refs.
2,111.
IR spectra of H2 adsorbed at 77 K on HZSM-5 zeolite preheated in vacuo at
different temperatures are presented in Fig.3. At moderately high temperatu-
res, when dehydroxylation has not yet started (770K) , two bands with maxima
at 4125 and 4105 cm-l are observed (fig.3 (a) 1.
With the increase of the pretreatment temperature and of the extent of sur-
face dehydroxylation their intensity decreases. On this ground we assign these
bands to hydrogen interacting with surface hydroxyl groups. Since the position
of the high frequency band is the same as when hydrogen is adsorbed on silica,
this band could be attributed to the molecules, perturbed by silanol groups.
Then the band with a lower frequency of 4105 cm-1 should be ascribed to hydro-
gen molecules interacting with the acidic bridged hydroxyls with stretching
 123

vibrational frequency of 3610 cm-1 .

Fig. 3. IR spectra of hydrogen, adsorbed at 77 K on HZSM-5 zeolites dehydro-

xylated in vacuo at various temperatures: (a) - 770 K. (b) - 970 K. (c) -
1220 K. (d) - HY zeolite preheated at 770 K under "deep bed" conditions.

If the pretreatment temperature of HZSM-5 zeolite is increased up to 910 K

its partial dehydroxylation takes place. This results in the decrease of the
bands intensity of the bridged hydroxyl groups. Simultaneously two new bands
from adsorbed hydrogen with maxima at 4010 and 4035 cm-l and the very large
values of low frequency shifts of 125 and 150 cm-l are appearing (Fig.3b).
They should be attributed to adsorbed hydrogen interacting with two different
kinds of Lewis acidic sites, which are formed after removal of hydroxyl groups
in accordance with scheme ( 3 ) .
There are also the following additional arguments in favor of the assign-
ment of these bands to hydrogen molecules adsorbed on trigonally coordinated
Si and A1 atoms of the zeolite crystal lattice. Firstly, if the dehydroxyla-
tion of H-high silica zeolites is carried out under still more severe condi-
tions and the dealumination of their crystal lattice really takes place, one
more low frequency band of adsorbed hydrogen with the maximum at 4060
cm-'appears [Fig.3c). Simultaneously the intensity of the band of adsorbed hy-
drogen with the maximum at 4010 cm-l decreases. This is easy to explain, if
this band is assigned to molecular hydrogen interacting with trigonaly coordi-
nated aluminum atoms, the number of which decreases upon dealumination. Then
the band at 4035 cm-l should be attributed to trigonal silicon atoms.
124

Such an interpretation is also confirmed by a similar, but much more dis-

tinct picture, which is observed after a high temperature pretreatment of HY
zeolite under more severe "deep bed" conditions, when dealumination really is
the main process. For instance. according to (ref.12) the degree of framework
dealumination of Y zeolite preheated at 770 K in a "deep bed" is as high as 85
-1
%. As seen from the Fig 3(d) in this case the band at 4060 cm ,which was pre-
viously attributed t o hydrogen interacting with extra lattice aluminum, really
predominates and the band at 4010 cm-l from trigonal lattice aluminum atoms is
practically absent.
The following simple suggestion may help in understanding the difference
in the dehydroxylation of hydrogen forms of faujasites and of high silica
zeolites:
The removal of aluminum from the crystal lattaicedoes not only disturb the
balance of the electric charges in their structure, but also changes the va-
lence angles and the hybridization of the orbitals in low coordinated Si and
A1 atoms being formed. Each of these sites possesses therefore a certain ex-
cess energy and is a source of some strains in the zeolite structure. When
stoichiometric dehydroxylation of faujasites occurs, the number of such
defects is very high and is comparable with the total A1 and Si content. For
instance, when full dehydroxylation of a zeolite with a Si to A1 ratio of 2
takes place, half of the A1 atoms and a quarter of Si atoms should be conver-
ted from the tetrahedral coordination into trigonal coordination. Then the to-
tal amount of low coordinated aluminum and silicon atoms will be about 30 %.
Such a perturbation of the zeolite crystal lattice is apparently too strong.
Therefore the stabilization of the crystal structure takes place resulting in
its dealumination and partial decomposition.
Unlike this, the percentage of lattice Lewis acidic sites which are formed
when high silica H-zeolites are dehydroxylated, does not exceed several per
cent. In other words, Lewis sites appear in their crystal lattice as a relati-
vely small number of structural defects. Therefore high silica zeolites remain
stable without dealumination or decomposition up to much higher temperatures.

ON THE PROBABLE ROLE OF LEWIS ACID SITES IN CRACKING OF PARAFFINS

At the moment there is no generally accepted opinion about the role of
extra lattice aluminum in catalytic transformations of hydrocarbons on zeoli-
tes. On the other hand there is also no doubt, that their mild steaming or de-
alumination results in considerable increase of catalytic activity.
Probably the best evidence of this effect was presented by Lago, Haag et.
al. (ref. 13). They showed, that the mild steaming of HZSM-5 at 773 K resulted
 125

in a considerable, about one order of magnitude, increase of the activity in

cracking of n-hexane. The more severe treatment decreased the activity, which
after prolonged steaming was even lower than that of the starting material.
The authors explained this effect by the appearance after mild dealumina-
tion of some new superacidic Broensted active sites. However they failed in
their direct experimental observation. Therefore this explanation is only of a
speculative character.
The effect of the mild steaming was reproduced by us in ref.14, where we
also investigated the Broensted and Lewis acidity of H E M - 5 zeolite at diffe-
rent stages of its dealumination. It was actually found, that the steaming
created several new types of Broensted acid sites, connected with extra latti-
ce aluminum ions. No one of them exhibited however any strong acid properties
as evidenced by OH stretching shifts created by adsorption of benzene. There-
fore the enhancement of catalytic activity after mild steaming is hardly con-
nected with an appearance of any new superacidic Broensted active sites.
On the other hand, the low temperature hydrogen adsorption indicated that
the mild dealumination created the extra lattice Lewis sites. Their number was
increasing with the time of water vapor treatment. This result allowed to exp-
lain the enhancement of the catalytic activity in the following more traditi-
onal and simple way:
According to ref.15 the cracking of paraffins proceeds via chain mechanism,
where both Lewis and Broensted acid active sites are involved:
R H + L - :C=C: + H2
+ +
Hsurf + ,‘c=c: --c
Rads
(41
+ +
Rads 1 :C=C: + R
‘ads
+ +

The Lewis sites play here the role of the dehydrogenating active centers,
resulting in formation of olefins. The latter are then transformed by Broens-
ted acid sites into adsorbed carbenium ions, which are involved in chain
propagation via /3 scission and hydrogen transfer reactions.
Since the steaming creates extra lattice Lewis active sites, this favors
the dehydrogenation of paraffins and the generation of adsorbed carbenium ions
at the initial stages of the treatment. At the same time the dealumination al-
so destroys the Broensted acid sites. These two factors do influence the cata-
lytic activity in opposite directions. Therefore after mild steaming the reac-
126

tion rate is increased. It reaches then some maximal value after moderate time
of steaming and goes down for the higher extent of the dealumination, where
the steam treatment results in a considerable decrease of Broensted acidity.
This explains the extreme character of the activity dependence upon the time
of high temperature water vapor treatment.
To check this explanation the special experiments were carried out in which
the cracking of n-hexane doped by small amounts of 1-hexene was studied on
steam treated and on untreated HZSM-5 samples. As one should expect, the cata-
lytic activity of the nonsteamed zeolite and of that one treated in optimal
hydrothermal conditions changed after 1-hexane addition in such a way that
they reached almost the same values. In other words the activity of the stea-
med zeolite became two times lower, whereas for the untreated sample 2-3 times
higher. Dehydrogenating activity of Lewis sites was also confirmed by the
increased H2 yield (by 1.5-2 times) in the cracking of n-hexane on mildly dea-
luminated zeolites as compared with initial H-form. Thus, the role of Lewis
sites in catalytic cracking was independently proved by purely chemical expe-
r iments .
Recently some other examples of modification effects in developing the
strong acidity of hydrogen forms of zeolites were reported (refs. 16-17). For
instance. Lunsford et.al. (ref.16) found, that dealuminated faujasites and
HZSM-20 zeolites prepared such, that they had a minimum amount of extra frame-
work aluminum were relatively inactive in cracking of hexane, which was used
as a test of strong acidity. Upon exchanging La+3 ions into the zeolites, the
cracking activity first increased with respect to lanthanum loading and then
went through a maximum. The authors explained these results by the model of
strong Broensted acidity. It was suggested, that lanthanum ions formed
[La(OH)2Lal+4 or La(OH)+2 species in 6 cages, which were responsible for the
withdrawal of electrons from the framework hydroxyl groups, thus making pro-
tons more acidic. In our belief this explanation sounds rather illogical, sin-
ce hydrolyzed lanthanum species definitely are of the basic character. There-
fore they hardly would increase the acidity of structural hydroxyl groups, but
rather neutralize them. It looks, that the more probable explanation is that
one similar to the already discussed above for extralattice aluminum ions.
According to it the role of dehydrogenating active sites is played by the lan-
thanum-oxygen acid-base pairs, which are the source of olefins, resulting in
the chain carbenium ion mechanism of cracking.

THE ACID-BASE PAIRS IN HIGH SILICA ZEOLITES MODIFIED BY Zn AND Ga IONS.

Another example, where Lewis acid-base pairs play the role of dehydrogena-
 127

ting active sites, represent the high silica zeolites modified by Zn and Ga
oxides. They are known as active catalysts for aromatization of light paraf-
fins (ref.18) and therefore attract the growing attention of a number of in-
vestigators.
There are rather strong indications that these catalysts are of bifunctional
nature combining the dehydrogenation of light paraffins on modifying oxides
with the consequent aromatization of olefins on super acid Broensted sites of
high silica zeolite. Therefore in our work (ref.19) the dehydrogenating cen-
ters of these catalysts were studied in frames of the similar approach of the
low temperature molecular hydrogen adsorption. In addition the distribution of
modifying oxides was also investigated by means of XPS and by ESR of adsorbed
bulky stable free radicals, which could not penetrate inside the zeolites mic-
ropores.
The most interesting results were obtained for the samples modified by Zn+2
ions. It was found, that both the ion exchange and the impregnation with zinc
nitrate decreased the intensity of the band of bridged acidic hydroxyl groups
with the stretching frequency of 3610 cm-l. In addition a shoulder from basic
ZnOH' groups at 3660 cm-' was observed.
On the other hand, the modification by Zn also resulted in appearance of
several different Lewis sites. This is evident from the Fig.4, where the IR
spectra of molecular hydrogen adsorbed at 77 K on the sample modified by Zn
are represented.

z,'L
+ HI

Fig.4 IR diffuse reflectance spectra of molecular hydrogen adsorbed at 77 K

on HZSM-5 zeolite modified by 3 weight % of ZnO and preheated in vacuo at
770 K. (a)-hydrogen adsorption on nonmodified sample.(bl-adsorption at 77 K
without any additional treatment.(c)- adsorption at 77 K after keeping the
sample in hydrogen at 300 K for 10 minutes.
128

The important point is, that the largest shift of adsorbed hydrogen consi-
derably exceeded that, which was earlier observed for hydrogen adsorbed on the
surface of the bulk ZnO (ref.20). This means, that the adsorption sites on the
surface of zinc oxide and in high silica zeolites modified by Zn+2 ions are of
the different nature.
This difference could be explained by the different nature of oxygen, which
surrounds Zn+2ions in both of these cases. In the modified zeolites this
could be the oxygen of the zeolite framework, which certainly is different
from that of ZnO. Such interpretation is confirmed by the following experimen-
tal results:
It was found, that the sites, which most strongly perturb adsorbed hydrogen
at low temperature do dissociatively adsorb it at room temperature. This is
evident from the spectrum (c) of the Fig.4, which shows, that after keeping of
modified ZnZSM-5 sample at room temperature in hydrogen and cooling it back to
77 K the low frequency band of adsorbed molecular hydrogen was disappearing.
Instead the growth of the band from the bridged acidic hydroxyl groups with
the stretching frequency of 3610 cm-l was observed.
This could be explained by the heterolytic dissociative adsorption of hyd-
rogen, which blocks the Lewis acid-base pairs and makes them unaccessible for
the adsorption of molecular hydrogen:
+ -

-Zn--0- t H2 - H
-Zn--0-
H
(5)

Since the stretching frequency of the resulting OH groups is the same as in

the hydrogen form of high silica zeolite, the corresponding oxygen atoms of
the acid-base pairs are those of the zeolite framework.
The acid-base pairs in zeolites modified by Zn+2 do also perturb light pa-
raffins. This is evident from Fig.5, where the IR diffuse reflectance spectra
of methane and ethane adsorbed at room temperature on ZnZSM-5 as well as on
HZSM-5 zeolite dealuminated by mild hydrothermal treatment are presented. In
addition to the lines from the physically adsorbed molecules marked by aste-
riks, the broad bands at 2750-2860 cm-' strongly shifted towards low frequen-
cies are observed. They resemble the corresponding IR bands from light paraf-
fins specifically adsorbed on Lewis acid-base pairs of aluminum oxide (ref.1).
The shifts observed for zinc-containing acid-base pairs are somewhat larger as
compared with extralattice aluminum ions in the steamed zeolite.
After evacuation these bands are removed more difficult than those from the
physically adsorbed molecules. Like i n the case of hydrogen at high temperatu-
 129

re paraffins are able to be adsorbed dissociatively. This is evident from dis-

appearance of the bands of molecular hydrogen if it is adsorbed at 77 K on
the samples preheated in hydrocarbons at elevated temperature. This effect is
completely reversible, since after evacuation at high temperature the low tem-
perature adsorption of hydrogen again resulted in appearance of the correspon-
ding IR bands.
The spectral study of GaZSM-5 zeolites was Just not so successful. For the
sample prepared by impregnation we did not observe by IR spectroscopy the in-
fluence of Ga ions neither on the intensity of the bridged acidic hydroxyl
groups nor on the formation of any new Lewis acid sites. This result was ra-
ther surprising, since the samples modified by gallium were also active in
aromatization of light paraffins.

Fig.5 IR diffuse reflectance spectra of methane (a,b) and ethane (c)

adsorbed at 300K and P=10 Torr on ZnO/HZSM-5 zeolite (a,c) and on the mildly
dealuminated HZSM-5 zeolite (b).

The explanation of this discrepancy was found, when we studied the chemical
composition of modified samples by XPS .It was found, that the external surfa-
ce of the zeolite micrograins was markedly enriched in Ga, whereas Zn ions
were distributed homogeneously inside the zeolite micropores. Therefore the
lack of IR observation of Lewis acid sites for gallium doped samples should be
explained by their low concentration inside the channels.
130

We observed these low coordinated gallium ions on the outer surface of zeo-
lite micrograins by more sensitive ESR technique. As a molecular probe the ad-
sorption of 2.2.6.6 - tetramethylpiperidine 1-oxyle stable free radical was
used, which due to its large dimensions could not penetrate inside the zeolite
micropores. The ESR spectra of this free radical exhibited the hyperfine
splitting from low coordinated Ga ions, which proved their existence on the
external surface of micrograins of modified zeolite (ref. 1 3 ) .

CONCLUSIONS
The increase of activity in transformations of paraffins after mild stea-
ming or modification of zeolites by various oxides is usually connected with
formation of some new super acidic Broensted active sites (ref.13,16,21).
The present paper supports an alternative explanation,according to which
the main effect of modification consists in creation of Lewis acid sites. In
the steam treated samples their role is played by extra lattice aluminum. It
is shown, that such active centers could dehydrogenate paraffins and in this
way assist the easier formation of adsorbed carbenium ions. This results in
higher reaction rate of cracking.
In the case of catalytic transformations of light paraffins to aromatics
the role of dehydrogenating Lewis sites is played by modifying Zn and Ga ions.
They differ in their location, since the former are homogeneously distributed
inside the zeolite micro grains, whereas the latter are mainly localized on
their outer surface.
It was also shown, that the Lewis active sites should be considered as
acid-base pairs, where both low coordinated cations and the neighboring basic
oxygen of the zeolite crystal lattice are equally important. The best molecu-
lar probes for their study are molecular hydrogen and paraffins, i e. the sub-
strates, which are involved in catalytic reactions with participation of such
active sites.

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facts, figures, future, Ed. P.A. Jacobs, R.A. Van Santen, Elsevier, 1989,
pp. 1173-83.
20 R.J. Kokes, Hydrogenation and related reactions over metal oxides, Proc. 5th
Int. Congr. Catal., Miami Beach, 1972, Catalysis, Ed. J.W. Hightower, North
Holland Pub. Co., 1973.
21 R.A. Beyerline, G.B. McVicker, L.M. Jacullo, I.J. Zilmiak, Influence of
framework and nonframework aluminum on the acidity of high-silica proton-
exchanged FAU-framework zeolite, J. Phys. Chem., 92(7) (1988), p p . 1667-70.
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 133
0 1991 Elsevier Science Publishers B.V., Amsterdam

COMPAKA'I'I V E MEASU KKMEN'FS ON ACIDITY OF ZEO1,ITES

Hellmut G. Karge
Fritz-Haber-Institut der Max-Planck-Gesellschaft Berlin, 1000 Berlin 33, FRG

A €3STKACT
Methods of identification of various acidic sites in zeolites (Brensted sites, different
types of Lewis sites, cations) are briefly reviewed. Similarly, techniques for deter-
mination of the density of acid sites are discussed and illustrated with selected
examples. In particular, a good agreement between the results obtained by IR (using
pyridine as a probe molecule) and ESR (employing NO) in determining Lewis site
densities of, for instance, progressively dehydroxylated H-Y is demonstrated. Emphasis
is laid on the discussion of techniques, such as titration, in aprotic solvents, IR with and
without probe molecules, 'H MAS NMR, temperature-programmed desorption and
microcalorimetric measurements of heats of adsorption of basic probe molecules, which
are suitable for characterising the strength of acidic sites. Quantitative evaluation of
TPD spectra using a kinetics model as well a s the combination of different methods is
described in more detail, and results obtained by various techniques on selected
examples of acidic zeolites are compared.

Most of the important reactions carried out over zeolite catalysts are acid-catalysed
even though there is a n ever increasing interest in zeolite catalysis on basic sites [ l - 2I.
The term "acidity of zeolites", however, is by no means unequivocal. "Acidity" could
designate (i) the nature of acidic sites (e.g. Brcdnsted sites 131, various forms of Lewis
centres such a s "true" Lewis sites [4-5], cations), (ii) the number or density of the
respective sites or, finally (iii) their strength. Although there exists a n overwhelming
evidence that a t least for the large majority of acid-catalysed reactions the acidic
Brplnsted centres of zeolites (acidic hydroxyls) are the relevant active sites [6-10!, there
is still a debate on the role of the Lewis centres [ll-191 in zeolite catalysis. In any event,
there i s no severe difficulty to discriminate between the various types of acidic sites. A
survey of the most relevant methods of distinguishing the various types of acidic sites is
presented in the first section. In fact, this can be rather brief since a number of
excellent earlier and also more recent review articles are available which cover this
subject [8, 20-231. Similarly, the determination of the relative or absolute density or
number of acidic sites will not be dealt with in great detail. Most of the techniques
suitable for identifying the nature of the acidic sites can be developed in such a way
that they provide quantitative information. Thus, in the second section some of the
important methods for quantitative evaluation of acidic sites in zeolites will be pre-
sented and for a few instances the results ofdifferent techniques will be compared.
134

A more difficult problem concerning the acidity of zeolites is the evaluation of the
acidity strength. Indeed, more recently some theoretical concepts have been developed
to rationalise the acidity strength of Bransted acid sites in zeolites [24-321.
They relate acidity strength to long range collective phenomena and/or more
localised effects of structure and chemical composition. Hence, theoretical ideas such a s
"activity" or "efficiency" (regarding the zeolite as a crystalline liquid, see Refs. [241,
[27]), Sanderson electronegativity (see Refs. [25],[261, [281, [301), topological densities
(see Ref. [31]), quantum mechanical effects of bond lengths and angles (see Ref. [291)
and deprotonation energies (see Refs. [29], [32]) are involved. Detailed discussions of
these concepts were presented by Dwyer [221 and Rabo and Gajda [231.
There is, however, an urgent demand to have a t hand reliable techniques which
enable us to characterise and measure the acidity strength of zeolite materials, not only
to verify or falsify theoretical concepts, even though this is certainly a n important
point. Progress in experimental techniques will extend the data base for further im-
provement of theoretical approaches to the phenomenon of acidity strength. A practical
need is felt to determine the acidity strength experimentally in a reliable manner, since
in many instances i t has become quite obvious that not only the number but also the
strength of acidic sites is particularly decisive for the behaviour of zeolitic materials in
sorption and catalysis (see, e.g. Refs. [331, [341).
Quite a number of methods have been suggested, developed and employed to
characterise the strength of acidic sites in zeolites. In the third part of this contribution
a n attempt is made to evaluate some of the more important ones and to illustrate them
by pertinent examples taken from the literature or own measurements. Special
emphasis is laid on the comparison of results obtained for one and the same acidic
zeolite sample by the use of different techniques for the determination of density and
strength of acidic sites.

1. THE NATURE OF ACIDIC SITES IN ZEOLITES AND TECHNIQUES FOR THEIR

DISCRIMINATION
Table 1 presents a list of techniques proposed for discrimination between the
various acidic sites encountered in zeolites. Pertinent references are also given; how-
ever, here and in the following text they are by no means exhaustive, due to the
extreme broadness of the field.
Possible acidic sites are the acidic OH groups, in particular the so-called bridging
H
ones in the = Si - 0 - A1 = configurations, i.e. potential Bransted acid centres (proton
donors). Furthermore, coordinatively unsaturated sites occur (electron pair acceptors),
e.g. "true" Lewis sites [4-5, 351 such a s A10+ or charged A1,0,"+ clusters or cations,
Me"+, or acceptor sites on tiny oxide particles inside or outside the pore structure.
 135

TABLE 1

NATURE OF ACIDIC SITES IN ZEOLITES

Examples Methods of Identification Ref.

Bransted Bridging OH; IR,IR + probes P O . 131
AI-OH; P-OH 'H MAS NMR, 15N NMR [39-421

0 Lewis ?AI
(framework) IR + probes [201
AIO +,[AI,0y](3X*21 27AlMAS, 15N NMR [39.411
Al-oxides ESR + probes [65-671
(extra-framework)
Other oxides
Cations, Men +

I IR + probes

Regarding the methods to distinguish between the various types, i t has been claim-
ed several times that Hammet indicators are non-specific whereas aryl indicators
should indicate only Bransted but not Lewis sites [36].This, however, was disproven
[37-38,76-771. It was shown by Karge [37]via U V M S transmission spectroscopy that,
for instance, triphenyl methanol, @,C(OH), reacts with a surface being free from
Bransted sites as well, giving the typical spectrum of @,C+ carbenium ions.
The most powerful and widely employed techniques for discrimination of acidic
sites are the IR and NMR spectroscopy used with or without probe molecules [a,20,39-
431.Acidic OH groups may be detected by the position of the corresponding OH stretch-
ing vibration in the range of ca. 3520 to 3650 cm-l [8,9, 20, 441 or by their typical
chemical shift in 'H MAS NMR [41,421. Adsorption of probe molecules on acidic OH'S
gives rise to characteristic features in the spectrum which also reveal the presence of
Bransted sites. Thus, after interaction with pyridine, typical bands stemming from ring
deformation modes occur a t 1632 cm-' ( w 8a) or ca. 1540 cm-l ( v 19b). Reaction with
ammonia results in the appearance of the v,(NH4+) band around 1445 cm-l. Similarly,
adsorption of 15N-pyridineon acid Bransted sites causes a chemical shift of S = 171-174
ppm vs. solid NII,NO, [39-401.
27Al MAS NMR allows for the determination of the number of A1 atoms tetra-
hedrally coordinated in the framework, Al'. Since tetrahedrally coordinated A1 corre-
sponds (in zeolites not modified via dealumination) to the presence of Bransted acid
sites, this provides another means to indicate those centres [431.
True Lewis sites (i.e. Al-containing species on extra-framework sites, AINF, [4-5,
35, 451)as well as cations can be identified via IR spectroscopy with the help of suitable
probe molecules such as NH,, pyridine, acetonitrile or CO. Ammonia molecules coor-
dinatively bound to true Lewis sites and I or cations give rise to a broad band around
136

1620 cm-l. The u(19b) band of pyridine attached to Lewis sites is usually more intense
and sharp bands occur around 1450 cm-I for true Lewis sites and in the range from 1440
to 1551 cm-l for cations depending on their Coulomb field [20, 46-47]. Similarly, the
band position of adsorbed acetonitrile and CO is affected by the nature (e/r) of the
respective cation [ 37,48-491.
In the case of IR spectroscopy usually only one type of Al-containing extra-frame-
work species is indicated by the probe, i.e. with pyridine just one band appears a t 1452
cm-l. Only in a few instances a doublet (1456,1451 cm-l) was observed [45,50]. In con-
trast, 27A1MAS NMR frequently reveals the presence of different types of extra-frame-
work Al. In fact, the interpretation seems to be difficult; however, besides octahedrally
coordinated extra-framework A1 also penta- and even tetrahedrally coordinated species
are being discussed [41,43,51-531.

2. DENSITY (NUMBER) OF ACID SITES IN ZEOLITES

Tables 2 and 3 present lists of methods which were applied to determine the den-
sity and / or number of Bransted and Lewis sites in zeolites, respectively.

'ABLE 2

DENSITY (NUMBER) OF BRQNSTED ACIDIC SITES

Method Remarks -
Ref.

Titration Restricted applicability [69,74-771

IR Spectroscopy Absorbance of bands of acidic OHs [20,13-14.91
andlor probes, e.g., PyH , NH4 , H2
+ +

(extinction coefficients required for

absolute numbers)
'HMASNMR Area of respective signal [41-42)
2 7 ~MAS
1 NMR Area of respective signal I431
29SiMASNMR Combined with chemical analysis [911
Ion Exchange Exchange capacity [601
Test Reactions Restricted applicability (34.62-641
Adsorption and Restricted applicability [83-84.891
Desorption of (no other adsorption sites involved; [94-1041
Probe Molecules or in combination with, e.g., IR)

Those methods which are reliable in discriminating the various types of sites (e.g.
IR spectroscopy, '13 NMR, 29Si and 27Al NMR spectroscopy) can be in most cases em-
ployed for quantitative measurements as well.
 137

In this context, i t should be mentioned that the NMR techniques provide the abso-
lute numbers of sites, n (sites), under investigation in a very straight-forward manner,
uiz. by the area of the respective signals. In contrast, the bands of IR absorbance, which
are typical of certain acidic sites, must be evaluated with the help of the appropriate
extinction coefficients according to

n (sites)= 1;'vdv
I

where E, d, v1 and w2 are the extinction coefficient, thickness of the sample, beginning
and end of the particular band, respectively. The extinction coefficient must be deter-
mined in an independent experiment (see, e.g. Refs. [54-561 ) and may depend on the
coverage of sites. However, in many cases i t is sufficient to use relative densities to
obtain the relevant information about the relationship between numbers of sites and,
e.g. catalytic or adsorption properties [9-10,201.
Figure 1 illustrates the application of IR spectroscopy and 'H NMR spectroscopy on
the determination of the number of Bronsted sites, respectively [3,57-581.

W
U
= 48.8 0Hh.c.
3670 3580 cm-' bridgin
acidic 08s v]
= 49.2 0Hh.c.

z
a
c

-
-
t-
5
wl
z
a 'I
z 7 4,s 2
I-
! E
I

I(1) IR-SPECTROSCOPY
J.E. Uytterhoeven. 1. G. Chrirtner and W. K. Hall
I ~ H
M A S N M R SPECTROSCOPY]
H.Pfeifer, D. Freude and M. Hunger
1. Phyr.Chem.69(1965)2117 Zeolites 5 (1985) 274
(2) J.E. Uytterhoeven. P. Jacobs, K. Makay and
R. Schoonheydt
1. Phyr. Chem. 72 (1968) 1768

Fig. 1 Determination of bridging acid OH groups in HY (90) by IR and 'H hIAS NMR.

Most of the other techniques indicated in Tables 2 and 3 suffer from certain restrictions.
With respect to the titration method, this will be elucidated in the third section. Deter-
138

mination of the ion exchange capacity, e.g. with NH4+, gives usually a good estimate of
the upper limit for the total number of acidic Brernsted sites, however, often even very
weak sites are involved, without any relevance to catalysis.
Adsorption and desorption of probe molecules requires, inter alia, t h a t only one
type of sites exists in the zeolite, otherwise the assignment of the amounts of adsorbed
or desorbed probe molecules might be erroneous. In such cases, where more than one
type of site is involved, the combination with IR and/or NMR measurements is
advisable [59-611. Finally, the evaluation of sites via the rate of suitable test reactions
is well established for a series of homologous zeolite catalysts [34,62-641. Comparison
of quite different types of zeolites could be misleading. This field, i.e. application of test
reactions for determination of density of active sites is not yet satisfactorily explored.
As already pointed out (see also Table 3), it is possible to identify and quantitative-
ly determine acidic Lewis sites by IR spectrosopy with the aid of suitable probe mole-
cules such as pyridine, ammonia, carbon monoxide and hydrogen. The direct measure-
ment of Al-containing extra-framework species (true Lewis sites) can be achieved via
27Al MAS NMR,provided the Al-content is not too low [43,53].

TABLE 3

DENSITY (NUMBER) OF LEWIS ACIDIC SITES

Method Remarks Ref.
0 IR Spectroscopy
-. -
Absorbance of bands of probes,
e.g., Py L, NH3 -,L, CO L, H2 -,L
(extinction coefficients required for
[20,13-14,91

absolute numbers)
0 27AIMAS NMR Requirements:A1 content not too low, 1431
Spectroscopy all Al observable (area of respective
signal)
0 29Si MAS NMR Combined with chemical analysis [91l
0 ESR Spectroscopy NO adsorption [65-681

However, ESR spectroscopy using NO as a probe, provides also a valuable tool not
only for identification but also for quantitative evaluation of Lewis sites in zeolites.
This was first shown by Lunsford et al. [65-671, see also Ref. [591. Figure 2 shows a n
ESR spectrum obtained after adsorption of NO on a n H-ZSM-5 sample [68]. It is almost
identical with the ESR spectrum of NO adsorbed on alumina [66-671. Double integra-
tion provides the spin density as a measure of the density of Lewis sites.
In a series of experiments, these densities were determined as a function of pre-
treatment temperature. As expected, the density of Lewis sites increases with pretreat-
ment temperature as a result of increasing dehydroxylation 1681. This is indicated in
Figure 3 by the corresponding increase of the spin density of NO adsorbed. In a parallel
 139

set of experiments the Lewis site density was determined through IR measurements of
the intensity of the 1452 cm-’ band after pyridine adsorption. Figure 3 demonstrates
that the results of both techniques are in very good agreement.

r
I : : ) p(N0) = 50Pa

Fig. 2 ESR spectra of NO adsorbed on

y-Al,O, and H-ZSM-5 (2) or CAZ 49

lo’* I 1
Adsorbent : H - ZSM - 5 (2) CAZ 49
3. Part = 10-5pa
Tad (Py) = 475 K (2h)
Tdel (Py) = 475 K (1 h)
z Tad(NO) = 298K ( l h )
- 0.6

a
W
n
m
- 0.3

0 I
600
I
700
1
800
I
900
I
1000 1100
10.0

A C T I V A T I 0 N T E M P E R A T U R E [K]

Fig. 3 Density of Lewis sites of H-ZSM-5 (2) or CAZ 49, measured through NO (ESR)
and pyridine (IR) adsorption
140

Table 4 displays comparative data of measurements of site densities obtained via

various methods. The relative densities (%) for Bransted sites were obtained via MAS
NMR (see AIF ) and IR (see A[OH] and A[PyH+]), those for Lewis sites via MAS NMR
(see AINF1, IR (see A[Py -B L] and ESR (see spin densities D[NO]). With the exception of
the PyH+ data the agreement is satisfactory. The determination of Brflnsted sites via
the density of pyridinium ions, (A[PyH+]),seems to be disturbed by the presence of a
relatively high amount of extra-framework aluminium (AINF)which may give rise to
(weak) Al-OH groups reactive towards pyridine or, another possibility, may affect the
extinction coefficients of the PyH+ species. The presence of Al-OH in H-ZSM-5 (21, i.e.
CAZ 49, was indicated by an IR band at 3680 cm-'; this band was missing in the case of
H-ZSM-5 (1).This would explain the high value of A(PyH+) of CAZ 49 compared to
CAZ 36.

TABLE 4

COMPARISON OF (RELATIVE) SITE DENSITIES MEASURED VIA IR, NMRAND ESR

1 Brcansted Sites I I Lewissites

I
[%I [%I [%I [%I ["/.I [%I
H-MD-1 100 100 100 100 100 _-
H-MD-2 65 63 84 95 84 __
H-ZSM-5(1) I 100 100 I 100 100 100 I 100

3. CHARACTERISATION OF THE STRENGTH OF ACIDIC SITES IN ZEOLI'I'ES

Titration of acidic sites
Tables 5 and 6 list a number of techniques frequently used for determination of the
strengths of Bransted and Lewis sites.
The titration technique was developed to characterise the acidity strength of solid
inorganic materials such as oxides and salts (see Tanabe, 1691 references therein) and is
still widely used in this area of research [70,71]. It was also employed in studying the
acidity of the classic silica-alumina cracking catalysts [37,72]. The particular procedure
is described in detail in the literature (see, for instance Refs. [34,36,69,72-731).
In zeolite chemistry, pioneering and careful work was carried out by Hirschler L361,
Beaumont et al. 1741, Kladnig 1751, Kittelmann [761 and Unger e t al. [771.
In fact, Beaumont et al. [74] obtained very interesting results when applying the
titration technique on faujasite-type X and Y zeolites. These authors found a distinct
 141

correlation between the degree of exchange of N a + against NH4+ (or H') and the
efficiency of thus created acidic hydroxyls. This enabled them to define a n efficiency
coefficient in analogy to the activity coefficient of electrolytes. In the case of H,Na-X
+
(Si/Al =1.23 or Al / [A1 Si]=0.45) this coefficient was u,=0.16 whereas for Y-type
+
zeolite, H,Na-Y (Si/Al = 2.43 or A1 / [A1 Si] = 0.29),a, = 0.6 was obtained. This was the
first evidence for a (collective)effect of the Si/Al ratio on the acidity of zeolites (compare
also Ref. [241).

TABLE 5

STRENGTH OF BRQNSTED ACIDIC SITES

Method Remarks Ref.

0 Titration Restricted applicability [ 36,34,74-771

0 TPD Probe molecules, e.g., NH3! (83-84,89-901

pyridine (eventually combined
with spectroscopy)
0 Microcalorimetry Adsorbates, e.g., NH3, pyridine, [94-104)
weaker bases (eventually
combined with spectroscopy)

0 IR Spectroscopy Shift of OH; with and without [28,1081

probe molecules, e.g. benzene, CO [lo91
UV-VIS Spectroscopy aromatics as probe molecules [1101

0 'HMASNMR Chemical shift of the 'H signal [41-42.1111

0 Test Reactions Various reactions requiring [1141

different acidic strength

TABLE 6

STRENGTH OF LEWIS ACIDIC SITES

Method Remarks -
Ref.

0 TPD Probe molecules, e.g., NHJ, pyridine (83-84,89-901

or weaker bases (eventually
combined with spectroscopy)

0 Microcalorimetry Adsorbates, e.g., NH3, pyridine or [94-1041

weaker bases (eventually
combined with spectroscopy)
IR Spectroscopy Adsorption of bands of, e.g. pyridine [20,14,91
or CO coordinated t o cations

0 ESR Spectroscopy Desorption of NO [a1

142

Even though the method was subject to frequent criticism [78-791, the agreement
between the total number of acidic sites (H, 2 -3.0) and the same number evaluated,
for instance, from the stoichiometry seems to provide some confidence in its reliability.
However, i t turned out that the procedure was obviously not applicable to other zeolite
structures such as mordenites [75-77,80411. The reason is not, as has been often
claimed, that the bulky indicator molecules cannot penetrate into the channels or pores
of structures other than faujasite [23,82]; mordenite for instance, is a large-port zeolite
with twelve-membered rings as pore openings very similar to faujasite. Moreover, it i s
questionable whether slight colour changes of indicator molecules inside the pore
structure would be detectable by the eyes of the experimentalist. However, the main
reason for the failure of the titration method in the case of many zeolites seems to result
from a very strong interaction of the solvent molecules with the acidic sites.
I I

b : 1 rnin. after injection of excess

butylamine (16 m mo1.g-1)
c : 7 h after injection

3680
Y
U
z
U
I-
-
I-

I
VI
z
4
L*
+

I I Fig. 4 Interaction of solvent (n-

,000 3500 3001 heptane) with H F (3650 cm-I ) OH
groups of H,NaY and in-situ titra-
W A V E N U M B E R [cm'] tion with butylamine

In the pore system of mordenite the replacement of the solvent molecule by the titrator
base (e.g., butyl m i n e ) is thus severely impeded. This is demonstrated by Figures 4
and 5 which contrast the different behaviour of H,Na-Y and H,Na-MOR in a titration
experiment followed in-situ by IR. Thus, one has to state that, regardless of other
difficulties, the method fails when applied to acidic zeolites such as mordenite, erionite
etc. This is in agreement with the above-mentioned findings [75-77,80-811.
 143

V- a v- -a
a afterdehydrationat 725 Kand 1O'Pa d after dehydration at 1 2 5 K and 10 5 Pa
b after admiwon at solvent. CCI, b after admiwon of ~ o l v e n l CCI.
. b after admission of solvent CCI.
c after 1st mje(tion of n butylamine c after 2nd mjeamn of n-butylamme c atterlnd mjert~onof n-butylamlnc
( 0 25 m mol q 11, 8 h 1025mmol (I-) t 2 h

I I
3800 2800
WAV E N U M B E R [cm-'1
Fig. 5 Interaction of solvent (CCI,) with acidic OH groups of H,Na-MOR and in-situ
titration with butylamine

It seems to work, however, with faujasite-type zeolites. In fact, in the case of a

homologous series of Y-type zeolites with systematically varied acidity strength a spec-

-
trum of the acidity strength distribution was obtained as is shown in Figure 6.

-
Y'
1 very strong H, c-8 2
0 2- strong -82<H0(-56
€ 3 3 medium -5.6 < H, 6-3.0
E
Y
L rc-cl weak -30< H, < 1 5
VI 5 very weak 1 5 < H, < 3.0
Y
+
m 2
-
0
U
a
LL
0 '
*
-
I-
VI
z
u o
HNaY BeNaY MgNaY CaNaY SrNaY BaNaY LaNaY

Fig. 6 Spectra of acidity strength of a homologous series of Y-type zeolites

144

Figure 7 demonstrates that only the fraction of the strongest sites (Ho 5 -8.2)correlates
with the rate of conversion of the test reaction, viz. disproportionation of ethylbenzene
MI.

D E N S I T Y O F V E R Y S T R O N G A C I D SlTES(H,<-8.2) [mmol.g-1]

Fig. 7 Rate of ethylbenzene disproportionation vs. density of strong sites in Y-zeolites

Temperature-programmed desorption of probe molecules

Temperature-programmed desorption of basic probe molecules is a widely used
method to characterise the strength of acidic sites in zeolites [83-841.Usually relatively
strong bases are employed such as ammonia or pyridine. To minimize the effect of the
adsorbate base on the strength distribution of the remaining (non-covered) acidic sites
the use of weaker bases is sometimes preferred (see, e.g. Ref. [85]).The amount of
desorbing species is usually monitored via GC or MS. It is worth noting that the rate of
desorption of the probe molecules might be affected by diffusion restrictions. Further-
more, the measurements may depend on experimental conditions such a s geometry of
the arrangement, heating rate, reliable temperature control of the sample vs. oven etc.
For example, two essentially differing geometric arrangements caused differences in
the results by 10-15%[861. Therefore, a warning is appropriate with respect to compari-
son of absolute TPD data obtained under different conditions. The factors indicated
above must be carefully taken into account. However, a ranking of the acidity strength
of members of a series of acidic zeolites investigated under identical conditions is
usually feasible.
In most cases of TPD characterisation of acidic sites in zeolites, the peak tempera-
tures of the TPD spectra are adopted as an indication of the (relative) strength of the
sites. However, the spectra are usually relatively broad and, moreover, TPD by itself
does not provide any information about the nature of the sites from which the probe
 145

desorbs. Therefore, several efforts were made by, for instance, V. V. Yushchenko e t a!.
[85], Dima and Rees [87], Hashimoto et al. [88] and Karge and Dondur [891 to evaluate
in a more quantitative manner the TPD spectra and/or to combine TPD with other
methods, such as IJi spectroscopy, to identify the types of sites releasing the probe
molecules.
Figure 8 displays, as an example, TPD spectra of ammonia desorbing from two dif-
ferent H-ZSM-5 samples, i.e. H-ZSM-B(l) or CAZ 36 and H-ZSM-5(2) or CAZ 49.
I I I I

T E M P E R A T U R E [K]

Fig. 8 TPD of ammonia from two different H-ZSM-5 samples, CAZ 36 and CAZ 49

It suggests a significant difference in acidity strength in that sample CAZ 49 exhibits a

peak temperature higher by 36 K than that of sample CAZ 36. A kinetics model, devel-
oped by Dondur and Karge [89-901was applied for evaluation. The results are shown in
Figures 9 and 10 and in Table 7 (vide infra). One recognizes that (i) the analysis of the
spectra according to the above-mentioned model reveals the presence of three types of
sites each of them possessing its own distribution of strengths and (ii) the differences
indicated by the most frequent activation energy of desorption, Edes,for the respective
sites are less than lo%, the accuracy of the measurements being in the order of 3%.
These relatively low differences in acidity strength were confirmed by calorimetric
measurements (vide infra). Nevertheless, the samples exhibited remarkably different
catalytic behaviour, e.g. in MTG reaction and coke formation [911, which seemed at
least to some extent to be correlated with both differences in number and strength of
the acidic sites.
The assignment of the sub-peaks obtained by evaluation of the original TPD spec-
tra (shown in Figures 9 and 10) was achieved by concomitant IR investigation of the
effect of dehydroxylation on the intensity changes of those sub-peaks. A more elegant
technique is the desorption of the probe molecules from a sample placed in an IR cell. In
146

.lo ’ I 1 I I I I I

-
w
n.
104
I
CATALYST : CAZ 36

0.4 - 1

mz
ao

ul
W
n

A C T I V A T I 0 N E N E R G Y 0 F D E 5 0 R P T I 0 N [k 1 m o 1’1
3

Fig. 9 Calculated distributions of the activation energies of desorption of NH, from

various sites of €I-ZSM 5 (1) or CAZ 36.

ul
W
n

A C T I V A T I 0 N E N E R G Y 0 F 0 E S 0 R P T I 0 N [k J . m o I ’1

Fig. 10 Calculated distribution of the activation energies of desorption of NH, from

various sites of H-ZSM-5 (2) or CAZ 49

this case the change of the partial pressure of the desorbing species (monitored by MS
or G C ) and the change in intensity of the corresponding adsorbate IR bands, both a s a
function of temperature are simultaneously measured [80,86,921. The peak maximum
in a TPD spectrum of ammonia desorbing from Bransted sites of a zeolite should, for
 147

instance, correspond to the maximum change in the intensity of the ammonium ion
band at 1445 cm I . An example for such simultaneousTPD-MS and IRmeasurements is
shown in Figure I I .

Tart. = 670 K

1450 cm-l

01

6 - S I T E S (11)

I I I
400 500 600 700 800 Fig. 11 Combined IR and MS during
T E M P E R A T U R E 0 F D E S 0 R P T l O N [K] TPD of NH, from hydrogen mordenite

I
1 I I I I I I I I
-

r
I

.
I-
A

-
0
r

-
-
Heating rate : 5 K . min-1
0.000 I I I I I I I I I I -
90 120 150 180 210
T E M P E R A T U R E [K]

Fig. 12 TPD of N O from two different H-ZSM-5 samples, CAZ 36 and CAL 49,
monitored by ESK
148

Valuable information giving a t least a n estimate of the strength of sites occurring

on a particular zeolite saniple may be provided by discontinuous desorption of bases.
Most frequently this is followed by IR, monitoring the change of the absorbance of
typical bands due to pyridine adsorption after heating the sample to fixed desorption
temperatures (see, e.g. Ref. [93I).
Temperature-programmed desorption of suitable probe molecules from Lewis acid
sites can be used in a n analogous manner asdescribed for Bransted sites [89-901.
An interesting new approach is the temperature-programmed desorption of N O
from Lewis sites, monitored by ESR, because, this probe appears to be very specific to
these types of sites (vide supra, Refs. [65-681).An example is illustrated by Figure 12
1681.

Microcalorimetric measurements
There are only a few research groups applying microcalorimetry to characterise
and compare acidity strength via the differential heat of adsorption, even though this
technique provides in a very clear-cut manner quantitative data for scaling the
strength of acidity. However, the technique requires very careful experimenting and is
frequently somewhat time-consuming. Important contributions came from the groups
of Auroux e t al. [59,94-971, Klyachko et al. [98-1011, Thamm et al. [102-1031, and
Khvoshchev et al. [ 1041.An example taken from a study of Klyachko et al. [981is shown
in Figure 13.

1 : Na - MOR (Si/AL= 5,O)

2 : H - MOR (Si / A l = 6.3)
3 : H-MOR (Si/AI=lO,O) o o o o
4:H-MOR (Si/Al=23,5)
Klyachko et al.
100 Acta Phys. Chem. 24 (1978) 183

50

1 3 5 7
C O V E R A G E [mmol 9-11

Fig. 13 Differential heat of adsorption of NH, on mordenites (after Klyachko et a]., ReT
1981)
 149

In the study by Kapustin e t al. [ l o l l interesting results were obtained with H-

ZSM-5 samples of systematically varied Si/Al ratios, employing TPD of ammonia for
the sake of comparison. The heats of adsorption of NH, derived from microcalorimetric
measurements and TPD were in satisfactory agreement. However, microcalorimetry
yielded a distribution of the strengths of strong acidic sites whereas TPD provided only
a mean value.
Similar to the situation in TPD investigations (vide supra) stronger bases a r e fre-
quently employed as probes, the use of weaker ones, however, seems to be preferable in
many cases 1961. When strong bases are the adsorbates, care must be taken to ensure
sufficient mobility to achieve adsorption equilibrium. Thus, for adsorption of, e.g.,
ammonia and pyridine higher adsorption temperatures are required which, in turn,
necessitates the maintainance of a good isothermicity of the whole set-up.
Moreover, the same problem arises in microcalorimetry a s with TPD investiga-
tions: only concomitant experiments identifying the sites of adsorption enable u s to
ascribe, in a unambiguous way, the measured heats of adsorption to the types of sites
which interact with the probe molecules under release ofthat energy [100,105].
Results of such studies, i.e. microcalorimetric measurements of NH, adsorption
onto H-ZSM-5 samples (paralleled by IR measurements of the relative amount of
BrGnsted and Lewis sites before and after dehydroxylation), are incorporated into Table
7 [1051.

IR spectroscopic measurements
IR spectroscopy is sometimes employed a s a sole method for determination of
acidity strengths of sites, in other words, not as a technique complementary to other
ones (vide supra). Thus, it was claimed that the band position (wavenumber) of the OH
stretching band of acidic OH groups is a measure of their strength. This was first dis-
cussed by Barthomeuf [24] when comparing different zeolite structures in the hydrogen
form; see also Refs. [26-28,1061. However, one has to be aware of the fact that other
factors, such as the environment might affect this band position as well, i.e. without
any significant relationship to the acidity strength. Most prominent examples are
positions of the high and low frequency bands of OH groups in the faujasite structure.
Their accessibility for more bulky probe molecules differs remarkably but not, in fact,
their strength [107]. I t seems to be even more dificult to rely on the small shifts of the
OH bands caused by slight but systematic variations of the acidic properties within a
homologous series of zeolite samples. An example is presented in Figure 14 (see Ref.
[47]) for a series of mordenites (see also Ref. [621).
Even though TPD measurements seem to provide support [62,801,the author
hesitated to interpret the small but systematic shift in the OH band positions as being
indicative of decreasing strength of Brflnsted sites in the sequence from H-MOR
through to Ba-MOR. As mentioned earlier, the OH stretching band of acidic OH groups
150

covers, without any doubt, a whole spectrum of sites with a more or less broad distribu-
tion of acidic strengths (vide supra). The fraction of sites falling into certain ranges of
strengths with corresponding OH modes may vary and, therefore, their super-
imposition may lead to shifts in the overall position of the envelope OH band.

I
3600 3580 3615 3605 3616 3618 3620 3620

3800-3400 3612
cm

W a v e n umber

Fig. 14 Wavenumbers ol'the stretching bands of acidic OH groups of a homologous

series of niordenites 1471.

An estimate of the strength of the acidic sites can be obtained from the shift of the
OH bands of the acidic hydroxyls upon interaction with suitable adsorbates such a s
benzene [28,1081 or CO [1091. The resulting shifted bands, however, caused by hydro-
gen or II bonding, are usually relatively broad and do not reveal more subtle differences
in acidity strength. Sometimes the observed shifts may provoke an overestimation or
the differences in acidity. This seems to be so with the results obtained with two
II-ZSM-5 samples (CAZ 36, CAI, 49) a s the comparison with TPD and microcalorimetric
data reveals (see Table 7).
Similar experiments were carried out in the U V M S region by Naccache e t al.
[110] using aromatic probe molecules.
The strength of Lewis sites, i.e. more specifically cations as electron pair acceptor
sites, can be reliably scaled by the shift of the bands of, for instance, pyridine, nitriles
or CO coordinatively attached to them. Examples are provided in the work by Ward
[20,46], Angel1 e t al. 148-491 and Karge [37,47].
 151

TABLE 7
COMPARISON OF MEASUREMENTS OF ACIDIC STRENGTH

Strong Brensted Sites Lewis Sites

Zeolite
TZIK Edc, [kJ.mol-'] 0;: [kJ.rnol-'l dv(0H) Ed,* [kJ-mol-']
H-MOR-D (1) 12 700 115 355 137
H-MOR-D (2) 17 690 115 360 140

H-ZSM-5 (1) 33 619 104 90' 337 130

H-ZSM-5 (2) 25 655 110 115' 3 59 137

'H MAS NMR Spectroscopy

Pfeifer and co-workers [41-42,1111 have demonstrated that the chemical shift in
'H MAS NMR spectra of acidic zeolites might be a suitable measure of the strength of
the related 'H-containing sites. Thus, in the case of HY a shift (in ppm vs. TMS) of
6 = 1.8-2.2 indicates the weak or non-acidic silanol groups (corresponding to the IR band
around 3740cm-'), 6=3.8-4.4 and S=4.8-5.6 are related to the two types of bridging
acidic OH groups with IR bands a t about 3640 and 3550 cm-l in faujasite-type acidic
zeolites, indicating a different environment but not a different acidity strength. A shift
of S = 2.6-3.6 ppm is, finally, ascribed to weak acidic OH groups associated with extra-
framework aluminium-containingspecies.
Also interesting relationships were found between the chemical 'H shifts and dealu-
mination of faujasite-type or mordenite-type zeolites via acid leaching or hydrothermal
treatment (steaming) [41,1111.
Basically, however, the situation with 'H-MAS-NMR measurements of the strength
of acidity is the same as encountered with IR. The signals observed are certainly cover-
ing a whole spectrum of sites with various strengths. 'H MAS NMR also does not,
hitherto, provide a direct means to determine the particular distribution of these acidi-
ty strengths.

Test reactions
A few studies attempted to employ test reactions not only to characterise the
density of acidic centres but also their strength [112-1143. The basic idea was that
different acid-catalysed model reactions may require acidic sites of different strengths
which would enable us, conversely, to characterise the strengths of catalytically active
acid sites in zeolites by the rates of a suitable set of model reactions. Thus, i t has been
152

pointed out, for instance, by Weitkamp [112] that isobutane alkylation by butene over
rare earth faujasite-type zeolites requires stronger sites than butene oligomerisation
and this, in turn, occurs on sites stronger than those necessary for butene isomerisa-
tion. Similarly, Karge e t al. [62,113] found, with regard to the required strength of
sites, the sequence dealkylation of ethylbenzene > disproportionation of ethylbenzene
> dehydration of cyclohexanol.
In a more recent study, Guisnet and co-workers [1141 used the following set of test
reactions: isomerisation and cracking of: ( l ) , n-hexane ( a t 673 K); (2), 2-methyl pentane
( a t 673 K); (3), 2,4 dimethyl pentane ( a t 623 K); (4), 1,2,4 trimethyl pentane (at 625 K);
isomerisation and disproportionation of: (51,o-xylene (at 623 K);(61, 1,2,4-trimethyl
benzene ( a t 625 K) and (7), 3,3-dimethyl 1-butene ( a t 473 K).The reaction rates were
extrapolated to 625 K.
Their results suggested t h a t the required strength of the acidic sites, catalysing
these reactions, decreases in the above sequence from (1)to (7).
I t appears that this approach could be further developed and may provide another
possibility of scaling the acidity strength of sites quantitatively through the activation
energies of a set of suitable model reactions.

CONCLUSIONS
While well-established techniques are available for identification of acidic centres
in zeolites and quantitative determination of their density, improved methods are still
required for characterisation and reliable measurement of acid strength and strengths
distribution. For this purpose, temperature-programmed desorption (TPD) of suitable
probe molecules seems to be appropriate provided that possible experimental sources of
error (limitations in mass and heat transfer, effects of geometrical arrangements, etc.)
are avoided. In this case, evaluation of the TPD data on the basis of a valid kinetics
model may provide quantitative results such a s number of types of sites involved, frac-
tional population of these sites, activation energies of desorption (Ed,,), and distribu-
tion of Edes. However, in order to identify the nature of the sites from which the probe
molecules desorb complementary experiments (such a s IR or 'H MAS NMR measure-
ments) are necessary. TPD of NO, monitored by ESR, seems to offer a valuable tool for
characterisation of Lewis sites.
Microcalorimetric measurements of the heat of adsorption released by sorption of probe
molecules onto acidic sites is a very attractive way to quantitatively determine their
strengths. However, analogous to the case of TPD, complementary measurements are
required to assign the calorific data to the types of active centres involved.
Correlating of the rates of a suitable set of test reactions to the strength of the cata-
lysing acidic sites is an attractive alternative. This method deserves further develop-
ment since it could provide a relative simple and fast technique which does not require
sophisticated equipment.
 153

ACKNOWLEDGEMENT

Contributions from colleagues, in particular from Dr. Vera Dondur, Prof. Dr. Richard
Fiedorow, Dr. Linda Jozefowicz, Dr. Jurgen Ladebeck, Dr. Jurgen Schweckendiek a n d
Dip].-Phys. Frank Witzel are gratefully acknowledged. The author is indebted to
Dipl. Phys. Uwe Hartel, Mrs. Erika Popovic and Mr. Walter Wachsmann for excellent
experimental assistance.

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G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 157
0 1991 Elsevier Science Publishers B.V., Amsterdam

ACDITY and BASICITY in ZEOLITES

D. BARTHOMEUF
Laboratoire de RCactivitC de Surface et Structure, URA 1106, C.N.R.S., UniversitC P. et M.
Curie, Paris, France

ABSTRAm
The paper presents correlations between the acidity and the basicity of zeolites. Basic sites are of
the Broensted or Lewis type. The last ones which occur the more frequently consist of the oxygen
atoms of the framework. The charge on the oxygen, which gives information on the basic strength,
can be calculated and the basicity can be experimentally measured using for instance pyrrole as a
probe molecule. Several parameters are identified as affecting the basicity. They are the
electronegativity of the framework atoms, the bonds angles and bond lengths, the structure ionicity,
the crystallographic sitting of the oxygen, the location of Al (pairs, Al gradients). The properties of
basic zeolites in adsorption and catalysis, their resistance to poisons, are presented in relation with
their basicity.

INTRODUCTION
For many years the attention on the main chemical properties of zeolites has been focussed on their
acidity which gives rise to a large number of applications in acidic catalysis. Little has been
published on the zeolites basic properties and on their applications in catalysis and adsorption (1-5).
It is well admitted that Broensted acids and bases are conjugated and that weak acids have strong
conjugate bases and reciprocally strong acids have weak conjugated bases (6). The existence of
protons in zeolites has to be associated with that of basic sites. The paper will consider the factors
which characterize the number and strength of both sites. It will not consider the case of cationic
framework which are not known presently, but it will focus on the family of (Si-AI) zeolites giving
reactions typical of basic centers. One of the first reaction tested in that sense in the side chain
alkylation of toluene with methanol (1,2) which is favoured on basic zeolites over the ring
alkylation catalyzed by acids. The catalysts are X type faujasites i.e. materials with a high A l
content and exchanged with Rb and Cs in the alkaline cation series. Dehydrogenation of
isopropanol is also favoured on the same type of catalysts (7).
158

NATURE OF ACID AND BASIC SITES

The study of protonic and non protonic acidity of zeolites has been the subject of very important
research. The Lewis acidity arises from Al or other cationic species, alkaline, alkaline earth or other
cations. In a similar way the basic sites may be considered of the Broensted or Lewis type. The
first one consists of basic OH groups and the second of the framework oxygen atoms. The charge
on these oxygen determines their strength. Some major differences have to be noted specifically for
zeolites in the characteristics of the acidity and of the basicity. Considering first protons, their
theoretical number is equal to the number of AlOb tetrahedra whose charge has to be neutralized,

i.e. to the A1 content. It is also accepted that their strength increases as the A1 content decreases.
The protons are mobile, jumping from oxygen to oxygen and may approach the reactant to form a
cxbocation. The number of Lewis acid sites (extraframework Al or compensating cation) depends
on the zeolite pretreatment for the Al or on the degree of cation exchange for the other cations. For
basic zeolites, most of the samples used do not contain much Broensted basicity, but mainly Lewis
basicity. The number of potential basic sites is equal to that of oxygen atoms in the framework. The
difference from one zeolite to the other is determined only by the charge on the oxygen, i.e. by the
basic strength and by the degree of heterogeneity of the charge distribution, some oxygen being
possibly more basic than others due to different bond angles and bond lengths. In addition and by
contrast with the protons these framework oxygen are not mobile and the reactant has to adjust
itself to the structure geometry which may induce structural selectivities in adsorption and catalysis.

STRENGTH OF BASICITY AND ACIDITY

A large number of studies, experimental (8) or theoretical (9) have been devoted to the
characterization of the acid sites, number, strength and location. The calculation based on the
principle of the equalization of the Sanderson electronegativity of the atoms constituting a
compound (10) gives an approach of the average charge on the proton (1 1) or on the oxygen
(1 2,13). The intermediate electronegativity of a substance. Sint. gives the mean electronegativity of
the atoms of the compound, which is the same for all of them. It suggests to rank the zeolites
according to their Sinl value. The results depend in fact only o n the chemical fomiula and not on
structural parameters. It will be shown funher that some advantage may be taken from this.

Acidity
The known increase in protonic acid strength with decrease in A1 content is exemplified in figure
1, curve a, giving the charge on the proton calculated from Sin1 (10,ll). The acid strength can also
be decreased by exchange of a part of the protons by metallic cations, the stronger sites being
exchanged first. It is also well accepted that these results obtained by considering Sinl values give
only trends. Each zeolite structure and topology will superimpose other specific parameters.
 159

Basicity
The paper is focussed mainly on Lewis basicity since the oxygen atoms exist in all the zeolites
frameworks. The Broensted basicity is less often present and in addition some OH may be
amphoteric which makes the study less clear (14). The Lewis base strength can be calculated or
determined experimentally.
i) Theoretical approach
Several methods can be used. Ab initio quantum chemical calculations have been applied to
small clusters (15.16). The use of the Sanderson electronegativity equalization principle (10) gives
an overage oxygen charge value. Curve b in figure 1 reports as a function of the A1 content the
average charge on oxygen for a protonic zeolite. The oxygen charge decreases as the zeolite
contains less Al, i.e. as the charge on the proton rises. This is in line with the concept of conjugated
acid-base pairs (12). One may at that point wonder how the material keeps its electrical neutrality
with a constant number of theoretical basic framework oxygen. It has to be kept in mind that
zeolites are oxyacids. Their formula can be written as T On (OH), by analogy with other oxyacids
such as CI On(OH), (12,17). In zeolites m expresses the Al atomic fraction i n the framework and
consequently the average number of protons per TO2 tetrahedron (n + m = 2). The fomiula for a
theoretical fully protonic X type zeolite (AI/AI + Si = 0.45) is T01.55 (OH)o.45. For a ZSM-5
material with AI/AI + Si = 0.04 (Si/AI = 24) it is T01.96 (0H)o.w. It is known in oxyacids that the
acid strength of the proton increases with n (18), i.e. with the number of oxygen free of protons.
This is in agreement in zeolites with the higher acid strengths at the lower Al contents, i.e. lower m.
The framework negative charge which compensates the positive charge of all the protons is shared
between a larger number of oxygen free of protons at low content, i.e., at high n. The charge bom
by each individual oxygen then decreases and the electrical neutrality is maintained.
The calculation of the average oxygen charges of zeolites fully saturated with alkaline cations
using the same Sanderson approach is reported in figure 1 (curves c to g) as a function of the Al
content. The change in oxygen charge as a function of cations electronegativity is given in figure 2
for different Al contents which correspond to usual zeolites compositions (X, Y,L, mordenite, beta
and ZSM-5). Both figures 1 and 2 show that the higher basicity strengths are obtained at high Al
content and low cation electronegativity. The lowest oxygen charge is obtained for the H forms.
Besides the chemical composition other parameters may affect the charges and their distribution in
the framework. It has been shown for a long time that the charge on the oxygen is larger as the
TOT or OTO angles are narrower and as the TO bonds are longer (19). Then the charge on oxygen
depends on the structure and in a given structure on the oxygen crystallographic site considered (4
types in faujasite, 10 in mordenite, 26 in ZSM-5). The introduction in a framework of elements
other than Si and Al will change not only the electronegativity but also the bond angles and bond
lengths and very likely the charge on the oxygen. For instance the replacement of Si by Ge in an X
zeolite increases the measured oxygen basicity (20) while the simultaneous rise in Sint value would
suggest a lowering of basicity. One may expect that the presence of other elements like B, P or of
all the elements known to exist in S A W S , MeAPSO's and EIAPSO's materials also generates very
160

-&1 62

n
E J
aJ 0.4
m 0.4 7
m
%
X ru
0
0
r 3
0
0.3 0.3
aJ %
n
m
L 1
0
m
r ln
u 0.2 lD
0.2 7J

0.1
0 0.1 0.2 0.3 Al/Al + S i

Fig, 1. Calculated charge on oxygen and on proton as a function of the A1 content. (a) (b) Protonic
zeolite and zeolites exchanged with (c) Li, (d) Na, (e) K, (f) Rb, (9) Cs

specific basicities. As to the structure effect, using the Electronegativity Equalization Method
@EM) (21) which differs from the Sanderson approach (10) in that it takes into account structural
parameters, it has been shown that the ionicity of the bonds in a zeolite depends on its
crystallographic structure. Usual zeolites are ranked in the order of ionicity FAU < LTL < MFI
< MOR (21) which is different from their Sin, order ( FAU < LTL < MOR < MFI (figures 1 and
2)). This means that the ionic charge on oxygen and proton in mordenite will be increased
compared to the ones in a less ionic structure, even of similar composition. In addition and
particularly for zeolites with a low A1 content the inhomogeneity in the A1 distribution (possible
paired sites, gradient of A1 concentration ...) will also make the true charge of some specific
oxygen atoms different from the average calculated one. One may expect that the experimental
measurement of basicity will reflect these influences of the structure and of Al location.
ii) Experimental measurement of basicity
Several methods have been proposed to measure the basicity of solid materials (22,23). Some of
them have been applied to the field of zeolites. The use of Co;? as adsorbate is not well suited since
infrared studies showed that physical and chemical adsorption occur simultaneously (24) and that
various and not well defined carbonated species may be generated (25). The shift in the NH
infrared wavenumber of pyrrole adsorbed on basic zeolites may be used to evaluate the basic
strength (20). It showed that NaX are more basic than NaY (20) which is in line with figures 1,2.
Applied to various zeolite structures exchanged with alkaline cations, it is seen (Table I) that some
samples do not show any basicity like ZSM-5 for instance, even in the Cs form (12). For the
faujasite structure pyrrole adsorption detected basicity for all the X samples from LiX to CsX. In
theyseries LiY was not basic and NaY close to the limit detected. These results suggest to draw in
 161

Rb Na
Cs K Li
-61
- 3.0

c
g 0.4
3
0 - - - - - -3.5
C
0
------- +
.-C
v)

a,
0.3
m
1
U
,4.5
9
4
0.2 I 1 8
0 1 2 E l ectronegativ i ty

Fig. 2. Calculated Sint and charge on oxygen as a function of cation electronegativity for usual A1
contents of zeolites (a) X, (b) Y, (c) L, (d) MOR, (e) Beta, (0 ZSM-5.

TABLE I
Shift of NH vibration of pyrrole adsorbed on zeolites and calculated average charge on oxygen

Zeolite

csx 240 - 0.461

NaX 180 - 0.413
KY 70 - 0.383
NaY 30-40 - 0.352
KL 30 - 0.356
Na-MOR 30 - 0.278
Na-Beta 30 - 0.240
CS ZSM-5 0 - 0.236
Na ZSM-5 0 - 0.225

(a) Shift of NH from the liquid (from 12)

(b) Charge on oxygen calculated from Sanderson electronegativity (10-12)

figures 1 and 2 the dashed lines which define the range of oxygen charges above which zeolites are
basic and below which the charge on the oxygen is not high enough to generate a significant
basicity. Such a range will be confirmed later in catalytic studies. The limit is around 3.5 for Sint
and -0.36 for the oxygen charge. It follows that none of the hydrogen form has strongly basic
oxygen. This is in general agreement with acid catalysis results. In the alkaline cation materials not
only ZSM-5 but also beta and mordenite should not show any basicity. Nevertheless pyrrole
adsorption studies could evidence an interaction of pyrrole with the basic sites of these two zeolites
(Table I). The oxygen charge in Table I is calculated for the actual composition of the materials
162

studied. It takes into account the fact that the cation exchange is not always 100 % for the major
cation. For X, Y and L zeolites the shifts of NH wavenumber upon pyrrole adsorption are in line
with the expected charge on oxygen while the NH shift obtained for mordenite and beta
demonstrate the existence of basic sites. These two zeolites are then examples of a strong influence
of the structure and/or of the Al distribution on the charge on oxygen which is not taken into
account in the Sanderson electronegativity calculation. In mordenite, cations are in location of low
symmetry and a rather large range of TOT angles exists (26). This structure induces a higher
ionicity of bonds than other structures do (21). In addition Al pairs have been proposed to exist in
niordenites (27). The existence of small bond angles, of a high bond ionicity and of Al pairs may
explain the presence of basic sites. The structure of beta zeolite has been determined (28) but little is
published for this zeolite on bond angles, bond lengths, bond ionicity and A l location. The
behaviour of beta zeolite in catalysis (29) suggests that it is less strongly acidic than its chemical
composition would suggest. Both this too weak acidity and simultaneously the present too high
basicity show a very strong influence on the framework charges of parameters related to the
structure and very likely on A1 location at this very low Al content (Al/Al+Si in the range of 0.07 to
0.09).
In the case of faujasite another probe has been also used to evaluate the basicity. Benzene just fits
the twelve ring window where it can interact weakly through the -CH with the basic framework
oxygen (30-33). I n the alkaline cation series the infrared shift of yCH and the amount adsorbed in
the 12-R window increases from the Li to the Cs form reaching a significant shift for the more
basic Cs materials (31). The LiY sample adsorbs benzene only very weakly on the oxygen showing
a weak zeolite basicity. These results are in agreement with the pyrrole adsorption results and with
the calculated results of figures 1 and 2 showing the limit basicity range. In beta zeolite a significant
interaction of benzene with the 12 R window is seen (34) which is surprising if one takes into
account only its Al content (i.e. Sinl) but which is in line with the pyrrole results.
iii) Correlations aciditv-basicitv
The opposite change in the charge of proton and oxygen seen in figure 1 should also exist for the
acidic strength of metal cation versus the oxygen basicity when no protons are present. It was
shown by the interaction of pyridine with the alkaline cations acting as Lewis sites that the Lewis
acidity decreases from Li to Cs in the alkaline cation series in faujasites (12,35).
It was also shown that the acid strength for a same cation is higher in Y than X (12) which is
parallel to the change in H+ charge with the Al content. One may conclude that generally speaking
the acid strength of a metal cation should be high at low Al content, i.e. in highly siliceous zeolites
or dealuminated materials, while the framework basicity should be low. This agrees with the
existence of conjugated acid-base pairs.
At this point the advantage of considering Sin1 for predicting trends in acid-base propenies of
zeolites has to be considered. The cases of mordenite, beta and GeX clearly show that the
predictions based on chemical composition alone are not confirmed by experimental results. A
major conclusion is that a strong influence of other parameters, (structure, topology, bond ionicity,
Al distribution) becomes very important for those materials. This opens a field of research for
 163

Characterizing what in zeolites properties (acido-basicity, ion exchange, influence on supported

metals ...) is relevant mainly to chemical composition or to other parameters. The characterization
of these parameters will lead to a better understanding and then to prediction of the properties.
Another consequence is the guide line given by these results for obtaining highly basic zeolites.
Following the trend of increasing basicity at high Al content, i n the faujasite family the highest
possible value is obtained in X. In mordenite and beta for which AVAI+Si ratios are 0.17 and 0.07
respectively one may expect quite higher basicity at high Al levels by a combined effect of Sin*,
structure, topology and Al location.
Once a given structure is ranked by comparison with faujasite taken as a reference, it would be
possible, for this structure to prepare a large series of samples with predetermined Lewis acidity
and basicity by choosing the right Al content and the right cation. The family of samples could then
be used to direct the properties in adsorption and catalysis.

USE OF BASIC ZEOLITES IN ADSORPTION

In adsorption, non protonic zeolites are commonly used i n order to prevent any catalytic
transformation of the adsorbates on acid sites. The Na or Ca forms of A, X, Y, mordenite ... have
been used extensively in fundamental studies or in applications (36,37). Besides separations of
mixtures based on differences in the kinetics of diffusion of the adsorbates in the zeolite pores a
number of separations rely on subtle differences between the adsorbates when they are in the
adsorbed state in the zeolite cavities and channels. Two examples will be given.
The first one concerns the separation of the four C8 aromatics. They have very close boiling
points and selective adsorption on zeolite is well suited in that it avoids very difficult distillation or
crystallisation separations. The preference of the zeolite for a given isomer strongly depends on the
solid. In the faujasite series KY prefers p-xylene (38-39). NaY m-xylene (40) and RbX and CsX
ethylbenzene (41). Ethylbenzene is rejected from CaY or CaX (42). A correlation was observed
between the Y zeolite acidity and the p-xylene selectivity (38). In the X and Y zeolites it was
shown that the order of preference for the isomers may be related to the adsorbent intermediate
electronegativity (5) i.e. to its basic character. The relative x basicity (43) of the aromatics
increases from ethylbenzene to p-xylene and to m-xylene (Table 11). The order of increased K
basicity parallels that of increased electronegativity of the zeolite selective for each isomer
(Table 11). The Cg aromatics interact only with the cations through their 7c electrons and due to
steric hindrance not with the framework oxygen as benzene does. The results of Table I1 suggest
that the interactions aromatic-cation are governed by a balance between the aromatic basicity and the
Lewis acid character of the cation in the zeolite, itself related to the zeolite electronegativity. For
beta zeolite, Figure 3 reports selectivity values in the separation of ethylbenzene from p-xylene in a
mixture of the four Cg aromatics (45). The selectivity factor a12expresses the ratio of the
concentrations of compound 1 in the zeolite and i n the liquid phase to the corresponding
concentrations of compound 2. Values of a12 higher than one indicate the preferred adsorption of
compound 1 in the zeolite. Figure 3 shows that any form of beta zeolite tested (protonic or saturated
with alkaline cations) is selective for ethylbenzene over p-xylene (and over the o - and m - forms
164

also) (45) as the basic faujasites NaX to CsX in Table 11.

TABLE I1
K basicity of c8 aromatics and Sin1 values for zeolites selective for each isomer

Zeolite Sint Selectivity for EB, PX or Ref

MX@)in a mixture of the
four C8 aromatics
- - -
EB PX Mx
(1.5)@) (1.6) (2.0)

Cs5oNa3d( 3.03 X 41c

Rb53Na33X 3.08 X 41,
RbyjMggNa14X 3.18 X 41,
KX 3.15 X 41c
NaX 3.25 X 41,
K%Na2Y 3.38 X 4 h
NaY 3.54 X 4ob

(a) EB : Ethylbenzene, PX : paraxylene, Mx : metaxylene

(b) K basicity (from 43 )

Rb
Cs K Na H

X
a
--.
m
W

0 1

0
9 4.0 4.1
'int

Fig. 3. Separation coefficient between ethylbenzene and p-xylene as a fonction of the intermediate
electronegativity of beta zeolite exchanged with (o)Cs, (0) Rb, (n) K, @) Na, (A) H.

The values of Sint for beta lie in a range - 4 to 4.2 - which is usually obtained in acidic zeolites
(Figure I). As previously for pyrrole (Table I) or benzene adsorption, beta zeolite looks like much
more basic that one would expect from the Sin1 calculation. This confirms the strong influence of
the structure or/and Al location on the charges born by the atoms in this zeolite. This is also in line
with the moderate acidity of this material (29).
The second example of separation on basic zeolites is given by the changes in the separation
 165

coefficient a between methyl-2 and methyl-1 naphtalenes (46). The authors observed a decrease in
the C I ~ M N I I M N coefficient as Sin, increases upon alkaline and alkaline earth ion exchange. The
curves are distinct for X and Y zeolites.

USE OF BASIC ZEOLITES IN CATALYSIS

Basic catalvsis
For a long time reactions involving zeolites containing metallic cations but no protons have been
proposed (47). Many of them may be relevant to basic catalysis, like reactions involving H2S. For
the transformation of furan to thiophene (47) it has been shown that H2S dissociation occurs to
generate mainly HS- and H+ species which are adsorbed in NaX on the Na+ cation and
framework oxygen respectively (48). The activity of X zeolites exchanged with the different
alkaline cations in the reactions of CH3OH CH3SH and C2HsOH a C2HsSH is the
highest for the zeolites with lowest Sint, i.e. for the most basic (49).
Reactions like isopropanol dehydration, alkylation with methanol of toluene or of other
aromatics and reactions involving heteroatoms (N,O ...) have been reviewed elsewhere ( 3 3 . It
has to be pointed out that for the toluene alkylation with methanol the alkylation of the ring or of the
chain is obtained on acidic or basic zeolites respectively. A correlation was shown between the
extent of alkylation in each case and the electrostatic potential of the cation, the lower the
electrostactic potential, the higher the side chain alkylation (50). A similar relationship was latter
obtained considering the zeolite intermediate electronegativity and the yield of products.
Interestingly the limit of acidic or basic zeolites defined by the selectivity of this reaction is at a
value of Sinl close to 3.5 which is in agreement with the limit range already reported in figures 1
and 2. Recently it was shown that the condensation of benzaldehyde with derivatives of malonic
esters has an increased activity for the fmjasites giving the highest NH shift in adsorbed pyrrole
i.e. having the strongest basicity from Table I. Similarly GeX zeolite is very active in condensation
reactions (53) which is in line with the strong basicity of this zeolite (20).
Supported metals
A few works are related to the study of metal supported basic zeolites. It is well known in the
field of acidic zeolites that the electronic properties of the metal are modified through an electron
transfer from the zeolite acid sites to the platinum particles (54). One may expect for basic zeolites
an effect in the opposite direction. The influence of such a metal-support interaction explains that
the extent of N i reduction is increased for the more basic NaX compared to NaY and that the
presence of Ce3+ cations , able to give Ce4+ ions and one electron favors this reduction in CeNaX
(55).
The catalytic properties of the supported metallic particles also depend on the acidic or basic
character of the zeolites. The hydrogenation of CO to olefins and paraffin over RuY zeolites
increases for the formation of unsatured hydrocarbons as the zeolite basicity rises from Ru
supported on Nay, to KY and CsNaY (56).
In the case of PtL zeolites in the alkaline cation form the activity for the dehydrocyclization of
n-hexane to benzene increases from Li to Cs form. This was related to an increased electron
166

transfer from the zeolite to the Pt particles (57). Such an explanation appears to be also valid for the
alkaline earth forms (58). Figure 4 reports the change in benzene yield in n-hexane aromatization as
a function of oxygen charge and Sin1 evaluated from (57,59). The more active catalysts (Rb and Cs

3.65 3.60 3.55 'int

1 I
'. I

-0.34 oxygen c h a r g e

Fig. 4. Benzene yield in n-hexane dehydrocyclization at 733 K (ref 59) as a function of Sinl and
oxygen charge of PtL zeolite exchanged with (0)H, ( 0 ) Li, (A) Na, 0)
K, g)Rb, (A) Cs.

forms) for the production of benzene have the lowest Sinlvalues. This reaction is monofunctionnal,
the active sites being the Pt atoms (59). The results confirm that a high zeolite basicity increases the
aromatization activity of the Pt sites. The change in the electronic state of Pt was also shown from a
decrease in the amount of CO adsorbed on Pt and in the benzene hydrogenation activity in L
materials (58). In a series of Pt faujasites of the X or Y type exchanged with H, Na or Cs cations,
the wavenumber of CO adsorbed on Pt particles decreases simultaneously with the benzene
hydrogenation activity from the acidic to basic zeolites in the order PtHY > PtHNaY > PtNaY >
PtNaX > PtCsX (44a,60,61). Simultaneously the apparent activation energy increases from 48 to
120 KJ.mole-1 which precludes any explanation based on diffusion due to the steric hindrance of
the big Cs ions. The results show that the intrinsic electronic properties of the platinum are
gradually changed following the decrease in acidity and increase in basicity of the zeolite.
Figure 5 gives a scheme summarizing the continuous changes in properties from the strongly
acidic to the highly basic zeolites. Choosing the right Al content and the right cation is a way to
adjust for a given zeolite the properties to the expected behaviour of the solid in adsorption or in
catalysis.
Resistance to sulfur
The experimental results presented here indicate that the zeolite basicity may direct the properties
of supported metal . Changes i n the metal particles properties may be induced not only by the
 167

zeolite but also by the species adsorbed on the metal. For instance sulfur atoms formed by
decomposition of sulfur compounds are electronegative and favor an electron transfer from the Pt
particles to the sulfur (62). In the case of Pt supported on acidic zeolites, the Pt-S bond is loose
since less electrons are available in the metal due to the Pt-acid interaction (62). One may expect that

4.0 3.5 3.0

I 1 I
'int
0.30 0.40
1 I
-6
(oxygen)

acidity basic i ty
4 strength
increase increase

-
4
increase

1 benzene
increase decrease
hydrogenation
4 e N-hexane
decrease increase a r o m a t i za t ion
4
increase decrease
* resistance t o S

Fig. 5. Change in properties of zeolites with their electronegativity.

on the opposite, due to the electron transfer from the basic zeolites to the Pt particles, more
electrons are available in the metal to form a strong bond Pt-S. Sulfur should be a stronger poison
for m a s i c zeolites than for Pdacidic zeolites. This is in fact observed, the PtKL or PtBaL zeolites
active in the n-hexane dehydrocyclization are very sensitive to sulfur (63).

CONCLUSION
The basicity of zeolites, like acidity, varies i n a large range from weak to strong. Several
parameters which direct this basicity have teen identified. They give trends and guide lines for the
increase in basicity. The easiest of these parameters to act on are the A1 content and the
electronegativity of the cation. For instance in the case of zeolites like mordenite or beta which
show some basicity despite their low Al level, an increase in the A1 content should give a stronger
basicity. In the search of new selectivities in adsorption and catalysis, the basic zeolites offer a large
range of opportunities.

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This Page Intentionally Left Blank
G . ohlmann c s t a!. (Editors 1, Cakdysis and Adsorption by Zeolites 171
(01991 Elsevier Science Publishers R.V., Amsterdam

MATRIX vs ZEOLITE CONTRIBUTIONS TO THE

ACIDITY OF FLUID CRACKING CATALYSTS

ROLAND VON BALLMOOS AND CHI-MI T. HAYWARD

Engelhard Corporation, Menlo Park, CN28, Edison, NJ 08818, USA

SUMMARY

The matrix of fluid catalytic cracking (FCC) catalysts

serves multiple functions: it gives the microspheres their
physical strength and the attrition resistance necessary to
withstand the stresses of rapid circulation in the FCC unit and
protects the soft zeolitic particles from abrasion. The matrix
also serves as a cracking component for gas oil molecules which
are too large to enter the zeolitic pores. This second function
is extremely important for achieving the high conversions and high
gasoline selectivities of today's FCC catalysts. The proper
choice of matrix chemistry and its balance with the zeolite
component are the keys to reduced gas and coke makes at high
catalyst activity while maximizing the liquid product yield.
We investigated the influence of low, moderate, and
strongly acidic matrices and their synergisitc contributions to
the catalyts' activity. "Staged bed" MAT experiments demonstrated
that the overall conversion and gasoline yield were drastically
increased when gas oil molecules could interact with the matrix
material first, before contacting the zeolite. Secondary cracking
on the matrix of products initally generated inside the zeolite
was negligible. The strength of the acid sites in the matrix
influences the coke make. A matrix component with moderate
acidity was found to result in the most beneficial selectivities.

INTRODUCTION
Modern fluid catalytic cracking (FCC) catalysts
represent a highly sophisticated class of materials. In
principle, they consist of approximately 15 to 35 wt-% of an
active zeolite component in an amorphous or clay matrix with a
minor amount of an oxide binder. Yet, on a microscopic scale
the composition of the 60 to 9 0 micron size microspheres is
considerably more complex: many different forms of zeolite Y, a
172

faujasite type material, with great variations in silicon-to-

aluminum ratios and rare earth levels are used depending on the
selectivity demands of the refiners.
Several recent reviews on FCC catalysts have been
published dealing with either overall catalyst properties and
performances [1,2,3] or investigating zeolite modifications and
their effects on selectivity [4]. They describe in detail the
effects of varying the silicon-to-aluminum ratio of zeolite Y and
highlight differences resulting from ultrastabilization
(dealurnination) by thermal, chemical, or thermo-chemical
treatments. The beneficial influence of the zeolite's rare earth
oxide (REO) content on stability and gasoline yields have been
known since the early days of FCC cracking with zeolites.
Ultrastabilized Y zeolites, however, generate higher octane
gasolines at a yield debit. In order to achieve an optimal
compromise, many of today's FCC zeolite components represent
ultrastabilized rare earth exchanged faujasites.
The equally significant variations in catalyst matrices
and binder materials are usually given less attention in
scientific investigations of cracking catalysts. Nevertheless,
several reviews have been published recently [5,6]. This
presentation focuses on the importance of the matrix contributions
to FCC cracking, the matrix properties, and their influence on FCC
catalyst selectivities.
Modern FCC catalyst matrices can be separated into
four classes: aluminas, silicas, silica-aluminas, and clays.
The chemical and catalytic functions of these matrices may vary
quite significantly, as demonstrated below, but they all share
some common functions as FCC matrices.
The matrix provides the suitable particle size and shape
for fluidized bed operation, nominally 60-90 micron spheres. FCC
zeolite particles are less than 2 microns in size and very soft.
The matrix materials render the microspheres attrition resistant
and reduce the loss of active zeolite components. Because the FCC
unit is heat balanced without much external heat input (only for
feed preheat to approximately 250 OC) the endothermic cracking
reaction requires the microspheres to serve as a heat transfer
medium to vaporize the feed and to crack the hydrocarbons. The
heat is provided by burning coke off the catalyst in the
regenerator. It is then transferred by the hot ( - 730 OC)
microspheres to the riser section of the unit. The matrix
furthermore serves as an adsorbent and scavenger for feed
contaminants such as nickel, vanadium, sodium, iron, sulfur, and
nitrogen. An additional function of the matrix is to provide
easy access for feed molecules to the active sites of the zeolite.
A major function of the matrix is the cracking of feed
molecules which are too large to enter the zeolite's pores. The
kinetic diameter of molecules with boiling points above
approximately 450 OC (atmospheric equivalent) is larger than the
7.5 A pore of faujasite [7]. Depending on feed cut points a
signifcant fraction of the molecules may fall into this category
of compounds which have to be cracked on the matrix first. We
have investigated this process in some detail by separating the
functions of the matrix and the zeolite. Some aspects of this
work have been published in a recent paper [a].

EXPERIMENTAL
The experimental catalysts used in this study were
commercial FCC microspheres with a clay based matrix which were
combined with surface area-stabilized silicas doped with metal
oxides to generate model matrix compounds with different intrinsic
acidities. We used an Engelhard rare earth exchanged US-Y
catalyst as the base case. The weakly acidic matrix material was
prepared by using a commercially availbale silica support modified
by a metal oxide. The moderatly acidic model matrix was based on
the same,silica modified with a group IIA metal oxide. The
strongly acidic matrix was generated by leaching aluminosilicate
clay microspheres. In some experiments, aluminum oxide was
deposited on the above silica to simulate a strongly acidic matrix
with variable site density.
The zeolitic FCC particles were steam deactivated
separately to simulate typical FCC equilibrium catalysts for 4
hours in 100% steam at 788 OC. The model matrix components were
either steamed at 732 OC for 8 hours in one atmosphere steam or
calcined at 580 OC to provide the target acid strength.
The catalysts' activity and selectivity patterns were
then determined in a modified MAT unit (modified ASTM D-3907
test). Figure 1 shows a schematic process flow diagramm of the
MAT test modified by Engelhard [9]. Figure 2 shows the catalyst
bed arrangement for the two different types of experiments. In
the "Catalyst on Top1@configuration, 3 g FCC catalyst were loaded
into the reactor tube on top of 3 g appropriately sized matrix
component. Because the reactor was of the down-flow type, the
zeolite-containing FCC catalyst was contacted by the feed first.
In the "Matrix on Top" configuration, the loading order was
inverted and the matrix component was added on top of the FCC
catalyst'bed. 1.2 g of a Mid Continent gas oil were fed in 48 s
(catalyst-to-oil ratio of 5 ) at 490 OC. The liquid product
syncrude was analyzed by GC simulated distillation (ASTM D-2887),
the gas fraction was analyzed by GC, and the coke on catalyst was
determined by a LECO coke analyzer. Activity is defined as weight
percent of gas oil converted to products boiling below 216 OC and
coke, or as a dimensionless activity based on second order
kinetics, where Activity = Conversion/(lOO - Conversion).
 w

ENGELHARDS MAT PROCESS FLOW SCHEME P

-1

CHROYATOORAPHK:
DELIVERV ZONE 'ROGEN

I
IL W l V E R V TUBE
CALIBRATION
GAS INLET

GAS COLLECTION
CATALYST BED
RESERVOIR

GLASS REACTOR
ZONE FURNACE
MEAT

0 % COOUNT

Figure 1: Schematic flow diagram f o r MAT unit modified by

Engelhard based on ASTM D3907 test.
 176
Q a,
-
.-
c,
P U
a, N
0
a,
S
-
a, I ' I'
0 LL
a,
.-X a,
L
c,
.--
c,
0
a,
N
Figure 2: Catalyst bed arrangement for "Staged Bed" MAT
experiments used to demonstrate the importance of matrix
cracking before zeolite cracking in FCC.
?
--
-1

Synergistic Interaction Between Matrix

-i

c
r.
9
ri
ID
..
W and Zeolite Increases Cracking Activity
MAT A c t i v i t y

2.5 -

I
2-
I

1.5 ~~

1-

0.5 -

0-
Matrix Zeolite Calculated Measured
Catalyst In MAT .Test
Activity = Conv./(lOO-Conv.)
J
9
Conversion to Prod. < 216 C
 177

RESULTS AND DISCUSSION

We are reporting three sets of experiments which
demonstrate the importance and beneficial effects of an optimal
balance between the zeolitic cracking component and the amorphous
matrix material: A first experiment highlights the synergistic
effects of matrix and zeolite cracking. A second set of data
shows that the matrix component is most effective in cracking
large molecules before they are further converted to gasoline
inside the zeolite. A third experiment distinguishes between
matrices of different overall activity, expressed as a combination
of acid strength and acid site density.
Zeolite - Matrix Synergism:
A rare earth exchanged zeolite catalyst with minimal
matrix activity showed an experimental MAT conversion of 5 2 wt%
(activity = 1.1). A moderate activity amorphous material, when
tested by itself in the absence of a zeolitic cracking component,
yielded 30 wt% MAT conversion (activity = 0 . 4 ) .
A third catalyst was prepared from a blend of the first
two materials. It had the same zeolite activity as the first,
combined with the identical amorphous matrix activity of the
second. If the effects of the matrix and the zeolite were
additive, the activity of Catalyst 3 would be calculated to be
1.1 + 0 . 4 = 1.5. In fact, when the MAT activity was determined
experimentally it was 2.2, with a conversion of 69 wt%. These
results are represented graphically in Figure 3 .
. The substantially greater than expected activity of
Catalyst 3 indicates that significant interactions between the
components occurs. The synergism can be explained by a mechanism
of initial matrix cracking of large feedstock molecules to smaller
fragments which are subsequently cracked into the gasoline and gas
range inside the zeolite. Approximately 20 % of the MAT gas oil
molecules are too large to enter the zeolite's pores. They have
to be cracked on an easily accessible matrix first. In fact, the
MAT data of Catalyst 2 showed 30% conversion, primarily of heavier
molecules which are cracked more easily over a moderately acidic
matrix. The matrix cracking does not produce converted products
in the gasoline range, but rather it generates "intermediate feed
molecules". The conversion of these harder-to-crack molecules
requires the enhanced activity of the zeolite. A recently
published study demonstrated the effectiveness of matrix-type
"bottoms cracking additives1'to conventional FCC catalysts in
increasing their activity [lo]. The results of our experiments
confirmed that separate particle matrix components were in fact
active in pre-cracking gas oil molecules.
The hypothesis of "matrix first" cracking was further
investigated by separating the matrix and zeolite components
178

TABLES

TABLE I - Staged bed MAT tests Moderate Matrix/REY

..................................................................
Description Matrix first Zeolite first
Conversion, wt% 69.0 51.0
Activity,conv./(lOO-conv.) 2.2 1.0
Yields,wt %
Bottoms ,>602OF (352OC) 10.2 24.5
Gasoline,Cg -421°F (216OC) 54.4 41.9
Dry Gas rH2-C2 1.0 0.6
Coke 3.1 2.2
Selectivities, (yield/activity)
Dry Gas 0.45 0.60
Coke 1.40 2.20
..................................................................

TABLE I1 - Staged bed MAT tests Moderate Matrix/=-USY

Description Matrix first Zeolite first

Conversion I wt% 75.05 65.75
Activity,conv/(lOO-conv.) 3.01 1.92
Yields, wt %
Bottoms, > 602OF (352OC) 6.84 12.66
Gasoline,Cg -421°F (216OC) 55.54 51.01
Dry Gas ,H2 -C2 1.50 1.20
Coke 4.06 3.18
Selectivities, (yield/activity)
Dry Gas 0.50 0.62
Coke 1.35 1.66
-_______________________________________------------
 179

physically and by reversing the order in which the gas oil

molecules contacted the active sites:

Importance of Matrix Cracking Before Zeolitic Cracking:

We designed "staged bed" MAT experiments to verify the
concept that conversion to desirable products depends on the feed
contacting the matrix first. For the matrix-on-top experiments
the FCC catalyst was carefully poured into the bottom of the MAT
reactor tube. The matrix component was poured on top of this bed
carefully to avoid mixing of the two components. The feed was now
forced to percollate through the Ilmatrix bed" first. In the
zeolite-on-top experiments the order of the components was
reversed. The spent catalyst beds were thoroughly mixed before
the coke analysis to obtain a reliable average carbon residue
number.
We repeated the experiment three times: first using a
lower activity grade, high rare earth catalyst combined with a
moderately active matrix, secondly using a more active "octane-
barrel" moderate rare earth catalyst with a moderatly active
matrix, and thirdly a combination of the octane barrel catalyst
with a more strongly acidic but not very active matrix (lower
surface area). The activity and selectivity results are
summarized in Tables I through 111, respectively.
In all three cases the effect of matrix cracking of the
fresh feed was clearly present. Very little conversion of zeolite
products occurred when the matrix was downstream of the FCC
catalyst. The MAT activity of the samples with the "matrix-on-
top" was 1.5 to over 2 times higher, depending on the initial
activity of the FCC component. Similar effects had been observed
before by other investigators [ll]. Figure 4 shows the drastic
conversion increase for the 9natrix-on-topIl sample to valuable
products, accompanied by a reduction in bottoms compounds (boiling
above 317 OC).
The absolute conversion differences between the less
active REY and the more active octane-barrel RE-USY catalyst
introduce a bias to the selectivity numbers: the REY yields high
gasoline (at lower octane), whereas in the other two comparisons
the gasoline yield is relatively smaller, but at higher octane.
The difference in conversion is largely due to the increased
production of wet gas (c3 and c4 olefins and paraffins) in the
experiments with the octane-barrel catalyst.

Matrix Type Optimizes Cracking Selectivity:

In a final set of experiments, we studied how the
product selectivity and octane yield can be optimized by selecting
a matrix with a balanced combination of acid strength and site
density. These experiments were carried out in the traditional
MAT configuration with fully blended components. REY was used as
the active FCC catalyst. The matrix types varied in composition
 Matrix Sets up Large Molecules for
Selective Cracking in Zeolite
Staged Bed MAT, wt-%

80
70
60
50
40
30
20
10
0
Conv. Activ. Gasol. Bottms Coke Dry Gas

Zeolite/Weak Matrix 0 Weak Matrix/Zeolite

 181

and, hence, intrinsic acid strength, and surface area. We

generated MAT data at 70 wt% conversion, shown in Table IV, which
are directly comparable.
Significantly different selectivities resulted depending
on the type of matrix used. Catalyst A, which had the lowest
matrix activity, produced the highest yield of coke and gas and
the lowest yield of the most valuable products, gasoline and LCO.
The reason for this adverse selectivity was overcracking promoted
by the few very strong acid sites on the matrix. Catalyst B, with
its moderatly active matrix, had the lowest coke and gas yields
and higher yields of the desirable products gasoline and LCO.
Catalyst c , which had the highest matrix activity, produced yields
that generally fell between those of Catalyst A and Catalyst B.
These results suggest that an optimum level of matrix
activity exists for each active zeolite component. If the
activity of the matrix is too low the desired level of heavy
molecule conversion cannot be achieved and the overall catalyst
activity is negatively affected. If the matrix activity is too
high, pr'imarily because the matrix acid sites are too strong, the
catalyst selectivities are severely shifted to undesirable
products, such as coke and gas.

Catalyst A B C

Matrix Activity LOW Moderate Moderate

Acidity Strong Weak Moderate
Surface Area Very Low Moderate High

MAT Yields @ 70 wt-% Conversion

Dry Gas wt% 1.3 1.1 1.2
c3 -I-c4 wt% 11.8 9.7 11.1
C5+ Gasoline wt% 53.0 55.9 54.2
Valuable Products
Gasoline+LCO wt% 71.2 75.6 74.7
Coke wt% 3.9 3.3 3.5
ic4/~4=ratio 2.1 1.5 1.3
..................................................................
182

CONCLUSIONS
Our experiments using REY and RE-USY catalysts with a
minimal matrix activity in combination with model matrix compounds
of increasing intrinsic acid strength have clearly demonstrated
the following principles:
- A strong synergism exists between matrix and
zeolite cracking under FCC conditions. The resulting
activity is higher than the sum of the individual
contributions.
- It is imperative that the larger feedstock
molecules contact the matrix component first t o convert
them to smaller fragments which can be cracked inside
the zeolite to gasoline products.
- Matrix activity is a combination of acid site
strength and density. A moderately active matrix
results in a properly balanced FCC catalyst with optimal
gasoline and coke selectivities.

The FCC catalyst matrix plays a key role in determining

overall activity, selectivity, and octane trends. The FCC
catalyst manufacturer can control the matrix activity and acidity,
allowing him to tailormake catalysts to meet specific refining
needs.

ACKNOWLEDGMENTS
We acknowledge the expert technical assistance of Mr.
Egberto Villanueva in preparing the Samples for this study. We
are indebted to Engelhard's Petroleum Catalyst hraluation group
for the many experiments, in particular those of the staged
bed configurations. Engelhard's Research Services group provided
the physical and chemical characterization of the samples. We
also thank S.H. Brown, M. Deeba, G.S. Koermer, J.B. McLean, E.L.
Moorehead, and D. Stockwell for many stimulating discussions.

REFERENCES
1. J. Scherzer, Catal.Rev.-Sci.Eng. , 31(3) , 215-354 (1989).
2. P.B. Venuto and E.T. Habib, IIFluid Catalytic Cracking with
Zeolite Catalystsl8, Marcel Dekker, New York (1979).
3. B.W. Wojciechowski and A . ?orma, IICatalytic Cracking
Catalysts, Chemistry and Kinetics", Marcel Dekker,
New York (1986).
4. Reference [l] above, and references therein.
5. A.G. Oblad, Oil and Gas Journal, March 27, 84 (1972).
 183

6. C.J. Groenenboom, "Zeolites as Catalysts, Sorbents, and

Detergent Builders@~,Stud.Surf.Sci.Catal. 46, Elsevier,
Amsterdam, 99 (1989).
7. A. Humphries and J.R. Wilcox, lIZeolite/Matrix Synergism in
FCC Catalysis8@,paper presented at the 1988 NPRA Annual
Meeting (March 1988).
8. C.T. Hayward and W.S. Winkler, Hydrocarbon Processing,
February, 55 (1990).
9. Engelhard Corporation, @IMicro Activity Testing of FCC
Catalystsll, The Catalyst Report, Engelhard Corporation,
Edison, NJ, USA (1988).
10. M.M. Mitchell, H.F. Moore, and T.L. Goolsby, llImprovementof
FCC Catalyst Performance with Bottoms Cracking Additives',
paper presented at the Spring AIChE Meeting, Orland0,FL
(1990).
11. R.E.. Ritter and G.W. Young, paper AM-84-57 presented at the
March NPRA Meeting (1984).
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 185
1991 Elsevier Science Publishers B.V., Amsterdam

ZEOSORB HS 30 - A TEMPLATE-FREE SYNTHESIZED PENTASIL-TYPE

ZEOLITE

K.-H. BERGK1, W. SCHWIEGER', H. FURTIG' and U. HADICKE2

' M a r t i n - L u t h e r - U n i v e r s i t y H a l l e - W i t t e n b e rg,
Department o f C h e m i s t r y , S c h l o R b e r g 2, H a l l e 4020, BRD

Chemie-AG B i t t e r f e l d - W o l f e n , B i t t e r f e l d 4400, BRD

SUvlMARY
The s u b j e c t o f t h i s p a p e r i s t h e s y n t h e s i s o f p e n t a s i l - t y p e

the various synthesis variables -

z e o l i t e s w i t h o u t t e m p l a t e s . We d e s c r i b e i n v e s t i g a t i o n s o f
s u c h as t h e c o m p o s i t i o n o f
the r e a c t i o n mixture, a p p l i c a t i o n s i n a t e c h n i c a l process
and, based on t h e z e o l i t e "Zeosorb HS 30", i n v e s t i g a t i o n s o f
t h e a f t e r - t r e a t m e n t f o r a s p e c i f i c adjustment o f t h e Al-content
i n the l a t t i c e o f the zeolite
a p p l i c a b i l i t y o f the catalyst.
-
which are important f o r t h e

INTRODUCTION
S i n c e 1966 t h e Chemie-AG B i t t e r f e l d - W o l f e n has been t h e
o n l y p r o d u c e r o f m o l e c u l a r s i e v e s i n t h e GDR. The development
s t a r t e d w i t h t h e s y n t h e s i s o f z e o l i t e 4A i n 1960. The r a n g e o f
t y p e s o f m o l e c u l a r sieve, w h i c h a r e produced f u r t h e r i n c l u d e s
t h e z e o l i t e s 3A and 5A, t h e f a u j a s i t e s 13X, 1OX and Y, morde-
n i t e and e r i o n i t e t y p e s and c u r r e n t l y a l s o t h e p e n t a s i l t y p e
Zeosorb HS 30 ( T a b l e 1). The z e o l i t e s a r e used i n v a r i o u s
a d s o r p t i v e and ca t al,,t i c processes.
The range o f p e n t a s i l t y p e b y m o l e c u l a r s i e v e s was w i d e n e d
b y u s i n g a s p e c i a l method. F o r a l o n g time the synthesis of
t h e s e t y p e s was c o n n e c t e d w i t h t h e a p p l i c a t i o n o f s u b s t a n c e s
deternining the structure, t h e s o - c a l l e d t e m p l a t e compounds,
as d e s c r i b e d i n r e f s . 1-3.

TABLE 1
Chemie-AG B i t t e r f e l d - W o l f e n as a m o l e c u l a r s i e v e p r o d u c e r

TYP e
A Fauj a s i t e E r i o n it e Mo r d e n i t e Pent a s i l
~~~~ ~~ ~ ~

Zeosorb Zeosorb Erionite Zeosorb Zeosorb

3A, 4A, 5A 13X, lox, Y VlOO HS30
delivery as powder ( a i r , dried, activated), as g r a n u l e
form:
186

The f i r s t work on t h e a p p l i c a t i o n o f o r g a n i c s u b s t a n c e s i n t h e
p r o c e s s of z e o l i t e f o r m a t i o n was c a r r i e d o u t b y BARRER and
DENNY ( r e f . 4) and KERR ( r e f . 5). T a b l e 2 shows a l i s t o f
v a r i o u s o r g a n i c compounds, w i t h w h i c h p e n t e s i l z e o l i t e s c o u l d be
pr oduc ed i n t h e y e a r s a f t e r 1966. We have grouped t h e s u b s t a n c e s
i n t o categories, such as o r g a n i c c a t i o n s , o r g a n i c a n i o n s and
n e u t r a l molecules, and h b v e l i s t e d t h e names o f t h e a u t h o r s and
the year o f publication, when t h e s e f a c t s w ere known. Important
s t a g e s a r e t h e w o rk s o f ARGAUER and LANDOLT ( r e f . RUBIN
l),
e t el. (ref. 2), KERR ( r e f . 5) and LOWE and AROYA ( r e f . 6).
From t h i s v a r i e t y and g r o u p s o f s u b s tances, the r o l e o f template
compounds i n t h e s y n t h e s i s p r o c e s s c a n be deduced t o b e u n c l e a r
and d i v e r s e ,
The a p p l i c a t i o n o f o r g a n i c compounds i n a process, w h i c h i s
otherwise e n t i r e l y inorganic, ceuses some p r o b l e m s f o r t h e
process i t s e l f , a s w e l l a s f o r t h e economy and t h e q u a l i t y o f
t h e products.
Such pr oble m s a r e , f o r instance:
- the cost o f t h e template;
- t h e p o l l u t i o n o f w e s te w a t e r ;
- s a f e t y problems i n t h e t e c h n i c a l process;
- t h e p o l l u t i o n o f t h e o r g a n i c component b y w aste gas d u r i n g
thermal decomposition;
- t h e c ar bon d e p o s i t s i n t h e z e o l i t e caused b y a p o s s i b l e
i n c o m p l e t e c o mb u s ti o n o f t h e o r g a n i c component.
These d i s a d v a n t a g e s demand t e m p l a t e - f r e e s y n t h e s i s . There-
fore, b e f o r e commencing r e s e a r c h and development w ork on t h e
synthesis of pentesil zeolites, i t was n e c e s s a r y f o r Chemie-AG
Bitterfeld-Wolfen ( a s a p r o d u c e r o f m o l e c u l a r s i e v e s ) and t h e
Research I n s t i t u t e a t H a l l e t o c o n s i d e r t h e b a s i c raw m a t e r i a l s
and t h e t e c h n i c a l f a c i l i t i e s w h i c h were a v a i l a b l e , i n o r d e r t o
make i n d u s t r i a l p r o d u c t i o n f e a s i b l e .
 187

TABLE 2
The d i f f e r e n t t y p e s o f o r g n n i c compounds, w h i c h c a n be used
f o r t h e syntheses o f P e n t e s i l z e o l i t e s

Type Example Author R eference/

year o f publication

Organic R~N+, R ~ P + A rg a u e r and L a n d o l t 1, 1972

cations Dwyer and J e n k i n s 7, 1976
polymeric Kerr 5, 1969
cationic
conpounds
................................
Organic Amine, Rubin e t e l . 2, 1975
molecules Bremer e t e l . 8, 1981
diamine R o l l me n n 3, 1978
alcohols, P o s t and Nanne 9, 1979
dioxane, Klotz 10, 1983
2- amino- Whit t am 11, 1982
-py r i d i n e
................................
Organic Alkylbenzol- Hugiwara e t a l . 12, 1981
anions s u l f onate,
polymeric Roscher e t a l . 13, 1984
anionic Lowe and Aro ya 6, 1983
compounds

SYNTHESIS OF PENTASIL TYPE ZEOLITE

The f i r s t p o s i t i v e r e s u l t s ( T a b l e 3) were o b t a i n e d i n
l a b o r a t o r y t e s t s which looked s p e c i f i c a l l y a t t h e aspect of a
c o n t i n u o u s s i m p l i f i c a t i o n o f t h e t e m p l a t e compounds. The
c l a s s i c a l t e m p l a t e compound TEA-3 ( t e t r a e t h y l a m m o n i u m i o d i d e ) ,
i t s f o r m a l p r e c u r s o r s TEA ( t r i e t h y l a m i n e ) and alkyliodide ,
s i m p l e amines, a t e c h n i c a l m i x t u r e o f amines and a l c o h o l and
NH3 were used. By t h i s method, s p r o d u c t c o n t a i n i n g 60 t o 80 %
p e n t e s i l c o u l d a l r e a d y be p ro d u c e d w i t h o u t u s i n g t e m p l a t e s .
A f t e r optimizing, t h i s c o n t e n t l e v e l c o u l d be i n c r e a s e d
considerably.
188

TABLE 3
S y n t h e s i s o f P ,n ta s i l zeolites with different additions at
175 OC and r e s t e d r e a c t i o n m i x t u r e s

Number Addition Composition of t h e Crystelli- Product

reaction mixture z a t i o n time composition
(2) / 203/ s i O 2 / H20/Z t / h/
Na 2 ~ ~l Ma.-%

TPA-J 5,7 1 100 1580 9,6 142 60 ZSM-5

40 Q u a r t z
TEA + ;? 1 28 750 16 240 30 amorphous
n-Butyl-
-bromid 70 ZSM-5
Technical 8,3 1 93,5 3877 36,7 168 80 ZSM-5
B u t y l am i n 20 Q u a r t z
mixture
N-P r o p y l - 8,3 1 93,5 3877 36,7 96 70 ZSM-5
amin 30 Q u a r t z
NH3 + 8.3 1 93,5 3877 36,7 48 20 sio2-x
C2H5-OH 80 ZSM-5
NH3 25,9 1 88,4 1820 55 24 8 0 ZSM-5
10 amorphous

From t h e s e t e s t s , t h e f i r s t p a t e n t a b l e r e s u l t s were o b t a i n e d ,
and t h e s e a r e l i s t e d i n T a b l e 4.
C a t i o n i c and/or a n i o n i c p o l y m e r compounds a s w e l l as a t e c h n i c a l
m i x t u r e o f amines a r e u s e d as t e m p l a t e s ( r e f s . 13-14). The f i r s t
template-free synthesis w i t h o r without the eddition o f n u c l e i
o f c r y s t e l l i z a t i o n are described i n refs. 15-17.

F i g u r e 1 shows a f i e l d o f s y n t h e s i s f o r t h e t e m p l a t e - f r e e type.
The phases w h i c h c a n be seen a r e shown b y p l o t t i n g t h e r e a c t i o n
t i m e a g a i n s t v a r i a t i o n s o f t h e SiOdA1203 molar r e t i o i n t h e
reaction mixture. I n a d d i t i o n t o t h e t a r g e t phase, pentasil
w i t h a M F I - s t r u c t u r e , m o r d e n i t e , q u a r t z and l a y e r s i l i c a t e s
can a l s o be seen. Each t i m e t h e S i O d A 1 2 0 3 m o l a r r a t i o was
i n c r e a s e d a d i f f e r e n t sequence o f phases c o u l d be seen.
A t a S i02/ A1 2 0 3 m o l a r r a t i o o f 20 - 25 c o n v e r s i o n f r o m t h e
amorphous phase i n t o m o r d e n i t e o c c u r s , a t a medium m o l a r r e t i o
o f 25 - 55 c o n v e r s i o n f r o m t h e amorphous phase i n t o q u a r t z v i a
P e n t a s i l oc c u rs , e t an even h i g h e r r a t i o c o n v e r s i o n f r o m t h e
amorphous phase i n t o q u a r t z v i a l a y e r - s i l i c e t e occurs.
 189

TABLE 4
E a r l i e r p a t e n t s f o r P e n t a s i l s y n t h e s i s (1982) of Chemie-AG
B i t t e r f eld- W o l f en

Number o f t h e p a t e n t Content

DD-WP 207 184 c e t i o n i c and a n i o n i c

p o 1ym e r ic comp o u n d s
DD-WP 207 186 template-f ree synthesis
DD-WP 207 185 organic-free, b u t b y use o f
ammonia
DD-WP 205 674 t e m p l a t e - f ree, w i t h . t h e a d d i t i o n
o f a c t i v a t e d seed m a t e r i e l s
DD-VIP 206 551 template-f ree w i t h vigorous
s t i r r i n g o r the addition o f
grinding bodies
DD-WP 206 979 t e c h n i c a l amin m i x t u r e as t e m p l a t e

I
300

I
~
7004

I
,
I
24

HS 20
k-i,f---/Yfj

/
48
I
72
'
BS YO

I
96
4.-""

r r n d r n o r ~

mordenih

I
720
Y I
14.0 h
tU

Fig. 1. A t e m p l a t e - f r e e synthesis f i e l d o f Pentasil type

zeolites. MFI: Pentosil type zeolites;
SS : s h e e t s i l i c a t e s .
190

ss

MF I

MOR

c---------r c---------r
5 um 2 um
/ /
F i g . 2. A r a s t e r e l e c t r o n microscope image o f t h e phases
observed i n t h e t e m p l a t e - f r e e s y n t h e s i s f i e l d .
MFI: P e n t a s i l t y p e z e o l i t e s f
SS : s h e e t s i l i c a t e e ;
MOR: M o r d e n i t e s .
 191

T h i s d e s c r i p t i o n shows t h a t when t h e SiO2/Al2O3 m o l a r r s t i o

i s i n c r e a s e d , c r y s t a l l i z a t i o n g e n e r a l l y s l o w s down. We have
named t h e r ang e s o f s y n t h e s i s , w h i c h were most i m p o r t a n t i n
o r d e r t o achieve t e c h n i c a l r e e l i s a t i o n . On t h e b a s i s o f t h e s e
r e s u l t s t h e p r o d u c t i o n o f t h e p r o d u c t was s t e r t e d . The f i r s t
co m m er c ial p r o d u c t t o be d e v e l o p e d was Zeosorb HS 30.
further, product8 with I SiOdA1203 m o l a l r a t i o o f 20 (HS 20) end
40 (HS 40) can b e m a n u f a c t u r e d and o f f e r ' e d .
F i g u r e 2 shows a p h o to g ra p h , t a k e n t h r o u s h an e l e c t r o n m i c r o -
scope, o f t h e phases t o be seen i n t h e f i e l d o f s y n t h e s i s .
Each phase has i t s c h a r a c t e r i s t i c morphology, so t h a t even
s l i g h t i m p u r i t i e s can be seen, although these i m p u r i t i e s cannot
y e t be shown b y means o f X-ray techniques.

THE TECHNICAL PROCESS OF SYNTHESIS

Based on t h i s s t u d y o f t h e l i m i t a t i o n s o f t h e f i e l d o f
s y n t h e s i s end t h e k i n e t i c s o f t h e c r y s t a l l i z a t i o n process,
an e n t i r e l y i n o r g a n i c , t e c h n i c a l p r o c e s s was developed.
I n F i g u r e 3 a scheme o f t h e c o u r s e o f t h e r e a c t i o n i s gi ven.
Based on a sodium a l u m i n a t e s o l u t i o n as a s o u r c e o f A1203,
a NaOH s o l u t i o n and water, an a l k a l i n e p r e p a r a t i o n i s p r o d u c e d
i n a f i r s t m i x i n g p ro c e s s . S i l i c a s o l used as a s o u r c e of S i 0 2 ,
i s added i n a subsequent m i x i n g p ro c ess. A f t e r homogenizing,
t h e r e a c t i o n m i x t u r e i s t r a n s f e r r e d t o an a u t o c l a v e end
c r y s t a l l i z e d under hydrothermal conditions. After the reaction
has ended and h a s been c o o l e d down, t h e p r o d u c t is s e p a r a t e d
fro m t h e m o t h e r l i q u o r b y f i l t r a t i o n . I t i s t h e n washed u n t i l
t h e o u t - f l o w i n g w a t e r has a pH v a l u e o f a p p r o x i m a t e l y 9 and
d r i e d a t e t e m p e r a t u r e o f 110 OC. The p r o d u c t - Zeosorb HS 3 0 -
i s a d r i e d powder o f sodium form. T h i s i s i t e c o m m e r c i a l form.
I f r e q u i r e d , HS 3 0 - p r o d u c t s c a n a l s o be s u p p l i e d i on-exchanged
( l o a d e d w i t h d i f f e r e n t c a t i o n s ) o r g r a n u l a t e d (bound w i t h c l a y ) .
192

MIXING lstep 1
MlXING 2 step I

L DRYING (770°C) I
I

0 o wder

F i g . 3. M a n u f a c t u r i n g p r o c e s s o f t e m p l a t e - f r e e Pentasil
type zeolite.

PROPERTIES OF THE PRODUCTS

When c om pa ri n g t h e p r o p e r t i e s o f t e m p l a t e - c o n t a i n i n g and
template-f ree synthesized products, according t o t h e i r S i O d
A1203 ratio, i t can be f o u n d t h a t t h e i r c r y s t a l l i n i t y , S i O d
A1203 ratio, mo rp h o l o g y and a c i d i t y cnn be v a r i e d s y s t e m a t i -
c a l l y i n t h e t e m p l a t e - f r e e v a r i s n t as w e l l , although t h i s i s
o n l y p o s s i b l e w i t h i n a s m a l l range. I n t h i s respect, there
a r e s i m i l a r and d i f f e r e n t t e n d e n c i e s . These a r e g i v e n i n
T a b l e 5.

For both synthesized variants, the C r y s t a l l i n i t y o f the

products, t h e volume o f t h e m i c r o p o r e s , t h e c o n t e n t o f
alum inium and t h e B r o e n s t e d a c i d i t y a r e i n t h e same p r o p o r t i o n ,
depending on t h e c o n t e n t o f t h e a v a i l a b l e A l . In o p p o s i t i o n
t o this, t h e r e a r e d i f f e r e n t t e n d e n c i e s f o r t h e volume o f u n i t
cells, t h e r a t i o o f s t r o n g l y a c i d i c t o weakly a c i d i c c e n t r e s
and f o r t h e volume o f mesopares.
 193

TABLE 5
Comparison o f t h e p r o p e r t i e s o f t e m p l a t e - c o n t a i n i n g and t e m p l a t e -
f r e e P e n t a s i l p r o d u c t s ( g e n e r a l t e n d e n c i e s depending on t h e
Si0,./A1203 ratio

S i m i l a r tendencies D i f f e r e n t tendencies

1. C r y s t a l l i n i t y 1. dep e n d e n c y o f t h e v o l u m e
o f t h e u n i t c e l l upon t h e
2. volume o f m i c r o p o r e s SiOgAl2O3 r a t i o

3. r e l a t i o n between t h e 2. r a t i o o f weak a n d s t r o n g
Si02/A1 0 r e t i o s o f a c i d i c centres
the reaztlon mixtures
a nd t h e p r o d u c t s 3. volume o f mesopores

4. dependence o f t h e
m o r p h o l o g y upon t h e
Si02/A1203 r a t i o

5. d i r e c t r e l a t i o n between
t h e A1 c o n t e n t and t h e
Broensted-acidity

F o r example, t a b l e 6 shows a c o m p a r i s o n o f c h a r a c t e r i s t i c d a t a
o f s e l e c t e d samples f r o m b o t h s e r i e s , e i t h e r with template
- letter S - o r without template - l e t t e r A. With an i n c r e a s i n g
Si02/A1203 r a t i o , the acidity, which i s given here as t h e
a d s o r b e d q u a n t i t y o f NH3, decreases i n b o t h s e r i e s . Th e v o l u m e
of t h e micropores, d e t e r m i n e d f rom n-Hexane adsorption isotherms,
is, w i t h an e q u a l volume, independent o f t h e SiOdA1203 m o l a r
r a t i o i n both series.
T h e vo lume o f t h e mesopores o f t h e s a m p l e s s y n t h e s i z e d w i t h
TPA-J i s t w o o r t h r e e t i m e s l a r g e r i n c o m p a r i s o n t o t h e
template-f ree v a r i a n t .
By c o m p a r i n g t h e m o r p h o l o g y o f t h e p r o d u c t s o f b o t h t h e
series (Figure 4), i t i s p o s s i b l e t o see t h a t w i t h an i n c r e a s i n g
SiO/A1203 m o l a r r a t i o t h e r e i s a l w a y s a change f r o m l o o s e
a g g r e g a t e s t o l a r g e r m o n o c r y s t a l s w i t h a smooth su-face.
A l t h o u g h t h e r e i s no d e t a i l l e d i d e n t i t y b e c a u s e t h e f o r m a t i o n
o f a s p e c i a l m o r p h o l o g y depends o n t o o many f a c t o r s , the
t e n d e n c y i s t h e same.
194

TABLE 6
Comparison o f p r o d u c t p r o p e r t i e s a c c o r d i n g t o t h e i r s y n t h e s i s
w i t h ( S ) and w i t h o u t ( A ) t e m p l a t e s (H-forms) SiOdA1203 r a t i o

Ternalate Product NH,-TPD Volume o f p o r e s

s 1 TPA-J 38 0,83 0,13 0,06

5 2 TPA-3 56 0,bB 0,16 0,06
5 3 TPA-J 124 0,46 0,16 0,05
5 4 TPA-J 204 0,20 0,16 0,04
5 5 TPA-J 3 64 0,13 0,16 0,03

A 1 no 22 1,53 0,17 0,02

A 2 no 32 1,21 0,16 0,Ol
A 3 no 58 0,BO 0,15 0,Ol

SPECIAL VARIANTS OF MODIFICATIONS

The p o s s i b l e v e r i a t i o n s d e s c r i b e d so f e r o n l y r e s u l t f r o m
t h e d i m e n s i o n s o f t h e shown f i e l d o f s y n t h e s i s . However, for
many a p p l i c a t i o n p u r p o s e s t h i s r o n c e o f p o s s i b l e v a r i a t i o n s i s
not sufficient, e s p e c i a l l y w i t h regard t o t h e SiOdA1203 molar
retio. Therefore, i t W F S t h e a i m o f o u r f u r t h e r work t o a c h i e v e
a b e t t e r adjustment o f t h e p r o p e r t i e s t o s p e c i a l demands b y
o p t i m i z i n g t h e s y n t h e s i s and m o d i f y i n g t h e p r o d u c t .
T h i s wes a c h i e v e d i n d i f f e r e n t WAYS:

1. By u s i n g s y n t h e s i s v a r i a n t s f o r w i d e n i n g t h e r a n g e o f t h e
S i 0 2/ A1 203-m o d u 1e .
2. V a r i n g t h e p r o p e r t i e s b y isomorphous s u b s t i t u t i o n o f t h e
n e t w o rk-f o r m i n g e l e m e n t s .
3. I n c r e a s i n g t h e module b y subsequent d e a l u m i n i z a t i o n .

By u s i n g s p e c i a l v a r i a t i o n s o f t h e s y n t h e s i s c o n d i t i o n s
(concentration o f a l k a l i metals, c r y s t a l l i z e t i o n time) , i t i s
p o s s i b l e t o extend t h e renge o f t h e module o f t h e s y n t h e s i z e d
p r o d u c t s t o 20 - 60 f r o m a s t a r t i n g m o l a r r a t i o o f 20 - 70.
K i t h an i n c r e a s i n g m o l a r r a t i o , the rate of crystallization
decreases. With a s t c r t i n g m o l a r r a t i o o f 80 -
100 t h e r e p r o d u c i -
b i l i t y is p o o r , a n d t h e r e w i l l b e a d e c r e a s e i n t h e c r y s t a l l i n i t y
of t h e products.
 196
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196

On t h e o t h e r hand we can see, t h a t t h e SiO$Al2O3 molar r a t i o

o f t h e p r o d u c t is a l w a y s a p p r o x i m a t e l y 10 u n i t s l o w e r compared
w i t h those s t a r t i n g compositions f o r template-free syntheses.
A s t o n i s h i n g l y enough, an e x t e n s i o n o f t h e p o s s i b l e S i 02/A 1203
m o l a r r a t i o t o 80 was p o s s i b l e , when p r o d u c t s c o n t a i n i n g f i v e -
membered r i n g s as a s t r u c t u r a l e l e me nt w ere u s e d a s n u c l e i .
We us ed o f f r e t i t e o r e r i o n i t e a s n u c l e i . Obviously, t h e r e i s an
i n t e r m e d i a t e d e c o m p o s i t i o n i n t o b a s i c el ements, w h i c h i s f a v o u r -
able t o the synthesis of pentasils, e s p e c i a l l y t h o s e w i t h MFI-
structure. It i s p o s s i b l e t o produce MFI-products w i t h a S i O d
A1203 m o l a r r a t i o o f 70 - 80 f r o m r e a c t i o n m i x t u r e s w i t h a
Si02/A1203 m o l a r r a t i o o f 100 and w i t h o f f r e t i t e o r e r i o n i t e
as n u c l e i , w i t h o u t any o t h e r c r y s t a l l i n e byproducts.
One more p o s s i b l e m o d i f i c a t i o n d u r i n g d i r e c t s y n t h e s i s i s t h e
i som or phous s u b s t i t u t i o n o f Al- o r S i -atoms i n t e t r a h e d r a l
p o s i t i o n s b y v a r i o u s hetero-atoms. T h e r e a r e many p o s - s i b i l i t l e s
f o r such a s u b s t i t u t i o n d u r i n g s y n t h e s e s w i t h t e m p l a t e s . Even
t h e c om plet e s u b s t i t u t i o n o f a l u m i n i u m i n t h e l a t t i c e b y e.g.
Fe- o r B-atoms i s p o s s i b l e ( r e f s . 18-21). S o - c a l l e d f e r r i t e s o r
b o r a l i t e s a r e formed. T h i s has n o t y e t been d e s c r i b e d f o r
t e m p l a t e - f r e e S y n t h e s i z e d v a r i a n t s . We s t u d i e d t h e i somorphous
s u b s t i t u t i o n o f B and Fe o n t h e b a s i s o f o u r s t a n d a r d t e m p l a t e -
f r e e s y n t h e s i z e d runs.

The r e s u l t s of t h e s y n t h e s e s w i t h b o r o n a r e shown i n F i g u r e 5.
The r e s u l t a n t r e l a t i v e c r y s t a l l i n i t y (compared t o a s t e n d a r d )
o f synthesized products obtained a f t e r a c r y s t o l l i z a t i o n time
( T K ) o f 24 o r 4 8 h o u rs , and a t a t e m p e r n t u r e o f 175 OC (TK),
depending on t h e S i 0 2 / A 1 2 0 3 m o l a r r a t i o i n t h e r e a c t i o n m i x t u r e ,
a r e shown. On t h e b a s i s o f a s t a n d e r d Si02/A1203 i n i t i a l r a t i o
o f 40, alum ini u m was c o n s t a n t l y r e p l a c e d t o a c e r t a i n p e r c e n t a g e
by B ( u p p e r l i n e o f F i g u r e 4), w h i a l e t h e r a t i o o f S i O d A 1 2 0 3 +
+B203 remained c o n s t a n t a t 40. Up t o a s u b s t i t u t i o n o f a p p r o x i -
m a t e l y 50% A l , w e l l - c r y s t a l l i z e d p r o d u c t s a r e o b t a i n e d . W i t h
l a r g e r boron content, the c r y s t a l l i z a t i o n of p e n t s a i l i s
suppressed. T h i s can be e x p r e s s e d b y t h e g r e a t d r e c r e a s e i n
crystallinity. A p a r t fro m M F I - t y p e z e o l i t e , amorphous phases
and l a y e r - s i l i c a t e s a r e s t i l l found, and t h e r e a r e a l r e a d y
t r a c e s o f more h i g h l y - c o n d e n s e d S I O -phases, such as c r i s t o b a l i t e .
2
 197

%&\ '

55 - sheet silicates
Cr - cristoba/i te
am - amorphous
I I I
50 700 750 21
product 5102/Ab 0
' -ratio

F i g . 5. S y n t h e s i s o f P e n t a s i l t y p e z e o l i t e s w i t h b o r o n
s t a r t i n g Si02/A1203 + B 2 0 3 - r a t i o = 40 TK = 175 OC

Vie can draw t h e c o n c l u s i o n , t h a t a complete s u b s t i t u t i o n o f

alum inium i n t e m p l a t e - f r e e synthesized products i s impossible,
and t h u s t h a t a l u mi n i u m p l a y s an i m p o r t e n t r o l e i n t h e f o r m a t i o n
o f t h e MFI-st r u c t u r e .
The e x p e r i m e n t s gave s i m i l a r r e s u l t s w i t h r e g a r d t o t h e
s u b s t i t u t i o n o f i r o n . W i t h a Fe:Al m o l a r r a t i o o f 0,6 there i s
o n l y a s l i g h t d e c re a s e f r o m 100% t o about 95%. B e g i n n i n g w i t h a
Fe : A l- m olar ratio, o f 0,7, t h e r e i s a s l i g h t decrease i n
crystallinity, w h i c h becomes q u i t e e v i d e n t a t 59% w i t h a m o l a r
r a t i o o f 1:1 ( t h i s means a 50% s u b s t i t u t i o n o f t h e A1 b y Fe).
From t h e s e r e s u l t s , s u b s t i t u t i o n w i t h b o r o n i s c o n f i r m e d i n
t h i s case a s w e l l . However, t h e s e p a r t i a l s u b s t i t u t i o n s can
a l r e a d y e f f e c t c e r t a i n changes i n t h e p r o p e r t i e s o f t h e p e n t s s i l
p r o d u c t s . I n p a r t i c u l a r , t h e y have an i n f l u e n c e on t h e morpho-
l o g y , t h e a c i d i t y , t h e l a t t i c e c o n s t a n t s and, t h e r e f o r e , o n t h e i r
a p p l i c a b i l i t y a s c a t a l y s t s o r components o f c s t s l y s t s .
Further p o s s i b i l i t i e s f o r modification are the so-called
p o s t - s y n t h e t i c processes. The p u r p o s e o f such a t r e a t m e n t is t o
TABLE 7 c
co
Q,
S t r u c t u r a l and a c i d i c p r o p e r t i e s o f HS 30 (H-forms) a f t e r t h e r m a l and h y d r o t h e r m a l t r e a t m e n t

Zeolite Type o f Treatment Extraction SiOd Total Number o f Lattice A1 0

t r e a tment temperature process soluhe
K
atoms 1) 2)

H-HS
H-HS
30
30
-
thermal
-1073
6 n HC1
EOTA, i n tic1
29.6
32.4
64.0
58.8
66.3
12.0
54.1
11.5
-
5.2
H-HS 30 thermal 1073 NH OH, i n HC1 31.4 60.6 12.0 12.7 3.4
H-HS 30 thermal 1073 6 8HC1 32.5 58.6 12.0 11.6 5.4
H-HS 30 hydro- 623 6 n HC1 313.5 49.9 30.7 32.3 14.1
the rmel
H-HS 30 hydro- 773 6 n HC1 55.7 34.9 15.1 14.2 29.1
t hermel
H-HS 30 hydro-
thermal
973 6 n HC1 71.8 27.3 2.4 - 36.7

" L a t t i c e A l " 8 T o t a l o f t h e number o f Broensted and L e w i s centres.

*) "Amorphous Al s o l u b l e " : D i f f e r e n c e between t h e t o t a l number o f A 1 atoms o f t h e i n i t i a l

z e o l i t e and t h e r e s p e c t i v e sample.
 199

remove A 1 f r om t h e l a t t i c e i n o r d e r t o a c h i e v e t h e r e q u i r e d
a c i d i t y . We t e s t e d Zeosorb HS 30 as a b a s i c m a t e r i a l i n t h e r m a l
and h y d r o t h e r m a l t r e a t m e n t processes. These p r o c e s s e s can b e
f o l l o w e d b y e x t r a c t i o n s t e p s f o r t h e d i s p o s a l o f t h e removed
alum inium ( t h e e x t r a - l a t t i c e a l u m i n i u m ).
The e f f e c t s t h a t can b e a c h i e v e d a r e shown i n f a b l e 7.
Th er m al t r e a t m e n t was c a r r i e d o u t a t t e m p e r a t u r e 8 f r o m 500 OC
t o 1000 OC i n a f l a t - b e d f o r a p e r i o d o f 0,5 t o 24 h. I n Table 8
some examples a r e g i v e n . 0 y c h o o s i n g t h e t e m p e r a t u r e and/or
p e r i o d o f treatment, t h e c o n t e n t o f A1 i n t h e l a t t i c e can b e
varied systematically.

TABLE 8
P e n t a s i l t y p e z e o l i t e Zeosorb HS 30 f i e l d s o f a p p l i c a t i o n i n
t h e GDR

-- cc aa tt aa ll yy ss tt
-- cc aa tt aa ll yy ss tt
for
for
a h y d r o - c r a c k - f o r m i n g p r o c e s s (Leuna)
a dewaxing p r o c e s s (Schwedt, BBhlen)
for
for
h y d r o r a f f i n a t i o n (Schwedt)
h y d r o t r e a t i n g (Schwedt)

However, i t i s i m p o s s i b l e t o re d u ce t h e t o t a l c o n t e n t o f A1
i n t h e samples, even u n d e r d r a s t i c e x t r a c t i o n c o n d i t i o n s . The
s p e c i e s o f A 1 o b t a i n e d b y t h e r m a l t r e a t m e n t remai n i n t h e
sample as e x t r a - l a t t i c e aluminium.
H y d r o t h e r m a l t r e a t m e n t makes a s p e c i f i c a d j u s t m e n t o f t h e
content o f A1 i n the l a t t i c e possible, end, apart from t h 3 t ,
t h e p c r t i o l e x t r a c t i o n o f t h e removed a l u m i n i u m ( u p t o 60%) from
t h e l a t t i c e system o f t h e z e o l i t e . T h i s i s i m p o r t a n t f o r t h e i r
a p p l i c a b i l i t y as c a t a l y s t o r c a t s l y s t c a r r i e r s . Comparing t h e
e f f i c i e n c y o f b o t h processes o f after-treatment, we f i n d t h a t :
- with b o t h p r o c e s s e s p r o d u c t s cen b e manufactured, that other-
w i s e can o n l y be s y n t h e s i z e d w i t h t h e h e l p o f t e m p l a t e s ,
- d u r i n g hydrothermal treatment the tempersture o f adjustment
f o r a c e r t a i n c o n t e n t o f A 1 i n t h e l a t t i c e can be
150 O C t o 200 OC l o w e r,
- i n comparison w i t h t h a t , l e s s equipment i s needed f o r t h e
thermal treatment.
A? P L I
CAT I
ONS
F o r s p p l i c a t i o n as c e t o l y s t c a r r i e r s , i o n exchange w i l l be
n e c e s s a r y i n most cases. F o r r e a c t i o n s u s i n g an a c i d i c c a t e l y s t
t h e H-form i s s u i t a b l e i n most coses. I t can be a c h i e v e d b y
+
!JH4 - i o n e x c h a n g e o r by t h e d i r e c t a c t i o n o f a c i d s , as Zeosorb
HS 30 i s s t a b l e t o a c i d s . F o r s p e c i a l p r o c e s s e s a m o d i f i c a t i o n
w i t h v a r i o u s m e t a l c a t i o n s w i l l be necessary. A modification
o f HS 30 w i t h Zn2+- o r K + - i o n s p r o v e d t o be s u i t a b l e f o r o b t a i n -
i n g a r o m a t i c s by p e t r o c h e m i c a l p r o c e s s e s . The c a t a l y t i c e x p e r i -
ments were c a r r i e d o u t a t t h e C e n t r a l I n s t i t u t e of O r g a n i c
C h e m i s t r y ( Z e n t r a l i n s t i t u t f u r O r g e n i s c h e Chemie) at Leipzig
under t h e supervision o f Prof. Anders.
O t h e r a p p l i c c t i o n s o f Z e o s o r b I-IS 30 i n i n d u s t r i z l ~ r c c t ? . " E i
in t i l e ?'X :,r? choi!ii i n T a b l e 8.
 201

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p e n t a s i l z e o l i t e , Z e o l i t e s 6 (1986) 233-260
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G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 203
0 1991 Elsevier Science Publishers B.V.,Amsterdam

SELECTIVE CONVERSION OF SYNGAS TO HYDROCARBONS BY ZEOLITES

Hiro-o Tominaga, Kaoru Fujimoto and Takashi Tatsumi

Department o f S y n t h e t i c Chemistry, F a c u l t y o f Engineering. The U n i v e r s i t y of
Tokyo, Hongo 7-3-1. Bunkyo-ku, Tokyo 113 (Japan)

SUMMARY
A s e r i e s o f s t u d i e s were made on the use o f z e o l i t e c a t a l y s t s f o r producing
selectively some s p e c i f i e d hydrocarbons from synthesis gas. They are
e x e m p l i f i e d by t h e s e l e c t i v e production o f gasoline, r i c h i n i s o p a r a f f i n s , by
Ru-Pt b i m e t a l l i c c l u s t e r supported on protonated Y z e o l i t e and t h a t of C3 and
C4 p a r a f f i n s , s u b s t i t u t e s f o r LPG, by use o f a h y b r i d c a t a l y s t comprising Y-
type z e o l i t e and methanol synthesis c a t a l y s t , etc. For e l u c i d a t i n g t h e
s p e c i f i c product s e l e c t i v i t y , r e a c t i o n mechanisms are discussed i n terms o f t h e
balance and p r o x i m i t y o f the r e l e v a n t d i f f e r e n t k i n d s o f a c t i v e s i t e s f o r
consecutive reactions.

INTRODUCTION
Fischer-Tropsch process i s i n i n d u s t r i a l o p e r a t i o n a t SASOL producing m o s t l y
aliphatic 1i q u i d hydrocarbons from synthesis gas. I t gives, however,
quantities of methane and o t h e r gaseous hydrocarbons as byproducts. In the
f i x e d bed reactor, operated a t lower temperature, a l a r g e amount o f medium wax
is a l s o produced. A d d i t i o n a l l y , non-hydrocarbon c o n s t i t u e n t s such as alcohol,
aldehyde and a c i d are found i n t h e l i q u i d product. Obviously t h e r e exists a
strong need t o improve the process f o r b e t t e r y i e l d and q u a l i t y o f t h e liquid
fuels.
In t h i s connection, carbon number d i s t r i b u t i o n s o f F-T synthesis products
over b u l k c a t a l y s t s , such as p r e c i p i t a t e d o r fused i r o n employed a t SASOL, are
g e n e r a l l y found t o f o l l o w "Schulz-Flory-Anderson (SFA) Law" ( r e f . 1). Provided
t h e l a w works, t h e l a r g e s t y i e l d o f gasoline, C5 t o Cll, can n o t exceed 48% by
weight a t a chain growth p r o b a b i l i t y f a c t o r a = 0.7 - 0.8.
Non-Schulz-Flory-Anderson k i n e t i c s , however, has been r e p o r t e d f o r zeolite
encapsulated Ru ( r e f . 2 ) and Fe ( r e f . 3) c a t a l y s t s , over which g a s o l i n e yield
was significantly improved. The use o f z e o l i t e as support f o r F-T synthesis
offers another advantage over t h e conventional b u l k catalysts: namely the
formation of branched-chain p a r a f f i n s ( r e f . 4) p o s s i b l y due to bifunctional
characteristics of t h e z e o l i t e supported c a t a l y s t . Isomerization of light
p a r a f f i n s f o r octane number improvement i s commercially c a r r i e d o u t on various
bifunctional catalysts consisting of noble metals such as Pt on acidic
supports i n c l u d i n g z e o l i t e .
204

I n view o f these, e x p l o r a t i o n o f t h e Pt-Ru b i m e t a l l i c c a t a l y s t supported on

zeolites was attempted and proved s u c c e s s f u l b y t h e p r e s e n t a u t h o r s t o obtain
h i g h octane g a s o l i n e d i r e c t l y f r o m syngas ( r e f . 5-9).
Another p o s s i b i l i t y t o produce a r o m a t i c r i c h g a s o l i n e from s y n t h e s i s gas may
be o f f e r e d by use o f h y b r i d c a t a l y s t c o m p r i s i n g methanol s y n t h e s i s c a t a l y s t and
pentasil type zeolite. During the course of this study, a particular
combination of t h e component c a t a l y s t s was found t o g i v e propane and butane
h ig h l y s e l e c t ive 1y.

SELECTIVE SYNTHESIS OF GASOLINE R I C H I N ISOPARAFFINS

C a t a l y s t p r e p a r a t i o n and r e a c t i o n
A s e r i e s o f z e o l i t e s c o n t a i n i n g Ru and/or P t were prepared by ion-exchange
w i t h an aqueous s o l u t i o n o f [Ru(NH3)6]C13 and/or [Pt(NH3)4]Clz a t 6OoC f o r 2 h.
Bimetallic catalysts were prepared b y simultaneous ion-exchange. After the
ion-exchange, t h e c a t a l y s t s were f i l t e r e d , washed s e v e r a l t i m e s u n t i l chlorine
was no longer detected, and then d r i e d i n air at llO°C. The exchanged
c a t a l y s t s were dehydrated s l o w l y i n s i t u under a He f l o w by s t e p w i s e h e a t i n g up
to 4OO0C, and f i n a l l y reduced w i t h HZ a t 4OO0C f o r 12 h. The abbreviated
d e s i g n a t i o n s o f c a t a l y s t i s , f o r example, HY2R2P which r e p r e s e n t a catalyst
w i t h 2% Ru and 2% P t by w e i g h t supported on p r o t o n a t e d Y t y p e z e o l i t e H

RESULTS AND DISCUSSION

S y n e r g i s t i c s o f a l l o y i n g Ru w i t h pt
Table 1 shows s y n t h e s i s gas conversion data, a f t e r 5 h on stream, w i h Ru-Pt
b i m e t a l l i c catalysts. R e s u l t s o b t a i n e d w i t h t h e HYER monometallic c a t a y s t and
the HY2RtHY2P physically mixed c a t a l y s t , consisting of equal amounts of
HYZR+HYZP, a r e a l s o included.
The HY2P c a t a l y s t was a poor c a t a l y s t f o r CO c o n v e r s i o n (ca. 0.1 %) w i t h 95
% selectivity for CH4. The CO c o n v e r s i o n over HYER2P was significantly
higher than that over HYPR. No s y n e r g i s t i c e f f e c t on CO conversion was
observed f o r t h e p h y s i c a l l y mixed c a t a l y s t HYER+HY2P, s u g g e s t i n g t h a t a close
p r o x i m i t y and i n t e r a c t i o n o f Ru w i t h P t a r e r e q u i r e d f o r h i g h a c t i v i t y . There
appears t o be l i t t l e d i f f e r e n c e i n carbon number d i s t r i b u t i o n among t h e three
catalysts. Whereas t h e HYER c a t a l y s t gave p r o d u c t s rich in branched-chain
hydrocarbons, Pt f u r t h e r increased t h e i / n r a t i o , provided i t was added by
simultaneous i o n exchange.
Fig. 1 shows the effect o f Ru metal loading on the carbon number
distribution for v a r i o u s Ru-Pt/HY catalysts, with a P t content of 2 wt%.
T h e i r c a t a l y t i c performances a r e a l s o l i s t e d i n Table 1. The CO c o n v e r s i o n and
O b v i o u s l y HY2R2P gave t h e b e s t r e s u l t s , w i t h a 66 % s e l e c t i v i t y f o r Cg-
 205

TABLE 1
S y n t h e s i s gas c o n v e r s i o n over HY z e o l i t e - s u p p o r t e d Ru-Pt c a t a l y s t a .
~~

CO c o n v e r s i o n S e l e c t i v i t y (wtW)
Cata 1ys t (XI Carbon number i/n ratio
‘1 ‘4 ‘5’ ‘4 ‘5 ‘6-‘10
HYER 6.5 6.5 24 66 6.8 30 11
HY2R2P 13 7.0 22 66 10 40 16
( HYZR+HYZP ) b 6.1 7.8 31 56 6.5 24 7.6
HYO. 5R2P 1.5 41 17 33 7.5 12 4.8
HY 1R2P 3.6 13 31 31 9.3 27 6.5
HY4R2P a5 90 1.6 5.2 0.2 4.4 3.0
HY8R2P 19 16 18 56 0.3 1.7 1.0

aReaction c o n d i t i o n s : 240OC. 1.5 MPa, W/F = 7.0 g-cat. h/mol, CO/Hz = 2/3,
a f t e r 5 h on stream.
bW/F = 14.0 g-cat. h/mol.

HYlR2P
0 HY2R2P
A HY4R2P

Carbon number

F i g . 1. E f f e c t o f metal l o a d i n g on carbon number d i s t r i b u t i o n (240 OC, 1 , 5

MPa, W/F = 7.0 g-cat. h/mol. CO/H2 = 3. a f t e r 5 h on stream.
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TABLE 2
Dispersion o f metal p a r t i c l e s and t u r n o v e r number

Particlg D from N(cgIC

Catalyst CO/Ma H/Ma size (A ) TEMa (10- / s )

HY2R 2.01 0.61 14 0.61 12.9

HY4R 1.18 0.53 18 0.47 15.9
HY2R2P 0.28 0.27 28 0.32 65.8
HYEP 0.09 0.23 35 0.27 0.94

aRefer t o t h e d e f i n i t i o n i n Ref. 6.
bVolume-area mean diameter determined by TEM.
CTurnover number f o r CO conversion a t 24D°C, 1.5 MPa and W/F = 12.5 g-cat.
h/mol.

C1 hydrocarbons being obtained.

Characterization o f catalysts
I n t h e p r e p a r a t i o n o f b i m e t a l l i c c a t a l y s t s , t h e main problem i s whether b o t h
elements are a l l o y e d o r not. The XRD p a t t e r n o f HY2R2P showed t h e presence o f
a broad diffraction band centered a t 28 = 40.7', characteristic of Ru-Pt
alloys. There was no XRD evidence o f a monometallic Ru or P t phase i n HY2R2P.
TEM observations showed t h a t the HYZR c a t a l y s t has a narrow particle size
distribution with a maximum f r a c t i o n below 10 A. Hence t h e metal particles
seem t o e x i s t i n supercages. On t h e o t h e r hand, HY2R2P and HY2P e x h i b i t e d wide
distributions: t h e mean m e t a l l i c p a r t i c l e s i z e s were 28 and 35 A, respectively.
The results o f H2 and CO chemisorption a r e given i n Table 2, which also
shows the d i s p e r s i o n o f metal (D) c a l c u l a t e d on t h e b a s i s of TEM, assuming
cubic metal c r y s t a l l i t e s . There seems t o be s a t i s f a c t o r y agreement between t h e
D values from TEM and H/M, suggesting t h a t t h e adsorption s t o i c h i o m e t r y can be
reasonably assumed t o be u n i t y f o r b o t h Ru and P t .
The turnover number f o r CO conversion, Nco, was c a l c u l a t e d on t h e b a s i s of
H2 chemisorption and t h e r e s u l t s a r e given i n Table 2. A comparison of the
turnover number of HY2R2P w i t h t h a t o f HYPR i s not straightforward, as a
considerable amount of hydrogen i s adsorbed on P t , where t h e s p e c i f i c activity
i s much lower. It i s tempting t o speculate t h a t t h e t u r n o v e r number o f HY2R2P
was increased b y a l l o y i n g Ru w i t h Pt. However, one must c o n s i d e r t h e g e n e r a l l y
observed trend o f increases i n t h e t u r n o v e r number w i t h increasing particle
size (ref. 10). Attempts t o improve t h e a c t i v i t y o f HY2R by increasing the
p a r t i c l e s i z e were unsuccessful.
It should also be noted t h a t t h e a d d i t i o n of P t resulted in a drastic
decrease in t h e (CO/M)/(H/M) = CO/H r a t i o . Chen e t al. suggested that for
 207

z e o l ite-supported Ru catalysts, the

turnover number for CO conversion
increased as t h e CO/H ratio decreased
(ref. 10). T h i s t r e n d was accounted f o r
by l e s s CO i n h i b i t i o n and hence a h i g h e r
CO hydrogenation activity for the
catalyst with a l o w CO/H ratio. The
data i n Table 2 suggest t h a t a similar
mechanism might hold for the Ru-Pt
HY2 R b i m e t a l l i c system.
2150
The s t a t e o f Ru and/or P t in HYZR,
2060
HYEP, and HY2R2P was i n v e s t i g a t e d by IR
spectroscopy. The spectra of CO
adsorbed over t h e t h r e e c a t a l y s t s after
e v a c u a t i o n a t 200°C a r e shown i n Fig. 2.
The bands a t 2076, 2040, and 2010 cm-I
HY2R2P were observed on HYPR. A broad band at
2070 cm-l on HYEP almost disappeared.
Hence the band a t 2060 cm-I could be
2400 2000 1900 ascribed t o CO adsorbed on Ru alloyed
W a v e n u m b e r (cm-') w i t h Pt. As t h e s t r e t c h i n g frequency of
CO adsorbed on Ru was h a r d l y dependent
Fig. 2. I R s p e c t r a o f CO adsorbed on t h e p a r t i c l e s i z e o f Ru, t h e observed
on HYZRZP, HYZR, and HYZP (after s h i f t seems t o be due t o t h e electronic
evacuation a t ZOO OC). l i g a n d e f f e c t o f P t , which was r e f l e c t e d
i n t h e CO c o n v e r s i o n a c t i v i t y .

I n f l u e n c e o f alkene a d d i t i o n
Alkenes a r e p r o b a b l y t h e p r i m a r y p r o d u c t s o f F-T s y n t h e s i s o v e r t h e z e o l i t e -
supported Ru c a t a l y s t s ( r e f . 11). The p r e f e r e n t i a l f o r m a t i o n o f branched-chain
alkanes .might be due t o t h e a c i d - c a t a l y z e d i s o m e r i z a t i o n o f the alkenes on
zeolite sites, f o l l o w e d d i r e c t l y by h y d r o g e n a t i o n t h e Ru s i t e s . It can be
expected that the r e l a t i v e r a t e s o f the acid-catalyzed and metal-catalyzed
r e a c t i o n s should determine p r o d u c t s e l e c t i v i t y .
To check t h e p o s s i b i l i t y of h y d r o c r a c k i n g r e a c t i o n s c o n c u r r e n t w i t h t h e F-T
synthesis, c6-c12 1-alkenes were a l l o w e d t o r e a c t t o g e t h e r w i t h s y n t h e s i s gas
over OAHYZRZP. The carbon number d i s t r i b u t i o n s o b t a i n e d w i t h t h e a d d i t i o n of
1-hexene, 1-octene, and 1-decene were examined, By s u b t r a c t i n g the portion
i n h e r e n t i n CO hydrogenation, a c a t i o n i c c r a c k i n g p a t t e r n can be achieved. For
example, the extensive formation of C4 f r o m C8 could be attributed to
208

hydrocracking over a c i d i c s i t e s o f the z e o l i t e . V i r t u a l l y no i n c r e a s e i n C1

and C2 i s c o n s i s t e n t w i t h t h e proposed r u l e s o f t h e carbenium ion mechanism.
Thus t h e f o r m a t i o n o f Cn-l and Cn-2 f r o m Cn c a n n o t r e s u l t f r o m s i m p l e scission
of the cn feed. T h i s t y p e o f c r a c k i n g decreased i n t h e o r d e r c6 > c8 >> C12.
Concurrently enhanced p r o d u c t i o n o f c 7 and c 8 f o r 1-hexene addition suggests
t h a t a dimerization-cracking process (eq. 1) i s t a k i n g place. The i n t e r m e d i a t e
adsorbed C12 s p e c i e s w i l l be f a i r l y u n s t a b l e and form the disproportionation
products. T h i s i s supported by t h e appearance o f an a p p r e c i a b l e amount o f C12
s p e c i e s on a d d i t i o n o f 1-hexene.

A sharp i n c r e a s e i n t h e r a t e o f h y d r o c r a c k i n g was observed for c8-Clo.

This i s i n agreement w i t h t h e expected r e l a t i v e easiness o f c a t i o n i c cracking
as a function of chain length. H y d r o c r a c k i n g on large pore zeolites is
considered to be preceded by c o n v e r s i o n t o m u l t i b r a n c h e d isomers, which is
e v i d e n t l y more d i f f i c u l t f o r s h o r t e r c h a i n alkenes. The d i f f e r e n c e between t h e
apparent alkene c o n v e r s i o n and c r a c k i n g y i e l d was i n c r e a s e d with decreasing
chain length, which was due to the increase in the portion of
disproportionation.
The c r a c k i n g b e h a v i o r o f 1-octene under a He f l o w o v e r m e t a l - f r e e DAHY was
also investigated. There were striking similarities between simple CO
hydrogenation o v e r DAHYZR2P and 1-octene c r a c k i n g o v e r DAHY i n t h e C3+ p r o d u c t s
d i s t r i b u t i o n and s e l e c t i v e f o r m a t i o n o f i s o a l k a n e s .
The a d d i t i o n o f p r o p y l e n e and cis-2-butene r e s u l t e d i n t h e increase i n the
y i e l d o f hydrocarbons h i g h e r t h a n t h e f e e d alkenes. These m i g h t be formed via
t h e i n c o r p o r a t i o n o f alkenes i n t o t h e c h a i n p r o p a g a t i o n s t e p o f F-T synthesis.
However, these i n c r e a s e s a r e most l i k e l y due t o t h e superimposed cracking of
o l i g o m e r s formed f r o m t h e f e e d alkenes on a c i d s i t e s o f t h e z e o l i t e s . I n fact,
a f t e r 5 h on stream, r e l a t i v e l y h i g h y i e l d s o f c6 and $ 3 s p e c i e s were observed
with t h e a d d i t i o n o f p r o p y l e n e and cis-2-butene, respectively, indicating the
occurrence o f d i meriz a t ion.
Comparison o f t h e r e l a t i v e p o r t i o n s found w i t h i n t h e C4-C9 ranges obtained
from s i m p l e CO hydrogenation and t h o s e from a d d i t i o n o f 1-octene and propene
demonstrated that t h e d i s t r i b u t i o n o f isomers from t h e addition of alkenes
resembles t h e one observed w i t h s i m p l e CO hydrogenation. Under t h e conditions
applied i n t h i s s t u d y t h e p r o d u c t s c o n s i s t e d m a i n l y o f branched alkanes. The
f r a c t i o n s o f monobranched alkanes were f a r above t h e e q u i l i b r i u m v a l u e s (e.g..
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31% f o r 2-methylpentane and 15% f o r 3-methylpentane). The amount o f dimethyl

compounds was relatively small and those with quartenary C atoms were
negligible. The s t r i k i n g s i m i l a r i t i e s i n t h e isomer d i s t r i b u t i o n between the
simple CO hydrogenation and a1 kene a d d i t i o n suggest t h a t t h e common mechanism
i s o p e r a t i v e f o r isoalkane formation.
The cracking probability o f n-octane i s compared to that of 1-octene.
Obviously n-octane was l e s s s u s c e p t i b l e t o hydrocracking than 1-octene. This
is what we would expect because carbenium i o n s can be easily formed from
alkenes. w h i l e t h e c l a s s i c a l mechanism f o r a c i d c r a c k i n g o f alkanes i n v o l v e s a
bimolecular hydride t r a n s f e r i n t h e r a t e determining step.

E f f e c t o f support
The carbon number d i s t r i b u t i o n o f the products from t h e CO-HE r e a c t i o n was
shifted t o t h e l i g h t s i d e i n t h e o r d e r : NaYZRZP ( r e f . 5) < HYZR2P < DAHYEREP
(ref. 6). When 1-octene was added t o s y n t h e s i s gas, t h e product distribution
was a f f e c t e d by concurrent c r a c k i n g o f 1-octene; w i t h apparent conversion o f 1-
octene a f t e r 2-3 h on stream i n c r e a s i n g i n t h e order: NaY2R2P (15%) < HYZREP
(26%) < OAHYZRZP (65%). As a r e s u l t , t h e y i e l d o f C3-C7 hydrocarbons increased
by 1-octene a d d i t i o n i n t h e same order: NaY2R2P < HY2RZP < DAHY2R2P.
TPD measurements o f NH3 revealed t h a t t h e amounts o f weak and s t r o n g acids,
d e f i n e d as t h e amount o f ammonia desorbed below and above 350 OC respectively,
were as follows: NaYZREP (1.51/0.20 mmol g-cat.-l), HY2REP (4.17/0.43 mmol g-
cat.-’), and DAHYEREP (3.42/0.68 mmol g-cat.-’). Therefore, the cracking
tendency o f 1-octene could be r e l a t e d t o t h e amount o f s t r o n g a c i d sites on
the catalysts: NaYZRZP < HYERZP < DAHYERZP. It is generally known that
cracking requires strong acid s i t e s (ref. 12).

Mechanism f o r s e l e c t i v e synthesis o f C -C Isoalkanes

34-
Over t h e HY and DAHY supported Ru and Ru-Pt c a t a l y s t s , no correlation was
observed between the metal p a r t i c l e s i z e and chain limitation; a metal
p a r t i c l e s i z e dependent mechanism f o r t h e sharp carbon number d i s t r i b u t i o n has
been r u l e d o u t ( r e f . 2). P l a u s i b l e secondary r e a c t i o n s and t h e r e a c t i v i t i e s o f
various feed alkenes, dependent on chain length, a r e summarized in Fig. 3.
01 igomerization and disproportionation proceed fast for light a1 kenes.
Cracking is observed to increase particularly in the CS-C10 range.
Hydroisomerization i s also favorable f o r heavy alkenes, e s p e c i a l l y c7 and c8
a1 kenes.
A p l a u s i b l e r e a c t i o n pathway f o r the synthesis o f g a s o l i n e range isoalkanes
is as follows: CO hydrogenation on t h e Ru-Pt b i m e t a l l i c a l l o y produces 1-
alkenes as the primary products, f o l l o w e d by various secondary r e a c t i o n s . The
210

Carbon number
of fed alkene 2 3 4 5 6 7 8 9 10 11

Cross chain
propagation

Fig. 3. S i g n i f i c a n c e o f secondary r e a c t i o n s as a f u n c t i o n o f hydrocarbon c h a i n

length.

light alkenes a r e oligomerized on t h e a c i d s i t e s t o form branched long chain

hydrocarbons, which are subsequently cracked to give disproportionation
products. Heavy alkenes formed by t h e F-T reaction could be similarly
converted to 1 i g h t branched hydrocarbons v i a s k e l e t a l isomerization. Since
o l i g o m e r i z a t i o n and c r a c k i n g a r e m u t u a l l y opposing r e a c t i o n s , t h e distribution
of carbenium i o n s on t h e s u r f a c e approximates t o t h e pseudo-equilibrium state
and hence the pattern of products obtained from different feeds is
s u b s t a n t i a l l y t h e same. The sudden drop i n t h e chain growth p r o b a b i l i t y i n t h e
range o f C8-Cl0 i s c o n s i s t e n t w i t h t h e sharp increase i n t h e h y d r o c r a c k i n g r a t e
in this region. Since alkenes a r e more s u s c e p t i b l e to the acid-catalyzed
reactions than a1 kanes, they have to undergo such reactions before
hydrogenation. Hence t h e p r o x i m i t y o f t h e metals and a c i d s i t e s as w e l l as an
adequate balance between t h e metal and t h e a c i d f u n c t i o n s has t o be achieved i n
o r d e r t o d i r e c t the r e a c t i o n towards t h e d e s i r e d products.

Durabi 1it y o f z e o l i t e supported Ru-Pt b i m e t a l 1 i c C a t a l y s t s

As is o f t e n the case f o r CO hydrogenation c a t a l y s t s , the a c t i v i t y of the
catalyst exhibited a decay with time on stream. General causes of
catalyst decay have been w e l l established, and i n v o l v e poisoning, coking, and
sintering of the solid. A better understanding of the mechanism for
deactivation is essential t o the development of practical catalysts with
improved a c t i v i t y , s e l e c t i v i t y and l i f e .
Fig. 4 shows the change o f CO conversion w i t h time on stream. The activity
change seems t o depend s t r o n g l y on t h e r e a c t i o n v a r i a b l e s . At 24OoC and 1.5
MPa. t h e i n i t i a l a c t i v i t y o f HYZRZP was r e l a t i v e l y low. The a c t i v i t y increased
sharply d u r i n g t h e f i r s t 3 h and then d e t e r i o r a t e d r a p i d l y . A t 24OoC and 5.1
 211

Fig. 4. A c t i v i t y change w i t h t i m e on stream. ( 0 : HYZRZP, 240 OC, 1.5 MPa,A

: HYERZP, 240 OC, 5.1 MPa, U : HYZRZP, 240 OC, 0.2 MPa. A : HYZRZP, 290 O C ,
5.1 MPa, 0 : DAHYZRZP, 240 OC. 1.5 MPa).

MPa, t h e r e was a r a p i d decay s i m i l a r t o t h a t observed a t 1.5 MPa. On t h e o t h e r

hand, r a t h e r s t a b i l i z e d a c t i v i t y was obtained a t 24OoC, 0.2 MPa o r 290°C, 5.1
MPa. Under these c o n d i t i o n s methane was t h e main product and t h e selectivity
for C5t hydrocarbons was low. The behavior o f DAHYZRZP was significantly
different from t h a t o f HYZRZP. Although the i n i t i a l a c t i v i t y and selectivity
to C5t for DAHYERZP were somewhat lower than those for HYZRZP, the CO
conversion increased g r a d u a l l y and then leveled o f f .
TPD of NH3 revealed t h a t t h e amount o f weak a c i d was l e s s and that of
strong a c i d was s l i g h t l y l a r g e r on f r e s h DAHYZRZP than on f r e s h HYZRZP. The
decrease in acidity during the reaction is probably due to carbonaceous
deposits. The l o s s o f surface acid, e s p e c i a l l y weaker acid, on HYZRZP was
reflected in t h e s i g n i f i c a n t decrease i n t h e isoalkane s e l e c t i v i t y . It is
suggested t h a t i s o m e r i z a t i o n i s catalyzed by weaker a c i d s i t e s . A relatively
l a r g e amount o f a c i d s i t e s remained on DAHYZRZP a f t e r use, which c o i n c i d e s w i t h
the remarkable branched isomer s e l e c t i v i t y on t h e aged DAHYERZP c a t a l y s t . The
difference in t h e p r o p e r t y o f t h e coke species between HYZRZP and OAHYEREP
could be r e l a t e d t o a c i d - p r o p e r t i e s such as t h e s t r e n g t h and d e n s i t y of the
acid sites.
212

SELECTIVE SYNTHESIS OF PROPANE AND BUTANE

Another p o s s i b i l i t y of p r o d u c i n g h i g h octane g a s o l i n e f r o m s y n t h e s i s gas is
to e n r i c h , by some means, i t s c o n t e n t o f aromatics. An i d e a had been already
presented by Chang e t a1 t o use h y b r i d c a t a l y s t s c o m p r i s i n g methanol synthesis
c a t a l y s t such as Z r o x i d e o r Zn-Cr mixed o x i d e and p r o t o n a t e d ZSM-5 ( r e f . 13).
I n o r d e r t o e x p l o r e b e t t e r y i e l d o f t h e aromatics i n g a s o l i n e b o i l i n g range,
a wide v a r i e t y o f combination o f methanol s y n t h e s i s c a t a l y s t s and z e o l i t e s have
been surveyed e x p e r i m e n t a l l y by t h e p r e s e n t a u t h o r s ( r e f . 14-17). The product
profile, i n terms o f carbon number and s t r u c t u r e , was found t o be a function
n o t o n l y o f a c t i v i t i e s o f the r e l e v a n t catalysts, but also o f proximity o f the
different kinds o f active sites participating i n the consecutive elementary
reactions. In this regard, the s i z e o f pore and crystal, especially of
zeolite. t o g e t h e r w i t h t h e way o f mixed, o r separate, use o f t h e two component
catalysts, p l a y t h e key r o l e . T h i s i s i n consequence o f t h e f a c t t h a t t h e f i n a l
p r o d u c t p r o f i l e i s s t r o n g l y dependent on t h e r a t e s o f i n t r a - a n d inter-catalyst
diffusions, i n competition o f t h e r a t e s o f surface reactions, o f t h e reaction
intermediates.
During the course o f t h i s study, a h y b r i d c a t a l y s t made of a particular
combination of t h e component c a t a l y s t s , e.g., commercially available Cu-Zn
methanol c a t a l y s t and DAY z e o l i t e , was found t o g i v e propane and butane, or
LPG, h i g h l y s e l e c t i v e l y , namely more t h a n 70% ( r e f . 18-20).
These w i l l be mentioned below.

Catalyst preparation
Several k i n d s o f methanol s y n t h e s i s c a t a l y s t were employed. Pd/ID catalyst
(Pd 4 w t % ) was prepared by i m p r e g n a t i n g a commercially a v a i l a b l e s i l i c a g e l
( F u j i Davison ID, s p e c i f i c s u r f a c e area 270 m2 /g, mean p o r e d i a m e t e r 140 A)
w i t h p a l l a d i u m c h l o r i d e from i t s a c i d i c aqueous s o l u t i o n , f o l l o w e d by d r y up i n
an a i r oven and r e d u c t i o n i n f l o w i n g hydrogen a t 400 OC. Cu-Zn(H) catalyst(Cu
40, Zn 23. A1 27 atom %, r e s p e c t i v e l y ) was prepared in this laboratory
following the method described by Shimomura. Cu-Zn(C) catalyst was a
commercially a v a i l a b l e from BASF (S8-45).
For t h e sake o f c o n v e r t i n g methanol i n t o a r o m a t i c hydrocarbons, different
kinds of a c i d i c z e o l i t e s were employed upon m i x i n g w i t h the above methanol
synthesis catalysts. ZSM-5 was prepared a c c o r d i n g t o t h e method d e s c r i b e d in
the patent: t h e i r c r y s t a l l i t e s i z e was c o n t r o l l e d by changing t h e temperature
o f hydrothermal synthesis. H-M stands f o r Zeolon 100H m o r d e n i t e o b t a i n e d from
Norton Co. De-aluminated Y t y p e z e o l i t e , DAY, was s u p p l i e d by Shokubai Kasei
I n d u s t r i e s , Ltd.
The H y b r i d c a t a l y s t s were o b t a i n e d as f o l l o w s : Equal p o r t i o n by weight of
 213

methanol synthesis c a t a l y s t and z e o l i t e were p h y s i c a l l y mixed and ground to

powders below 100 mesh sieve. The powders were f a b r i c a t e d under p r e s s u r e into
a d i s k , which was f i n a l l y crushed t o g r a n u l e s w i t h a 20/40 mesh s i e v e f o r use
i n the a c t i v i t y test.
In some cases, granular mixtures o f t h e two component catalysts were
employed for t h e assessment o f t h e i r performance i n comparison w i t h that of
powdery m i x t u r e s - t h e standard h y b r i d c a t a l y s t s .

RESULTS AND DISCUSSION

I n Table 3 summarized a r e t h e observed changes i n t h e performance o f hybrid
c a t a l y s t due t o t h e d i f f e r e n t c o m b i n a t i o n o f t h e two components. Largest y i e l d
of hydrocarbons was o b t a i n e d by a c o m b i n a t i o n o f Cu-Zn(C) and DAY, where the
presence o f oxygenates, methanol and d i m e t h y l e t h e r , i n t h e p r o d u c t suggested
that the activity of DAY f e l l s h o r t o f converting methanol, the primary
p r o d u c t on Cu-Zn(C), s u c c e s s i v e l y t o hydrocarbons, i n particular to aromatics.
It i s a l s o noteworthy t h a t DAY g i v e s propane and butane a t a h i g h selectivity
of 65 - 75 %.
T h i s i s v e r y much o u t s t a n d i n g when compared, i n Fig.5. with the
experimental r e s u l t s so f a r p u b l i s h e d and a l s o w i t h t h e maximum v a l u e for C3
plus C4 p r e d i c t e d by t h e SFA law ( r e f . 20).
S i g n i f i c a n t amount o f a r o m a t i c hydrocarbons was o b t a i n e d by combining e i t h e r
ZSM-5 or H-M as z e o l i t e with methanol synthesis catalyst. However, the
aromatics were m o s t l y polymethyl benzenes.
It is generally accepted t h a t both proper acidity and pore size are
p r e r e q u i s i t e t o t h e c a t a l y s i s f o r conversion o f methanol t o aromatics. In view
of the acidic c h a r a c t e r , observed by temperature programmed desorption of
ammonia, o f a l l o f t h e z e o l i t e s employed i n t h i s s t u d y have a s i m i l a r profile
which gives t h e second peak, s m a l l e r t h a n t h e f i r s t , a t around 330-350 OC

(ref. 17). I n spite o f this, DAY o n l y c o u l d h a r d l y g i v e aromatics. Therefore,

the reason f o r t h e l a c k o f a r o m a t i c s may be a t t r i b u t e d t o t h e p o r e s i z e of Y
t y p e z e o l i t e which i s s i g n i f i c a n t l y l a r g e r t h a n t h o s e o f ZSM and mordenite. The
larger t h e pore s i z e , t h e l a r g e r t h e r a t e o f d i f f u s i o n o f t h e p r o p y l e n e which
are produced from methanol i n t h e pore o f z e o l i t e . T h i s was demonstrated by a
simple adsorption experiment of propylene on t h e zeolites by use of a
c o n v e n t i o n a l vacuum system as i n d i c a t e d i n T a b l e 4 . Based on t h e s e f i n d i n g s , it
is presumed t h a t t h e small o l e f i n s a r e e a s i l y g e t o u t o f t h e l a r g e p o r e of Y
type z e o l i t e b e f o r e t h e y o l i g o m e r i z e s t o form aromatics.
Residence t i m e o f t h e o l e f i n s i n z e o l i t e p o r e i s a f u n c t i o n n o t o n l y o f p o r e
size but also of c r y s t a l l i t e s i z e . Therefore, an experiment was made to
identify how t h e c r y s t a l l i t e s i z e o f t h e z e o l i t e employed i n hybrid catalyst
affect the product profile. A s shown i n T a b l e 5 , the yield of aromatics
214

TABLE 3
Synthesis gas conversiona over h y b r i d c a t a l y s t s b : E f f e c t o f t h e
combination on product y i e l d .

Methanol c a t a l y s t Pd/ID Cu-Zn( H) Cu-Zn( C )

Zeolite ZSM-5(A) H-M DAY ZSM-5(A) DAY DAY

Product y i e l d ( C%)
Hydrocarbons 9.6 8.0 12.6 17.0 15.9 35.7
Oxygenates tr. tr. tr. 0.6 1.5 5.3
CO2 5.4 3.3 10.0 16.2 14.7 30.7
Coke 0.6 3.1 1.9 - 0.4 -
Hydrocarbon d i s t r i b u t i o n (CW)
c1+c2 25.7 52.5 22.0 21.2 11.7 13.9
c3 33.3 24.8 41.6 26.9 17.8 24.7
c4 6.2 5.3 26.3 12.7 49.4 49.6
c5+ 4.2 6.4 10.1 35.5 21.1 11.9
Aromatics 30.6 10.6 tr. 3.8 0 tr.

aReaction c o n d i t i o n s , H2/CO=2/1; 573(K); 2.1(MPa);

W/F=3.4(g.cat h/mol).
bPowdery m i x t u r e o f methanol c a t a l y s t s and z e o l i t e a t equal weight.

M 6o
C

I I I I I I

1 2 3 4 5 6
Carbon number / -
Fig.5 Comparison o f hydrocarbon d i s t r i b u t i o n s by C number i n synthesis gas
conversion f o r lower p a r a f f i n production.
 215

TABLE 4
In-pore d i f f u s i o n r a t e a o f propylene i n z e o l i t e

Zeolite HZSM-5 H-mordeni t e DAY

105D/r02(min-1)b 3.1 3.3 9.2

aobserved a t room temperature

bD,diffusion c o e f f i c i e n t (cm2min-l); ro, r a d i u s o f z e o l i t e
c r y s t a 1(cm)

TABLE 5
Synthesis gas conversiona over h y b r i d c a t a l y s t Pd/ID+ZSM-5b
: Effect o f z e o l i t e c r y s t a l s i z e on product d i s t r i b u t i o n

(A) (6) (C)

ZSM-5 c r y s t a l s i z e (um) 2.1 1.3 0.8

Hydrocarbon y i e l d (CX) 10.6 10.0 8.8

C number d i s t r i b u t i o n (CX)
C1 12.4 4.2 13.6
c2 13.3 39.5 27.7
c3 33.3 28.0 44.2
c4 6.2 4.3 6.6
c5t 4.2 1.8 2.3
Aromatics 30.6 22.3 5.5

aReaction conditions, H2/CO=2/1; 623(K): 2.1(MPa); W/F=lO(g-cat. h/mol).

bPowdery m i x t u r e o f the two components a t equal weight.

increased i n p r o p o r t i o n t o t h e c r y s t a l l i t e size.
P r o b a b i l i t y o f hydrogenation o f t h e o l e f i n s escaped from z e o l i t e i s another
factor t o determine t h e product p r o f i l e . The r a t e depends on p r o x i m i t y o f the
a c i d s i t e s and t h e hydrogenation s i t e s , i n o t h e r words, t h e mode o f m i x i n g the
two component c a t a l y s t s . H y b r i d c a t a l y s t so f a r employed i n t h i s study is a
powdery mixture. I n comparison w i t h t h i s , g r a n u l a r m i x t u r e s a r e proposed and
tested. Two stage processing o f synthesis gas represents t h e extreme case of
separate use, where the f i r s t reactor i s loaded with methanol synthesis
catalyst, while t h e second one w i t h z e o l i t e t o which t h e e f f l u e n t s from the
f i r s t r e a c t o r are supplied w i t h o u t separation o f unconverted s y n t h e s i s gas.
The performances o f t h e r e s p e c t i v e mode o f using t h e two component c a t a l y s t s
are compared i n Fig.6, indicating t h a t the v e r s a t i l i t y o f product profile is
216

2-Stage

Granular

Mixture

Powdery
Mixture

Cata 1y s t
30

30

--n
30i JL
l
DME

Product
-
&

1
Dp:O. 8mm

D :1.7mm

n
Dp: 0.5mm

Dp :0.3mm

-riF1
D :0.8mm
P

2 3
Carbon number
4 5 6+ arom.
/ -

Fig. 6 Product p r o f i l e s depending on t h e use o f t h e component c a t a l y s t s :

Reaction c o n d i t i o n s , 623K; 2.1MPa; W/F = 3.19 o f c a t . h/mol; H2/CO=2/1; two-
stage,Cu-Zn(H)+T-A1203 ( f i r s t ) p l u s DAY (second): granular mixture i s of
g r a n u l e s o f Cu-Zn(H) and DAY: powderly m i x t u r e i s t h e s t a n d a r d h y b r i d c a t a l y s t ,

COtH2 CH30H 2CH30CH3

C nH2nt 2 -+--
"> Methyl benzenes

Fig.7 Consecutive c o n v e r s i o n o f s y n t h e s i s gas over h y b r i d c a t a l y s t .

 217

due t o t h e c o n s e c u t i v e r e a c t i o n scheme d e s c r i b e d i n Fig.7 ( r e f . 20).

For t h e increased p r o d u c t i o n o f a r o m a t i c s from s y n t h e s i s gas, an advanced
two stage r e a c t i o n system has been studied. The f i r s t r e a c t o r i s loaded w i t h a
hybrid catalyst, c o m p r i s i n g methanol s y n t h e s i s c a t a l y s t and alumina, which
permits deep c o n v e r s i o n o f s y n t h e s i s gas i n t o methanol and dimethyl ether.
These a r e converted i n t o a r o m a t i c s i n t h e second r e a c t o r o v e r ZSM-5. Thus the
CO conversion of 91% and hydrocarbon y i e l d of 57% were attained. The
hydrocarbon i s analyzed t o a p r o f i l e v e r y s i m i l a r t o t h a t o f t h e MTG process
( r e f . 21).

REFERENCES

1. M.E. Dry, " C a t a l y s i s - Science and Technology", (ed by J.R. Anderson and M.
Boudart,), Springer-Verlag, B e r l i n , Vol. 1, 1981, p.159.
2. H.H. N i j s and P.A. Jacobs, J. Catal. 65, (1980) 328-334.
3. D. B a l l i v e t - T k a t c h e n k o and I. Tkatchenko, J. Mol. Catal., 13, (1981) 1-10.
4. D.L. King, J. Catal., 51 (1978) 386-397.
5. 0. Okuda. T. Tatsumi, K. Fujimoto, and H. Tominaga, Chem. L e t t . , (1983)
1153-1 156
6. T. Tatsumi. Y.G. Shul, T. Sugiura, and H. Tominaga, Appl. Catal., 21,
(1986) 119-131
7. Y.G.
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Shul, T. Sugiura, T. Tatsumi, and H. Tominaga, Appl. Catal.. 24,
(1986) 131-143.
8. T. Tatsumi, Y.G. Shul, Y. A r a i . and H. Tominaga, "Proc. o f 7 t h I n t e r n l .
Z e o l i t e Conference." ed. b y Y. Murakami, A. Iijima and J.W. Ward,
Kodansha- E l s e v i e r , Tokyo (1986), pp.891-898.
9. Y.G. Shul, Y. A r a i , T. Tatsumi, and H. Tominaga, B u l l . Chem. SOC. Jpn.,
60, (1987) 2335-2341 .
10. Y.W. Chen, H.Y. Wang and J.G. Goodwin, Jr., J. Catal., 83, (1983) 415-427.
11. Y.W. Chen, H.T. Wang and J.G. Goodwin, Jr., J. Catal., 85. (1984) 499-508.
12. A. Corma and B.W. Wojciechowski, Catal. Rev.-Sci. Eng., 27. (1985) 29-150.
13. C.D. Chang, W.H. Lang and A.J. S i l v e s t r i , J. Catal.. 56 (19790 268-273.
14. K. Fujimoto, Y. Kudo and H. Tominaga, Nippon Kagaku K a i s h i , (1982) 206-212.
15. H. Saima. K. F u j i m o t o and H. Tominaga, Chern. Lett., (1984) 1777-1780.
16. K. Fujimoto. Y. Kudo and H. Tominaga, J. Catal., 87 (1984) 136-143.
17. H. Saima, K. F u j i m o t o and H. Tominaga, B u l l . Chem. SOC. Jpn., 58 (1985)
795-802.
18. K. Fujimoto, H. Saima and H. Tominaga, B u l l . Chem. SOC. Jpn.. 58 (1985)
3059-3060.
19. K. Fujimoto, H. Saima and H. Tominaga, J. Catal., 94 (1985) 16-23.
20. K. Fujimoto, H. Saima and H. Tominaga, Ind. Eng. Chem. Res. 27 (1988) 920-
926.
21. K. Fujimoto, K. Asami, H. Saima, T. Shikada and H. Tominaga, Ind. Eng.
Chem. Prod. Res. Dev., 25 (1986) 262-267.
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G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 219
0 1991 Elsevier Science Publishers B.V., Amsterdam

129XeNMR OF ADSORBED XENON FOR THE DETERMIN'ATIOP OF 'OID SPACES

Q. CHEN, M.A. SPRINGUEL-HUETAND J. FRAISSARD

Laboratoire de Chimie des Surfaces, AssociC au CNRS, URA 1428, UniversitC
P. et M. Curie, 4, Place Jussieu, 75252 Paris, Cedex 05 (France)

SUMMARY
The 129Xe-NMR of adsorbed xenon is a technique generally used at room
temperature for determining some zeolite properties, specially void spaces
(dimensions of channels or cages, structural defects...). This study indicates
more exactly what experimental conditions should be used, depending on
the nature of the sample and the property studied; namely: influence of
temperature, of Si/Al ratio of zeolite and more generally of chemical
composition of molecular sieves. Applications are related to complex
structures and intergrowth of structures.

INTRODUCI'ION
Many properties or defects of zeolites or metal-zeolites are difficult to
detect by classical physico-chemical techniques. For example: short-range
intergrowth of structure, short-range crystallinity, size of supported metal
particles too small to be detected by electron microscopy .... That is why, in
1978, Fraissard et a1 (ref. 1) started to search for a new molecular probe in
order to elucidate some zeolite properties which are normally difficult to
handle.
The central idea of this project was to find a molecule, non-reactive,
particularly sensitive to its environment, to collisions with other chemical
species and to the nature of adsorption sites, which could be used as a probe
for determining certain zeolite properties in a new way. In addition, this
probe should be detectable by NMR since this technique is particularly
suitable for investigating electron perturbations in rapidly moving
molecules.
Xenon is an ideal probe because it is an inert gas, monoatomic. with a
large spherical electron cloud. From the NMR point of view, the 129Xe isotope
has a spin of one-half. Its natural abundance in xenon is 26% and its
sensitivity of detection relative to the proton is 10-2. The high polarizability
of t h e xenon atom makes it very sensitive to its environment. Small
variations in the physical interactions with this latter cause marked
220

perturbations of the electron cloud which are transmitted directly to the

xenon nucleus and greatly affect the NMR chemical shift.

CHEMICAL SHIFT OF XENON ADSORBED IN A ZEOLITE

Fraissard et al. (ref. 2) have shown that the chemical shift of adsorbed
xenon is the sum of several terms corresponding to the various
perturbations it suffers:
6 = 6ref-k 6s -k 6xe + & A S -k 68 -k 8M (1)

Gref represents the chemical shift of gaseous xenon at zero pressure,

taken as the reference; therefore S r e F 0 .
6s corresponds to the chemical shift extrapolated to zero pressure. For
- a
solid with no electrical charges, it depends on the mean free path, 1 , of
xenon, imposed by the zeolite structure, which depends on the dimensions of
the cages or channels and on the ease of xenon diffusion (ref. 3). 6 x e
corresponds to the chemical shift due to Xe-Xe interactions. This term
becomes predominant at high xenon pressure.
The main information have
been generally obtained from the
analysis of the variation of the
chemical shift against the xenon
concentration at 26°C. The amount
of xenon adsorbed is expressed as
the number, T I , of atoms per gram
of anhydrous zeolite or the number
of atoms, ns, per cage (zeolites Y, A,
erionite etc.). When the Xe-Xe
collisions are isotropically
distributed (large spherical cage)
the relationship 6 = f ( n ) is a
straight line (see Fig. 1-1). The
slope, dS/dn is proportional to the
0 17 local xenon density and, therefore,
inversely proportional to the "void
Fig. 1. Variation of the chemical shift volume". If the Xe-Xe collisions are
6 against the xenon concentration n anisotropically distributed (narrow
(see the text). channels) the slope of this function
increases with n (see Fig. 1-2).
When there are now in the void space strong adsorption sites (SAS) which
interact with xenon much more than the cage or channel walls, each xenon
 221

spends a relatively long time on these SAS, particularly at low xenon

concentration (ref. 3). The corresponding chemical shift 6 will be greater than
in the case of a non-charged structure (see Fig. 1-3). When n increases, 6
must decrease if there is fast exchange of the atoms adsorbed on SAS with
those adsorbed on the other sites. When n is high enough the effect of Xe-Xe
interactions becomes again the most important and the dependence of 6 on n
is then similar to that of curve 1 in Fig. 1-1. In this case an+o which is the
chemical shift extrapolated to zero concentration depends on the nature and
number of these strong adsorption sites.
Often these SAS are more or less charged, and sometimes paramagnetic,
cations. The theoretical curve 1-3 is then displaced downfield (see Fig. 1-4).
The difference expresses the effect, 8 ~ of
. the electrical field and, if it exists,
8~ due to the magnetic field created by these cations (refs. 3,4).

FAST SITE EXCHANGE AND MEAN FREE PATH

The previous results have been mainly obtained at 26"C, it being assumed
that at this temperature the experimental chemical shift is the average value
of the shift of xenon in rapid exchange between a position A on the pore
surface (defined by 6,) and a position in the volume V of the cavity or
channel (defined by <6+) (see Fig. 2):

where Na and NV are the number

of xenon atoms in each state. This
equation is valid whatever the
xenon concentration, then for n = 0
6=6s.
6a depends on the void space.
< 6 " > is a function of 6a and the
distance travelled by the xenon
atom between two successive
collisions. In fact, 6, = 6a when the
Fig. 2. Fast exchange model. 6a and aV xenon leaves the surface. 6 , t h e n
are the chemical shifts of xenon decreases during the journey
adsorbed on the wall and in the free between sites 1 and 2, whence the
space. need to determine a mean value,
*>.
In order to obtain by this technique precise data on the void space of a
zeolite of unknown structure and on the dimensions of structural defects,
222
-
Fraissard et a1 (refs. 5,6) have calculated the mean free path, 1 , of xenon
-
imposed by the structure and determined the dependence of 6s on 1 :
6 s = 6a -a
a+ 1
where a is a constant.
The case of the infinite cylinder and the sphere can be rigorously solved
by calculation:
-
infinite cylinder : 1 = Dc - Dxe
-
sphere : 1 = 1/2(Ds-Dxe)

Dc, Ds and Dxe are the diameters of the cylinder, the sphere and the xenon
atom, respectively.

F: Ferrierite
Z-5, 48, 12: Z S M J , 48 and 12
A-5, 11, 17: A1m4-5, 1 1 and 17
S-34, 37: SAPO-34 and 37

b
0 1 2 4 6 e A i
-
Fig. 3. Variation of against the mean free path 1 .

With a more complicated structure we must feed the computer the real
structure of the zeolite considered. Then we circulate a xenon atom within
this space, assuming that the velocity vector is random and all directions are
 223
-
equally probable. The mean free path, 1 , is obtained by averaging the
distances between successive collisions.
The result thus obtained for various model zeolites is shown in Fig. 3-1.
This curve has enabled us to determine the characteristics of the void
volumes of unknown structures or structural defects. But certain points have
to be considered more closely. For example, is 26OC a high enough
temperature for the rapid exchange model to be used? Up to what point is
the effect of the A1 concentration negligible? And, more generally, what is
the effect of the chemical composition of the solids, in particular of AlPO4,
SAPO, etc? It is obvious that if one increases 6 a or the probability of state A
one must in theory increase the experimental 6 value. But, as we shall see
-
later, the magnitude of this variation depends also on <tiv>, which depends
not only on 6 a but also on 1 , compared to 6a. Therefore, it is necessary to
study the influence of the different parameters aforementioned.

INFLUEiNCT OFTEMPERATURE
The chemical shift variations with xenon concentration 6 = f(n) at
different temperatures are illustrated in Figs. 4 and 5 for NaY and ZSM-5
samples, respectively, pretreated at 4OOOC and 10-4 torr.
Figure 4 can be divided into two
6 regions, I and 11, corresponding to
E the xenon concentration range of
a
at A Ocn,cl and 1<nQ<2, respectively.
When T>O"C, 6 varies linearly with
n in both regions. The slope of the
6 = f(n) variation decreases with
increasing temperature. When
T<O°C, 6 = f(n) is still linear and its
slope decreases slightly with
temperature in region I1 (line AB).
On the contrary, in region I, the
6 = f(n) variation changes from
linear to concave. More precisely,
at low n, the chemical shift value is
constant (line CD) up to a certain
value of the xenon concentration,
Fig. 4. 6=f(n) variations for Y zeolite nc. then increases with xenon
at temperatures TOC: (0) -100; (1> -80; concentration.
(0) -60; Q -40; (A) -20; (0) 0; (0) 27; In the case of ZSM-5 (see Fig. 5),
50; @) 80;e) 100. between -100 and 27°C. the
224

chemical shift at very low

xenon concentration is
almost independent of
temperature. At high xenon
loading, the chemical shift
decreases slightly with
temperature (maximum 2
ppm). Above 27"C, the
chemical shift decreases
with increasing temperature
for a given xenon
concentration. At low
loadings the slope of the 6 =
Fig. 5. 6=f(n) variations for ZSM-5 zeolite f ( n ) variation seems to
at temperatures PC:(0) -100<T<27; increase very slightly with
N) 50; Q 80; ($3 100. temperature.

The temperature dependence of 6 , ( T ) is illustrated in Fig. 6. The

difference in 6 s between -100 and +lOO"C is about 38 ppm for NaY and 6
ppm for ZSM-5.

6s
E -
I
0.
Q

90 -

70

50 -
1
T,,,,,,,,,,,,,,
-100 0 100 TVC

Fig. 6. 6 , variations against temperature T for samples: (0) Y and (o)ZSM-5.

Before we discuss these results it is important to know from what

minimum temperature the rapid exchange model is valid.
 225

Equation (2) can be transformed by the same formulation as depicted in

ref. 6 to:

where Dxe is the xenon diameter, P a and p v are the xenon density in the
adsorbed state and in the free space, respectively. A and V are the surface
area and the volume of the free space, respectively. K (K=pa/pV) is the
reduced probability ratio of xenon residences on the surface (A) and in the
free space (V). It depends upon the zeolite structure and the temperature. C
(C=V/ADxe) is a constant for a given system.
To see whether the fast site exchange model is valid, and if it is valid,
then in what temperature range, we rearrange equation (3) to:

Furt hermore :

6a-6.s )/dT) = - dLnK AE

[ dLn(- --d T
&<$> --%*

0 l l , l , , l , l ,

- between the xenon in the two

-\
-
h

A
- O\O
states A and V. It is a constant
for a given system. Therefore, if
m
Y I \ the model is valid, then the
Ln [ (6a-6s)/(6s-<6v>)]=f( I I T ) plot
“0,
2 -0.5 - -
co: \O
should be a straight line.
To get the experimental
-e
“0,
c;l Ln [ (6a-6s)/(6s-<6v>)]=f(1I T ) plot
we need to know 6aand <av>. As
\ \ Q \

\O - the 6a value measured at -100°C

-1.0 - I l l l l l l l , and the value reported by
226

obtain the experimental plot illustrated in Fig. 7. One can see that at high
temperature (T>30°C) the plot is a straight line which means the model is
valid (ref. 8).
- the rapid exchange model and, firstly, the
Let us consider then
dependence of <tiv> on 1 . When the xenon leaves the surface 6v=6a. Then, if
- -
1 is small <tiv> is hardly less than tia. On the other hand, when 1 is large the
xenon atom has time to lose the memory of the perturbation, caused by
adsorption, before the next collision with the surface. <tiv> can therefore be
very small, even zero, given that the electronic relaxation is very rapid.
When the temperature T falls, the residence time of adsorbed xenon
increases and, consequently, the probability na/na+nv of this state. The
variation of 6 then depends on <tiv>. It will be very small if <6v>-6a (ZSM-5)
or, conversely, very large if < & V > < < & a (Nay). This study of the temperature
dependence is a way of checking the size of the pores in which the xenon is
adsorbed.

EFFECT OF THE Si/Al RATIO OF ZEOLITES

That the effect of the internal electrical field on the chemical shift of
adsorbed xenon is negligible at 26OC has only been checked for faujasite
either with Na+ cation or decationized. In this case the 6=f(n) relationships

Fig. 8. 6=f(n) (full lines) and line width Av=f(n) (dotted lines) variations for
ZSM-I1 with Si/Al: (0) 30; (A) 40;(0) 80; (a) 160; (+)
OQ.
 221

are almost parallel straight lines and, for constant n , 6 decreases by

4 ppm when Si/A1 increases from 1.28 to 54. But what happens with zeolites
which have narrow pores? To answer this question we have studied ZSM-5
and ZSM-11 zeolites with various Si/Al ratios.
The 6=f(n) relationships for the ZSM-11 samples are of the characteristic
shape observed for these zeolites: continuous increase of 6 with n with a
marked change of slope for n=8x1020 Xe atoms/g (see Fig. 8). The chemical
shift extrapolated to zero concentration, as, increases with [All. But this
variation shows a break at about [A1]=2 Al/u.c. (see Fig. 9). The results for
ZSM-5 are similar to those for ZSM-11. It is observed first of all that the
dependence of as on [All is greater for narrow channels (ZSM-11 and ZSM-5)
than for large cavities (Y).This difference is again due to <tiv>. In the first
case c6,>-6,; consequently, any increase in 6, with Xe-wall interaction leads
at the same time to that of the experimental 6. In the second case, the
influence of the variation of 6 a on 6 is minimized by the small value of <tiv>.
An important and unexpected
feature of this study of ZSM-5
6’ and ZSM-11 is the demonstration
PPA that the Xe-wall interactions
I

Hot
t
115 -
115

110 -
I
I
I-/

I
change for a definite value of the
aluminium concentration [A1]=2
Al/u.c., as indicated by the break
in the 6,=f[A1] plot, in agreement
I
II
with several analogous

1
/i/ I II O ZSM-5 observations reported (refs.
1 00 55L, h2 Y
p P0.AO I A ZSM-11 9,10,11). This observation allows
I
I us to state that A1 is not
I I I 1
randomly distributed in the
Allur. lattice but that its distribution
depends on its concentration.
Fig. 9. Variation of against [All for The break in (also in the signal
(A) ZSM-11 and (0) ZSM-5. width and the amount of xenon
adsorbed) for [A1]=2 Al/u.c. could
correspond to the presence or absence of an A1 atom at the channel
intersections. We would mention finally the difference between ZSM-5 and
ZSM-11 for [A1122 A1h.c..
228

INFLUENCE OF THE CHEMICAL COMPOSITION: ZEOLITES, AlPO4, SAP0 AND

MAP0
We have studied the adsorption of xenon on many zeolites and
aluminophosphate based molecular sieves whose names and characteristics
are listed in Table 1.

TABLE 1
Chemical shift tis of 129Xe adsorbed on molecular sieves and characteristics of
the void spaces
--------~-----
Molecular sieve 6 s PPm Characteristics of the void space

Faujasite Y 60 Sphere, diameter 13A with four

prism openings at 109"; 12-ring: 8A
SAPO-37 58 The same structure as Faujasite
A, ZK-4 87 Sphere, diameter 11.4A; six 8-ring
openings 4-5A depends on the cation
90 Unidimensional barrel-shaped
channels; 12-ring openings of 7.1A;
maximum diameter, 9A
R 73 Unidimensional channels, regular
cylinders, 12-rin diameter: 7.4A
Erioni te 98 i
Cage, 15.1 x 6.3 ; six 8-ring openings
3.6 x 5.2A
AlPO4- 17 72 The same structure as Erionite
ZSM-5 110 Tridimensional interconnecting
channels; 10-rings: 5.1 x 5 . 5 4 and
5.4 x 5.6A
ZSM-12 90 Unidimensional channels.12-ring
diameter: 5.5 x 5.9A
Theta- 1 130 Unidimensional channels, 12-ring
diameter: 4.4 x 5.5A
VPI-5 49 Unidimensional channels, regular
cylinders, 18-ring diameter: 12- 13A
AlPO4-5
SAPO-5 56 Unidimensional channels, regular
MAPO-5 cylinders, 12-ring diameter: 7.3A

A1P04-1
SAPO-11 I 120 Unidimensional channels, 10-ring
diameter: 3.9 x 6.3A

-
It is sometimes difficult to calculate 1 for certain structures and the
values are probably approximate (ZSM-5, ZSM-11 -and EU-1, etc.).
Nevertheless, we must remark that the experimental [tis,1 ] points are either
 229

on the initial curve defined by Fraissard et a1 (ref. 5,6) (see Fig. 3-I), on a
curve parallel to the first one (Fig. 3-11) or, much more rarely, between the
two. More exactly, all the points corresponding to solids-with low or zero
cation concentration are located below curve I, for 0 . k 1 <3A. For a given
structure, when the xenon diffusion is very easy, the experimental points
are on the first curve, whatever the composition of the solid (zeolite Y and
SAPO-37). The points for AlP04-5, SAPO-5 and MAPO-5 are identical,
whereas those for erionite and AlP04-17 (same structure) are different.
Comparison of the 6 = f(n) curves of these two solids shows that xenon
diffusion appears to be easier in AlP04-17. In fact, the 6 increase, which is
linear in the first part of the curve, expresses the Xe-Xe interactions. For
erionite, 6 increases very little in this range. The passage from one cage to
another is easier in AlP04-17, perhaps because there are no cations, which
cause steric hindrance in erionite, or because of a more symmetrical opening
which requires less deformation of the xenon atom. Moreover, the xenon
adsorption rate is much greater for AlPO4-17.
If the same value of the mean free path
-i is assumed for AlP04-17 as for
erionite, the point of the coordinates [ 6 , , 1 ] is very much below the first
-
6,=f( 1 ) curve (Fig. 3-1). The value of the mean free path in the two solids
are not, of course, strictly identical; the Si-0 and P - 0 bond lengths are not
equal and the T-O-T angles must vary slightly from one compound to
another, which may explain the slight difference in the xenon diffusion.
Although we cannot explain in detail why there are two curves in Fig. 3,
they can be used to study zeolites and more generally all the porous solids
regardless of their composition.

APPLICATION TO THE STUDY OF COMPLEX STRUCTURES AND INTERGROWTH

OF STRUClVREiS
VPI-5
The characteristic signal a shows the expected linear dependence
6 = f(PXe) (6,=49*2 ppm). But for all the samples studied there is also a
second, narrow, signal h. characteristic of reproducible defects which could
correspond either to the beginning of the transformation into AlP04-8 or,
more likely, to the existence of 16-membered T-rings (see Figs. 10,ll).
Signal c in Fig. 10 corresponds to AlPO4-11 impurity.

PolvtvDe Y
We have studied two samples, denoted polytype Y-1 and polytype Y-2.
The polytype Y-1 sample shows no detectable defects. For polytype Y-2, the
230

200 100 PPm 0

Fig. 10. NMR spectra of xenon adsorbed on VPI-5 treated at 573K.

Fig. 11. Intercalation of a 16-membered T-ring ribbon (*) in the framework

proposed for VPI-5.

presence of two signals at temperatures of 26°C or higher indicates that

there are two differentiated zones. The higher value of 6s for the second
signal corresponds to slower xenon diffusion and/or smaller internal volume.
At low temperature (T<O°C), where the Xe-surface interactions become
predominant, the fact that there is only one signal indicates that the pores
are identical throughout the sample. Conversely, at high T the Xe-surface
interactions are less important and the xenon probe is more sensitive to the
free volume. The sample must therefore include, in addition to a well-
 231

crystallized free zone, a region where the pores are blocked or limited which
makes xenon diffusion more difficult.

ZSM-8
The spectra mostly consist of two signals corresponding to structures
ZSM-5 and ZSM-11. Table 2 summarizes the spectral characteristics and the
conclusions.

TABLE 2
Characteristics of the 129Xe-NMR on ZSM-8 and conclusions
I _ - ~ - - ----
Si/AI Spectral characteristics Conclusion

40 one symmetrical large signal intergrowth at short distance

80 two signals for Pxe>1200 torr intergrowth at long distance
160 two signals for PXe>SOO torr intergrowth at long distance
>1950 two signals for PXe>80 torr intergrowth at long distance

CONCLUSION
These complementary studies indicate more exactly what experimental
conditions should be used for the 129Xe-NMR technique, depending on the
nature of t h e sample and the property studied. This technique is
increasingly able to provide original results difficult to obtain by other
methods.

1 T. Ito and J. Fraissard, NMR study of the interaction between xenon and
zeolites A, X and Y, in: L.V.C. Rees (Ed.), Proc. 5th Int. Conf. on Zeolites,
Naples, Italy, June 2-6, 1980, Heyden, London, 1980, pp. 510-515.
2 J. Fraissard and T. Ito, 129Xe n.m.r. study of adsorbed xenon: A new
method for studying zeolites and metal-zeolites, Zeolites, 8 (1988) 350-
36 1 , (and references therein).
3 T. Ito and J. Fraissard, 129x8 nuclear magnetic resonance study of xenon
adsorbed on zeolite NaY exchanged with alkali-metal and alkaline-earth
cations, J. Chem. SOC.,Faraday Trans. 1, 83 (1987) 451-462.
4 A. Gedeon, J.L. Bonardet, T. Ito and J. Fraissard, Application of 129Xe NMR
to the study of Ni2+Y zeolites, J. Phys. Chem.. 93 (1989) 2563-2569.
5 J. Demarquay and J. Fraissard, 129Xe NMR of xenon adsorbed on zeolites.
Relationship between the chemical shift and the void space, Chem. Phys.
Letters, 136 (1987) 314-318.
232

6 M.A. Springuel-Huet, J. Demarquay, T. Ito and J. Fraissard, 129Xe NMR of

xenon adsorbed on zeolites: determination of the dimensions of the void
space from the chemical shift 8(129Xe). Studies in surface science and
catalysis, 37 (1988) 183-190.
7 T.T.P. Cheung, C.M. Fu and S. Wharry, 129Xe NMR of xenon adsorbed in Y
zeolites at 144K. J. Phys. Chem. 92 (1988) 5170-5180.
8 Q. Chen and J. Fraissard, in preparation.
9 G. Debras, A. Gourgue, J.B. Nagy and G. De Clippeleir, Physico-chemical
characterization of pentasil type materials. 111. High power solid state
27AI. 23Na and 29Si n.m.r. of precursors and calcined samples, Zeolites, 6
(1986) 161-168.
1 0 A. Auroux, P.C. Gravelle and J.C. Vedrine, Microcalorimetric study of the
acidity of H-ZSM-5 zeolite, in: L.V.C. Rees (Ed.), Proc. 5th Int. Conf. on
Zeolites, Naples, Italy, June 2-6, 1980, Heyden, London, 1980, pp. 433-
439.
1 1 C. Naccache and Y. Ben Taarit, Recent developments in catalysis by
zeolites, in: L.V.C. Rees (Ed.), Proc. 5th Int. Conf. on Zeolites, Naples, Italy,
June 2-6, 1980, Heyden, London, 1980, pp. 592-606.
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 233
0 1991 Elsevier Science PublishersB.V., Amsterdam

DIFFUSION OF HYDROCARBONS IN A AND X ZEOLITES AND SILICALITE

DOUGLAS M. RUTHVEN, MLADEN EIC AND ZHIGE XU

Department of Chemical Engineering, University of New Brunswick, Fredericton, NB
Canada
ABSTRACT
Diffusion of a range of different hydrocarbons in A and X zeolites and
silicalite has been studied by gravimetric, chromatographic and zero length
column (ZLC) methods. The ZLC diffusivities for CHq and C2H6 in 5A and 13X at
low temperatures are only slightly smaller than the corresponding NMR self
diffusivities, extrapolated to zero concentration. Data for the Cg aromatics in
silicalite show satisfactory conformity between gravimetric and ZLC measurements
but the diffusivity values are higher than most previously reported values, with
only about one order of magnitude difference between the isomers. The
diffusional activation energies for p-xylene, ethylbenzene and o-xylene are
almost identical. First results of a detailed study of diffusion of large
aromatic molecules (dimethyl naphthalenes and tri-isopropyl benzene) in NaX
zeolite are also reported.
INTRODUCTION
Because of the practical importance of zeolites as catalysts and selective
adsorbents, coupled with their academic interest as examples of geometrically
regular micropore systems, the study of zeolitic diffusion has attracted much
attention from both experimentalists ad theoreticians. A wide variety of
experimental techniques have been applied, including both 'microscopic' and
'macroscopic' methods. The microscopic methods (principally NMR and neutron
scattering) yield direct information concerning the molecular mobility, and hence
the self-diffusivity, whereas the macroscopic measurements generally yield the
transport diffusivity (the quotient of the flux and the negative concentration
gradient) although, by the use of isotopically labelled species the macroscopic
methods can be adapted to measure self-diffusion. Since self-diffusion and
diffusive transport are physically different phenomena, their coefficients are in
general different. However, simple physical reasoning, as well as most detailed
quantitative theories, suggest that the self-diffusivity and the transport
diffusivity should converge in the low concentration limit. This has been
confirmed experimentally for several systems although there are also some well
documented discrepancies.( 1 * 2 )
A simple classification of the commonly used macroscopic experimental
methods, according to the quantity measured and the nature of the measurement,
is given in Table 1. The methods of category A3 account for the large majority
of the reported data. They have the advantage of experimental simplicity but
they are subject to the intrusion of extracrystalline resistances to heat and
mass transfer, so the analysis and interpretation of the rate data is not always
straightforward.
234

Our own recent experimental studies, by chromatographic and gravimetric

methods, have been directed to the study of three classes of zeolite system for
which there is either little available data (large hydrocarbons in zeolite X ) or
for which there are large discrepancies in the reported diffusivity values (light
alkanes in A and X zeolites, aromatics in silicalite). A summary of these
results is presented here.
Table 1

Experimental Methods for Measurinn Transport

Diffusion in Microporous Solids

A. Transient Measurements

A1 Following the evolution of the concentration profile in response to a change

in external concentration.
- Optical techniques
- X-ray techniques
- NMR spin mapping
- ESR spin mapping

A2 Flux measurements
- Time lag measurements for diffusion through a membrane
- Transient Wicke-Kallenbach
A3 Uptake rate measurements. (Following the variation of the mean sorbate
concentration averaged over a particle).
- Batch methods (gravimetric, volumetric, piezometric, frequency
response)
- Flow methods (chromatography, ZLC etc.)

B. Steady State Measurements

B1 Steady state flux through a membrane
- Permeation
- Wicke-Kallenbach
B2 Effectiveness factor in catalytic reaction.

EXPERIMENTAL METHODS
Gravimetric
Gravimetric uptake rate measurements were performed in a Cahn vacuum
microbalance systems, using small zeolite samples (10-12 mg) with incremental
pressure steps (to avoid the problems associated with the analysis of integral
uptake rate data). To maximize heat transfer and minimize external mass transfer
resistances, the zeolite sample was spread as thinly as possible over the balance
pan. Where possible, measurements were repeated with different crystal sizes and
different adsorbent sample configurations in order to confirm the dominance of
intracrystalline resistance. In the experiments reported here the volume of the
system was sufficiently large relative to the quantity of sorbent that the
sorbate pressure, following the initial step, remained essentially constant. The
simple expressions for the uptake curve for an infinite isothermal system were
 235

therefore used to interpret the uptake curves(3):

m
t = I - -6 m 2 2 2
Spherical Particles: - I -1 e -n II Dt/R (1)
(radius R) n2 n=l n2

m m
Parallel-sided Slab: -t-- 1 - -8 I -exp[-(Zn+l) 2 2 2
n Dt/4?. 1 (2)
(half-thickness 1 ) mm n2 n=O (2n+1)

-
ZLC
In the zero length column (ZLC) meth~d(~-~)
a small sample of zeolite
crystals (- 2 mg) held between two sinter discs, is equilibrated with sorbate and
then purged with helium (or argon) at a high flow rate. The hydrocarbon content
of the effluent stream is monitored continuously using a chromatography detector
(thermal conductivity or flame ionization). The conditions of the experiment are
adjusted to ensure that the desorption rate is controlled by diffusion out of the
crystals, rather than by the purge rate. This may be achieved by using a
sufficiently high purge flow. The absence of significant external resistance may
be confirmed by replicate measurements with He and Ar as the purge gases and the
dominance of intracrystalline diffusion may be confirmed by varying the crystal
size.
The mathematical model used to interpret the ZLC desorption curves assumes a
linear isothermal system with perfect mixing through the thin bed and adsorption
equilibrium maintained at the crystal surface. For such a system the desorption
curve (for a set of uniform spherical particles) is given by:

m - pn2Dt/R2
- -- 2 L I (3)
0 n=l [ p t~(L-1)1
n

where pn are the roots of the equation:

pn cot pn t L - 1 = 0 (4)
Purge Flowrate .
. Crystal .
2
and EVR
L = 3(1-~)KDz = 1 -3 Volume KD (5)

For large values of L, pn + nv and Eq. 3 reduces, in the long time region to:

The diffusional time constant is readily found from the slope of a plot of log
(c/co) vs t.
If external film resistance is significant the analysis remains the same
except that the expression for L (Eq. 5 ) is replaced by:
236

It is evident that external film resistance may modify the intercept of the
semilog plot of c/co vs t but it has no effect on the limiting slope.
For a parallel sided slab of half-thickness Q, the expressions corresponding
to Eqs. 3-6 are:

-a 2Dt/Q2
m n
-= 2L
0
z e
n=l [an2+L(L+1)1

where are the roots of the equation:

2
a t a n a = L = EVQ (9)
n n ( 1-E)KZD

For large L, an (2ntl)n/2 and Eq. 8 reduces, in the long time region, to:
+

-r- 2 2
-n Dt/4Q
2
co (Ltl) e (10)

DIFFUSION OF AROMATIC HYDROCARBONS IN SILICALITE

Representative uptake curves showing the difference in kinetic behaviour
between o-xylene, p-xylene and ethylbenzene in large crystals of silicalite
(40x50~105pm) under comparable conditions, are shown in figure 1. The curves
all conform well to the simple isothermal diffusion model for a parallel sided
slab (Eq. Z), rather than for a sphere (Eq. 11, since the intercepts approximate
8/n2 (rather than 6/n2). This suggests that diffusion probably occurs
predominantly through the straight channels of the silicalite pore system (which
run between the large parallel faces of the crystals). This conclusion has been
confirmed by measurements with different crystal sizes which show the time
constant varies with the square of the crystal thickness, rather than with the
mean equivalent spherical radius.
The diffusivities 'for ethylbenzene are almost independent of concentration
in the low concentration region but the diffusivities for p-xylene show a
stronger trend (increasing with concentration) presumably reflecting the more
favourable form of the equilibrium isotherm. Only limited uptake measurements
were performed with o-xylene since, as a result of the low diffusivity, these
experiments are tedious and time consuming.
Diffusion of the same three sorbates (as well as benzene for which the data
have been previously reported was also studied by the ZLC method. Representative
response curves are shown in figure 2. The coincidence between the curves
measured, under similar conditions, with He and Ar vs purge gases confirms the
absence of any significant extracrystalline resistance to mass transfer. In view
of the evidence from the uptake measurements the parallel sided slab model (Eq.
8) was used to derive the time constants which are summarized in Table 2.
 1.0

8
E 8 p=0-0.103 Torr
'- 0.1

1
E
-
\ PX, p=0;0.12 To;r , , ,
~/12.~~10-3

0.01
0 10 20 30 LO 50 60 70
Time (rnins)
Figure 1 Gravimetric uptake curves at 125OC ( % = 20 vm).

1 I I I I

1.9 2.1 2.3 2.5 2.7 2.9 3.1

0
1 0 ~ 1 ~
0-
Figure 3 Temperature dependence of limiting
diffusivities for benzene (x),
p-xylene ( 0 ) . ethylbenzene ( ) and
I.L 0-xylene ( A ) . Filled symbols,
,cc.-c. ta
gravimetric,open symbols ZLC. w
-a
238

Table 2
Summary of ZLC Diffusivity Data for Aromatic
Hydrocarbons in Silicalite Crystals

Sorbate Temp. Pu e Flow L DX$O9-,) E

(Deg. C) (cm'gSTP/min) (cm .s W/mol)

Benzene 50 4 227 1.0

75 4 105 1.8
100 4 91 3.1 27.0
100 2 46 2.7
150 4 87 11.0

p - Xylene 80 60 11 2.8
80 100 23 2.9
100 60 37 4.1 30
150 60 55.6 11.9
150 (Ar) 60 40.0 11.8
200 60 51.3 43

Ethylbenzene 70 60 19.5 0.8

70 100 25 0.92 30
100 60 28.5 2.0
150 60 66.7 7.3
150 (Ar) 60 55.5 5.6
200 60 91.0 29

o-Xylene 100 30 323 0.36

150 30 95 1.24
200 15 476 2.9 33
250 15 571 7.84
Purge was He except where indicated as Ar.

In ref.(7) the ZLC data for benzene were interpreted according to the spherical
particle model. These values have been recalculated based on the parallel sided
slab model for consistency with the xylene data.

Figure 3 shows a comparison between the ZLC data and the gravimetric values
(extrapolated to zero concentration). It is evident that the agreement is
satisfactory. There is little difference in diffusivity between benzene and
p-xylene and the diffusional activation energies are all similar (- 30 kJ/mol).
In contrast with the results of earlier studies, the present data show no
evidence of any significant deviation from the simple diffusion model and the
differences in diffusivity between the C8 isomers are much smaller than has been
previously rep~rted.(~*~)The similarity in the activation energies implies that
the difference in diffusivity cannot be attributed to differences in repulsive
interaction energies resulting from the difference in critical molecular
diameters.
 239

DIFFUSION OF METHANE AND ETHANE IN ZEOLITE A AND X

The ZLC method provides one of the more useful techniques for studying rapid
diffusion processes since, by careful attention to detail it is possible to
reduce the dead volume of the experimental system to a fraction of a millilitue
and hence to reduce the response time essentially to that of the detector. By
the addition of a refrigeration system the operating temperature range has been
extended to -1OO"C, thus making it possible to measure diffusion of the light
alkanes (CH4 and C2H6) in 5A and 13X zeolites. The results of such measurements
are summarized in figures 4 and 5 and Table 3 where comparative NMR self-
diffusivity data(1°-12), extrapolated to zero concentration, are also shown. For
both 5A and 13X the measurements performed with two different crystal sizes show
good agreement, thus providing convincing evidence of intracrystalline diffusion
control.
In contrast to earlier ZLC data for the higher paraffins in NaX(6) which
show large discrepancies with the NMR self-diffusivities, the agreement of the
present data for CHq and C2Hg in both 13X and 5A can be considered satisfactory.
A discrepancy of this magnitude is easily accounted for by the natural tendency
of an NMR self-diffusion measurement to err on the high side (as a result of
relaxation effects) and for a sorption rate measurement to err on the low side
because of the emphasis on the tail of the desorption curve. The activation
energies also show qualitative agreement and the surprising observation that the
activation energy for C2H6 in 13X is higher than in 5A is confirmed by both NMR
and ZLC data. However, the c2%-13X system at the higher temperatures is close
to the limit of the ZLC technique (half time less than 1 sec.) so these data and
consequently the activation energy for this system are subject to a large margin
of error.
Table 3

Comparison of NMR and ZLC Diffusivity Data

for CH4 and C2Hg in 5A and 13X Zeolites
ZLC Data
Do at 200K E
system ( cm2.s-1) (kJ/mole) (cm2. s-1) (kJ/mole)

CH4-5A 10-6 3.7 4~10-~ 6.3

C2H6-5A 31c10-~ 5.9 1.4~10-~ 6.3

C2H6-13x 10-5 9.6 2.5 ~ 1 0 - ~ (14.6)

ZLC data are at zero concentration; NMR data extrapolated to zero from data at
higher concentrations.
240
I .
:.
; * 0 5A ( 55 pm) 1
'.4- '..*
i 0 13X ( 1 0 0 pm)
I

.I;
1 A 13x ( 50 pm)
~

1
ClCO

.01

,001
0 10 20 30

t (I)

Figure 4 ZLC desorption curves for C2H6 in 5A and

13X crystals at 183K.

4 5 6 4 5 6
1 0 ~ 1 (~
K1)

Figure 5 Temperature dependence of limiting diffusivities

(ZLC) and NMR self-diffusivities for CH4 and
C 2 h j in 5A and 13X crystals.
 241

TRANSITION STATE THEORY

Because of its simple cubic structure 5A zeolite provides an ideal model
system for the application of transition state theory. This was recognized many
years ago(13*14) but the available diffusivity data used in the earlier
comparisons were derived from measurements with small commercial 5A crystals.
More recent evidence suggests that a substantial fraction of the windows in these
samples were probably blocked thus invalidating the quantitative comparisons
between theory and experiment. It is therefore appropriate to reconsider such a
comparison on the basis of the more reliable diffusivity data now available.
According to transition state theory, in the low concentration limit where
self- and transport diffusivities become identical, the diffusivity is given by:

*
where uz and uz represent the potential energies of a molecule within the cage
(equilibrium state) and within the window (transition state). To avoid the
difficulties associated with the evaluation of the partition function for a
molecule within the cage (f,) one may make use of the equilibrium relationship:

-AHo/kT fZ (ug-uz)/kT
K = K e =- (12)
kT'Fe
B
where ug is the potential energy for the vapour phase (zero), thus obtaining:
.b

or comparing with the Arrhenius form (D = ,

D e-E/RT):
* *
D = -6 2 . -fZ . - = u - u - A H o vO
E -

m hKo f' ' R k k

g

where Vo is simply the difference in potential between the transition and

equilibrium states. fi, the partition function per unit volume of the gaseous
species may be expressed as the product of the internal, rotational and
translational contributions:
fi = fCrans * frot * fint (15)
so, if it is assumed that the molecule in the transition state retains the same
internal and rotational freedom as in the equilibrium state and there is no
significant additional freedom of motion in the plane of the window:
*
*
fZ = frot * fint .
. -fZ = 7
f,
g
1
;
trans
D, =
ti2
;ran,
(16)
 Table 4 N

Absolute Rate Theory: Coqmrism of Predicted a d IIc.8ured Oiffusivities i n 4A and 5A Zeolites b

Theorg Em.*
6 6
System Crystals K x10 Ano oDmlo ODX1O Method Ref.

2 -1 2 -1
(molecule/ (kJ/nole) (a.s ) (an .s )
cage.Torr)

Ar-4A 3.2 p (Linde) 1.06 14 4.4 1.2 3.7 24.2 grav. (15)
Derrah
mmmtaic Kr-4A 3.2 rn ( L i d ) 1.26 17.7 1.2 0.12 10 33.8 grw.

Xe-5A 20-50 pn 1.29 22.5 1.0 2.8 0.36 (1.0) WR PFG

cn -4A 36 Im, 7.3 In 1.5 18 12 1 12 24.2 grw.

4
'Spherical CH4-5A 20-50 c 1.9 10.8 10 45 0.22 3.8 mR PFG

tqs' CF4-5A 3.6 p (Lindc) 0.38 24.7 3.7 2.5 1.5 3.8 grav.

CF -5A 27.5 p, 55 p 1.49 21-7 0.93 19 0.05 27.6 grav.

4
0 -4A 3.2 p (Lindc) 1.23 13.4 5.2 6.6 0.8 18.8 grsv.
2
diataic N -4A 36 P 7.3 m 1.o 17.6 7.0 5.0 1.6 24.2 grw.
2
W -5A 55 P, 27.5 0.35 21 .o 41 42 1.o 10.0 UC
2
linear u) -4A 36 m, 7.3 m 0.019 47.5 211 9.0 23.4 23 grw.
2
triatanic
(17)
c n -u n m. 7.3 P 1.39 24.7 5.0 4.8 1.oc 34.3 grav. Y'ucel
2 6
(11)
ply- C H -5A 20-50 ~n 0.4 20.0 17 10 1.7 5.9 WR PFG Caro
2 6 4.
atamic C H -5A 27.5. 55 P 0.4 20.8 17 7.3 2.3 6.7 ZLC xu
2 6
(19)
nC H -5A 27.5 pin, 55 0.86 42.6 3.0 3.1 1.o 19.2 grav. Yucel
4 10
(6)
nC tl -5A 34 p, 7.3 P 0.86 42.6 3.0 1.o 3.0 18.8 ZLC Eic
4 10
*The nargin of u u e n a i n t y in the experirrntal a c t i v a t i m energies i s probably about ZkJ/nole.
This corrcopmS t o a factor of 2-3 i n the valucs dcrived for 0.,
Ibpblished experimental data obtained at U.N.B.
Experimental 0, values are frm taperatwe depenance of 0 or D
o woo'
where fkrans = (21nnlcT/h~)~/~e
is the translational partition function (per unit
volume) for the free gas phase.
It is in principle possible to estimate the potential energies of molecules
in the cage and windows from theoretical potential calculations. Such estimates
are, however, very sensitive to the precise values assumed for the molecular
radii since, particularly for the molecule in the window, the attractive and
repulsive forces are of similar magnitude. In comparing experimental data with
the theory it is therefore more satisfactory to consider only the pre-exponential
factors. Such a comparison is shown, for several simple sorbates, in Table 4 .
In view of the obvious approximations in the theory and the uncertainty in the
experimental values of D,, the agreement between theory and experiment is
remarkable. The ratio (D,)theory/(Dm)expt is, for most sorbates, close to unity.
Values less than unity can be rationalized by restricted rotation of the
transition state and values greater than unity can be explained by some
contribution from degrees of freedom in the plane of the window. Evidently, for
most sorbates, these two effects must either be small or they must compensate.
The close agreement for polyatomic molecules such as n-butane seems at first
sight surprising since one might anticipate significant restriction of rotation.
However, the butane molecule is probably not in the linear conformation and even
though it probably does not have complete rotational freedom in the window, the
additional degrees of freedom (torsional oscillations about the centre of mass)
may very well compensate fully for restriction of the three dimensional rotation.
The most significant discrepancy is for C02 for which the predicted value of D,
is substantial greater than the measured value. Since the free rotation of a
long linear molecule such as CO2 is bound to be severely reduced in the
transition state this deviation is clearly understandable.
In the original application of transition state theory to diffusion in 5A
zeolite, attempts were made to estimate the effect of restricted rotation and the
contribution from degrees of freedom in the plane of the zeolite window. The
broader perspective which is now possible as a result of the improved data base
suggests that such detailed analysis was probably not justified. The simplified
treatment leading to Eq. 16 appears to be quite adequate for most small molecules
while Eq. 14 may provide a useful basis for more refined calculations.

DIFFUSION OF LARGE AROMATIC MOLECULES IN ZEOLITE X

Results of an experimental study of diffusion of large molecules in 13X
zeolite are summarized in figures 6 and 7. The data of tri-isopropyl benzene at
200°C show exactly the same pattern of behaviour as has been commonly observed
for smaller molecules in 5A and for the c8 aromatics in 13X. The strong
244

1,3,5 Tri Isopropyl Benzene NaX -

N

0 10 20 30 40 50 60
Concent rot ion (mg/g)

Figure 6 Concentration dependence of diffusivity (D)

and corrected diffusivity (Do) for tri-IPB
in 13X crystals at 473K.

-
Gravirnetric Data,
10-12 ' 1 ' 1 ' I I ' ' ' ' ' '
1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2
1 0 ~ 1 (K-')
~

Figure 7 Temperature dependence of corrected (limiting)

diffusivities for dimethyl naphthalene isomers
in 13X zeolite.
 245

concentration dependence appears to be due entirely to non-linearity of the

equilibrium isotherm and corrected diffusivities, calculated according to:
D = Do (dllnp/dllnc) (17)
are essentially constant.
The data obtained by gravimetric and chromatographic methods (for the
dimethyl naphthalenes) are quite consistent. Despite the differences in critical
molecular diameter (Table 5 ) there is evidently little difference in either
diffusivity or activation energy between the DMN isomers. These data thus
support the conclusion drawn previously from the similarity in the diffusivities
(in NaX) between the xylene isomers, that the diffusional activation energy is
determined by the kinetic diameter of the freely rotating molecule rather than by
the critical diameter (the diameter of the smallest circumscribing cylinder).

Table 5
Critical Molecular Diameters of Some Aromatics Molecules
Diameter A
Benzene 6.9
Toluene 6.9
p-Xylene 6.9
o-Xylene 7.3
Naphthalene 7.3
2-6,2-7 DMN 7.3
1-2,l-5,1-6 DMN 7.9
1-3 DMN 8.6
1-4 DMN 9.1
Mesitylene 8.4
Tri-isopropylbenzene 9.3

Notation
c/co ratio of outlet concentration to initial concentration in ZLC experiment
D diffusivity (intracrystalline) (cm2.s-1)

Do limiting value of D (as c + 0 ) or corrected diffusivity (Eq. 17) (cm2.s-l)

Dm molecule diffusivity (cm2. s-1)
D self diffusivity (intracrystalline) (cm2.s-1)
E activation energy (J/mole.deg)
fz,f2 partition functions for adsorbed molecule in equilibrium and transition
states
frot,fint rotational and internal contributions to partition function
partition function per unit volume for free gas ( cm-3
fi
h Planck's constant (erg. sec)
k Boltzmann constant pre-exponential factor (erg/deg.)
K, KO Henry's Law constant (moleucles/cage.dyne/cm2)
II half-thickness of crystal (cm)
L defined by Eqs. 5 , 7 or 9
m mass of a molecule
246

mt/m, fractional approach to equilibrium

p sorbate partial pressure
R equivalent radius of crystal
T absolute temperature
uz-ug difference in potential between transition state and
free gas
Vo defined by Eq. 14
z thickness of adsorbent bed (ZLC)
Sh Sherwood Number
%,Bn roots of Eqs. 9 and 4
E voidage of adsorbent bed (ZLC)
6 lattice parameter (cm)
-AHo heat of adsorption at zero coverage (erg/molecule)

Acknowledgement: We are grateful to Dr. David Hayhurst for providing us with

samples of large silicalite crystals. Financial support was provided, in part,
by the Imperial Oil Company of Canada.

References

1. J. Karger and D.M. Ruthven, Zeolites 2, 267 (1989).

2. J. Karger and D.M. Ruthven, Diffusion in Zeolites, John Wiley, New York
(1991).
3. J. Crank, Mathematics of Diffusion, Oxford University Press, London (1956).
4. M. Eic and D.M. Ruthven, Zeolites 8, 40 (1988).
5. M. Eic, M. Goddard and D.M. Ruthven, Zeolites 8, 327 (1988).
6. M. Eic and D.M. Ruthven, Zeolites g, 472 (1988).
7. M. Eic and D.M. Ruthven, 8th Internat. Zeolite. Conf., Amsterdam, July 1989,
Proceedings, p. 897, P.A. Jacobs and R.A. van Santen eds., Elsevier,
Amsterdam (1989).
8. P. Wu, A. Debebe and Y.H. Ma, Zeolites 2, 118 (1983).
9. K. Beschmann. G.T. Kokotailo and L. Riekert, Chem. Eng. Process 22, 223
(1987).
10. J. Caro, J. Karger, H. Pfeifer and R. Schollner, Z. Phys. Chem. Leipzig 256,
698 (1975).
11. J. Caro, J. Karger, G. Finger, H. Pfeifer and R. Schollner, Z. Phys. Chem.
Leipzig 257, 903 (1976).
12. J. Karger, H. Pfeifer, M. Rauscher and A. Walter, J. Chem. SOC. Faraday
Trans I, 76, 717 (1980).
13. D.M. Ruthven and R.I. Derrah, J. Chem. SOC. Faraday Trans I. 8,2332
(1972).
14. J. Karger, H. Pfeifer and R. Haberlandt, J. Chem. SOC. Faraday Trans I, 76,
1569 (1980).
15. D.M. Ruthven and R.I. Derrah, J. Chem. SOC. Faraday Trans I, 2. 2031
(1975).
16. J. Karger, H. Pfeifer, F. Stallmach and H. Spindler, Zeolites - in press.
17. H. Yucel and D.M. Ruthven, J. Chem. SOC. Faraday Trans I, 76, 60 (1980).
18. H. Yucel and D.M. Ruthven, J. Chem. SOC. Faraday Trans I, 76, 71 (1980).
19. H. Yucel and D.M. Ruthven, J. Colloid Interface Sci. 2,186 (1980).
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 241
0 1991 Elsevier Science Publishers B.V., Amsterdam

ATLAS OF ZEOLITE STRUCTURE TYPES:

PAST- PRESENT- FUTURE

W.M. MElER
Institute of Crystallography, ETH Zurich, 8092 Zurich, Switzerland

ABSTRACT

The 'Atlas of Zeolite Structure Types' is a periodically updated data compilation

of observed zeolite-type frameworks. Apart from being useful as a work of reference
it reflects the progress in zeolite structural chemistry. This paper describes some uses
of Atlas data including framework densities, pore diameter values, loop configurations
and fault planes. In addition, some recurrent misconceptions are discussed.

INTRODUCTION

For over two decades the 'Atlas of Zeolite Structure Types' (refs. 1,2) and its
forerunner (ref. 3) have reflected the
enormous progress made in the
elucidation of the framework structures
of zeolites and zeolite-like materials.
Fig. 1 shows that the current growth
rate of over 6 new structure types
per year is quite unprecedented. What
looks like an exponential growth is due
to two developments:
(a) the recent advances in the methods
of crystal structure analysis, in
particular powder diffraction
methods (refs. 4,5), and
(b) the greatly expanded range of
compositions of zeolite-type
"I
53
I
61

molecular sieves explored in Fig. 1. Development of the number

more recent years (refs. 6-8). of known zeolite structure
types over the years.
248

The available structural information on zeolite-type materials is very substantial

indeed. It raises the need for the Atlas and the other data compilations published on
behalf of the 1ZA Structure Commission (refs. 9,lO). The principal aims of the Atlas
project have been:
(a) to provide a reference work (both for crystallographers and non-crystallographers)
based on data which has been subjected to critical evaluation (normally
published),
(b) to promote some desirable uniformity in recording such data,
(c) to fill in gaps in available data, and
(d) to facilitate studies and analyses of data.

The following account describes some examples of uses of the Atlas which were not
dealt with previously (ref. 11).

SILICATE AND PHOSPHATE MICROPOROUS MATERIALS

From a chemical point of view zeolite-type silicates and phosphates apparently

constitute two distinctive categories of microporous materials. This appears to be
particularly evident in synthesis. Table I (which is based on the isotypes listed in
the Atlas) shows, however, that there are three, rather than two distinct groups of
framework types. Apart from those associated with silicates and phosphates there is a
sizeable group of structure types which have been found to occur both in silicates and
phosphates. Comparative in-depth investigations of isotypes in this latter group in
particular offers new insight into synthesis/structure relationships. An example is the
structure refinement of SSZ-24, the silica analogue of AIP04-5 (ref. 12).

Table I also shows that while the present structure-orientedactivity is greatest in the
field of phosphates, the silicates still make up the majority of zeolite structure types.
The structure types which have been approved by the IZA Structure Commission (SC)
since the last Atlas appeared in 1988 have been marked by a plus (+) in the Table. In
addition to these, seven structure types (listed in Table I) are under consideration for
clearance by the SC at present. A current listing of the zeolite structure type codes
can be found in the Appendix.
 249

TABLE 1

Microporous zeolite-type materials

excluding interrupted frameworks

Silicates Both silicates and phosphates Phosphates

more abundant first established

as a silicate as a phosphate
ABW HEU MON + AEL
AFG KFI MOR ANA AFI AFS
BIK JBW + MTN CAN AST A N +
BOG + LAU M U CHA BPH + AFY
BRE LIO MTW ERI APC
CAS + LOS NAT FAU APD
DAC LOV NON GIS All-
DDR LTL OFF LEV ATV +
DOH LTN PAU LTA Aww +
EAB MAZ PHI RHO VFI +
ED1 ME1 + SGT SOD (c)
EPI MEL STI (d)
EUO MEP THO
FER MER TON );:
GME MFI YUG (g1
GOO MFS + (a)
(b)

(a) Beta (e) AIP04-18 + not included in ref. 1

(b) ZSM-20 (f) AlP04-31
(c) AIP04-8 (9) AIP04-41
(d) MAPO-39

POROSITY AND FRAMEWORK DENSITY

The pore volume of zeolite-type frameworks can be expressed in terms of the

framework density (FD), which is defined as the number of tetrahedral atoms per nm3
and is listed in the Atlas for each structure type. The distribution of FD-values as a
function of the smallest ring(s) in the network has been shown to be of considerable
interest (refs. 13,14). Fig. 2 is an updated version of the earlier diagram prepared in
250

1988. The gap defining the boundary between microporous and dense networks has
gained further support by the new data, and the postulated range for zeolite-type
materials has been confirmed. A particularly noteworthy addition is the data point
relating to ZSM-18 (MEI), the second framework containing 3-rings, which was
reported only recently (ref. 15). Earlier, only lovdarite, a beryllosilicate, was known to
contain 3-rings. The new structure type ME1 is very significant for it demonstrates that
silica can also form tetrahedral nets containing 3-rings (without Be being needed).

T-atoms / nm3

size of smallest rings

Fig. 2. Distribution of framework densities (FD) as a function of the smallest ring(s)

in the network. Updated version of diagram in ref. 13. Data points refer to
dense (+), previous (*) and new (0)zeolite-type structures, and low density
tetrahedral networks (O).
 251

This bodes well for the synthesis of low-density materials based on 3-ring structures in
the silica field.

The FD is obviously related to the pore volume but does not reflect the size of the
pore openings. Customary values are frequently given or assumed for the free
diameters of channels with 8-, 10- and 12-ring apertures. It should be clear from Fig. 3
(which is also based on Atlas data) that the crystallographic free diameters for the
various types of apertures fall into a wide range. There is even a considerable overlap
of the respective ranges for 8-, 10- and 12-ring openings. Hence, sorption properties
have to be interpreted with caution when predicting the type of ring openings in
structurally unknown materials.

...._
18-ring aperture I......
li

........
14-ring i........
l i

#
12-ring

I
1O-ring [ 15 J
...........
9-ring ...........
1 2 :

8-ring

Fig. 3. Range of crystallographicfree diameters for different ring openings. The

arrows indicate the customary values assigned to 8-, 10- and 12-ring
apertures. The number of pertinent structure types is given in each bar.
252

The customary values for 8-, 10- and 12-rings (applying to LTA-, MFI- and FAU-type
materials) are marked by arrows in Fig. 3. This Figure also includes relevant data for
VPI-5 with 18-ring channels (refs. 16-18) and for AIP04-8 with 14-ring channels
(ref. 19). These are the most open framework structures to date, and both have
unidimensional channel systems.

SOME MISCONCEPTIONS

Among the most widespread misconception is the belief that large unit cell
constants are indicative of large apertures. Fig. 4 should make it clear that there is
no such correlation, no matter whether minimum or maximum unit cell constants are
considered.

LTN-
LTN-
PAU- -
-

AFS-

FAU-
-

Fig. 4. Minimum (a) and maximum (b) unit cell

constants compared to largest ring openings.
 253

A more serious illusion is the belief that close resemblance between powder
diffraction patterns is sufficient to assign a structure type. This may hold in some
special cases. In general, however, the assignment or the establishing of a structure
type based on the similarity of XRD powder patterns is full of pitfalls. This has become
evident in a number of instances. For example, PHI and GIS were confused for well
over a decade, and later EAB and ERI were repeatedly mixed up. In one instance,
even the Structure Commission assigned a code to a structure type which turned out
to be in error (ref. 20). The code ATF of the erroneous structure type of AIP04-25 had
to be discredited, and according to the rules of the SC is not to be used again. The
correct structure has been assigned the code ATV. DLS is certainly an indispensable
tool for simulating and evaluating possible framework structures but a reasonable
agreement between an experimental XRD pattern and one based on DLS atom
coordinates does not give enough evidence for the correctness of a framework
topology. Even in cases in which this qualitative approach led to basically correct
framework topologies subsequent refinements have invariably revealed significant
differences. A good example of this kind is ZSM-12 (refs. 21,22). In the originally
proposed structure the channel dimensions were 5.5 x 5.9 A but structure refinement
later on showed these to be 5.6 x 7.7 A.

SIGNIFICANCE OF LOOP CONFIGURATIONS AND FAULT PLANES

The utility and significance of loop configurations (LC) has been demonstrated
before (ref. 11). In a study on the evaluation of hypothetical zeolite frameworks,
Brunner (ref. 23) determined the relative abundance of various possible LC. One of
the more frequently occurring LC consists of a pair of edge-sharing 4-Yktgs. This is
shown in Fig. 5 together with two pertinent conformations. While the 'cis' conformation
(i) had been observed in 22 known zeolite frameworks, the 'trans' conformation (ii)
had not been recorded but was noted to occur in the proposed framework for VPI-5.
Brunner's findings cast some doubt on the correctness of the VPI-5 framework
structure at an early stage. Meanwhile, it has been found by extensive structure
refinements and NMR studies that the VPI-5 framework is not purely tetrahedral
(ref. 18). Instead, it is 4-connected (containing some octahedral At) and it even
appears that a strictly tetrahedral network of this type is unlikely to be obtainable.
254

Fig. 5. A common loop configuration

and associated conformation
(from Brunner, ref. 23).

For a considerable proportion of the frameworks covered in the Atlas, fault planes
have been listed. This allows predictions at a glance as to the likelihood of stacking
faults, twinning, and disorder. These possible defects are of considerable importance
in the characertistics of these materials and their catalytic applications.

OUTLOOK

The number of established zeolite-type framework configurations will soon approach

one hundred. Compilations, which are extensive enough and which contain carefully
examined data, can be expected to be of increasing interest to both theoreticians and
practitioners in the field. The need for computer-based data files can be clearly
foreseen. The available printed versions of the compilations issued by the SC are
already based on computer files to a large extent . In the future it is to be expected that
the huge amount of structural information, once prepared for efficient use in the form of
well-documented data bases combined with good search routines, can be used as a
source for new insights in zeolite chemistty. The first step in this direction has already
been made (ref. 24). One important goal is the ability to predict which of the enormous
number of hypothetical networks can be synthesized and in what system(s).

ACKNOWLEDGEMENTS

The author thanks Dr. Lynne B. McCusker and other members of his group for
helpful discussions. Continued support by the Swiss National Science Foundation
(grant 20-25256.88 at present) is also gratefully acknowledged.
 255

Appendix

List of zeolite structure type codes

approved by the IZA Structure Commission (on behalf of IUPAC)

up to June 1990
Structure types not included in the 1988 Atlas are marked by a plus (+)

ABW Li-A(BW) KFI ZK-5

AEL AIP04-11 LAU Laumo ntite
AFG Afghanite LEV Levyne
AFI AIP04-5 LIO Liottite
AFS MAPSO-46 LOS Losod
AFT + AIP04-52 LOV Lovdarite
AFY COAPO-50 LTA Linde Type A
ANA Analcime LTL Linde Type L
APC AIPO4-C LTN Linde Type N
APD AIPO4-D MAZ Mazzite
AST AIP04-16 ME1 + ZSM-18
ATT AIPO4-12-TAMU MEL ZSM-11
ATV + AIP04-25 (revised structure) MEP Melanophlogite
AWW + AIP04-22 MER Merlinoite
BIK Bikitaite MFI ZSM-5
BOG + Boggsite MFS + ZSM-57
BPH + Beryllophosphate-H MON + Montesommaite
BRE Brewsterite MOR Mordenite
CAN Cancrinite MTN ZSM-39
CAS + Cs-Aluminosilicate (Araki) M-n ZSM-23
CHA Chabazite MMI ZSM-12
-CHI Chiavennite NAT Natrolite
DAC Dachiardite NON Nonasil
DDR Deca-Dodecasil 3R OFF Offretite
DOH Dodecasil 1H - PAR Partheite
EAB TMA-E(AB) PAU Paulingite
ED1 Edingtonite PHI Phillipsite
EPI Epistilbite RHO Rho
ERI Erionite - ROG Roggianite
EUO EU-1 SGT Sigma-2
FAU Faujasite SOD Sodalite
FER Ferrierite STI Stilbite
GIS Gismondine THO Thomsonite
GME Gmelinite TON Theta-1
GOO Goosecreekite VFI + VPI-5
HEU Heulandite -WEN Wenkite
JBW + Na-J(BW) YUG Yugawaralite
256

REFERENCES

1 W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types (IZA Structure
Commission, 1978).
2 W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types, Second extended
edition, Buttetworths, 1988.
3 W.M. Meier and D.H. Olson, Adv. Chem. Series, 101 (1970) 155-168.
4 Ch. Baerlocher, Zeolites, 6 (1986) 325-333.
5 L.B. McCusker, Acta Cryst. (in preparation).
6 S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan and E.M. Flanigen,
J. Am. Chem. SOC.,104 (1982) 1146-1147.
7 B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan and E.M. Flanigen,
J. Am. Chem. SOC.,106 (1984) 6092-6093.
8 E.M. Flanigen, B.M. Lok, R.L. Patton and S.T. Wilson, Proc. 7th Int. Zeolite Conf.,
Tokyo (Elsevier, 1986) 103-112.
9 W.J. Mortier, Compilation of Extra-Framework Sites in Zeolites. Butterworths
(1982), pp. 67.
10 R. von Ballmoos and J.B. Higgins, Collection of Simulated XRD Powder
Patterns for Zeolites. Zeolite Special Issue 10 (1990) 313s-514s.
11 W.M. Meier, Studies in Surface Science and Catalysis, 49 (1989) 691-699.
12 R. Bialek, W.M. Meier, M. Davis and M.J. Annen, Zeolites (submitted for
publication).
13 G.O. Brunner and W.M. Meier, Nature, 337 (1989) 146-147.
14 M.E. Davis, Nature, 337 (1989) 117.
15 S.L. Lawton and W.J. Rohrbaugh, Science, 247 (1990) 1319-1322.
16 C.E. Crowder, J.M. Garces and M.E. Davis, Advances in X-ray Analysis, 32
(1988) 507-514.
17 J.W. Richardson, Jr., J.V. Smith and J.J. Pluth, J. Phys. Chem., 93 (1989)
8212-8219.
18 L.B. McCusker, Ch. Baerlocher, E. Jahn and M. Buelow, Zeolites (submitted
for publication).
19 R.M. Dessau, J.L. Schlenker and J.B. Higgins, Zeolites, 10 (1990) 522-524.
20 J.W. Richardson, Jr., J.V. Smith and J.J. Pluth, J. Phys. Chem., 94 (1990)
in press.
21 R.B. LaPierre, A.C. Rohrman, J.L. Schlenker, J.D. Wood, M.K. Rubin and
W.J. Rohrbaugh, Zeolites, 5 (1985) 346-348.
22 C.A. Fyfe, H. Gies, G.T. Kokotailo, B. Marlerand D.E. Cox, J. Phys. Chem. 94
(1990) 3718-3721.
23 G.O. Brunner, Zeolites, 10 (1990) 612-614.
24 J.M. Newsam and M.M. Treacy, Zeofile, in preparation.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 251
0 1991 Elsevier Science Publishers B.V., Amsterdam

ZEOLITES AS MEMBRANES : THE ROLE OF THE GAS-CRYSTAL INTERFACE

Richard M. Barrer
Chemistry Department, Imperial College, London, SW7 2AZ, United Kingdom

ABSTRACT
Steady flow through a porous cystal membrane is associated with concentration
distributions across the gas/crystal interfaces which cannot represent true equilibrium. Steady
state distributions have been modelled from mass balance equations for a membrane where a
fraction of the flow enters the crystal directly from the gas phase and the remainder enters via
an externally adsorbed layer. The same fractions are assumed for the nett flow through the
exit surface. Special cases of the general equations investigated numerically or otherwise
include : the extent of departures from equilibrium across interfaces; the ideal flow when these
departures tend to zero; the ratios of ideal to measured flows; and ratios of true intracrystalline
diffusivities to apparent diffusivities obtained from steady flows by assuming equilibrium
across interfaces. In fast sorptions and desorptions non-equilibrium distributions across the
gas/solid interface may also result in differences between true intracrystalline diffusivities and
those obtained by incorrectly assuming equilibrium.

INTRODUCTION
Zeolite membranes provide in principle a means of continuous scparation based on
differences in the shapes and sizes of molecules. If they contain catalytic centres they can also
be envisaged as membrane reactors. In steady flow, independently of any model, more
molecules of diffusant enter the crystal than leave at the ingoing surface. T h a c imbalances
require that concentrations just within the crystal cannot have their equilibrium values (ref. 1)
at either surface, so that it is of interest to examine their scale. The imbalances have recently
been modelled quantitatively for gases obeying Langmuir's isotherm when all molecules enter
the crystal via an externally adsorbed layer (ref. 2). In this paper the model will be extended to
include, for very wide windows, possible entry directly from the gas phase simultaneously with
entry from the externally adsorbed layer. Also considered is the effect of imbalance betwecn
forward and reverse flows across the gas/crystal interface in transient state sorption and
desorption kinetics. Aspects of surface resistances have already formed the bases of other
papers (refs. 3-5).
The treatment for a single crystal applies also to membrana consisting of a monolayer of
porous crystals on a macroporous support, in which gaps between porous crystals in the
monolayer are filled by a non-permeable medium which adheres permanently to the sides of
the crystals, but leaves their top and bottom surfaces free of the adhesive. In another kind of
membrane the porous crystals comprise a discontinuous phase embedded in a continuum. Such
membranes will not be considered here.
258

(a)
GAS CRYSTAL GAS

%
x= 0
el
DISTANCE - %-I 9n
x=l

(b)
GAS CRYSTAL GAS

AE

x=o
DISTANCE - x =I

Fig. I . (a) The energydistanre curve for entry to the rrystal from an externally adsorlml
layer. ( b ) The energv4istance curve alien entry to tlic crystal takes plare directly froin t l w
gas phase.
C C denote constant Concentrations in the gas phase at x = 0 and x = Ircspertively.
go’ gl
Oo , @,denote fractions of external sites of type A occupied at x = 0 and x = 1 respectively.
O1. On denote fractions of internal sites occupied a t x = 0 and x = I respcctively.
.
E, E, denote activation energies for entry from external sites and for intracrystalline diffusioii
rcsprtively.
AEs , AE are energies of dcsorption from sites of type A and from intrarrystallinr sites
respcctivrly.
 259

MODEL
Sorption is assumed to obey Langmuir's isotherm for which diffusivity is independent of
concentration (ref. 6). A single crystal membrane, bounded by planes x = 0 and x = 1 separates
a constant gas phase concentration C at x = 1, with C > C Inside the crystal activatcd
d go gr
diffusion occurs involving energy harriers of height El. Molecules of diffusant may enter or
leave the crystals via an externally adsorbed layer, for which the cncrgy of desorption is A E ~ .
Fig. l a shows the energy - distancc configuration, the energy levels and the nomenclaturc
involvcd. If the windows are widc cnough some moleculcs may pass directly from the gas phase
to intracrystalline sites, for which the energy - distance curves and nomenclature are shown in
Fig. lb. Of the nett flow J through unit area of surface the fraction F2 J occurs as in Fig. l a
and a fraction F1 J as in Fig. lb, wlicre (F1 + F2) = 1.
A t and around channel mouths at x = 0 there are sites of type A from which the molecules
comprising F2 J enter the crystal and possibly sites of type I3 from which they do not. There is
however constant exchange of molecules between the two kinds of site and between each kind ol
site and the gas phase. In steady flow there is nett transport f2 J from the gas to the B-typc
sites and hcncc from B- to A-type sitcs. There is also nctt transport of fl J from the gas phase
to sites of type A and therefore (fl + f2) J = F2 J from these sitcs to the interior of the crystal.
In addition there is nett transport F1 J from the gas phase directly into the crystal. These
mechanisms are shown schematically in Fig. 2.

Entrv at x = 0 Exit at x =I
Gas Phase Sit,esesp

F1 7 /Sites A<-Sitf2es J B

li2J
Sites 1

Fig. 2. Mechanisms of cntry to and exit from the porous crystal mcmbrane.

STEADY FLOW WITIIIN A POROUS CRYSTAL MEMBRANE

The flow J will always refer to that through unit cross-scction normal to x. It was then
shown that J is given by (ref.2):
sk
J=- (O1-On) =- CXP (- E1/RT) (01-On)
(11 - 1) (n - 1 )
260

whcre s is the number of energy barriers of hcight El pcr unit arca in each of (n-1) planes
normal to x and k = kl exp (-El/RT) is the rate constant for jumping from onc energy well
over the barrier El to the next well. (n - 1) per channel denotes the number of barriers
bctwcen x = 0 and x = 1 and n is the corresponding number of cncrgy wells (i.e. sorption sites).
O1 and On are the fractional occupancies of sites 1 just within thc crystal at x = 0 and of sites n
just within the crystal at x = 1. They are not equilibrium but steady state values. To find
them the processes of Fig. 2 at and across the gas/solid interface must be considcrcd.

‘I’HE MASS BALANCE EQUATIONS

For direct entry from the gas to the crystal at x = 0
F1 J = sk C ( 1 - 01)- skb exp (-AEIRT) O1
a go (2)
where AE is the energy of desorption and sk,. and skb exp (-AE/RT) are rate constants pcr
unit area for entry to sites 1 and dcsorption from sites 1, respcctivcly. For cntry to the crystal
from sites of type A
F2J = skcexp (-Es /RT) 0, ( 1 -el)-skdexp[-(AE-AEs+ Es)/RT] Ol(l-Oo) (3)
where Es and (AE-AEs + Es) are tlic respcctive activation energies for entry from type-A to
sites 1 and for the conversc of this process (Fig. la). skccxp (-Es/RT) and skdexp [-(AE,
-AEs+ Es)/RT] are the corresponding rate coefficients. 0, is the fractional occupation of sitcs
of type A. In addition, for the extcrnally adsorbed molecules we have, in terms of Fig. 2,
fl J = ya Cgo (1 - Oo) - yb exp (-AEs /RT)0, (for type A sites) (4 1
f2 J = 7’a Cgo (1 - 0:) - 7; exp (-AES /RT) 0; (for type B sites) (5)
where ya, 7; are respcctive rate constants pcr unit area for adsorption on type A and type B
sites, and yb (exp (-AEs /RT) and 7; exp (-AEi /RT) are the corresponding desorption rate
constants. 0: is the fractional occupation of sitcs of typc B from which tlic energy of
desorption is AEg.
The sum of equations 2 and 3 tlicn gives the flow J through unit area of interface which is
also given by equation 1. This sum can Ix rearranged to give O1 as
O1 =
kaC o+ kcexp (-Es/RT)Oo- J/s
(6)
kaCgifkbexp(-AE/Rr + +
kcexp (-E SIRq 0, k [,exp I-(AE-AE s + E s ) ~ K 1 ’ ~ ( * ~ o )
In the same way at x = lone finds
on=
 261
kaC I+ kccxp ( - E s / R T ) O I + J/s
(7)
kaCgl+kbexp(-AE/RT) +
kcexp (-E ,IRT)0 l+kdexp[-(AE -AEs+Es)litrl'l( 1 4 3 l )
where @/isthe fractional occupation of A-typc sites at x = 1. A t cquilibrium

I< = ( k a / k b ) e x p ( A E / R T ) = O 1eq / C g o ( l - O l C q ) = 0 ncq /C g l ( 1 - 0 neq ) (8)

=(ra/rb)exp(AEs/RT)=O
o w /C go ( 1 - 0 o w ) = 0kq/C gl (1-0kq ) (9)

KSi = (kc /kd) exp [(AE-AEs) / RT] = 0 (1 - 0 ) / 0 (1 -0 )

leq mq mq leq
=Onec,(l-O ) / 0 (1-0 ) (10)
h b neq
Froiii tlicse equations one also lias
I<SI. = K/I< S (11)
and
kc /kd = ka ?b /kb^l, (12)
With the aid of equation 9 cquation 4 can bc transformcd (ref. 2) to givc at x = 0

(13)

cxprcssion at x = lis

M'itlioiit going through all the sleps, equations 6 and 7 with the aid of the eqnations S to 14 can
bc transformed to the cxnressions

wlicre
r = cxp [(AE- AEs +Es)/ItT]
A= ( k b / k d ) ~ p [ ( -AEs)/RT]
E~
Equations 15 and 16 show that O1 < OlCq and On > 0 , and that the tliffcrcnccs
nccl
(Ole(, - 01)and (On - 0 ) are not equal except, in the IIcnry's law rangc. Equations 15 and
ncq
16 also show that the imbalanccs (Olcc, - O1) and (Oil - 0ncq ) increasc as the flow J through
unit area increases, i.e. as the permeability increasrs.
When f l J / y C in equations 13 and 14 is << 1 0,-> 0 and o1-> Olcq. \I'hcn
a g ocrl
O0 antl O1in equations 6 and 7 arc respectively replaced hy 0 and 0 thc tcrms involving
ocq kq
f l J/yaCg i n eqnations 15 and 16 do not appear and tliese equations become
262

(20)

If O1 and On in equation 1 are replaced using equations 15 antl 16 tlic result is a cubic i n J.
When this substitution is made using cquations 19 and 20, on the other hand, one obtains lJie
linear equation

- Sk (21)
('lcq - 'neq) = id
Jid is the value of J when the second terms on the r.1i.s of equations 19 and 20 arc respectively
<< 0 1ecl and << OIlet1, i.e. when 0 1 -> Ole(, antl 0 I1 -> 0 neq'

An important case arises whcn at x = 1 a near-vacuum is niaintained for wliicli f l J / y C:

a gl
may no longer he small, while at x = 0, 0, -> 0 as assumed in deriving equation 19. I n
oeq
thcsc circumstances equation 16 bcconics
J [I'/Skd + K f , /?,I
0 =0 (22)
11 neq + A +
(I< - K , ) fl .]/ya + 1
and
......

+
kl'(1 - Ole )

- sk
+ ( l - ooeti)l

- (n-I)(Qleq
'(11

-Oncq) = J id
sk [ I ' / S k d
-1) [ A + (I< -
I<fl/ya]
K s ) f l J/ya + 1
1
(23)
Equation 23 is a qiiatlratic i n J. Important quantities inclutle Jitl, J i d / J antl f l .J/y C wliicli
a 6'
will lx considered in turn.

Estimation of Jid
Jitl was estimated in reference 2 for assigned values of I<C and of C /C which was
go' go @
taken to be 100. I n equations 21 or 23 k = k l cxp (-lC1/RT) and k l N vx, the vibration
frequency in the xedirection of the sorhctl niolcciile rclat.ive to it,s site. The value a.ssigiietl was
12 -1 3
5 x 10 s . The number of sites, s, per tin- just within the crystal was cqiiatctl with tlic
2
number of windows per cm . This number was calculated previously for a series of zrolitcs (ref.
2) antl the value 5 x 1013 was taken (corrcct for ZShl-5). This may be a lower limit for s
because just within each window tlicrc ma,y he several sites. For ( n -1) we have
(n -1) = l/d (24)
wliere d , the jump distance per unit, tlirfiision st,ep, wa.s t,a.ken as 5 x 10-8cm and 1 as 10-2cm,
which is close to t,he values i n recent siriglc crystal memhrane studies (rcfs.7-9).
 263

Tlie calculatcd values of Jid are reproduced i n Table 1 for several values of I<C and of
go
El/Rr. Table 1 indicatcs thc extreme sensitivity of Jid to the activation encrgy El and
temperature T , as indicatcd by tlic ratio E I / R T , and it suggests tlie scale of tlic ideal flows
which the crystal could generate. For a menibranc consisting of a monolayer of crystals, with
intcr-crystal gaps filled by an impermeablc substance, an active arca of 100 m 2 of crystal
surface would increase the throrigliputs by a factor of lo6 , but the fabrication of such
iiicnibrancs is so far an unsolved problem. At T = 301.9K the activation energies, El, in tlic
Tahle would be 9, 6, 4.2 and 3 kcal mol-I and at 90K these cncrgies would bc 2.6S, 1.79, 1.20
and 0.S9 kcal mot-' respectively. The maximum flow is found when K C = (C / C
go go g l *

TABLE 1
Jitl (cm3 at s.t.p. l~-1cm-2) for parametcrs assigiied in the text and for scvcral values of
KC and E1/RT. C /C = 100
go go .@

KCg0 ('leq -Ones) Jid when E1/RT is:

15 10 7 5

50 0.6471 3.31 x lop2 4.91 98.6 728.6

10 0.9192 4.19 x 6.22 125.0 923.3
5 0.7959 4.01 x 5.96 119.7 844.7
1 0.4901 2.51 x 1 0 8 3.71 74.7 551.8
0.1 0.0899 0 . 1 6 lop2
~ O.G8 13.7 101.2

Tlie Ratios JidU

With k = k l exp(-E1/RT), and with I? from eqiiation 17 and h from cquatioii IS
substituted into equation 21, it is seen that tlic resultant expression contains tlic ratios k l / k d
atid kb/kd. Thc cncrgy wells involving thcsc coefficient have identical or vcry similar contours
near tlic minima so tliat with kl-vx we expcct

kb-Fl vx ; kc1-F2 vx (25)

because, of the molecules leaving tlic crystal, the fract,ion F1 enters the gas phasc tlircctly and
the fraction F2 enters tlic externally atlsorbctl Iaycr. With (n - 1) = l/d (cqn.24) cqn.21 and 23
become rcspcct ivcly
264

TABLE 2
Particular cases of equations %G and 27
Conditions J .I tl / J (cqn.26)

F1 = 1 I + tl ( 2 - Olcq - Onctl) exp [(AE- E l ) / R l ] (2s)

F1 = 1; Olcq, Oncq<<l 1 + 2d CXII [(AE - El)/RT] (29)
r

F$, = 1; all 0's << 1 1 + csp (bAE/RT] (32)

tl
I:] = 1; 0 << 1 l - t 7 ( 2 - - 0 1cq ) exp [(AE - E,)/RT]
ncq
FI = 1; Olcq, 0 < < 1 +
1 2tl esp [ ( A E - E l ) / R T ]
ncq 7-

1 + (skll\f / y a )
(I\ -
CX~, [(AEs
I\7s) f , J / T ,
-

+
A15 - E,)/RT]
1 I (35)
 265

Several special cases arc suinmarisctl i n l’able 2, i n which 6AE = (AE - AEs + Es - E l ) , and
so is the difference hctwccn tlic a c t i v a t h energy for desorption from within the crystal to the
cstcriially adsorbed layer, ( A E - AEs + Es) , (sce Fig. la) and the activation energy for
intracrystalline diffusion, El. In all tlic expressions in Table 2 the terms ((I/[) cxp (6AE/RT)
or ((I/[) cxp ( A E - E1)/RT appear. Their numcrical cvaluation shows t1ra.t thcsc terms can be
vcry large down to very small (Tahle 3). I f tlir former, J will he much less than Jid; if thr
Iatt.cr, J.Id /.I -> 1. The values EAE must Iiavc, at. several temperatures, to givc thc valucs of
(d/l) cxp (EAE/RT) in the second column arc shown in the last five columns of Table 3. I t is
notktl t1ia.t 2/(n - 1) = 2d/l is tlic ratio of tlic numl)cr of harriers across thc two interfaces a t x
= 0 antl x = 1 to the numbcr of intracryst.allinc barriers.

6AE/RT (tl/l)csp (EAE/RT) bAE/kcal mo1-l at T/I< =

78 90 19.5 273 301.9

‘LO 2.4’LG x lo3 3.009 3.576 7.75 1O.S.5 12.00

I
15 1.635 x 10 2.3% 2.GSR 5.S1 S.14 9.00
10 1.101 x l o 1 1.550 1.78s 3.S75 5.12 6.00
7 7.421 1.085 1.252 2.712 3.SO 4.20

I n Table 4 (ref. 2) values of J.I d /.I are given, according to equation 31, with tl = 5 x 10-scni

antl C / Cg l = 10. The figures crnpliasisr again that low tcinpcratrircs and vcry sinall
go
crgstallitcs will favow high valurs of .Iitl /.I and convcrsrly thc higlrcr the tcmpcraturc and the
n

Iilrger tlic crystal tlic iriorc iicarly will .litl /.J approac1i unity. TIIUS,for I = 10-”cin ant1 at ~ O K
.J is rnuclr less than Jitl /.I for all EAE > 2 kcal inol-l , and if 1 = 10-2cm the sa1iic is true for all
6AE 2 3.0 kcal mol-’ . A t 301.91i, oil tlre other liantl, .I.Id / J is vcry close or close to unity for
all l i a ~< 6.0 kcal rno1-l . Large values of ME could inc~ica.tepartial blockage of wintlows
giving access to t,lie int.rrior of the crystal due to special causes (refs. 3-5).
266

Estimation of fl J/Y& Cg
I n deriving equation 26 it was assumed that Oo = 0 and Q I = Okq, so tlial i n eqwitions
oeq
13 and 14 f l J/X. C must be << I . This assumption will now he examined.
h g
2
y C is the number of molccnlcs per second per cm that are adsorbed on sites of type A
a g
(at or around channel mouths). l'liis numhcr will bc less than hut of thc same order as the
nnrnhcr of collisions per second per cni2 . This collision numhcr is C c/4 whcrc c is the average
g
spcctl of a molecule, so that ya is less than but tlic same order as c/4. Likewise f l will be less
hut of the same order as unity so that a reasonable approximation to f l J / y C will be 4.J/tC' .
" g g
The maximum value of this term is 4JiCl/CC . .JiCl can be taken from Table I , after conversion
6
-I cni-2
to niolcculcs s . C is i n molcciilcs cni-"' and the avrrage spcctl in cni s-I. Tallle 5
g
gives values of c for a number of gases as well as the collision nninlxrs (molecnlcs s -'cm -2)
according to the ideal gas law at one atmosphere pressure.

TABLE 4
Jitl/.J according to cqnation 31(') for different values of I<C and bAE (kcal n7oI-l). C / C
= 1o and (I = 5 x 1o -'
cm
go go )gl

2.0 3.0 4.2 6.0

90 10-2 0.1 l.GS3 IS4 1.50 x lo5 3.53 x lo9

1.o 1.507 137 1.1%x lo5 2.62 x 10'
4
5.0 1.300 SI.3 6.59 x 10 1.55 x 109
50.0 1.067 1S.N 1.47 x 104 3.46 x 10
S
I I I
6
90 0.1 7.83 1831 1.50 x 10 3.53 x 10 10
1.0 (3.07 136 1 1.12 x 10
G 2.G2 x 1010
5.0 4.00 80.4 6.59 x 10' 1 5 5 x 1010
50.0 1.G7 181 1.47 x 105 3.46 x 10
9
I I I

301.9 10-2 0.1 1.011 1.209

1.o 1.0062 1.154
5.0 1.0055 1.092
50.0 1.0011 1.021

301.9 0.1 1.11 3.09

I .o I .ns 2.54
5.0 1 ,055 1 .92
50.0 1.011 I .21
 267

Argon may be taken from Table 5 as a sample diffusant. Then in steady flow through
single crystal membranes one obtains for 4Jid /C C the values in Table 6. The mcmhrancs
g
have been assigned a nuinher of values of El /RT and there is a range in KC In each case
go'
C has the value appropriate for 1 atm pressure at the temperatures T = 90K or 301.91<, and
go
Cgo /Cg,is 100. Other parameters uscd in estimating Jid were: 1 = 10-2 cm; (1 = 5 x 1012 5 -1
aiid s = 5 x 1013~ m - ~
as ,for Table 1. Clearly at 1 atm one is well justified i n taking
0 =0 , and, with C = lo-' C as i n Table 6 , one is also justified in taking
o oeq gl 60
0 1-- 0 Pq'

hlolccnle cs at: c c /4 x at:

g
901; 301.91; 90k 301 .OK
0.971 1.77s 1.950 1.051
0.GS7 1.257 1.400 0.7G4
0.691 1.266 1.409 0.769
0.345 0.631 - 0.354
"2 0.2607 0.475 0.532 0.2902
co 0.2609 0.47s 0.532 0.2904
0'2 0.2440 0.447 0.495 0.2716
Ar 0.21SG 0.400 0.44G 0.2433
C02 0.2os1 0.351 - 0.2316

I n equation 27 , which is applicable wlicn a near varitiim is maintained on the exit side of
tlie nicnil~ranc,the tcim [(I< - KS)( f l J/ya) + 11 arises. The cqiiation is simplifictl if it can he
shown that ( K -I$) ( f l lily,) is << 1. As previottsly, we assitme f1/ya-4/C and the flow, .J,
is replaced by its maximiim value, .lid . For the rlioscn valucs of KC the Langmuit
g
eqtiilil~riumconstant, I<, was found when the pressure at the ingoing face of tlie crystal was
taken as 1 atm. At this pressitre for the ideal gas C = 2.431 x lo1' rnoleculcs c 1 ~ 1 -at~ 301.91<
g
arid S.155 x 10 I9' at 9OK. If one then again t a k a the average speed, C, for A r from Table 5 as
the example the valrtes of 41</c-fl ate those i n Tablc 7.
268

TABLE 6
4 J i d / t Cgo for Ar at 90K and 301.9K ,for membranes having the parameters givrn i n the text
and with C / C = 100.
go gl

50 0.6471 90 0 . 5 5 5 ~ 1 0 - ~
301.9 1.O 17x lo-' 1.509x lo-'
0.8182 90 0.702x 1or9
301.9 1.2s6x10-9
5 0.7857 90 0.674~10-~
30 1.9 1.253~10-~
1 0.4901 90 0.42 1x I o-{)
301.9 0.772x.10-9
0.1 0.0899 90 0.077 1x 1 0-9
301.9 0.14 13x 10-9

Values of .lid were next calculal~ctlfor 1 atm pressure of tliffrisant at x = 0 and iicar-vaciiulr1 ill,

x = 1 (Omq -> 0). As iii Talde 1, the valrics of .Jicl at 90K (as molcciilcs s - ~ c I T - ~arc'
) sriclr
that 4 Jid K/c is always orders of inagnitutlc less f,lra.n 1 so that a fortiori the same' must be I r11e
of 4Jid (I< - Ks)/c. It therefore scciiis plol)able that the term (I< - I< ) f , l / can
~ ~be oiiiit.t.ctl
s 1
from equation 27, 34, and 35 untlcr inost, cspcriinciital contlitioas.
TABLE 7
Values of q u a n t i t i e s needed t o find 4Jid K/C f o r Ar. Ingoing pressure 1 atm.
J i n molecules s-l K i n molecules -' cm3., c- i.n cm s-'.

4K/C a t Jid a t 90K f o r E1/RT equal t o :

Kcgo %eq
90K 301.9K 20 15 10
- 5

50 0.9804 3 . 7 6 ~ 1 0 - ' ~6 . 1 3 ~ 1 0 - 2~ .~5 3 ~ 1 03~. ~ 7 5 ~ 1 05~. ~5 6 ~ 1 01~. 1~ 2 ~ 1 08 .~2~6 ~ 1 0 ~ '

10 0.9091 7 . 5 3 ~ 1 0 - ' ~ 1 . 2 3 ~ 1 0 -2~.~3 4 ~ 1 03~. ~ 4 8 ~ 1 05 ~. 2~ 1 ~ 1 01~. 0~ 4 ~ 1 07 .~6~6 ~ 1 0 ~ '
5 0.8333 3 . 7 6 ~ 1 0 -6. ~ ~I ~ X I O - ' ~2 . 1 5 ~ 1 0 ~3' . 1 9 ~ 1 0 ' 4~. 7 3 ~ 1 0 ' 9~ . 5 0 ~ 1 0 ' 7~. 0 2 ~ 1 0 ~ '
1 0.5000 7 . 5 3 ~ 1 0 - 1~ .~2 3 ~ 1 0 - 1~ .~2 9 ~ 1 01~. ~ 9 1 ~ 1 02 ~. 8~ 4 ~ 1 05 ~. 7~ 0 ~ 1 04 ~. 2~ 1 ~ 1 0 ~ ~
0.1 0.0909 7 . 5 3 ~ 1 0 - ~ ' 1 . 2 3 ~ 1 0 - 2~ .~3 4 ~ 1 03~. ~4 8 ~ 1 05 ~. 1~ 6 ~ 1 01~. 0~ 4 ~ 1 07 ~. 6~ 6 ~ 1 0 ~ ~

N
W
0)
270

‘1’a.blc 4 thcrcfore shows some conditions untlcr which Did/D greatly cxcccds or approaclics
app
unit,y. If equation 37 is used to int,crpret measured stcatly flows in terms of D a1w where .I.Id / J
cxceeds unity a variety of values of D coultl result in the same zeolite according to tho
aPl)
choice of variablcs which dctcrniine the extent of non+quilihrium across ttic gas/crystal
interface (inter alia I, T , C antl C ). As 1 and/or T increase tlic D will converge toward
go gl aPP
Did. Moreover, diffusivitics can vary among different samples of t,he same zrolito if thcsc
samples conta.in variable amounts of part.ial int,racrystallinc blockages, as considered i n ref. 2
for lkiimensional channcl systcnis.
From Jid = (skld/l) cxp (-El/R.T) (Olcq -Oncq) = Ditl CSat,(0leq - 0ncq )/[, whcrc
csat= s / ( ~is the npta.ke in molecules wlicii o= 1, wc Iiavc for tlic int.racrysta\linc
tliffusivity in an itlcal crystal:
I)icl = k l d 2 CXP (-E1/RT)
(39)
This expression is implicit in thc calcula.t.ion of -1.It1 i n ‘I’ahlcs 1 and 7. k l , tl a n d El will
vary according to the porous cryst.al antl the diffnsant. With the prcvioris assignnicnt,s k l = vx
= 9x s-’ and d = 5 x 10 -’ cm , D~~~for (liffcrcnt. valncs of E ~ / R Tis as follows:
El/lt?. 20 15 10 7 5 3.33

I)i(l/cnl‘Ls-l 2 . 6 ~ 1 0 - ~ ’ 3 . S ~ 1 0 - ~ . 5 . 7 ~ 1 0 - ~ 1 . 1 4 ~ 1 0 - ~ S . ~ X I O - ~4 . 5 ~ 1 0 ~ ’

El at 301.91<
12.0 9.0 6.0 4.2 3.0 2.0
kcal nio1-l
Thus the simple cqnation 39 yiclrls physically rc1asoiial)le valucs of I). id for t,hc ahovc clioice of
k l antl (I.

‘1’ It A NS I ENT FLOW

I n non-steady flow the niass halancc cquat ions at and across the gas/crgstal intcrfaccs
apply exactly as tlicy do i n stcatly flow. IIowevcr, i n cqiiations 1.5 and 16 for the nori-steady
state the flows through unit area a t x = 0 antl x = 1 are functions of time, antl tlicreforc so arc
O1 and 01,just witliiii the crystal a t tlicsc 1)oiintlarics. T w o important cxaniplcs of non-steady

flows will tx briefly considered:

(i) The single crysthl niemhranc is i n sorpt,ion equilibrium wit,li the gas at, concent,ration
C At t = 0 , C at x = 0 only is inst,anta.neously raised to C and t.hc system
gf gl go’
t.licrcaftcr rclaxcs t,owartl the stcatly state of flow, wit.11 C and C licltl constknt. For
go d
greater simplicity, in place of cqiiat.ions 1.5 and 16, for the externally adsorhcd layers
 271

it is assumed that 0 = 0
0 ocq and O1= OlCqas in equations 19 and 20. Tlicn
J 1 ( t ) = [OleC,- O1 (t)] R1 = - Csat D ( t l O / t l ~=
)~ (40)
and at x = 1
J n ( t ) = [On ( t ) - 0 neq ] R2 = -Csat D ( t l O / d ~ =
) ~1 (41)
The respective cocfficicnts, with the aid of equations 17, 18 and 25, bccomc

Ill =
did ( A +1 - OOe )
-
skl {F1 + F, (1 - OOe ) exp [ ( A E , - Es)/RT]}
( 1 - 0 1cq) ( 1 - 0 1c q ) exp (AEIRT) (42)

R =
skd ( A + -
+
1 - Ole ) skl {F1 F2 ( 1 - O l e ) e x p [ ( A E s - Es)/RT]}
I1 (1 - 0 ( 1 - 0n e q ) exp (43)
ncq)
Eqiialions 42 and 43 show thosc properties of a sorbatesorbent system which, in addition
to .J(t), will determine tlie differences between 0 and 0 ( t ) just within tlie crystal. The
cq
coefficients R1 or RI, arc the same for t,ransicnt, and steady flows and thcrcforc thc ratios
J1 ( t ) / [Oleq - 0 , (t)] or J n (1) / [On ( t ) - OnCq] arc constant for all t. If transient
solutions of Fick's second equation arc required they must satisfy tlic boundary condition
O1 = O1 ( t ) a.nt1 0n = 0n (1) for a.ll t > 0 (44)
ratlicr than solutions bascd upon the assumption
O1 = Olcq and OI1 = 0 for all t > 0 (15)
ncq
(ii) The sccontl example is that of sorption and tlcsorption kinctics, in which flow decays
from an initial niaximum va.luc to zero at eqiiilil~riiim. At time t = 0 for sorption the
concentration at x = 0 a.nd x = 1 is instantaneously raised from C to C and kcpt
gl go
constant at that value. Tlic system tliercafter relaxes from its prcvious sorption
equilibrium to t,hc new equilibrium. For a cryst,al with a I-dimensional channel system
parallel with the xdircctioii
J ( t ) = 0 = - J ( t ) = / = [@cq - 0 ( t ) ] R = -Csat D((l@/dx)x = 0 (46)
For tlcsorption, when at t = 0, C is instantancously lowered to C the corresponding
go .d
expression is
-J (1,) = 0 = J (t,) = 1= (0 ( t ) - 0 ] 0 = - C sa.t D ( t l B / d ~ ) ~ = (47)
C(l
I n tlirsc expressions a positive sign is given to J (t) whcre flow is in the direction of x
incrca.sing. The symmct,ry of tlic situation at each intcrfacc means that R1 = RI1 = R in
equations 42 and 43. Otherwise comments made for transicnt, flow in tlic membrane apply
equally to solption~llesorptionkinetics. Especially if J ( t ) is initially large the time
dependence of 0 ( t ) a n d its difference from 0 may be such that solut,ions of Fick's
ccl
second equation ba.scd on 0 = 0 for all t > 0 at x = 0 and x = 1 (equation 45) arc no
cq
212

longer suitable for evaluating tliffusivities.

In many past attempts to reconcile tliffusivitics obta.inetl from sorption kinetics with
the large diffusivity values mcasurahlc by pulsed field gradient N M R , the sorption kinetics
method has involved extremely small half-lives for the sorption and initially large flows
.](I,). Initial tirnc tlependcncc of 0 (I,) is tlien masimiscd as arc initial differences between
0 and 0 (t). Time dependence of 0 just within the intcrfa.ccs i n such circiimstanccs m y
cq
therefore have to he atldctl to the othcr known limitations to obtaining meaningfill
tliffusivities from very fast sorpt,ion rates. For the pnrpose of finding diffusivitics the
sorpt,ion kinetics method should best he confined to slow or very slow uptakes wlicn nearly
all the limitations encountered with very fast uptakes are avoided.
While, for consta.nt C t,lie relation between 0 (t,) just wit.liin tlic crystal and tlic
go '
t.iine is not known, it coiild for fast upthtkes he a st,rong fnnction of time. One empirical
function of tinic for 0 ( t ) just, within s = 0 or x = 1 is
@ ( t ) = O (l-cxp(-/3t))fort>O (48)
crl
when the cryst,al is init,ially free of sorhate antl at t = 0 is exposcd t,o a const,ant external
concentra.tion of the sorhate. For p = IX and all t > 0 equation 4s givcs 0 ( t ) = 0
eq
while, as t -> 0 and for finite p, it givcs 0 ( t ) -> 0.
Solutions of the diffusion equation have hccn given by Crank( lo) for tlic bounclary
condition of equation 4s for diffusion i n I-, 2- or klirnensions. For a splicrc of ratliris x
his plots of relative upt,akes as a fiinct,ion of tlinicnsionless time, Dt/a2 , become
increasingly signioid as /3 tlecreases and t,lie half-lives, tlI2, of the sorption process
3
increase strongly wilh decreasing /3 for constant D/a- , as thc following approximate
values of Dtl/'_/a 2 show:

pa"/D = o;, 5.0 1.0 0.5 0.1

3
Dtl/,/a- = 19 SI 1!J0 5S0 2S70
In the above circumstances apparcnt diffusivit,ies ohtainc~lfrom half-lives by neglecting
tlic role of 0 can, for finite 8, he very significa,nt,ly less than the true value. The larger the
2
value of pa / D the more nearly is Dt 1/2 /a2 given 11y t ~ i csolution of the diffusion equation
for 0 = 0 at the surface of entry for all t > 0.
cq

CONCLIJDING REMARKS
It has becn the purpose of this paper antl its pictlecessor (ref. 2 ) to model the transpoit
piopcrtics of single crystal membranes taking into acconnt the processes occurring at and
acioss the mcmbiane surfaces as well as tliose witliin the crystal. In the present paper the
iiiotlel has hwn extentled to include the possibility of simultaneous entry to the crystal both via
an externally adsorbed lajer antl tliicctly fioin the gas phi1sr. Tlic role of tlic mass balance
equations across tlic surface has also 1w.w extentled to sorption~esorption kinetics.
 273

I n t.hc previous paper (ref. 2) thc important role of partial blockagcs located along
l-dimcnsional ( 1 - D ) channcl systems was niodcllcd and examined numerically. The papcrs
show how the modcrating effect of the mass balance equations at and across mcmbranc surfaces
will increase with decreasing thickness and falling tempcraturc. Some numerical estimates
indicate that undcr conditions when the intcrface cffccts havc littlc influcncc upon flow at room
tcrnpcrature these effects may dominatc flow at low tcmpcraturcs, such as OOK. \Vliere flow is
reduccd by partial blockages distributed along 1 - D clianncls thc reduct.ion is indcpcndent of
membrane thickness and can be vcry large (ref. 2).

REFERENCES
1 R.M. Barrer, in "The structure and Propcrtics of porous Matcrials". Eds., D.H. Everett
and F.S. Stone, (Butterworth). 195S, p.170
2 R.M Barrcr, J.Chcm. SOC.Faraday Trans., 1990, SG, 1123.
3 M. Kocirik, P. Struvc, K. Fiedlcr and hi. Bulow, -1. Chcm. Soc. Faratlay Trans. I , lOSS, 81,
3001.
4 M. Kocirik, A . Zikanova, P. Struvc and hl. Bulow, i n "Zeolitcs: Facts, Fiqurcs, Future".
Eds. P . A . Jacobs and R.A. van Santcn (Elscvicr), 19S9, p.925.
5 J . Kargcr, II. Pfcifcr and W. Ileink, i n Proc., Gth Int. Zeolite Conferencc, Eds. D. Olson and
A. Bisio (Butterworth) 19S4, p.lS4.
G I1.M. Barrcr, Langmuir, 19S7,3, 309
7 D.L. Wernick and E.J. Osterhuher, i n Proc. 6th Int. Zcolite Confcrcncc, Etls. D. Olson and
A. Bisco (Butterworth) 1983, p.123.
S A. Paravar and D.T Hayhurst, in Proc. Gtli Int. Zcolitc Confcrcncc, Eds. D. Olson and A
Bisio (Buttcrworth) 1984, p.217.
9 D.T Hayhurst and A.R Paravar, Zcolitcs, ISSS,g, 27.
10 J.Crank, "Thc Mathematics of Diffusion" 2nd Edition, (Clarcntlon Prcss), 1975, pp.53, 75
and 92.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 275
1991 Elsevier Science Publishers B.V., Amsterdam

THE ROLES OF METAL AND ORGANIC CATIONS IN ZEOLITE SYNTHESIS

D.E.W. VAUGHAN
Exxon Research and Engineering Company,
Rt. 22 East, Annandale, New Jersey, U.S.A., 08801.

SUMMARY
The position is taken that the crystallization products of a gel are the
key to understanding the important gel intermediate structures and therefore
the mode of zeolite genesis. Reviewing the products of reactions in sodium
and potassium aluminosilicate gels leads to the conclusion that extended sheet
(Na) and columnar ( K ) sub-structures are the important structure building
units. The smaller base metal cation controls the nature of the sub-structure
and the larger cation the ways in which such units interconnect to form
specific zeolites.

INTRODUCTION
Much recent interest in modes of zeolite genesis has focused on the role
of small molecular clusters as major participatory species in the direction and
development of zeolite structure types, relying mainly on developments i n
such techniques as NMR (1,2,3) and Raman spectroscopy (4) combined with
increasingly powerful computer hardware and software capabilities which
facilitate infinite peak deconvolution and search-match abilities. S u c h
methods reveal much new information about the complexities of the silicate
and gel systems of interest, but they give little guidance to those researchers
interested in creating, and preferably tailoring, new zeolite structures.
Indeed, it is probable that species observed in solution during zeolite
crystallization are primarily "spectator species" in a state of dynamic near
equilibrium in a reactive system in which the "participatory species" are
constantly scavenged by the growing zeolite(s) or their structure additive
sub-units.
An alternative approach, examined i n part by Liebau for silicates i n
general ( 5 ) and by Barrer for zeolites i n particular (6), is to look at larger
216

entities, such as sheet or chain structures, and to examine how these

interconnect in various ways to form t h e many different structures which
characterize the crystallization systems of interest. The products and their
inter-relationships are the starting point rather than the gel systems. T o this
author it is this latter approach which not only explains much of the available
experimental data, but offers some opportunity for designed syntheses within
the limitations of the specific system of interest. This paper will evaluate
numerous minor cation substitutions on the products of separate series of
syntheses in sodium aluminosilicate and potassium aluminosilicate systems.
The focus will be mainly on the low silica: alumina ratio gels and products
where the reactivity, and therefore the multiplicity and diversity of zeolites,
is high. At lower temperatures less stable products survive longer and can
therefore be analyzed and recognized. The more rapid the approach to
thermodynamic equilibrium (represented by higher density zeolite mineral
equivalents) the lower the probability of detecting novel and interesting
products.

CRYSTALLIZATION PRODUCT OVERVIEW

T h e approximate composition range of primary interest in this
discussion is:

2-4 (Na,K)20: xM20: A1203: 6-15SiO2: 100-200H20

where M is either a Group 1A or simple alkylammonium cation and x is less

than 1.O. T h e initial ("metastable") main crystallization products at
temperatures between 90 and 180°C using sodium or potassium silicates or
colloidal silica are:
Na K
FAU LTL
FA U - b ss in t ergr o w t h s OFF
GME ERI
MAZ
ECR-I
MOR
beta
The phases stable at long reaction times are CIS, PHI and MER, with the first
dominating the sodium system and mixtures of the lattcr two the potassium
system. Mixtures are common in most of the experiments in this composition
range, but pure products can be made in high yield by suitable "fine tuning"
 277

of the gel compositions and choice of raw materials. ANA (pollucite)

dominates the crystallization of any gel composition containing caesium and,
with the exception of CSZ-1 and -3, frequently inhibits nucleation over most
of this composition range. In understanding the products of these systems
recent high resolution structure imaging results have been invaluable
(7,8,9,10). (Throughout the IZA structure codes will be used to indicate
structure type (1 l ) , with lower case indicating proposed structures, or
"inter g r o w n " p h a s e s where the i n d i c a t e d s t r u c t u r e p r e d o m i n a t e s .)
(Oualification: This discussion is based on broad generalizations made on the
basis of an overview of many experiments. Specific phases and phase
combinations are influenced by numerous experimental factors, particularly
raw materials and nucleation effects. Specific references should be consulted
for these details.)

GME
GIS MAZ
MER LTL
PHI OFF

MAZ

Figure 1. The building units characteristic of the many structures under

discussion can be readily derived from the Si12 unit in the center of the figure
by rearranging a few S i - 0 linkages. Rapid re-equilibration of the system
maintains the supply of those removed by the growing zeolites.
278

In terms of derived secondary building units (sbu) or similarly sized

clusters all the structures may be readily derived from the Si12 unit shown in
Figure 1 by a small number of S i - 0 bond changes. The rapid equilibration of
such a system would ensure a constant supply of nutrient sbu to the growing
zeolite crystals, but these would always be at a low concentration and
therefore not expected to be observed in the solution or gel.

LAYER STRUCTURES DOMINATE THE SODIUM ALUMINOSILICATE SYSTEM

Various Si/AI ratio faujasites are the dominant products in this system
for almost the whole range of M species evaluated, as detailed in Table 1 . In
the cases of K and Rb substitution only morphology effects are evident, with
the tendency to form platelet crystals of FAU. Substitution of larger cations
such as Li (hydrated) and C s not only accentuates the development of platelet
forms (ZSM-2 and 3; CSZ-I and 3), but introduces faults and defects associated
with the bss connectivity of the "faujasite" sheets. (The so called Breck
structure-6, first proposed as a theoretical structure by Moore and Smith
(1 3), formed by connecting "faujasite" sheets together to give the hexagonal
structure shown in Figure 2 (16)) These effects become more pronounced
with increasing Si/AI ratios, but phase stability pushes the system more
towards MOR at gel Si/AI over about 6, with that zeolite dominating as the
primary product when the Si/AI exceeds about 8.

The addition of alkylammonium cations yields higher ratio zeolite Y

(13), but gmelinite like impurities (gme) co-crystallize more readily than in
the organic free gels in the absence of agitation. (Growth of these gme
products is usually greatly accelerated in stirred crystallizations, probably as
a result of "collision breeding" of nuclei of this "phase". As the crystallizing
solutions are homogenized before each sample is removed i n a single batch,
sequentially sampled to obtain a timed crystallization profile, the sampling
mode may i n fact promote the gme component. One notes that t h e basic
building u n i t of GME is the same as that for CIS, MER and PHI, as shown i n
Figure 1.) The notable exceptions are the development of MAZ in TMA
systems and ECR-1 i n DMDE(0H) containing gels at higher temperatures,
indicating that the "mazzite" sheet is more stable than the "faujasite " sheet.
FAU usually precedes MAZ in these crystallizations at M<0.6. With increasing
gel Si/AI ratios TMA continues to promote MAZ; TEA systems move towards
beta (a racemic mixture of two enantiomorphic sheets (15,16)), and in some
special cases the highly intergrown "defective" structure ZSM-20 ( 1 7):
DMDE(OM), TPA and TBA gels promote the formation of high silica FAU (ECR-4
 279

(18) and 32 (19) respectively). MTE(0H) (methyltrihydroxyethyl-ammonium)

directs the product to ECR-30 (20) (bss).

TABLE 1
Phase development with sodium as the primary cation

Secondary Cation(M) Products at 100°C Products at 15OOC

Li pZSM-2/3 -> CIS GIS -> ANA

Na FAU/GME -> CIS MOR/GIS -> ANA
K pFAll -> MER GIS/PHI -> ANA
Rb pFAIJ -> MER PHI -> ANA
cs pC~Z-1/3-> ANA ANA
TMA FAU -> MAZ MAZ
DMDE(0H) FAU ECR-1 ->ANA
TEA FAU -> GIS FAU/gme -> GIS -> ANA
TPA FAU/gme -> GIS FAU/gme -> GIS
TBA FAU/gme -> GIS FAU/gme -> ANA

Arrows indicate progressive development with increasing crystallization time.

gme is an material comprising mainly gmelinite with some chabazite like
intergrowths. p indicates distinctive platelet morphology.
TMA= tetramethylammonium; T E A = tetraethylammonium; DMDE(OH)=
dihydroxyethyldimethylammonium; TPA= tetrapropylammonium; TBA=tetra-
butylammonium.
ZSM (Mobil), CsZ (Grace Co.) and ECR (Exxon) are proprietary designations.

Products based on FAU sheets

With the exception of MAZ and ECR-1, all the initial products in this
system comprise various arrangements of FAU sheets. The sheet itself is
seemingly specifically sodium "templated". In the absence of a specific
secondary influence these always assemble in the FAU arrangement. One
notes that at lower Si/Al ratios the organic templates are not trapped within
the zeolite, possibly because of the large number of cations required for
charge balancing the structure. At higher Si/Al ratios the symmetrical
alkylammonium cations are occluded in the FAU but d o not seem to induce
detectable bss intergrowths. (ZSM-20 i s somewhat of an exception here in
that the large amount of it is randomly intergrown fau-bss, strongly
influenced by the specific structure of the gel.
280

FAUJASITE ( F A 4
Pure 1 or pure 2
layer type 1

layer type 2
(mirror image of layer 1)
BRECK'S 'STRUCTURE 6' (BSS)
Alternating 1 and 2

Figure 2. The sheet structure of FAU, consisting of double 6-ring connected

sodalite cages, may have two kinds of connectivity. The cubic ABCABC kind of
arrangement characteristic of FAU (X, Y , ECR-4, ECR-32)and the hexagonal
ABAB arrangement characteristic of ECR-30 (bss). If carbon atoms replaced
sodalite cages, the former would have the diamond structure and the latter
the lonsdaleite structure.

It is interesting to note that the later part of the crystallization - represented

by the crystal the overgrowths and outgrowths - is almost pure FAU(17).) The
large Li and C s cations d o however induce a significant and measurable
amount of mis-stacking in the form of twin planes or bss layers. The
asymmetric MTE(0H) clearly stabilizes the ABAB stacked (ECR-30) form.

Products based on MAZ sheets

MAZ is stabilized by TMA, but as the MAZ sheet is also present in ECR-1
(8), TMA is therefore not a necessary prerequisite for the stability of this
structure, although it may stabilized it at low temperature by occlusion of
TMA in the gmelinite cages. Rather it is a more stable structure than the FAU
sheet at higher temperatures (100-160°C). to be replaced at even higher
temperatures (and independently at higher Si/AI ratios) by the more stable
mordenite sheet, reflected in frequent low levels of MOR with ANA in the
 281

base metal gel products. ECR-1 is a "boundary phase" between MAZ and MOR,
specifically templated by DMDE(0H) (21), these materials having structures
related as shown in Figure 3. The MAZ and MOR sheets may be connected in
two different ways, at c=O and 1/2, and it is possible that ECR-1 may be a
mixture of the two forms (22). Coherent overgrowths of MAZ on ECR-1 (8) and
MOR on MAZ have also been reported(23).

MAZ ECR- 1 MOR

Figure 3. ECR-1 is a boundary phase between the crystallization fields of MAZ

and MOR, comprising connected alternating mazzite and mordenite sheets. I t
can be viewed as a recurrent intergrowth of MAZ and MOR. Coherent
overgrowths of one structure on another have also been observed in this
system.

COLUMNAR STRUCTURES DOMINATE THE POTASSIUM ALUMINOSILICATE

SYSTEM.
LTL dominates this composition range, demonstrating much
morphological variability (size and shape) as functions of secondary cation,
temperature and mixing. Na, Cs and TMA have the most pronounced
influence, primarily by stabilizing OFF and in some cases ERI. As in the
sodium aluminosilicate system, the presence of caesium promotes pollucite -
to the exclusion of all other phases. Details are given in Table 2. At lower
Si/Al ratios highly intergrown chabazite like products (the materials
designated G by Barrer and coworkers (24)) frequently appear as minor or
major products, and at higher ratios MOR may be a minor component.

Apart from TMA inducing the formation of OFF and OFF/ERI mixtures
(ERI always the minor component), the alkylammonium gels produced mainly
282

LTL, frequently having relatively high Si/AI ratios near the limit of the Linde
L composition range of 2.6 to 3.45 (25). The presence of the alkyl ammonium
cations also greatly slow the sequential reaction to more dense products,
presumably by inhibiting the nucleation of the denser zeolites PHI and MER.
OFF and ERI may crystallize either as separate crystals (26) or as a crystalline
intergrowth of the Linde T type (27), but in these experiments they were not
differentiated.

TABLE 2
Phase development with potassium as the primary cation.

Secondary Cation(M) Products at 100°C Products at 15OOC

Li LTL LTL -> PHI

Na LTL LTL
K LTL -> MER LTL -> MER/PHI
Rb LTL -> MER LTL -> MER
cs ANA ANA
TMA OFFER1 OFF/ERI
DMDE(OH) LTL LTL/OFF/ERI
TEA LTL LTL
TPA LTL LTL
TBA LTL LTL

Products based LTL type columns

LTL and OFF are assembled from the same columns of double 6-ring
linked cancrinite cages and the ERI column is similar, differing only in a "flip"
in the cancrinite cage linkages, as shown i n Figure 4. Although much has been
made of the ABC 6-ring sheet stacking relationship of OFF and ERI (and many
other structures too (see ref. 28 for a good review)), LTL does not belong to
that structural group and would not therefore be expected as a c o -
crystallization product if such a sheet dominated the gel structure. The co-
crystallization of LTL and OFF/ERI with an apparent epitaxial interface in
hammer shaped crystal associations (with the hammer head LTL and shaft
OFF) requires a common interfacial structure (29).
 283

LlNDE L OFFRETtlE ERlONlTE

Figure 4. The columnar structures and relationships in LTL, OFF and ERI.

Structures based on 4-ring chains

The major secondary and stable products in both systems - CIS, MER
and PHI - all have structures based on the same edge shared 4-ring chain
(Figure 1) linked together in the ways shown in Figure 5 , and identical to that
in GME. Similar chains are the main feature of OFF, M A 2 and LTL, as shown in
Figure 1.

PHILLIPSITE MERLlNOlTE QISMONDINE

Figure 5. In GIs, MER and PHI the same chain of 4-rings is connected in the
ways shown to form sheets which constitute the extended building unit.
284

The most stable product at temperatures over about 160°C f o r all

compositions studied is A N A , which comprises a structure of corner shared 4-
ring chains.

DISCUSSION
The data discussed i n this paper represent three groups of related
zeolites which crystallize and often co-crystallize over a small range of
synthesis conditions - FAU/bss; MAZ/MOR/ECR-1; LTL/ERI/OFF. Their
associations can be better understood if the critical structure determining
units are seen as being much larger than the sbu small cluster groups
generally favoured as the important structure building units. In these cases
the structure of the extended structure (sheet, column, chain, etc) is
seemingly determined by the Group 1A base metal cation and the manner i n
which they join together is determined by the charge and configuration of the
larger secondary cation.

Figure 6. Small extended structures (discussed above) have been observed in

the early stages of agglomeration for a 12-ring zeolite (electron micrograph
by Dr.S.B.Rice). The agglomerated 12-rings are similar to the individual micro-
domains observed in a crystal rnozaic of zeolite LTL by Teresaki et al (29).

When there i s no significant secondary influence a prefered structure

characteristic of the primary cation will predominate - FAU or LTL in the
 285

cases cited. T h e recent remarkable observation of stable m i c r o clusters o f

columnar rings (Figure 6) and the micro-mozaic structure of a n L T L crystal
(29) not only support this concept, but indicate a possible m e c h a n i s m o f
nucleation and growth in zeolite systems b y aggregation and annealing of
ck
sev ral weakly bonded such micro-clusters.
T h e advantage of the extended structure approach is that it facilitates
some degree of synthesis guidance and the possibility of tailored syntheses. It
i s particularly useful w h e n a p p r o a c h i n g g r o u p s of theoretical s t r u c t u r e s
having c o m m o n extended structures, many of which are now in stages of
characterization (30). However, the detection and characterization of extended
structures in solutions and gels will require more extensive research in areas
of Laser Raman spectroscopy and low angle scattering with neutrons and X -
rays.
In addition to the groups of structures discussed a b o v e m a n y similar
p r o b l e m s a n d o p p o r t u n i t i e s occur with ZSM-5/11 (31), f e r r i e r i t e ( 3 2 ) ,
mordenite (33), ALPO-5/ VPI-5 (34). Theta-l/ZSM-23 (35) and many others.

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4. P.K.Dutta and D.C.Shieh, J.Phys.Chern., 90 (1986) 2331-4.
5 . F.Liebau, "Structural Chemistry of Silicates.", Ch. 7 and 8, Springer-Verlag.
(Berlin), (1985) pp.90-160.
6. R.M.Barrer, "Zeolite Structures" in "Zeolites: Science and Technology.". NATO
AS1 Series #80, Ed. F.R.Ribeiro et al, (1984) pp.35-82.
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12. D.E.W.Vaughan, "Microstructure and Properties of Catalysts.", MRS Symp.
Proc. 11 I , Eds. M.M.J.Treacy, J.hl.Thomas and J.M.White. (1988) 89-100.
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Surf. Sci. Catal. #28, Ed. Y.Murakarni, A.lijirna and J.W.W;ird, (1986) 207-214.
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16.J.M.Newsam, M.M.J.Treacy, W.T.Koetsier and C.B. decruyter, Proc.Roy.Soc.,

A320 (1988) 475.
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Am.Chem.Soc. Symp.Ser.#398, Ed.hl.L.Occelli and ll.E.Rohson, (1989) 544-559.
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Scr. #31 I , Eds. S.E.Bradley, M.J.Gattuso and R.J.Rertolacini, (1989) 303-318.
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(I.ondon), (1982) 208.
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26 I.S.Kerr, J.A.Gard, R.M.Barrer and 1. Galabova, Amer. Mineral., 5 5 (1970) 441-154
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I,.B.Sand , (1971) 230-236.
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30. J.V.Smith, Chem.Rev.,88 (1988) 149-182.
3 I . G.T.Kokotailo and W.M.Meier, in "Properties and Applications of Zeolites.", Chem.
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32. R.Gramlich-Meier, W.M.Meier and B.K.Smith. Zeit.Kristallogr.. 169 (1984)
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33. J.D.Sherman and J.M.Bennett. Proc. 3rd Intl. Zeolite Conf., Amer.Chem.Soc.
Adv.Chem.Ser. 121, Eds. W.M.Meicr and J.R.Uytterhoeven. ( I 973) 52-65.
34. J.W.Richardson,Jr.. J.V.Smith and J.J.Pluth, J.Phys.Chem., 9 3 (1989) 8212-
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 G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 281
0 1991 Elsevier Science Publishers B.V., Amsterdam

TEMPERATURE DEPENDENCE OF NUCLEATION OF ZEOLITES I N ALKALINE

ALUMINOSILICATE GELS I N HYDROTHERMAL CRYSTALLIZAIPION CONDITIONS

S.P. ZHDANOV, N.N. FEOKTISTOVA and L.M. VTJURINA

I n s t i t u t e of S i l i c a t e Chemistry of t h e Academy of Sciences of
t h e USSR, Nab. Makarova 2 , Leningrad 199034, USSR

ABSTRACT
The paper p r e s e n t s a f u r t h e r development of s t u d i e s i n z e o l i t e
c r y s t a l l i z a t i o n k i n e t i c s c a r r i e d out e a r l i e r i n the l a b o r a t o r y
of t h e authors. It was shown t h a t by performing a j o i n t a n a l y s i s
of c r y s t a l l i z a t i o n curves d e s c r i b i n g z e o l i t e c r y s t a l growth i n
a l u m i n o s i l i c a t e g e l s i n t h e process of t h e i r hydrothermal cry-
s t a l l i z a t i o n and of d a t a on s i z e d i s t r i b u t i o n z e o l i t e c r y s t a l s
i n t h e f i n a l products of g e l c r y s t a l l i z a t i o n i n combination with
t h e i r pretreatment at d i f f e r e n t temperatures before subsequent
isothermal c r y s t a l l i z a t i o n , one can a t t a c k t h e problem of
studying temperature dependences of z e o l i t e n u c l e a t i o n r a t e i n
t h e c r y s t a l l i z i n g gels.

INTRODIJCT I O N
Since experimental s t u d i e s s t a r t e d publishing t h e k i n e t i c s
of z e o l i t e s c r y s t a l l i z a t i o n /1/ and up t o our days, t h e constru-
c t i o n of S-shaped k i n e t i c curves d e s c r i b i n g t h e growth of z e o l i -
t e mass i n t h e process of a l u m i n o s i l i c a t e g e l s isothermal cry-
s t a l l i z a t i o n h a s remained t h e most common method of d i s p l a y i n g
experimental r e s u l t s of such i n v e s t i g a t i o n s . These k i n e t i c depen-
dences a r e i n most c a s e s w e l l described formally by t h e following
equation:
Zt/Zf = Z = ( 1 - e-ktn) (1 1
where Zt - mass of c r y s t a l s i n t h e c r y s t a l l i z a t i o n product which
were formed during t h e time t from t h e beginning of c r y s t a l l i -
z a t i o n ; Zf - mass of c r y s t a l s i n t h e f i n a l c r y s t a l l i z a t i o n pro-
duct; k and n - dimensionless c o n s t a n t s depending on g e l com-
p o s i t i o n s , temperature and some o t h e r c r y s t a l l i z a t i o n c o n d i t i o n s
(seed, g e l ageing e t c . ) . However, such curves do not b e a r any
information on t h e b a s i c k i n e t i c parameters of c r y s t a l l i z a t i o n :
l i n e a r r a t e of c r y s t a l growth and n u c l e a t i o n rate.
The p o s s i b i l i t y of experimental s t u d i e s of t h e s e parameters
f o r r e a l conditions of z e o l i t e c r y s t a l l i z a t i o n on t h e example of
a Due t o i l l n e s s o f Prof. Zhdanov the paper could not be presented i n Leipzig.
288

Na-A zeal-ite w a s shown i n /2/.The methods d e s c r i b e d i n /2/ en-

a b l e d i r e c t d e t e r m i n a t i o n of l i n e a r r a t e of z e o l i t e s c r y s t a . 1
growth, s t u d i e s of t e m p e r a t u r e and c o n c e n t r a t i o n dependences of
c r y s t a l growth r a t e and s t u d i e s of n u c l e a t i o n k i n e t i c s i n c r y s -
t a l l i z i n g g e l s /3-9/. P a p e r s / 7 , 8 / c o n s i d e r g e n e r a l p o s s i b i l i t i e s
t o s t u d y t h e t e m p e r a t u r e dependence of n u c l e a t i o n i n g e l s on t h e
b a s i s of t h i s method.
The p a p e r i n q u e s t i o n p r e s e n t s t h e r e s u l t s of a more d e t e i l e d
study i n t h i s f i e l d .

SXPXRIT':SrJT
The a l u m i n o s i l i c a t e g e l s s t u d i e d were of t h e f o l l o w i n g compo-
s i t i o n s : 2,76 Na20 A1203 1,91 Si02 409 H20 and 3 , 7 2 Na20'
4.l2O3 . 2,8 S O 2 351 H20 t h e f i r s t of them c r y s t a l l i z i n g i n t o
Na-A z e o l i t e s , t h e second i n t o Na-X ones. A l u m i n o s i l i c a t e g e l s
were p r e p a r e d by mixing a l k a l i n e s o l u t i o n s o f sodium s i l i c a t e
0
and a l u m i n a t e end were c r y s t a l l i z e d at 90 C a f t e r p r e l i m i n e r y
h o l d i n g f o r 8 h o u r s at 0, 7 , 27, 40, 60, 70 and 80°C f o r Ba-A
and f o r 72 h o u r s a t -12, - 5 , 0, 9 , 20, 40, 60 and 8 O o C f o r Na-X.
One sample of each k i n d of g e l was c r y s t a l l i z e d at 90° w i t h o u t
thermal p r e t r e a t m e n t . The above h o l d i n g of samples b e f o r e c r y s -
t a l l i z a t i o n e n a b l e s one t o f o l l o w t h e e f f e c t of t e m p e r a t u r e of
p r e l i m i n a r y t h e r m a l t r e a t m e n t on c r y s t a l l i z a t i o n k i n e t i c s and on
i t s f i n a l r e s u l t s . The e x p e r i m e n t s were based on t h e measurements
by means of an o p t t c a l microscope o f s i z e s of t h e l a r g e s t c r y s -
t a l s found i n t h e c r y s t a l l i z i n g g e l s at v e r i o u s p e r i o d s of t i n e
from t h e b e g i n n i n g of i s o t h e r m a l h e a t l n g o f samples. F o r Na-A
t h e edges of c u b i c c r y s t a l s were measured and f o r Ya-X - the axes
of o c t ahedre. The above measurements e n a b l e t o d e t e r m i n e g r a p h i -
c a l l y the l i n e a r r e t e o f c r y s t a l g r o w t h , t o follow i t d u r i n g t h e
whole c o u r s e of c r y e t e l l i z e t i o n p r o c e s s and t o determine t h e end
of t h e p r o c e s s ( t h e time of c r y s t a l l i z a t i o n ) by t h e d i s c o n t i n c a -
t i o r i of c r . y s t a l growth. For a l l t h e samples t h e h i s t o g r e m s were
determined which c h a r a c t e r i z e c r y s t a l s i z e d i s t r i b u t i o n i n t h e
f i n a l c r y s t a l l i z a t i o n products.
The time wher t h e growth of each mode o f c r y s t a l s s t a r t e d was
determined and t h e c u r v e s c h a r a c t e r i z i n g n u c l e a t i o n k i n e t i c s we-
r e c a l c u l a t e d from t h e s e h i s t o g r a m s and from t h e date. 0 x 1 l i n e e r
growth ret e .
 289

RESULTS AND DISCUSSION

The c u r v e s i n f i g . 1 and 2 d e s c r i b e t h e v a r i a t i o n i n dimensions
of t h e l a r g e s t c r y s t a l s of Na-A ( f i g . 1 ) and Na-X ( f i g . 2 ) z e o l i t e s
i n t h e i n v e s t i g a t e d g e l s i n t h e p r o c e s s of t h e i r c r y s t e l l i z a t i o n
at 90OC. Curves 1 i n b o t h f i g u r e s a r e f o r g e l samples c r y s t a l l i -
zed by h e a t i n g o n l y e.t c r y s t a l l i z a t i o n t e m p e r a t u r e . A l l o t h e r
c u r v e s a r e f o r g e l samples which have been t h e r m a l p r e t r e a t e d
( b e f o r e c r y s t a l l i z a t i o n a t R s t a n d a r d 90°C t e m p e r a t u r e ) 8 h o u r s
f o r g e l P and 2 4 h o u r s f o r g e l X et t e m p e r a t u r e s lower t h e n t h e
s t a n d a r d t e m p e r a t u r e of t h e i r subsequent c r y s t a l l i z a t i o n . The
p r e t r e a t m e n t t e m p e r a t u r e OP each sample of the g e l s s t u d i e d is
g i v e n n e a r t h e r e s p e c t i v e curve. A l l t h e c u r v e s have the same
s l o p e and c o n s i s t of t h r e e p a r t s : t h e i n i t i a l l j n e a r p a r t whose
s l o p e i n d i c a t e s t h e c r y s t a l growth r a t e ( 0.5A1/bt ) and the
length - the time i n t e r v e l with coxstant grovth r a t e , a s h o r t e r
p a r t of n o n s t a t i o n m y growth and R h o r i z o n t a l p a r t where 110
growth of c r y s t a l s i z e s was o t s e i ~ e d .

13

10

.L
0"
20 40 60 i-;O 2,h
F i e . 1. GrowtIn i n c r y s t a l . s i z e o f t h e l a r g e s t Na-A z e l i t e c r y s -
t a l s ( 1 max ) i n c r y s t a l l i z i n g g e l s a t gOOc a f t e r thermal pre-
treatment ( t i s marked n e a r t h e c u r v e s ).
Pr
 290

Fig. 2. Growth of c r y s t e l s i z e of t h e l a r g e s t ITa-X c r y s t a l s i n

cr.~ s t a l l i z i n g g e l s at ?O°C a f t e r t h e n v l p r e t r e a t m e u t a t d i f f e -
r e n t temperatures.
The v e r y f a c t of t h e e x i s t e n c e of e n i n i t j a l l i n e a r p a r t i n
e v e r y c c r v e ( f i g . 1 end 2 ) e n a b l e s one t o conclude t h a t a t l e a s t
i n t h e time i n t e r v a l c o r r e s p o n d i n g t o t h e s e p a r t s of t h e c u r v e s ,
t h e c r y s t a l s i n d i f f e r e n t samples of t h e g e l s u n d e r o b s e r v a t i o n
had a c o n s t a n t growth rate. Eloreover, t h e f e c t t h a t ell t h e s e
c u r v e s have t h e same s l o p e means t h a t t h e l i n e a r r e t e of c r y s t a l
growth was t h e same f o r ell the samples and independent of t h e
t e m p e r a t u r e of p r e l i m i n a r y g e l t r e a t m e n t ( t 1. However, c u r v e s
Pr
1 and 2 d i s p l a y a n obvious e f f e c t of s u c h t r e a t m e n t on t h e s i z e s
of t h e l a r g e s t c r y s t a l s f o u n d j n t h e f i n e l c r y s t a l l i z a t i o n pro-
d u c t s and on d u r a t i o n of c r y s t a l l i z a t i o n (Z') determined by t h e
time when v i s i b l e c r y s t a l growth i s over. T h i s time I s marked i n
f i g . 1 end 2 by a c r o s s i n g of dashed c u r v e s . The r e s p e c t i v e d a t a
f o r b o t h z e o l i t e s a r e g i v e n i n T a b l e 1.
The c h a r a c t e r i s t i c changes due t o t h e t e m p e r a t u r e of p r e l i m i -
nary t r e a t m e n t of t h e g e l ( t ) were a l s o observed t o have some
Pr
e f f e c t on t h e p e c u l i a r i t i e s of z e o l i t e c r y s t a l s s i z e d i s t r i b u t i o n
i n t h e f i n a l c r y s t a l l i z a t i o n products. One may see s u c h changes
f o r Ra-A z e o l i t e i n t h e h i s t o g r a m ( f i g . 3 ) . F i n a l l y , t h e e f f e c t
of t h e t e m p e r a t u r e of gels t h e r m a l p r e t r e a t m e n t ( t ) i s c l e a y l y
Pr
observed 011 l , t e r u n of t h e c a r v e s d e s c r i b i n g t h e growth o f z e o l i -
t e c r y s t a l s mass i n t h e p r o c e s s of g e l j s o t h e r n o 1 c r y s t a l l i z a t i o n .
Fig.4 e l s o g i v e s such k i n e t i c c u r v e s f o r Ve-A z e o l i t e . They are
TABLE 1
The e f f e c t o f g e l s pi*etr.eetrnent t e m p e r a t u y e on c r y s t e l s i z e s , c r g s t f i l l i z a t i o n t i m e and
nuc l e a t i o n
~

00 7" 27 O 40 O 600 700 800 90°

23 20 18 16 18 19 20 23
90 72 66 62 64 66 70 96
Na- A 1.84 1.43 1.06 0.85 1.22 7-49 1.87 2.44
3.62 2.82 2.09 1.67 2.40 2.94 3.6e 4.81
2.76 3.55 4.79 5.97 4.16 3.41 2.71 2.08
59 53 47 43 43 43 44 61

-120 -5 O 00 90 200 40° 60 O 800 900

10 35 41 35 33 51 54 5'5 60
2 5 5.6 5.2 4.8 6.7 7.1 7.5 7.8
Na-X 0.035 1,16 1.18 1.17 1.05 3.95 5.71 6.01 7.14
0.069 2.28 2.33 2.31 2.07 7.78 11.3 11.8 14.10
145 4.39 4.29 4.33 4.82 1.29 0.89 0.84 0.71
7.16 5.64 5.63 5.64 5.68 5.11 4.95 4.93 4-85
292

0.08

0.04

40 GOo 700
d
0.08 a

0.04

800 90"
n

0.08

0.04

0 61 16 t7 16 1,Y
Pig.3. Iiistograms o f t h e f i n a l c r y s t a l l i z a t i o n p r o d u c t s i n g e l
Ka-A samples a t 90°C a f t e r a p r e t r e a t m e n t at d i f f e r e n t tempera-
tures.
._ .

Fig.4. The curve8 of z e o l i t e Sa-f, c r y s t a l mass growth ( i n L / b f

.. I . - I"

f r a c t i o n ) i n t h e p r o c e s s of i s o t h e r m a l c r y s t a l l i z a t i o n a t 9b.C
a f t e r pretreetment at d i f f e r e n t temperatures. The c u r v e s were
c a l c u l a t e d from t h e d a t a i n f i g . 1 and 3.
 293

c o n s t r u c t e d on t h e b a s i s of d a t a i n f i g . 1 and t h e h i s t o g r a m s i n
f i g . 3 by means of r a t h e r s i m p l e c a l c u l a t i o n s . The method of con-
s t r u c t i n g such c u r v e s i s d e s c r i b e d i n /5,9/ ( s e e also / l o / and
/12/). The S-shaped curve8 i n f i g . 4 a r e well d e s c r i b e d by equa-
t i o n (11, t h e v a l u e s of k and n c o n s t a n t s v a r y i n g w i t h e a c h
p a r t i c u l a r case. These c o n s t a n t s g r a p h i c a l l y determined from
-
I n ln 11-z 1 n . t dependence e n a b l e one t o f i n d t h e p o s i t i o n of
t h e bend p o i n t o f k i n e t i c c u r v e s tinf a c c o r d i n g t o :

(2)
T h i s r e l a t i o n f o l l o w s from t h e second d e r i v a t i v e Z w i t h r e s p e c t
to t . The p o s i t i o n s and s l o p e s o f t h e c u r v e s i n f i g . 4 which
are i n t h i s c a s e determined by tinf v a l u e s one may s e e t h a t t h e
k i n e t i c s of c r y s t a l mass growth i n the p r o c e s s o f g e l s i s o t h e r m a l
c r y s t a l l i z a t i o n i s s t r o n g l y dependent on
tPr
. I n c i d e n t a l l y , as
i t i s seen from t h e d a t a i n Table 1 t h e g e l c r y s t a l l i z a t i o n time
depending on g e l p r e l i m i n a r y p r e t r e a t m e n t t e m p e r a t u r e changes
unevenly and p a s s e s a minimum c o r r e s p o n d i n g t o a temperature
tPr
c l o s e t o 4 Oo C f o r Ha-A z e o l i t e and t o 20OC f o r Wa-X z e o l i t e . As
t h e l i r - e a r rate of c r y s t a l growth is independent of t the
Pr
observed e f f e c t of t h e t e m p e r a t u r e of g e l s p r e l i m i n a r y t r e a t m e n t
on t h e d u r a t i o n of t h e i r c r y s t a l l i z a t i o n , t h e s i z e s of largest
c r y s t a l s and t h e c h a r a c t e r of c r y s t a l s i z e d i s t r i b u t i o n i n t h e
f i n a l p r o d u c t s may be account f o r o n l y under t h e c o n d i t i o r . o f non-
monotonous dependence of n u c l e a t i o n r a t e i n gels on t h e tempera-
t u r e i n t h e temperatura j i . t e r \ - r l s t u d i e d . This has been p o i n t o u t
e a r l i e r / 7 , 8 / b u t no a t t e m p t s have been made t o e s t i m a t e q u a n t i -
t i v e l y t h i s dependence. Such a n e s t i m a t i o n seems q u i t e r e a l i s t i c
t a k i n g i n t o c o n s i d e r a t i o n t h e above - mentioned independence of
c r y s t a l growth l i n e a r r a t e on t h e i r s i z e s which was also n o t e d
e a r l i e r /4,5/. I n such a c a s e t h e number of n u c l e i formed i n t h e
p r o c e s s of g e l c r y s t a l l i z a t i o n may be determined by t h e number of
c r y s t a l s i n the f i n a l c r y s t a l l i z a t i o n p r o d u c t s i f t h e volume of
a p a r t i c u l a r number o f c r y s t a l s , f o r i n s t a n c e , of 100 c r y s t a l s
i n t h e f i n a l product w a s known.
The volume of 100 c r y s t a l s ( Vlo0) may be c a l c u l a t e d from t h e
histogram according t o t h e equation:

where 4 - t h e p r o p o r t i o n of c r y s t a l s of each mode, di- their

d i a m e t e r s and o t h e r measurable l i n e a r dimensions, K - t h e geo-
294

m e t r i c a l c o e f f i c i e n t l i n k i n g d3 w i t h t h e volume Vi
The number of c r y s t a l s p e r u n i t product mass is determined
.
from :
Nf 100 / V1oop (4)
where p i s c r y s t a l d e n s i t y , t h e v a l u e s Vlo0 and Nf being
given i n Table 1. One may s e e from t h e t a b l e t h a t t h e d u r a t i o n
o f c r y s t a l l i z a t i o n ( 2 )of g e l s p r e t r e a t e d at d i f f e r e n t tempera-
t u r e s ( t ) r e g u l a r l y v a r i e s w i t h Nf which may be c l e a r l y seen
Pr
when comparing t h e r u n of curve8 1 and 2 i n fig.5.

10-8

2
6

Fig.5 .
The dependence of c r y s t a l l i z a t i o n time and of t h e o v e r a l l
number of c r y s t a l n u c l e i N growing i n g e l s from pretreatment
temperature: t h e f i g . on t h & l e f t i s f o r Na-A, on t h e right for -
Na-X.
Sinee, as it was pointed e a r l i e r , t h e number of c r y s t a l s i n
t h e f i n a l products of g e l . c r y s t a l l i z a t i o n e q u a l s t o t h e number of
t h e i r n u c l e i , t h e data i n fig.5 show t h a t t h e change i n c r y s t a l l i -
z a t i o n time r e s u l t i n g from g e l pretreatment a t d i f f e r e n t tempera-
t u r e s i s due t o temperature dependence of g e l n u c l e a t i o n r a t e i n
t h e r e g i o n studied.
The data i n fig.1 and 2 enable one t o conclude t h a t at t h e
temperature of m a x i m a l n u c l e a t i o n and a t lower temperatures down
t o O°C n u c l e a r s i z e s do not s i g n i f i c a n t l y grow. A t h i g h e r tempe-
r a t u r e s ( t ) not only f r e s h n u c l e i a r e being formed b u t a l l t h e
Pr
n u c l e i g r o w i n s i z e due t o a considerable i n c r e a s e i n c r y s t a l
growth r a t e . It is displayed i n t h e observed v e r t i c a l s h i f t s of
 295

l i n e a r p a r t s of t h e curves which i n c r e a s e with temperature growth

of g e l pretreatment.
The r e s u l t s obtained i n t h i s paper make i t c l e a r t h a t t h e w e l l
known ageing e f f e c t i n g e l s ( t h e i r being h e l d a t room temperature)
is one p a r t i c u l a r case of t h e e f f e c t of n u c l e a t i o n temperature
dependence on c r y s t a l l i z a t i o n r a t e . In t h e a u t h o r s ' opinion t h e
development of n u c l e a t i o n i n such g e l s is connected w i t h t h e
so-called r i p e n i n g process leading t o i r r e v e r s i b l e changes i n
c o l l o i d a l g e l s t r u c t u r e /4,5/. The d r i v i n g f o r c e of t h i s process
i s t h e tendency of t h e c o l l o i d a l system t o minimal f r e e energy.
This process appears t o be r e s p o n s i b l e f o r t h e development of g e l
n u c l e a t i o n under o t h e r temperatures studied. The Fjharp i n c r e a s e
of c r y s t a l l i z a t i o n r a t e of Na-X a l u m i n o s i l i c a t e g e l s a f t e r t h e i r
f r e e z i n g i s obviously not connected w i t h t h e process of ripening.
It seemingly r e s u l t s from a phase disbalance when t h e l i q u e d
phase of t h e s e g e l s h a s been f r o z e n out. The mechanism of t h i s
e f f e c t is not y e t q u i t e c l e a r .

CONCLUSION
The i n v e s t i g a t i o n s i n question develop an experimental techni-
que f o r studying n u c l e a t i o n of z e o l i t e s i n a l u m i n o s i l i c a t e g e l s
and i t s temperature dependence. Study was made of t h e e f f e c t of
a l u m i n o s i l i c a t e g e l s thermal pretreatment on t h e c r y s t a l l i z a t i o n
r a t e , t h e degree of c r y s t a l d i s p e r s i o n i n Na-A and Na-X z e o l i t e s
formed and on n u c l e a t i o n i n gels.

REFERENCES
1 D.W. Breck, E.M. Flanigen, 'Molecular Sieves', SOC. Chem. Ind.,
London, 1968, pp. 47-61.
2 S.P. Zhdanov, 'Molecular Sieve Z e o l i t e s - l ' , h e r . Chem. SOC.,
Washington, 1971, pp.20-43.
3 S.P. Zhdanov, h o c . 3rd Intern. Conf. on Molecular Sieves,
Louven Univ. Press, 1973, pp.25-29.
4 S.P. Zhdanov and N.N. Samulevich, Adsorbents, t h e i r Prepara-
t ion, P r o p e r t i e s and Application, Nauka, Leningrad, 1978,
pp.10-16.
5 8.P. Zhdanov and N.N. Samulevich, Proc. 5 t h Intern. Z e o l i t e
Conf. (Ed. L.V.C. Rees) Heyden, London, 1980, pp.75-84.
6 S.P. Zhdanov, S.S. Khvoshchev and N.N. Samulevich, S y n t h e t i c
Z e o l i t e s ( i n Russian), Chimij a , USSR, 1981.
7 S.P. Zhdanov, N.N. Feoktistova, E. Jahn, Izv. &ad. Nauk Ser.
K h i m . (1986) 1720-1724.
8 N.N. Feoktistova, L.M. Vtjurina, Izv. &ad. Nauk Ser. Khim.
(1 988) 727-730.
9 S.P. Zhdanov, S.S. Khvoshchev and N.N. Feoktistova, S y n t h e t i c
296

Z e o l i t e s , vol. 1, Gordon and Breach S c i e n c e P u b l i s h e r s , 1990.

10 R.Y. B a r r e r , Ilydrothermal Chemistry of Z e o l i t e s , Academic
Press, 1982.
1 1 C o l i n S. Cundy, I3.N. Lowe, D.TZ. S i n c l a i r , C r y s t a l Growth, v o l .
100 (1990) 189-202.
12 R.U. B a r r e r , Z e o l i t e s , vol.1 (19131) 130-140.
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 297
0 1991 Elsevier Science Publishers B.V., Amsterdam

SYNTHESIS O F PIPERAZINE AND TRIETHYLENEDIAMINE USING

ZSM-5-TYPE ZEOLITE CATALYSTS

J. WEITKAMP', S. ERNST1, H.-J. BUYSCH2 and D. LINDNER3

1 University of Stuttgart, Institute of Chemical Technology I, Pfaffenwaldring 55,
D-7000 Stuttgart 80 (Federal Republic of Germany).
2 Bayer AG, Werk Uerdingen, P. 0. Box 166, D-4150 Krefeld 11 (Federal Republic of
Germany)
3 University of Oldenburg, Department of Chemistry, Chemical Technology, Ammerlaender
Heerstrasse 114-118, D-2900 Oldenburg (Federal Republic of Germany)

SUMMARY
The synthesis of piperazine and triethylenediamine from ethylenediamine in ZSM-5-t e
C
P
zeolite catalysts was investigated. With strongly acidic HZSM-5, large amounts of by-pro ucts
were observed (viz., pyrazine, 2-picoline, resin-like substances and cracked products).
Reducing the strength of the acid sites by ion exchange with alkali metal cations strongly
improved the selectivities for the desired products. This effect was further enhanced by the
addition of water vapour to the feed. From the zeolites tested in this study, KZSM;5 appears
to be the best catalyst: At T = 340 "C, W/F,, = 196 gh/mol and I ~ H ~ On m: A = 12,
conversion of ethylenediamine decreased only from30 % to 80 % after more than three days
time on stream. During this time, selectivities for piperazine and triethylenediamine remained
nearly constant above 95%.

INTRODUCTION
The classical fields of industrial catalysis by zeolites comprise large volume refinery
processes, viz. catalytic cracking, hydrocracking, isomerization or dewaxing, and the
production of petrochemical commodities (e.g., ethylbenzene synthesis via the Mobil/Badger-
process or xylene isomerization) (refs. 1-3). More recently, research in catalysis focusses on
the use of zeolites for the production of more valuable products, viz. organic intermediates
and fine chemicals (refs. 4-6). For this purpose, a broad variety of zeolite structures and
compositions, and the complete set of techniques for their modification are nowadays
available. The challenge, however, is to identify products which can be manufactured with
higher selectivities, in an environmentally more acceptable manner or otherwise more
economically by using tailored zeolite catalysts.
The present paper reports on the synthesis of piperazine (PIP) and triethylenediamine
(TEDA or DABCO, 1,4-diazabicyclo[2.2.2]octane), two organic intermediates in the
production of pharmaceutical products and plastics, respectively. They are currently
manufactured commercially using non-zeolitic catalysts. Piperazine is produced by reacting an
ethanolamine/ammonia-mixture on a Raney nickel catalyst at temperatures from 150 to
298

220°C and pressures between 10 and 25 MPa. The synthesis of triethylenediamine from
ethylenediamine, diethylenetriamine or diethanolamine is catalyzed by amorphous silica-
alumina at atmospheric pressure and temperatures around 360 "C. Both processes suffer from
relatively low selectivities for the desired products. Hence, several expensive separation steps
are required downstream of the reactor (ref. 7).
In the literature, there is only scarce information on the use of zeolite catalysts for the
production of piperazine and triethylenediamine, using as feed such compounds as N-(2-
hydroxyethy1)-piperazine (ref. 8,9), ethanolamine (refs. 10,l l), ethylenediamine (ref. 11) or
diethylenetriamine (ref. 11).
In the present study, an attempt was undertaken to replace the conventional catalytic
systems by more selective zeolite-based catalysts. Among the advantages offered by zeolites
are their shape selective properties and the possibility to tailor the nature, density, strength
and distribution of their acid sites.

EXPERIMENTAL
Zeolite ZSM-5 with Si/AI=40 was synthesized from an alkali-free gel according to the
procedure outlined by Ghamami and Sand (ref.12). HZSM-5 was obtained by calcination of
the as-synthesized material for 16 hours at 540 "C in air followed by ion exchange with a In
aqueous solution of NH,CI and a further calcination at 420 "C. Li, Na, K, Rb and Cs
exchanged samples of ZSMd were prepared by dispersing the zeolite powder two times for
eight hours in a I n aqueous solution of the respective chloride salt. The zeolite powder was
pressed without any binder, crushed and sieved. The size fraction between 0.2 and 0.5 mm was
used for the catalytic experiments. They were performed in a flow-type apparatus with a fixed
bed reactor. Product analysis was achieved by on-line sampling and temperature programmed
capillary glc. Ethylenediamine (EDA), either pure or in admixture with water vapour, was
used as feed and nitrogen as carrier gas.

RESULTS AND DISCUSSION

The first experiments were conducted with H Z S M J as catalyst. Under typical reaction
conditions (T=340 "c, W=0.28 g, W/FEDA=186gh/mol, PEDA=2.1 kPa, pN2 cj 100 kPa),
severe catalyst deactivation takes place. In addition, a variety of side reactions (e. g., cracking,
polymerization to resin-like substances) occur beside the formation of the two desired
products. Typical data after 2 hours time on stream are: XEDA=24%, SP,,=35 70,h D , , = 6 %.
This unsatisfactory picture is completely changed if H Z S M J is replaced by NaZSM-5.
Pertinent results are depicted in Figure 1. Catalyst deactivation, although still present, is
considerably slowed down when compared to HZSMJ. Side reactions like cracking or
polymerization are now strongly suppressed. The sum of the selectivities for the desired
products piperazine and triethylenediamine has improved to ca. 70 %. Based on these results,
the unsatisfactory performance of HZSM-5 can be tentatively assigned to the presence of
 299

100

80
8?

v,
.- 60
L
0
a 40
0
W
X
20

0
0 2 4 6 8 10 12 14 16 18 20

TIME O N STREAM, h
Fig. 1. Conversion of ethylenediamine in NaZSM-5. Reaction conditions: T=340 "C,
W=O.28 g, W/F,,= 186 gh/mol, pEoA=2.1kPa, PN*U 100 kPa

strong Bronsted acid sites in this catalyst: If the interactions between these acid sites and the
basic feed or product molecules are too strong, the desorption of the products will be severely
hindered and the residence time of the basic reactants at the acid sites will be uncontrollably
high which results in the occurrence of consecutive reactions like cracking or polymerization.
To overcome the problem, two principle solutions can be envisaged: (i) the addition of an
inert component (e.g., water vapour) to the feed, which competes with the basic reactants for
the acid sites or, (ii) decreasing the interactions via a reduction of the acid strength. The latter
possibility already proved to be successful in the present case. With the aim to further increase
the selectivities to the desired products and the stability of the catalyst, additional experiments
were conducted to (i) investigate the influence of water vapour and, (ii) clarify the influence of
the strength of the acid sites by varying the alkali metal ions exchanged into ZSMJ.
Table 1 summarizes the influence of different amounts of water vapour added to
ethylenediamine in the feed stream. From these data, the conclusions can be drawn that with
increasing amounts of water in the feed (i) the selectivities for the desired products piperazine
and triethylenediamine increase, and (ii) the tendency for the formation of cracked products
decreases. Therefore, a molar ratio of 12 for H,O/EDA in the feed was used for all further
experiments.
It has been found earlier (ref. 13) that the strength of the acid sites in Z S M J zeolites can
be tailored by ion exchange with different alkali metal ions: When such catalysts are
characterized by temperature programmed desorption of ammonia (TPDA), the temperature
300

niiZo: ~ E D A 0: 1 1:l 4: 1 12:1

45 53 58 71
54.3 56.1 57.6 59.0
16.3 20.1 27.1 35.0
8.4 6.8 3.1 1.0
3.4 3.3 2.0 not determined

8.7 6.3 5.6 3.5

100
Li+ NCl+ K' Rb' Cs'
80
A;E - 400
0
w
v,
L
._ 60
*\ - 320 -0

4
n
0 a
< 40
- 240 t
n )i
W
0
X E
20 - 160

0
50
I I

100
I I

150
I
'
80
200

CATIONIC RADIUS, pm
Fig. 2. Activities and selectivities of ZSM-5 zeolites exchanged with different alkali metal
cations (reaction conditions: T=340 "C, W/FEDA=186 gh/mol, hH,O : ~ E D A= 12,
W = 0.28 g)
 301

of maximum desorption rate decreases with increasing ionic radius of the exchanged alkali
metal cation. Hence, the strength of the acid sites decreases from LiZSM-5 to CsZSM-5.
Therefore, Lit-, K+-, Rbt- and Cs+-exchanged Z S M J zeolites were also included in the
investigations. The results are depicted in Figure 2. For the sake of clarity, only the conversion
of ethylenediamine (XED*) and the selectivities for the two major products (S,,,, bDA) are
plotted against the radius of the alkali metal cation. The data were taken after 16 hours time
on stream, when with all catalysts a nearly stable stage was reached. The catalytic activity
declines in the sequence KZSM-5 > RbZSM-5 > CsZSM-5 > NaZSM-5 > LiZSM-5.
Obviously, there is no direct relationship between the height of ethylenediamine conversion
and the strength of the acid sites as characterized by TPDA. Probably, the interactions of the
basic reactants with LiZSM-5 and NaZSM-5 are too strong to allow for a fast desorption of
the desired products. As a consequence, consecutive reactions, i. e. coke formation are
favoured. Starting from KZSMJ with its considerably weaker acid sites, there is a decline of
conversion which corresponds to the decrease of acid strength with increasing cationic radius.
With all alkali metal cation exchanged ZSM-5 zeolites, high selectivities for the desired
products (above 90%) are observed. The remaining percentage of selectivities is made up by
pyrazine, 2-picoline and cracked products.
To achieve even better selectivities and yields, conversion of ethylenediamine was varied by
varying the reaction temperature. The selectivities observed for piperazine and
triethylenediamine are presented in Figure 3. The general trend holds for all catalysts:
100 I I I I 50 I I I I

M = Lio, Nav. KA

R b o , Csc
P
80 40
x x
a a
n
a W
m I-
60 30
~ I I I I

40 20
0 20 40 60 8 0 100 0 20 40 60 80 100
’ % ’ %!
Fig. 3. Variation of selectivities for piperazine and triethylenediamine in MZSM-5 (M=Li,
Na, K, Rb, Cs) with increasing conversion of ethylenediamine. , X
( was varied by changing
the reaction temperature, all other parameters were kept constant as given in Fig. 2).
302

Increasing conversion leads to a decreasing selectivity for piperazine with simultaneously

increasing selectivity for triethylenediamine. This can be easily understood since
triethylenediamine forms in a consecutive reaction from piperazine and ethylenediamine
(under simultaneous formation of two molecules of ammonia per molecule piperazine
converted). Since the sum of the selectivities for PIP and TEDA remains almost constant
above 90 %, this conversion/selectivity relationship offers a certain flexibility for a possible
industrial process. Depending on the market's demand for piperazine and triethylenediamine,
the selectivities can be adjusted such as to meet the requirements.
For a commercial process, one could envisage to perfom the reaction at elevated pressure.
Therefore, the conversion of ethylenediamine/water mixtures was investigated at pressures up
to 3.0 MPa in a fixed bed flow-type apparatus made from stainless steel. Pertinent results are
summarized in Table 2. The general trends are in agreement with the data obtained at atmo-

TABLE 2
Influence of total pressure on activity and selectivity of NaZSM-5 (T-340 "C,W =0.28g,
h 2 0: = 12).

1.0 4.2 97 46.7 63.8 25.8 5.6 4.2

1.0 8.4 48 61.0 56.1 30.6 3.3 4.2
1 .o 8.2 188 87.1 44.4 37.8 3.4 6.3
3.0 8.1 65 62.2 57.7 31.7 3.4 5.0

spheric pressure, viz. with increasing conversion the selectivity for triethylenediamine
increases at the expense of piperazine. However, the sum of the selectivities never reaches the
high values attained at atmospheric pressure, i. e., far above 90 %. Surprisingly,
diethylenetriamine (DETA) was formed with selectivities between 2 and 6 %. This is in
contrast to the experiments at 100 kPa, where these high selectivities for DETA could not be
observed.
One selected catalyst, KZSM-5, was tested under atmospheric conditions with regard to its
time on stream stability in an experiment extended to 76 hours (cf. Figure 4). Over the whole
period, only a slow deactivation is observed. After about three days, conversion still amounts
to ca. 80 % with excellent selectivities to piperazine (ca. 59%) and triethylenediamine (ca.
38 %). Only small amounts of 2-picoline (S< 1%) and cracked products (S CII 2 %) are
detected. The reasons for the slow but continuous deactivation are not yet clear. There are at
least two possible explanations, viz. deactivation by coke formation or extraction of aluminum
species from lattice positions due to the hydrothermal environment (high temperature and
high concentration of water vapour). More work is underway to clarify the mechanism of
deactivation and to develop specific techniques for regeneration of the spent catalyst.
 303

100 I I I I I I I I I

80 - -
x
.-
cn
L
0

n
<
w
X

0 8 16 24 32 40 48 56 64 72 80

TIME O N STREAM, h
Fig. 4. Conversion of ethylenediamine in KZSM-5; reaction conditions as in Fig. 2.

CONCLUSIONS
The synthesis of piperazine and triethylenediamine was investigated using ZSMJ-type
zeolite catalysts. Conversion of ethylenediamine over strongly acidic HZSM-5 zeolite resulted
in fast catalyst deactivation and unacceptable low selectivities for the desired products. As a
working hypothesis, this was attributed to the strong interaction of the basic reactants with the
Bronsted acid sites which results in prolonged residence times and favours consecutive
reactions. Hence two main directions were followed in order to improve the performance of
the catalyst: (i) Reducing the strength of the acid sites by ion exchanging HZSM-5 with alkali
metal cations and, (ii) adding water vapour to the feed, to make use of competitive
adsorption/desorption effects. The combined application of both measures was successful:
With KZSM-5 as catalyst and a water/feed of rh,o : tiem = 12, the sum of the selectivities
for piperazine and triethylenediamine could be increased to more than 95 % at conversions
above 80 % and with excellent time on stream stability.

ACKNOWLEDGEMENTS
Financial support by Bundesministerium fur Forschung und Technology (BMFT) of the
Federal Republic of Germany is gratefully acknowledged.

REFERENCES
1 N. Y. Chen and T. F. Degnan, Chem. En Progr., 48 (1988) 32-41.
2 N. Y. Chen, W. E. Garwood and F. G. bwyer, Shape Selective Catalysis in Industrial
A plications, Marcel Dekker, New York, 1989,303 p.
3 d Holderich and E. Gallei, Chem.-1ng.-Tech, 56 (1984) 908-915.
304

4 W. Holderich, M. Hesse and F. Naumann, Angew. Chemie, 100 (1988) 232-251.

5 W. Holderich, in P. A. Jacobs and R. A. van Santen (Editors), Zeolites: Facts, Figures,
Future, Studies in Surface Science and Catalysis, Vol. 49, Part A, Elsevier, Amsterdam,
Oxford, New York, To 0,1989, pp. 69-93.
6
294.
%
H. v. Bekkurn and H. . Kouwenhoven, Recl. Trav. Chirn. Pays-Bas, 108 (1989) 283-
7 G. Heilen, H. J. Mercker, D. Frank, R. A. Reck and R. Jackh, in Ullmann's
Encyclopedia of Industrial Chemistry, 5th edn., Vol. A2, Amines, Aliphatic, VCH
Verlagsgesellschaft, Weinheirn, 1985, pp. 15-17.
8 R. A. Budnik and M. R. Sandner, Europ. Patent Appl. 158 319, Oct. 16, 1985, assigned
to Union Carbide Corp.
9 W. Holderich, K. Schneider, H. Lermer and W. Best, Europ. Patent Appl. 263 463, Oct.
5, 1987, assigned to BASF AG.
10 H. Satoh and M. Tsuzuki, WO 87 03 592, June 18,1987, assigned to Idemitsu Kohsan.
11 J. Disteldorf, N. Finke and W. Hiibel, Europ. Patent Appl. 313 753, May 3,1989,
assigned to Hiils AG.
12 M. Ghamami and L. B. Sand, Zeolites 3 (1983) 155-162.
13 J. Weitkamp, D. Lindner and S. Ernst, in Projektleitung Material- und
Rohstofforschung, Forschungszentrurn Jiilich (Ed.), Proceedings of the Status-Seminar
"Katalyseforschung",at Fritz-Haber-Institute of the Max-Planck-Society, March 1, 1990,
in press.
G. 6tilmann a!. (Editors ), C'ata!ysis and Adsorption hy Zeolitm 305
63 1991 Elsevier Science Pul)lishers H.V., Amsterdam

DIFFUSION EFFECTS ON THE KINETICS OF TOLUENE HETHYLATION

AND XYLENE ISOHERIZATION ON HZSH-5 ZEOLITES

F . BAUEB, J. DEBHIETZEL and U. JOCKISCH

Central Institute for Isotope and Radiation Research,
7050 Leipzig (CDR)

SUHHARY
By using carbon-14 labelled compounds diffusion effects in
heterogeneous catalysis can be assessed. The formation of poly-
methylated aromatics in the conversion of toluene uith methanol
on HZSH-5 zeolite catalysts is mainly a consecutive reaction, but
different diffusivities of the reactants give gaseous hydrocar-
bons, toluene and poly-methylated aromatics via a direct synthe-
sis from methanol. In xylene isomerization diffusion influences
the concentration profiles leading to wrong mechanistic reaction
mode 1 s.

INTRODUCTION
Kinetic studies only allou to drau conclusions about the rate
determining step of a reaction sequence; therefore mass transfer
to and from the external surface of the catalyst and/or mass
transfer into and out of the catalyst pores can lead to results
uhich are contrary to chemical theory. Especially in zeolite
catalysis, diffusion disguised kinetics are to be expected -
methylation of aromatics and isomerization of xylenes on HZSH-5
zeolites may serve as examples.
In methanol/toluene mixtures only a fraction of the methanol
participates in the reaction as alkylating agent, uith the re-
mainder being converted mainly to gaseous hydrocarbons (ref. 1 ) .
By using I3C(ref. 2)- or 14C(ref. 3)-labelled compounds it can
be shoun that aromatics are formed from methanol too, and the
portion of this pathuay have been assessed. Furthermore, diffu-
sion effects in medium pore size zeolites are responsible for the
violation of the validity of Broun's LFE relation ship (ref. 4)
estimating the alkylation rate of aromatics by the nature and the
number of substituents.
In xylene isomerization on medium pore size zeolites different
diffusion rates causes concentration profiles uhich are best
represented by a triangular reaction scheme (ref. 5 ) including
the unrealistic 1,3-methyl shift.

EXPERIHENTAL
For catalytic purpose, a commercial HZSH-5 zeolite catalyst
(Leuna-Uerke, GDR) uith a Si02/A1203 ratio of 56 and containing
20 X A1203 binder was crushed and sieved (0.2 - 0.4 BB). The
zeolite was highly crystalline to x-ray diffraction pattern and
according to SER pictures had a particle size in the 2 - 5 Pm
range. The quartz glass microreactor (ref. 6 ) was packed w i t h
0.25 g catalyst grains diluted uith the same amount of quartz.
Nitrogen was used as carrier gas (volume ratio 1OOO:l). 14C-
methanol and 14C-benzene ( Isocommerz 1 uero used uithout further
purification. Ring-label led 14C-toluene and 14C (7.81-para-xylene
were synthesized and checked for radiochemical purity a s uell as
for accuracy of label position (ref. 7). The reaction products
uere analyzed by radio gas chromatography using a dinonyl-
phthalate/Bentone-34 on Chromosorb U-AH-DHCS column uhich was
connected W i t h a katharometer and a proportional counter as
detectors.

RESULTS AND DISCUSSION

Hethylation of toluene
In accordance uith t h e homogeneous Friedel-Crafts methylation
of aromatic hydrocarbons the heterogeneous catalyzed reaction on
zeolite catalysts can not be stopped after the first step and in
a sequence of consecutive reactions polymethylated aromatics are
formed.

toluene +neOH, xylene +neoH, trimethy lbenzene +neoH

This reaction sequence up to hexamethylbenzene is a consequence

of the stabilizing action of alkyl groups on the transition state
of reaction. Thus, toluene reacts faster than benzene uith alky-
lating agents forming favorably ortho- and para-xylene (ref. 8 ) .
Unlike the homogeneously catalyzed alkylation and the Pischer-
Tropsch process the chain growth does not exceed the formation of
C10-hydrocarbons in Hobil's methanol-to-gasoline(HtG) process as
a consequence of the shape selective properties of HZSH-5 (ref.
9). Although the high content of aromatics makes the HtG products
a good motor fuel the successive methylation reaction yields the
undesirable 1.2.4.5 tetramethylbenzene (durene) uhich can lead to
"carburetor icing" due to its high melting point (352 K). There-
fore kinetic studies on the alkylation of toluene uith methanol
on HZSH-5 catalysts have of special interest for the reduction
of durene content.
Fig. 1 and Table 1 demonstrate the application of the kinetic
isotope method (refs. 10 and 3) on the reaction of 14C-toluene
with methanol. The time dependence of concentrations may be
interpreted as consecutive reactions, But the characteristic
concentration maximum for xylenes which is to be expected for
 307

such a type of reaction is not observed.

" I
-4

i i I I Fig. 1.
Comparison between ob-
served (dots) and cal-
culated (line, model l )
concentration-time de-
pendence of toluene me-
thylation at 693 K uith
a ZSH-5 catalyst

It should be noted that the conversion of toluene does not exceed

40 and methanol is even at short residence times totally
X
consumed. The product composition shoms that in a side reaction
methanol reacts preferably to gaseous hydrocarbons as ethene.
propene and butene. Therefore, in analogy to the HtG process the
formation of aromatics should be considered in mechanistic
studies.
It is to be supposed that the diffusivity of methanol in the
HZSH-5 framework is higher than that of toluene. The same ratio
may be valid f o r the adsorption of the two reactants at the acid
centers. In both cases adsorbed methanol molecules react prefer-
ably uith each other and form polyaethylated aromatics via inter-
mediates which are not in a adsorption/desorption equilibrium
uith the gas phase. That means, the methylation o f toluene on
HZSH-5 can be described as .triangular* reaction model.

toluene +HeoH, xylenes +HeoH trimethylbenzenes

\I/ methanol
[model 1)

Using labelled aromatics the portion of methyl transfer reactions

(methylation and disproportionation) and the direct build-up of
aromatics from methanol resp., is indicated by the molar radio-
activities of the products (Table 1).

TABLE 1
Hethylation of toluene and xylene on HZSH-5 catalyst -
Product composition (mass and activity X ) and relative molar
activities of aromatic components (toluene and xylene i n the
reaction mixture= 1.00) at 693 K, 0.1 HPa N2. 3 g/(g.h)

methanol/ 14C-to luene methano 1 / 14CHg-p-xy 1 ene

___ ~~ ~

mass activ. rel.mo1. mass activ. rel.mo1.

component percentage activity percentage activity

benzene 0.3 0.1 - 0.1 - -

toluene 65.9 69.1 0.88 1.6 0.7 0.33
par a-xy 1ene 14.8 13.6 0.76 55.9 59.5 0.87
meta-xylene 8.9 8.2 0.85 23.7 25.1 0.87
ortho-xylene 4.7 4.3 0.89 8.7 7.6 0.79
Me-Et-benzenes 2.2 1.9 0.82 0.6 0.5 0.77
tri-lie-benzenes 3.2 2.8 0.78 9.4 6.6 0.65

In the reaction of an equimolar toluene/methanol mixture only

between 76 and 69 X of xylenes are formed via methylation. The
portion of the direct synthesized aromatics from methanol depends
on the reaction conditions, the diffusion path inside the
crystallites and the kinetic diameters of reactants. Dessau and
La Pierre (ref. 2) found uith 13C-methanol/toluene mixtures a
portion of 5 t o 34 X C1-synthesis of xylenes and 29 - 40 X of
trimethylbenzenes if the average diameter of the crystallites is
1 Pa. I f small crystallites of 0.02 P B are used the C1-synthesis
of xylenes is reduced to 2 - 10 X (19 - 24 X f o r trimethyl-
benzens). These results correspond w i t h ours ( 1 1 - 24 X for
xylenes, 18 - 22 X for trimethylbenzenes) taking into account
the different reaction conditions and crystallite dimensions ( 2 -
5 Pm). This direct synthesis of aromatics from methanol prevents
a total suppression of durene formation in the HtG-process.
It should be noted that the presented data are only represen-
tative for the participation of methylation and C1-synthesis
resp., i n the formation of aromatics. The lou portion of C1-
synthesis of seta-xylene and ortho-xylene should not be inter-
preted as an consequence of their formation at or near the exter-
nal surface. According to Dessau and La Pierre (ref. 2) the for-
mations of methyl-ethyl-benzenes and trimethylbenzenes near the
external surface (and a high value of the molar radioactivity)
are to be expected, but lower values than those for meta- and
ortho-xylene resp. uere observed indicating that the formation of
trimethylbenzenes from C1-species is higher than i n the case of
xylenes. In connection with this fact the sequence of methylation
 309

rate and conversion of aromatics (at 693 K and 2 g/(g'h)) have to

be considered:

benzene (53 X conversion) > toluene (41 X ) > xylene (22 X )

As mentioned above, this sequence on medium pore size zeolites

does not agree uith those in homogeneously catalyzed reactions
(ref. 4) and on large pore size zeolites (ref. 1 1 ) because of
different diffusivities of the main reaction products. If the
methylation experiments are carried out under the same rate
limiting step then the theoretically expected ratio of the reac-
tion rates should be observed. This is t h e case uhen the methyla-
tion rates of benzene and toluene are determined under the rate
limiting diffusion of xylenes. Therefore a 1:l:l mixture of
methanol/benzene/toluene uas transfor8ed in three experiments
over the catalyst changing in each run the labelled compound
(Table 2). This is a typical tracer experiment in multi-component
systems. The distribution of radioactivity, using 14C-benzene and
14C-toluene as tracer, s h o w a higher conversion of toluene than
benzene corresponding w i t h a higher incorporation of 14C-methanol
in the xylene formation than in the toluene formation. These
results on HZSH-5 zeolites confirm the rule that the reactivity
of aromatics and the stability of the transition state increases
uith the number of methyl groups.

TABLE 2
Hethylation of a mixture of benzeneltoluene uith methanol
on HZSH-5 catalyst - Product composition (mass and activity X )
at 693 K, 0.1 HPa N2, 40 g/(g-h)
mass radioactivity
14C-methanol 14C-benzene 14C-toluene

Cg-C7-fract ion 0.8 11.0 0.2 0.3

ben Zen e 39.1 0.7 91.8 0.2
toluene 52.7 21.4 7.3 87.4
ethylbenzene 0.1 0.9 0.1 <o.1
para-xylene 4.6 38.9 0.4 8.8
meta-xylene 0.9 7.5 0.1 1.0
ortho-xylene 1.0 7.4 0.1 1.0
Et-He-benzenes 0.2 4.1 - 0.4
Trine-benzenes 0.6 8. 1 - 0.8

Isomerization of xylenes
The isomeritation of xylenes has been investigated on a great
variety of catalysts. The results of earlier papers on the
homogeneously catalyzed conversion (aluminum chloride is an
example of a widely used catalyst) were consistent with a se-
quence of intramolecular 1,2-methyl shifts around the aromatic
ring (ref. 12 - 14).

ortho-xylene === meta-xylene para-xylene (model 2)

A 1.3-methyl migration, i.e. a direct para-ortho reaction, is not

alloued. The scheme of consecutive reaction steps has also been
confirmed under heterogeneously catalyzed conditions (refs. 13
and 1 5 ) . But there are exceptions to this mechanism; an inter-
molecular aethyl shift via toluene and/or trimethylbenzenes siru-
lates a "direct" para-ortho reaction pathuay (refs. 16 and 17).

1,2,4-trimethylbenzene
/+
ortho-xylene reta-xylene
it @
1 para-xylene (model 3)
\ f l \
1,2,3-trimethylbenzene 1,3,5-trimethylbenzene

Especially on zeolites uith strong acid sites toluene and tri-

methylbenzenes are produced by disproportionation of xylenes. On
larger pore zeolites disproportionation comes up to 60 X of
isomerization (ref. 18). In analogy to the 1.3-methyl shift by
transmethylation an intramolecular para-ortho conversion via
C5,Cg-ring isomerization has been observed on bifunctional cata-
lysts under hydrogen pressure (ref. 1 9 ) .

Fig. 2.
Comparison between ob-
served (dots) and cal-
culated (line. model 2)
concentration-time de-

5
~-
I .5
-.+ Dendence of xvlene iso-
aerization a t 693 K
uith a ZSH-5 catalyst
l i n e ih)

Besides these chemically understandable para-ortho reaction path-

 311

ways mass transfer effects can also result in a triangular reac-

tion scheme. Chutoransky et al. (ref. 18) found a dependence of
the reaction rate constant kortho-para and kpara-ortho resp., on
the crystalline size of the catalyst particles. For small parti-
cles no direct ortho-para pathway was observed, but for large
crystallites a triangular reaction network had to be considered.

ortho-xylene 7-xylene
\.para-xy 1 ene (model 4 )

The concentration profiles of xylenes within toluene methylation

on zeolites can be used for elucidating the mechanism of isomeri-
zation of xylenes. The high para-xylene content of the initial
product distribution (Pig. 2) is the result of shape selective
diffusion.
The estimation of the model parameters uas done by nonlinear
regression methods using the thermodynamic equilibrium ratio to
minimize the number of unknown parameters. Because of the
unknoun initial product distribution of xylenes two additional
variables had to be calculated. The triangular reaction scheme
(Pig. 3) gives a significant better fit than a series mechanism
(Pig. 2 ) . Table 3 contains a comparison of the calculated reac-
tion rate constants of model 4 with literature data.

Fig. 3.
Comparison between ob-
served (dots) and cal-
culated (line, model 4
and model 5 resp. 1 con-
centration-time depen-
dence of xylene isome-
0 rization at 693 K uith
I
I I
I .5 a ZSH-5 catalyst
llnc l b )

In spite of differences caused by various reaction temperatures

312

(573 K - 693 K) the different participation of the rate constants

kpara-ortho in the brutto consumption rate of para-xylene on
zeolite and amorphous catalysts resp.. is striking. Uhereas on
alumina the para-ortho conversion is very slou (and therefore
could be nearly neglected), on redium pore size zeolites the
theoretically "not alloued" 1.3-methyl shift pathuay is nearly
30 % of the overall para-xylene conversion.

TABLE 3
Isomerization of xylenes on various catalysts - Reaction rate
constants (and 95 % confidence intervals) of model 4

HZSH-5 HZSH-5 A1203 A1203

(this uork) (ref. 5 ) (ref. 20) (ref. 17)

kpara-met a 1.0 f 15% 1.0 1.0 1.0

kmeta-ortho 0.88 2130% 0.33 0.80 0.29
kpara-ortho 0 . 4 2 f 40% 0.39 0.09 0.04
kp-olzkpara- 0.30 0.28 0.08 0.04

A partition of the para-ortho pathuay into transmethylation and

diffusion is possible by including toluene and trimethylbenzene
concentrations in reaction modeling (model 4 ) . However this pro-
cedure increases the number of unknoun reaction model parameters
and needs therefore further studies; but a rough estimation of
transmethylation can be made by means of the extent of xylene
disproportionation. After Bankos et al. (ref. 21) the dispropor-
tionation of xylenes on ZSW-5 zeolites does not exceed 3 - 7 X of
the isomerization rate (see content of benzene in Table 1). and
therefore transmethylation has only a small contribution to the
conversion of xylenes on medium size zeolites. Hence, the rate
constant of the "direct" para-ortho pathuay is an indication of
mass transfer and/or sorption effects of the catalyst under
study. Unlike amorphous A1203 catalysts strong diffusion dis-
guised kinetics in xylene isonerization have to put into con-
sideration on HZSH-5 zeolite catalysts.
This assumption is supported by the high error of the rate
constant kmeta-ortho (Table 3) - the confidence interval includes
the value Zero. As Fig. 3 obviously shous the mechanism of xylene
isomerization on the investigated ZSH-5 zeolite uhich consists of
2 - 5 pm large crystallite particles can be described by a vir-
tual parallel reaction scheme (model 5 ) uithout any loss in t h e
goodness-of-fit.

meta-xylene
4-
para-xylene (model 5 )
% ortho-xylene
 313

This conclusion does not mean that from the view point of
Chemical theory the isomerization of xylenes on zeolite catalysts
consists of two simultaneous reactions, but only that the contact
time dependence of the gas phase concentrations (which are the
result of CheBiCal and sorption/diffusion effects within the
catalyst particles) is well represented by a parallel reaction
network.

REFERENCES
1 N.Y. Chen, J. Catal., 114 (1988) 17
2 R. Dessau and B. La Pierre, J. Catal.. 78 (1982) 136
3 F. Bauer. R. Hanisch, U. Jockisch and Chr. Wienhold,
Chem. Techn., in press
4 H.C. Brown, J. Amer. Chem. Soc., 78 (1956) 6255
5 J.D. Collins, R. J. Hedina and B.H. Davis,
Can. J. Chem. Eng., 61 (1983) 29
6 J. Dermiettel, F. Bauer. H. Rosseler, U. Jockisch, H. Franke,
J. Klerpin and H.J. Barz, Isotopenpraxis, 12 (1976) 57
7 F.D. Kopinke, J. Dermietzel, U. Jockisch and G. Rauber,
Isotopenpraxis, 22 (1986) 388
8 R.H. Allen and I.D. Yates, J. Amer. Chem. SOC.,
83 ( 1961) 2799
9 C. Chang and A. Silvestri, J. Catal., 47 (1977) 249
10 H. B. Neimann and D. Gal, The kinetic Isotope
Hethod and its application, Acaddmia Kiado. Budapest, 1972
11 E. Dumitriu, S. Oprea and V. Hulea, Rev. Roum. Chim.,
32 ( 1987) 525
12 R.H. Allen and L.D. Yats. J. Amer. Chem. SOC.,
81 ( 1959) 5289
13 K.L. Hanson and A.J. Engel, AIChE J., 13 (1967) 260
14 H.C. Brown and H. Jungk, J. Amer. Chem. SOC., 77 (1955) 5579
15 S. Zimnieuict, H. Pilarczyk and K. Kalinski,
Chemia Stosouana, 17 (1973) 235
16 H.A. Lanewala and A.P. Bolton, J. org. Cher., 34 (1969) 3107
17 F. Bauer, J. Dermiettel, H. Rosseler and H. Koch.
Chem. Techn. , 28 ( 1976) 144
18 P. Chutoransky and F.C. Duyer, Adv. Chem. S e r . .
121 ( 1973) 540
19 J. Dermietzel, H. Rosseler. U. Jockisch, Ch. Uienhold,
H. Franke, J. Klempin and H.J. Barz. Isotopenpraxis,
14 (1978) 14
20 K.H. Robschlager and E.G. Christoffel. Can. J. Chem. Eng.,
58 ( 1980) 517
21 I. Bankos. J. Papp and D. Kallo, Acta Chim. Hung.,
119 ( 1985) 179
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors),CatQlySiSand Adsorption by Zeolites 315
01991 Elsevier Science PublishersB.V., Amsterdam

IRON-CONTAII.IING ZSI-5 TYPE ZEOLITES USED IN THE

C0UP L ED MET HA N 0L- H Y DR 0CAR B 0N CR A CK ING ( CMH C )

A. BIARTIN*’, S. NOWAK’, B. LUCKE’, W. WIEKER2 and B. FAHLKE2

’Central Institute of Organic Chemistry, Academy o f Sciences,
Rudower Chaussee 5 , 1199 Derlin, ( G . D . R . )
2Central Institute of Inorganic Chemistry, Academy of Sciences,
Rudower Chaussee 5 , 1199 Berlin, (G.D.R.)

ABSTRACT
Different iron-containing H-ZSK-5 type zeolites have beenused
as catalysts for the CKHC process with n-butane as hydrocarbon
feed. Furthermore, these iron-containing zeolites have been in-
vestigated as catalysts in methanol conversion and in n-butane
pyrolysis, the two single reactions of the coupled process. The
incorporation of iron into silicon-aluminium catalysts led to an
increased lifetime, a higher hydrocarbon conversion as well as
stable olefin yields o f such samples compared to silicon-alumin-
ium-containing zeolites during the CbiHC process. Beside a lower
deposition o f coke a higher amount o f carbon dioxide was obser-
ved during the reaction. Furthermore, it was found that a partial
decoking ( u p to 70 wt.-% of deposited coke) occurs during regene-
ration by steam treatment at reaction temperatures.

I rl TH 0DUCT I0N
In the field of zeolite catalysis, the synthesis of light ole-
fins from methanol has been one of the most important subjects
for the last ten gears (e.g. refs. 1-4). Catalysts applied in this
reaction are narrow-pore zeolite types (refs. 5 , 6 ) . The short
lifetime, connected with a strong coke deposibion, is thc I ost
serious p d > o b l e : i cuch zeolite types. 23rL-5 type zeolites are
io18

described and used for the olefin production from methanol feed
as \!ell, but the olefin selectivity is lover than that of the
narrow-pore type zeolites.
Recently, metal-ion-containing zeolites (e.g. containing
gallium, chromium, vanadium and iron) with pentasil pore structure
have becn assumed to be catalysts for methanol transformation into
olefins with both high selectivity and prolonged catalyst lifetime
(e.g. refs. 7-9). Since the synthesis, characterization, and
investigation o f their catalytic performance in various reactions
(refs. 7-15) these different metal-ion-containing ZSM-5 type
zeolites have got a great influence in some catalytic reactions,
316

e.g. methanol conversion to gasoline, lower olefins, and aromatics

or paraffin conversion to aromatics. In comparison with silicon-
aluminium, the amounts of lower olefins in methanol conversion
could be increased mainly by ZSM-5 type zeolites with different
amounts of iron incorporated (refs. 8 , l O ) . Furthermore, in connec-
tion with the lower acidity of such zeolites, a decrease in the
deposition of coke has been observed (ref. 1 0 ) .
The combination of methanol and hydrocarbon transformation
(CiiIIC) into lover olefins and aromatics was previouslydescribed
in detail (refs. 1 6 - 2 1 ) . At high temperatures, up to 953 K , the
addition of hydrocarbon to a methanol feed in a defined ratio
leads to the conversion o f both methanol and hydrocarbon into low-
er olefins, gasoline, and aromatics in a nearly thermoneutral
reaction in the presence of H-ZSM-5 zeolites.
The CI4HC process has been investigated with n-butane as hydro-
carbon feed a n d various kinds of iron-containing H-ZSM-5 type
catalbsts in comparison to the same investigations with only a
silicon-aluminium-containing zeolite catalyst as described earlier
(refs. 1 6 , 1 7 , 2 1 ) . Furthermore, some experiments o n the methanol-
to-olefin reaction ( I d T O ) at lower temperatures (ca. 6 7 3 K ) and o n
the n-butane pyrolysis ( 7 7 3 - 9 5 3 K ) have been carried out. De-
-eking cycles proceeded under steam and subsequent air treatment.
Iloreover, some results of the physical characterization of
these zeolites will be presented in this paper, e.g., investi-
gations of temperature-programmed (TPD) desorption of ammonia,
electron paramagnetic resonance ( E P R ) and X-ray diffraction (XRD).

EXPE R II4EN ‘I‘A I,

Apparatus and procedure
Isjethano1 and crude n-butane ( 9 2 X n- and 8 7; i-butane) were
used as feed €or the C N H C investigations. Some experiments under
LIT0 conditions were carried out with pure methanol and n-butane
was used as feed in pyrolysis tests. A l l investigations were
carried out in a bench-scale reactor (quartz glass, catalyst vol-
ume ca. 30 ml) (ref. 1 7 ) . The reaction products were analyzed by
on-line gas-chromatography (ref. 2 2 ) .
All conversion data and product yields described in the tables
and figures have been calculated on the C H 2 part in the feed.
After the reaction the zeolite catalysts could be regenerated by
steam at ca.873 - 9 5 3 1.:
 317

Catalyst synthesis
The synthesis of iron-ZSId-5 and iron-aluminium-ZSl,~-5 products
were carried out according to the method of Szostak and Thomas
(ref. 23). Fe(N0 solution o r an equimolecular mixture of
3 3
Fe(NO3I3 and A l ( N O < ) solution was acidified with H2S04 (96 :.)and
3 3
then mixed with 4.51.1 I!a,H2 2Si04. These quantities of the reactants
were chosen in order to get the required silicon-to-iron and
silicon-to-iron-to-aluminium ratios in the reaction mixture. To
the resulting gel 0.1 mol of tetrapropylammoniumbromide per mol of
Si02 was added and, after vigorous stirring, the reaction mixture
was heated in stainless-steel autoclaves at 443 1: for 24 hours
under autogeneous pressure. During thermal treatment the auto-
claves were rotating. The resulting solids were filtered, washed,
and dried.
After synthesis the organic template was destroyed by calci-
nation at ca. 823 K. The ion exchange was carried out with 0.511
NH4C1 or NH4N03 solution (each sample four times for two hours at
353 K). The ammonium-containing zeolites were calcined stepwise
from 573 K t o 823 K to get the H-form. The zeolite powder was then
treated with pure silica (65 wt.-% zeolite and 3 5 wt.-% Si02) to
form catalyst pellets. In general, three catalysts have been used
for the CPiHC investigations (sample A : silicon-to-eluminium = 22
( f o r comparison); sample B: silicon-to-aluminium = 25; sample C:
silicon-to-iron-to-aluminium = 50:l:l).

Characterization methods
The acidity of some samples was determined by the TPD of ammo-
nia. These experiments were performed by gas-chromatographic
measurement of the amount of ammonia desorbed upon heating ammo-
nia-treated samples (treated with ammonia at 393 K and followed
by desorption of physically sorbed ammonia at the same temperature
€or 30 min) at a rate of' 1 2 deg/min.
The EPR spectra of the products were recorded on a Varian E 4
spectrometer operating at X-band microwave frequency.
The X-ray powder patterns of the polycrystalline iron- or iron-
aluminium-silicate samples obtained were performed with a Guinier
equipment.
318

RESULTS AND DISCUSSION

Characterization of iron-containing ZSL-5 zeolites
(i) Temperature-programmed desorption of ammonia (TPDA). The
TPDA plot (P'ig. 1 ) clearly demonstrates the weaker Bronsted
acidity of iron-containin& zeolites as well as the ireakness of
such siteo in iron-aluminium-containing zeolites in comparison to
t h e vell-kriovn ZSL-5 (silicon-eluminium) zeolites. Framework alu-
minium (sample A) results in two peaks at ca. 500 and 710 I<.
I'ramework iron (sample B) with the weaker acidity shows one broad
peak at 585 1:. Finally, the framework iron and aluminium in one
sample (sample C ) result in the same peaks known from framework
aluminium, but the high-temperature peak indicating the strong
Bronsted acidity is decreased.

-I

- 7 r s I 1

673 673 873 TIKI

Yig. 1 . TPDA of ZSld-5 samples: Fig. 2 . EPR spectra o f freshly

( A ) silicon-to-aluminium=22, (€3) synthesized (a) and used (b)
silicon-to-iron=25, L C ) silicon- ZSB-5 zeolite (sample B , sili-
to-iron-to-aluminium=50:1:1 con-to-iron=25

(ii) Electron paramagnetic resonance spectroscpy (EPR). The EPR

spectra of the freshly synthesized zeolite (sample B ) (Pig. 2a)
suggested evidence for at least three different types of iron
sites with g = 4.3, 2 . 3 and 2.0 as described in the literature
(e.g. refs. 2 4 - 2 6 ) . The signal at g = 4 . 3 could be assigned to
Fe3+ in tetrahedral coordination in the zeolite framework. The
 319

signals at g = 2.3 and 2.0 have been assigned, according to data

given in the literature (refs. 24,271, to Fe3+ in occluded oxides
and hydroxides (g = 2.3) and to Fe3’- in 011 symmetry in cationic
sites of the hydrated zeolite (g = 2.0). After strong hydrothermal
treatment of the catalyst samples during CIHC reaction (873 -
953 K) the resonance at g = 4.3 disappeared completely (Fig. 2b).
In agreement with other methods (e.g. IR spectroscopy), this ob-
servation gave evidence o f a nearly complete outbreak of the
framework iron. We found a corresponding phenomenon o f a rapid
and complete withdrawal o f framework species during CLHC reaction
on pure aluminium-containing H-ZSM-5 zeolites (refs. 1?,28).

(iii) X-ray diffraction (XRD). All of the X-ray diffraction

patterns of the investigated iron- and iron-aluminium-silicate
samples have been nearly identical to that o f aluminium-ZSM-5
without iron incorporation. This indicates that the materials
obtained have the same crystalline structure as aluminium-ZSM-5.

Methanol-to-hydrocarbon conversion
Table 1 describes comparison between the three catalyst samples
A , E, and C during methanol conversion after two hours time on-
stream at 673 K and a WHSV o f 0.8 h-’ under atmospheric pressure.

TABLE 1
Methanol conversion and product distribution on ZSM-5 samples A ,
B and C (673 K , WHSV = 0.8 h-’, atmospheric pressure)
~ ~

Catalyst Sample Conversion* Yield*

Methanol C,-C 4 L‘ -c liquid

paraffins olefins hydrocarbons

Si-A1 A 92 30 35 17
Si-Pe B 97 8 58 19
Si-Fe-A1 C 93 26 33 20

t ”t ,-70

In the four columns the conversion of methanol, the yields of

lower paraffins (C1-C4), lower olefins (C2-C4), and liquid product
amount are shown for every catalyst under the same reaction con-
ditions. The olefin yields are very high on pure iron zeolite
(sample B) in comparison to aluminium-containing zeolites. The
amount of paraffins increased with increasing aluminium-content
320

in the catalyst, while the amount of olefins decreased. The cata-

lytic behaviour of the zeolite samples A and C is nearly the same.
The lower conversion o f methanol on pure aluminium-containing
zeolite (sample A ) and its lower yield in liquid hydrocarbons
could be caused by a faster deactivation of this sample.
The results show that additional aluminium-containing iron-
ZSIil-5 zeolites are not very selective for the generation of lower
olefins, because the primarily formed olefins are further conver-
ted to higher hydrocarbons, such as aromatics and higher paraf-
fins. These observations are related to the stronger acid sites
of the additionally incorporated framework aluminium. 2514-5 zeo-
lites with lower Bronsted acidity containing solely iron proved to
be more effective and selective f o r methanol conversion into ole-
fins.
At higher temperatures the methanol conversion was complete
and, as expected, the amounts o f carbon oxides, hydrogen, and me-
thane increased drastically. Furthermore, the formation of coke
was advanced. This is also known from aluminium-containing zeo-
lites (refs. 16,171.

n-Butane pyrolysis
The cracking activity has been checked stepwise with the same
catalytic systems from 773 up to 953 K under atmospheric pressure
and a WHSV = 1.3 h-I. Table 2 depicts the results of pyrolysis at
773, 873 and 953 I[ on iron-ZSM-5 zeolite (silicon-to-iron = 25).

TABLE 2
Products obtained by n-butane pyrolysis using ZSM-5 sample B
-1
(silicon-to-iron = 25) as catalyst (WHSV = 1.3 h , atmospheric
pressure)

Temperature Conversion* Yield*

(K) n- But ane C2-C4 Methane
'2-'4
paraffins olefins

773 6 1.2 2.4 1.4

873 38 4.8 18.5 14.8
953 68 7.1 36.9 19.8
* wt.-%
The n-butane conversion has increased with increasing reaction
temperature. Main products have been lower paraffins and olefins
and, at higher temperatures, also methane.
 321

Furthermore, the n-butane conversion on iron-containing ZSE-5

zeolites is weaker (Fig. 3 ) compared with that on aluminium-con-
taining zeolites. Despite of the lower cracking activity of such
zeolites (iron-ZSM-5), it has been observed that there is a p r o -
longation of the reaction time resulting from a lower deposit of
coke. This smaller amount of deposited coke could have also been
caused by the lower acidity o f the Bronsted sites in iron-contai-
ning zeolites.

I:;
& $
0 -
u r
,

1
,

2
,

3 tlhl

Fig. 3. n-Butane conversion on ZSI-1-5 zeolites in pyrolysis reac-

tion depending on time on-stream: key as for Fig. 1.

By additional incorporation of aluminium during the synthesis

of iron-containing zeolites (samyle C ) the conversion of n-butane
could be increased, but the level of decrease in conversion re-
mained the same a s in investigations with solely iron-containing
sample.

Iron containing ZSM-5 type zcolites in the CWHC reaction

The preferred mixture of methanol and n-butane for the CMHC
reaction was calculated by adding up the standard reaction enthal-
pies (law o f constant adding u p o f heat by HESS) as described in (
ref s. 16-18).
‘Ihe C L I I C investigations were carried out at temperatures up to
953 K , atmospheric pressure and a WIiSV of ca. 3 h-I. The feed ra-
tio o f methanol-to-n-butane was 3 : l .
A3 expected, from the n-butane pyrolysis results, the n-butane
conversion during CWHC was lower than that with solely aluminium-
containing sample. The conversion level (ca. 40 wt.-%), however,
remained nearly constant during time on-stream (Pi&. 4 2 ) . Uain
products were lower olcfins and, beside a large amount of carbon
monoxide, a defined yield of carbon dioxide was obtained. Apart
322

from this, t i l e yliids of the wanted products were low and caused
a l o w cracking activity of these zeolite types under C L H C con-
ditions (Fig. 4b).

l'ig. 4. n-Butane conversion (a) and olefin yields (b) on sample E

(silicon-to-iron = 2 5 ) at 9 5 9 K in C I i H C reaction

The use of zeolites containing both iron and aluminium effected

the supposed rising of the hydrocarbon conversion level shown
during the investigations of n-butane pyrolysis. Already after 9 0
minutes time on-stream the n-butane conversion on silicon-iron-
cluniiiiium zeolite (sample C) was higher than o n silicon-aluminium
zeolite (sample A ) (ref. 17). After four hours a significant de-
crease in hydrocarbon conversion on silicon-aluminium zeolite was
observed, whereas the decrease on silicon-iron-aluminium zeolite
was very l o i r (I'ig.5a). The decrease in n-butane conversion led
also to a decrease in the yield of olefins formed (sample A), as
shown in lig. 5b, but the olefin yields obtained on sample C were
nearly constant after three hours time on-stream.
These data reflect the more stable hydrocarbon conversion o n
iron-containing zeolites and the higher level of hydrocarbon con-
version and olefin production on thc silicon-iron-aluminium cata-
lyst as well.
Generally, the stable conversion rate connected with stable
olefin yields caused the prevention of catalyst deactivation in
the C6:HC reaction by incorporation of iron into zeolite. The con-
sequence is the prolongation of' catalyst lifetime.
 323

3 6 9 tlhl
.
N
u 3 6 9 tlhl

Fig. 5. n-Butane conversion (a) and olefin yields (b) on sample C

(silicon-to-iron-to-aluminium =50:1:1) at 953 K in CMHC reaction
in comparison with sample A (silicon-to-aluminium = 2 2 )

Regeneration o f iron-containing ZSM-5 type zeolites

During the CICHC investigations on iron-containing zeolites a
distinct decrease in coke formation in comparison with silicon-
aluminium zeolites was observed, also found by Inui during metha-
nol transformation tests (ref. 10). Furthermore, a higher amount
o f carbon dioxide was formed during the reaction and a lower
amount of water was determined than calculated. Iron-oxide phases
formed during the reaction by a nearly complete withdrawal of
framework iron should stimulate gasification processes simultane-
ously (known also from water-gas shift reactions) (refs. 29,30).
These points led to considerations concerning a regeneration
method only by steam. During decoking steps by steam and argon as
carrier gas at ca. 953 K the deposited coke could be removed up
to 70 wt.-% (ref. 3 1 ) . A complete decoking could be obtained by
a followed decoking by air. Probable reasons for a lower deposit
of coke during methanol transformation, CMHC and the gasification
activity of the used zeolites during decoking are a lower amount
of reobtained water and higher yields of carbon dioxide compared
to solely aluminium-containing zeolites.

CON C LUS I O N S
Iron- and iron-aluminium-containing 281-5 type zeolites were
used as catalysts for the CMHC reaction as well as for single re-
actions of methanol conversion and n-butane pyrolysis. During the
CMHC reaction with the above zeolites a lower decrease in cracking
activity could be obtained together with a prolongation of the
catalyst lifetime. One reason for this fact could be due to the
324

lower acidity of these catalysts compared to aluminium-ZSM-5, and

to the lower deposit of coke by burning the deposits on formed
iron oxide phases.

A CKN 0W L E DG E ME N T
The authors would like to thank I r s . H.Poethke and I.Irs. U.Hahn
f o r their assistance in the experimental work and Dr. R.Liick f o r
the EPR measurements.

REFERENCES
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and E'.Okazunii in Y.Murakami, A.Iijima and J.W.Hard (Eds.),
Proc. VIIth 1nt.Zeolite Conference, Tokyo, Kodansha (Tokyo) -
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12 T. Inui, H.I#latsuda, O.Yamase, A.Nagata, K.Fukuda, T.Ultawa and
A.Miyamoto, J. Catal., 98 (1986) 491
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Appl. Catal., 57 (1990) 203
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S.G.Hegde, Acta Phys. Chem., 31 (1985/1-2) 137
25 B.Borade, Zeolites, 7 (1987) 398
26 A.N.Kotasthane, V.P.Shiralkar, S.G.Hedge and S.B.Kulkarni,
Zeolites, 6 (1986) 253
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rohstoffe aus Kohle, Georg-Thieme-Verlag (Stuttgart),
1977, p . 114
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Kh.M.Minachev (Eds.), Catalysis by Zeolites, Akaderniai Kiado,
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This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 327
0 1991 Elsevier Science Publishers B.V., Amsterdam

DISPERSION DEPENDENT SELECTIVITIES OF SYNGAS CONVERSION ON

FAUJASITE ENCAPSULATED Pt, Pd OR Ir

N.I. JAEGER, G. SCHULZ-EKLOFF and A. SVENSSON

Institut fiir Angewandte und Physikalische Chemie,

Universitzt Bremen, 2800 Bremen 33

ABSTRACT
Metal phases of fine as well as coarse dispersions for Pd. Pt
or Ir are grown within a NaX matrix. The mean particle sizes
obtained under nearly identical reduction-agglomeration conditions
follow the order Pd > Pt > Ir. For comparable metal dispersions
the activities for syngas conversion or methanol formation as well
as the selectivities for methanol formation exhibit the order Pd >
Pt > Ir. A fraction of carbonaceous species deposited during
catalysis can be removed by hydrogen as methane, whereas oxygen is
needed for the conversion of the residual coke fraction to carbon
dioxide.

INTRODUCTION
It was found, that the methanol formation activities and
selectivities of Pd, Pt or Ir on silica gel follow the order Pd >
Pt > Ir [ref. 11. It was suggested that this order corresponds to
the tendency of the metal to fill its d-shell [ref. 21. Increasing
activities and selectivities for methanol formation with increas-
ing metal dispersion is reported for Pd on silica gel [ref. 31 and
Pt in faujasite X [ref. 41. A metal dispersion effect was found
for the water-gas shift reaction (WGSR) on Pt/NaX, which was ana-
logous to that one obtained for the methanol formation Iref.51.
In the following the methanol formation activities and
selectivities of faujasite X supported Pt, Pd or Ir catalysts,
exhibiting different metal dispersions, are evaluated to clarify
the different influences of metal type or metal particle size.
Additionally, the amounts of coke deposited by the reaction are
determined.
328

EXPERIMENTAL
PreDaration of the catalysts
Iron-free faujasites NaX (Si/Al ratio 1.2) were prepared by
hydrothermal crystallizations. The metals were introduced as the
ammine-ion-complexes from aqueous solutions of the chlorides
([Pt(NHa)4]2'; [Pd(NH3)4]2+; [1r(NIi3)~ClJ2*)- The loaded zeolites
were washed until chloride-free and dried at 353 K.
The autoreduction of the specimens was carried out using a
temperature program (2-3 K/min) up to temperatures between 573 and
673 K in either streaming argon or oxygen. In the case of samples
treated under oxygen the reduction was completed with hydrogen at
373 - 573 K for 1 h.
The materials investigated, the reduction treatment and the
surface average diameter, d = Inid13/Znid_Lg of the metal
crystallites are listed in Table 1. The surface average diameter
-
ds was calculated from the histograms in order to represent the
contribution of the surface more adequately. In the formula ni is
the number of crystallites within the diameter di and di+dd while
-
di = &+Ad/2. The histograms of the metal dispersions listed in
Fig. 1 were evaluated from electron micrographs. The number of
metal surface atoms/g metal was calculated from the particle size
distribution. A sphere was taken as a justifiable approximation
for the observed crystallites and the specific gravity of the bulk
metals was used. The evaluated metal surfaces were used for the
calculation of the dispersion D and the normalized activities or
turnover frequencies, respectively.
The global crystallinity of the samples was found to be
maintained even in the case of metal particles growing beyond
supercage dimensions within the zeolite matrix [ref.5].The metal
loading in atom-% was kept constant for all catalysts in order to
maintain a constant Bronsted acidity which results from the
complete reduction of the metal ions.

Catalytic measurements
The syngas conversion to methanol and methane was studied in a
continuous flow stainless steel reactor (volume: 1.6 cm3). A
fluidized bed was established by means of an external vibrator.
 329

TABLE 1
Composition, reduction, surface average diameter and dispersion
D of the catalyst.

Material Metal loading Reduction treatment L D

atom-% wt-% nm

PtX/O2 g.aAo.2 5.9 heated to 673 K at 1.8 0.7

2-3 K/min in flowing
0 2 , held 5 h, HZ
passed at 513 K for 1 h

PtX/Ar g.ako.2 5.9 heated to 613 K at 5.2 0.3

2-3 K/min, in flowing
Ar, held 5 h

PdX/Oa 10f0.2 3.4 heated to 573 K at 3.1 0.4

2-3 K/min in flowing
0 2 , held 5 h, HZ
passed at 313 K €or 1 h

PdX/Ar 10A0.2 3.4 heated to 513 K at 11.2 0.15

2-3 K/min in flowing
Ar, held 16 h

IrX/02 10k0.2 6.0 heated to 593 K at 1.0 0.95

2-3 K/min in flowing
0 2 , held 11 h, HZ
passed at 563 K €or 1 h

IrX/Ar 10A0.2 6.0 heated to 593 K at 2.1 0.5

2-3 K/min in flowing
Ar. held I h

The experiments were carried out at 2 MPa total pressure with

H2/CO ratios between 1.5 - 4, temperatures between 523 - 623 K and
a space velocity (STP) of 9315 h-1. 500 mg of the pressed and
granulated catalysts (grain size 0.355-0.71 nun) were used in the
experiments.
Analysis of the reaction products was carried out by on-line
gas chromatography. The concentrations of COZ and CH4 were
monitored by infrared analyzers.

Characterization of the carbon deposits

Consecutively, hydrogen as well as oxygen were passed through a
glass reactor (2 ml), containing a used catalyst (350 mg). Normal
pressure and a space velocity around 640 h-' were applied. The
330

Fig. 1. Histograms of particle size, metal mass and metal surface.

The bars represent integer numbers. Sections of representative
transmission electron micrographs are inserted.

heating rates were 5 K/min, and the final temperature was 723 K.
The evolutions of methane under hydrogen and of carbon dioxide
under oxygen were monitored by infrared analyzers.
 331

RESULTS
Metal disDersions
The metal phases are located inside the faujasite matrix, as
could be gleaned from the uniform distribution of the metal
particles in the specimens for electron microscopy obtained by
ultrasonic fragmentation of zeolite crystals, and as was assured
by photoelectron spectroscopy [ref. 61. The growth of particles
beyond supercage dimensions is accompanied by local zeolite
framework fragmentations and reconstructions, as evidenced by
*qSi-NMR spectra [ref. 71 and adsorption isotherm analysis [ref.
51. The recognized mesopore texture, generated in the metal phase
containing zeolite matrix, discloses that the metal particles are
surrounded by halos of free space and, thus, are fully accessible
for chemisorbing and reacting molecules.
The found surface average mean particle sizes follow the order
Pd > Pt > Ir for both types of applied reduction conditions (Table
1). The reverse order is valid for the heats of vaporization or
heats of fusion [ref. 8 1 , i.e. the energy of atom abstraction from
metal clusters. Thus, the tendency for sintering by an Ostwald
ripening mechanism should follow the order given above. Sintering
by particle migration and coalescence can be excluded for
faujasite accomodated metal phases. Only slight increases of the
mean particle sizes are observed for the used samples as compared
to the fresh ones.

Svnaas conversion
The results of the syngas conversion (cp. Table 2 ) show several
significant features. Firstly, the turnover frequencies of syngas
conversion, i.e. for the sum of methane and methanol formation,
follow.the order Pd > Pt > Ir at comparable dispersions of the
metal. Secondly, for the metals exhibiting high activities, i.e.
Pd and Pt, the turnover frequencies increase with increasing metal
dispersion. Thirdly, the metal type effect as well as the metal
dispersion effect are even more pronounced considering the
methanol activities separately. Furthermore, the increase of the
methanol selectivity with increasing metal dispersion is valid for
all metals studied here. Identical features, i.e. the metal type
effect as well as the metal dispersion effect, are observed for
the activities of carbon dioxide formation resulting from the
simultaneous WGSR. Traces of higher hydrocarbons and dimethylether
are found in the product spectrum but are not considered further.
332

TABLE 2
Turnover frequencies TOF (mole of product/gram-atom of metal
surface atoms-s),selectivities S ( T 0 F (methanol)/TOF (methane)) and
relative selectivities S r e I (selectivity of fine
dispersion/selectivity of coarse dispersion) for the syngas
conversion at H s / C O = 2.33, 573 K, 2 MPa, SV (STP) = 9375 f
75 h-1 after 250 sin time-on-stream.

Sample 4L TOF ( MeOH ) TOF (CHI S Sre I

nm x 104 x 103
PtX/On 1.8 6.8 1.8 0.38
5.4
PtX/Ar 5.2 3.0 4.3 0.07

PdX/Os 3.7 21.0 1.9 1.10

4.8
PdX/Ar 11.2 6.1 2.7 0.23

IrX/02 1.0 0.5 0.4 0.13

1.3
IrX/Ar 2.7 0.9 0.9 0.1

The found features are valid for all reaction parameters where
the kinetic regime is preserved, i.e. where differential
conversions and sufficient distances from the thermodynamic
equilibrium of methanol formation [ref. 91 are maintained. For
instance, the metal dispersion effects become more prominent with
increasing pressure or space velocity. For the methane formation
the kinetic regime is maintained in any case, due to the
sufficient distance from equilibrium [ref. 91 under the chosen
reaction conditions. This means, that the mutual influence of the
extent of methane formation and the extent of methanol formation
can be neglected [ref. lo]. Furthermore, methanol and methane are
formed on different sites by two independent routes, presumably
[ref. 31.
The syngas conversion on fresh catalysts is always
characterized by induction periods in the beginning of the
reaction, as has repeatedly been reported previously [refs. 3, 11,
121.

Deposition of carbonaceous species

The fraction of carbon deposits which can be removed by
hydrogen show a relatively simple pattern in the temperature
 333

programmed reduction spectrum (Fig. 2a). although it comprises the

removal of carbidic carbon from the metal surface [ref. 131 as
well as hydrogenation of carbonaceous species on the support by
spillover hydrogen [ref. 141. The temperature programmed

PIX/O,-

PlX/Ar ----

0
U
T
- I
b
0.2
I
,--
!
PdX/O,-
PdX/Ar ----
I I
,\"
75
> 0.1-

0 -* r-' 1
- --- ----+
#
/
\

Fig. 2. a: Temperature programmed hydrogenation of coke deposits

to methane on different Pt dispersions. b: Temperature programmed
evolution of COZ from oxidation of the residual coke not removable
by hydrogen on different Pd dispersions.
334

oxidation of the residual coke fraction, however, can exhibit a

more complex pattern (Fig. 2b). This type of carbonaceous species
is, presumably, located at the support exclusively [ref. 31. Both
types of coke do not affect the activity of the syngas conversion
with time-on-stream, contrary to observations reported for the
methanol formation on faujasite Y supported Pd [ref. 31.

DISCUSSION
Obviously, faujasite X is a favourable support for the study of
metal dispersion effects in catalysis, since the occluded metal
particles have a low tendency for sintering, but are fully ac-
cessible to reaction mixtures. Although the relatively high Bron-
sted acidity favors the methanation selectivity in the syngas
conversion [cp. ref. 31. the found metal type effect as well as
the metal dispersion effect in the methanol formation activity and
selectivity are parallel with analogous results obtained with the
support silica gel [refs. 1.31. Strong metal-support interactions,
like formation of new phases or deposition of zeolite fragments on
the metal phase, were never observed for the applied metal/fauja-
site X system under the reduction and catalytic conversion con-
ditions used here. The observed effects can, therefore, be re-
ferred to the variations of the metal type or metal dispersion
only. It is interesting to note, that the metal dispersion effect
can surmount the metal type effect, e.g. the fine Pt dispersion is
more active in the methanol formation than the coarse Pd
dispersion (cp. Table 2).
Up to now, the effects of metal type or metal dispersion in
syngas conversion activities or selectivities are poorly
understood. Won-dissoziative chemisorption of carbon monoxide.
which might be a prerequisite for methanol formation, is found on
each of the three metals. The postulates on the participation of
Men+ surface sites in the syngas conversion [ref. 151 and the
influence of the COz/CO ratio on the density of Men+ surface sites
[ref. 161 cannot be falsified, since the methanol activities and
selectivities vary analogously to the corresponding WGSR. An
influence of the carbonaceous deposits on the catalytic effects,
as has been suggested elsewhere [ref. 41, is still uncertain,
since the fraction of carbon located on the metal surface only,
could not be evaluated separately.
 335

ACKNOWLEDGEMENT
Financial support by the Deutsche Forschungsgemeinschaft is
gratefully acknowledged. We are indebted to Drs. A. Kleine and R.
Lamber for taking the electron micrographs and to Mrs. U. Melville
for carryingout the temperature programmed hydrogenation and
oxidation of the coke on the used catalysts.

REFERENCES

1 M.L. Poutsma, L.F. Elek, P.A. Ibarbia, A.P. Risch and J.A.
Rabo, J. Catal. 52 (1978) 157.
2 K. Klier, in "Catalysis of Organic Reactions" (W.P. Moser,
Ed.), Marcel Dekker, New York 1981, p.195.
3 F. Fajula, R.G. Anthony and J.H. Lunsford, J. Catal. 73 (1982)
237.
4 N.I. Jaeger, G. Schulz-Ekloff and A. Svensson, in "New
Developments in Zeolite Science Technology" (Y. Murakami, A.
Iijima and J.W. Ward, Eds.), Elsevier, Amsterdam 1986; Stud.
Surf. Sci. Catal., vol. 28, p. 923.
5 N.I. Jaeger, J. Rathousky, G. Schulz-Ekloff, A. Svensson and
A. Zukal, in "Zeolites: Facts, Figures, Future" (P.A. Jacobs
and R.A. van Santen, Eds.), Elsevier, Amsterdam 1986; Stud.
Surf. Sci. Catal., vol. 49 B, p. 1005.
6 G. Schulz-Ekloff, D. Wright and M. Grunze, Zeolites 2 (1982)
70.
7 G. Schulz-Ekloff and N.I. Jaeger, Catalysis Today 3 (1988)
459.
8 R.C. Weast, CRC Handbook of Chemistry and Physics, CRC Press,
Brea Raton 1984/85.
9 H. Landolt and R. Bbrnstein, Zahlenwerte und Funktionen
II.Bd., 4. Teil (Kalorische Zustandsgrbpen), Springer, Berlin
1961.
10 E.J. Henley and E.M. Rosen, Material and Energy Balance
Computations, Wiley, New York 1969, p. 367 ff.
11 M. Ichikawa and K. Shikakura, in "New Horizons in Catalysis"
(T. Seiyama and K. Tanabe, Eds.), Elsevier, Amsterdam 1981;
Stud. Surf. Sci. Catal., vol. 7 8, p. 925.
12 N.I. Jaeger, A. Jourdan, G. Schulz-Ekloff, A. Svensson and G.
Wildeboer, Chemistry Express 1 (1986) 697.
13 A.T. Bell, in "Structure and Reactivity of Surfaces" (C.
Morterra, A. Zecchina and G. Costa, Eds.), Elsevier, Amsterdam
1989; Stud. Surf. Sci. Catal., vol. 48, p. 91.
14 W.C. Conner, in "Hydrogen Effects in Catalysis" (Z. Paal and
P.G. Menon, Eds.), Dekker, New York 1988, p. 338.
15 E.K. Poels and V. Ponec-, Catalysis - A Specialist Periodical
Report, The Royal Society of Chemistry, London 1983, vol. 6,
p. 196; and references therein.
16 K. Klier, V. Chatikavanu, R.G. Hermann and G.W. Simmons, J.
Catal. 74 (1982) 343.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 337
0 1991 Elsevier Science Publishers B.V., Amsterdam

CONTRIBUTION OF 13C NMR SPECTROSCOPY TO THE ANALYSIS OF SURFACE

COMPOUNDS FORMED IN THE TRANSFORMATION OF ACETONE ON ZEOLITES

V. BOSAEEK, L. KUBELKOVA and J. NOVLKOVL

J. Heyrovsky Institute of Physical Chemistry and Electrochemistry
Czechoslovak Academy of Sciences, 182 23 Prague 8, Czechoslovakia

SUMMARY
The formation of the protonized form of acetone on HZSM-5 and
HY zeolites at room temperature has been demonstrated by high
resolution solid state NMR spectroscopy. As the reaction
temperature increases, this form undergoes gradual dimerization
folbowed by further transformations. At temperatures of about
180 C cyclization and the formation of undesorbable compounds with
polyalkylaromatic character take place. The coke formed mostly
exhibits aromatic character; the appearance of the signal at
154 ppm (TMS) indicates the presence of oxygen bonded to an
aromatic ring. The presence of either an ethereal bond or of
bonding of the phenoxy groups formed with the participation of
lattice oxygen is suggested.

INTRODUCTION
Acetone can be converted to various hydrocarbons over the acid
forms of zeolites(refs.1-3). These reactions are known to take
place via aldolization and dehydration followed by cyclization,
aromatization and cracking (refs. 4-7). Analysis of the mechanism
of these reactions in the liquid phase revealed that the
protonized form of acetone is formed in acid solutions; the enol
form is converted to diacetone alcohol (DAA). After dehydration,
this compound is then converted to mesityloxide (MO). Recent
studies have shown that a similar mechanism probably occurs in the
heterogeneously catalyzed transformations of acetone over acid
catalysts (refs. 4-6).
Various spectroscopic techniques have been employed in the
investigation of the mechanisms of catalytic reactions on solid
phase surfaces.The development of high resolution NMR techniques
for solids has also began to permit the analysis of adsorbed
complexes with low mobility on the catalyst surface (refs. 8-11).
In this study, acetone adsorbed on decationated zeolite
surfaces was studied at various temperatures by 13C HR NMR in
order to identify the surface species which could take part in the
reaction mechanism. To obtain information about the intermediate
338

products of the reaction, the samples were analysed at various

time intervals both in the static and/or the dynamic ( flow )
arrangement.

EXPERIMENTAL
Materials
Decationized samples of Y and ZSM-5 zeolites differing in their
Si/Al module were used. The samples were supplied by the Research
Institute of Oil and Hydrocarbon Gases (WRUP), Czechoslovakia.
The ammonium form NH4 ,Nay-70 was decomposed in vacuum at 35OoC,
HZSM-5 zeolites with Si/Al ratio equal to 13.5 and 22.5 were
prepared from the Na parent zeolite by decationization with 0.5 M
HN03 and calcination at 550OC.
The samples for the NMR measurements were activated overnight
in a vacuum at 550OC and transferred in sealed ampouls to the
adsorption apparatus, where acetone was adsorbed in defined
quantities. The ampoules were then resealed under vacuum . They
were openeded prior to the NMR measurements under an inert
atmosphere ( N2) and transferred into the ceramic rotors for NMR
measurements.
Technique
The HR NMR spectra were measured with a BRUKER MSL-200
spectrometer equipped with magic angle spinning (MAS) technique.
As the study was carried out to investigate the adsorbed
molecules with restricted mobility at room temperature, the
spectra were measured by the cross-polarization method (CP) which
is efficient in the investigation of organic solid substances by
13C HR NMR (ref.11). This technique has a favourable effect, not
only on the signal intensity of 13C nuclei, but also on their
relaxation. It was found from the dependence of the signal
intensity of the spectrum on the contact time that the optimum
contact time for the energy transfer from H ' to I3C (under the
Hartman-Hahn conditions) was 2 - 3 ms. The rr/2 pulse for
excitation (5-6 u s ) and 0.05 s aquisition time were employed. The
number of scans required to obtain spectra with an acceptable
signal/noise ratio depended both on the adsorbed amount and on the
isotopic composition of the acetone used. For a small adsorbed
amount of acetone, 13C-enriched acetone-2-13C was employed, as
indicated in the figure captions. 13C CPMAS NMR spectra were
measured at 50.32 MHz with 20 or 25 kHz band width. The repetition
delay was 4 s , and 10 s in some cases. The ceramic rotor spinrate
 339

was 4.7 - 5.0 kHz. The data obtained by IR spectroscopy and mass
spectrometry were also included in the discussion. The details of
these techniques and results are described elsewhere (ref.12).

RESULTS and DISCUSSION

Adsorption of acetone at room temperature
We were especially interested in the interaction of acetone
with the highly acidic structural OH groups of HZSM-5 and HY
zeolites under conditions preceding the chemical reaction.The 13C
CPMAS NMR spectra of adsorbed acetone were measured with samples
containing various adsorbed amounts, as the dependence of the
signal position on the adsorbed quantity was expected. This effect
should appear as a result of an exchange process as described by
Bernstein et al.(ref.l3 ) . for acetone on silica gel. Spectrum (a)
in Fig.1. for the small adsorbed quantity N=0.2 mmo1.g-’ of
adsorbed, isotopically enriched acetone-2-13C (96%) exhibits an
intense signal at 224 ppm (TMS), a weak signal at 209.9 ppm in the
carbonyl nuclei NMR region and a signal at 28.9ppm in the -CH
region. With increasing acetone adsorption (0.2-2.7 mmo1.g -13)
primarily the intensity of the signal at 209.9 ppm is increased
whereas the signal at 224 ppm becomes only a shoulder and, in
addition, a further weak shoulder appears at 204 ppm (see Fig.
2.).
For samples with higher adsorbed quantities of acetone, further
signals appear in the spectrum at room temperature, indicating
slow chemical transformation of acetone in the adsorbed phase.
When acetone has been adsorbed on zeolite for two months, the
original signals of physically adsorbed acetone (209.9 and 3 0 ppm)
and its protonized form (224 and 29 ppm) were accompanied by new
signals indicating dimerization with the formation of DAA
1
characterized by signals at 210 ppm ( X = O ) , 73.5 ppm (-C-OH),
I
56.6 ppm (-CO-CH2-CO), 34 and 30 ppm (-CH3), as well as the
formation of dimers of the acetylacetone (AAC) keto-enol tautomer
type, characterized by a broad signal at 187 ppm (enol and keto
*I *I
form = C-OH and -CH2- C=O, respectively) , 93.7 ppm (=*CH-), 56.6
ppm (-CH2-) and 2 8 ppm (-CH3). This dimerization evidently takes
place because of the formation of the protonized form of acetone,
indicated by a signal at 224 ppm (see Fig.l., curve (a)). For low
adsorption of 0.2 mmo1.g-’ acetone on zeolite containing 1.0
mmo1.g-I of acid centers, the signal position should be
characteristic for the protonized acetone, even if an exchange
340

s I 1 8 I s
300 200 100

Fig.1. I3C CPMAS NMR spectra of adsorbed acetone at 50.32 MHz on

HZSM-5 zeolite (a) 0.2 mmol/g of acetone-2-13C(96%)at 25°C
(b) spectrum after admission of NH at 130°C (acetone/NH3
ratio = 2:l ) , NS=270 , (c) spectruii as for (b) but for
acetone/NH ratio = 1:l
* spinning sidebands, spectra normalized to the highest
peak with CY=lO units.
 341

process takes place (ref.13). The 4 value of 250 ppm for

protonized acetone in a superacid published by Olah et al.
(ref.14) is higher than the value observed by us, however, this
discrepancy can be interpreted in terms of the influence of the
interaction of the protonized form with the zeolite lattice. IT
addition , this difference could be associated with proto
mobility resulting from the equilibrium (CH,),+C-OH
-
+ 0 Z '
(CH3) 2C=O---HO Z , but the relatively narrow signal at 224 ppm ar
its invariability with the adsorbed amount do not support this
explanation.
Further evidence for the correspondance of the signal at 224
ppm to the protonized acetone form is the discovery that a
reaction with protonized molecules occurs after the admission of
ammonia in various quantities; the intensity of the signal at 224
ppm gradually decreases (see Fig. l., curves (b), (c)) and a new
signal appears at 200 ppm. In addition, the -CH3 signal intensity
at 29 ppm also decreases and a new high-field- shifted signal
appears at 23 ppm. As we have already noted, both new signals are
in very good agreement with the signals of the dimethylimmonium
cation described by Olah et al.(ref.l5). This species is also
probably created during the interaction of NH3 with protonized
acetone (ref.16).

The chemical transformation of acetone at temDeratures above 25OC

The processes already detected at room temperature are
accelerated by heating the zeolite samples with adsorbed acetone.
At the same time, new mechanisms come into action, as can be seen
from the spectra in Fig.2. Spectrum (b) measured for a sample
after treatment at 18OoC for 1 h indicates further chemical
transformations. This is mainly a significant decrease in the
intesities of the signals corresponding to the various forms of
acetone (224 and 210 ppm) .The disappearance of the signals which
are typical for DAA (73.5 ppm) and AAC (93.7 ppm) also indicates
their transformation into other types of hydrocarbons. The
dehydration of DAA to MO ( observed also by IR spectroscopy - see
ref.12) seems to be probable, the presence of the latter being
indicated by the signals at 197.0 ppm (>C=O), 153.0 ppm ( >* CP =)
and probably by a weak signal hidden in the shoulder of the signal
at 124 ppm ( = C " < ) . The signal of this a-carbon would be weak, as
it is created from a carbon type which has not been enriched with
the 13C isotope.
 342

~ . . .I .
. . . . , . ... 1 . . . . 1 . ... 1 . . . . 1 . ,

300 200 100 ppm 0

Fig.2. 13C CPMAS NMR spectra at 50.32 MHz on HZSM-5

(a) 2.5 mmol/g of acetone-2-13C(lO%) at 25'C ....after 2
days,- after 2 months, NS = 560
(b) sample (a) after heating at 180°C for lh,
(c) sample (b) after heating at 280°C f o r 0.5h, NS = 2 5 6 0
( normalized spectra as in Fig.1.).
 343

Another interesting signal in the N M R range of carbonyl

compounds is the broad signal with a maximum at 177 ppm which
could indicate the formation of a carboxylic compound, e.g. acetic
acid, or which could correspond to Some form of a cyclic ketone
.
(isophorone?) The signals at 137 and 129 ppm are characteristic
for simple aromatic compounds: their presence has also been
demonstrated in the desorption products. Spectrum (c) in Fig.2.
obtained for the same sample after further heating to 28OoC for
0.5 h corresponds to the formation of alkylaromatics. In this
spectrum, the signals at 138.5 and 129.3 ppm predominate and are
very close to those exhibited by trimethylbenzene and similar
alkylaromatics (ref.17). The high-field-shifted signal of -CH3 is
also evidence for this fact. Both the signal at 180 ppm and the
methyl signal at 20 ppm most probably correspond to the acetic
acid which was found by mass spectrometry in the desorption
products. Similarly, C7 - Cll aromatics were also found in the
desorption products. Isobutene was not found in the adsorbed state
while it appeared in the desorbable gaseous products.

Analysis of the coke deposits after reaction of acetone

Similar problems to those ocurring in the analysis of coal and
other fossil fuels (refs.18-20) are encountered in the analysis
of coke deposits on catalysts. The distinction between aromatic
and olefinic hydrocarbons represents an especially difficult
problem as they exhibit NMR signals in an overlapping region at
110 - 140 ppm. In this respect, the combination of the chemical
treatment of coke deposits with 13C NMR analysis seems to be
useful (ref.21); this combination permits us to distinguish
between olefinic and aromatic bonds on the basis oftheir different
reactivities.
The spectra depicted in Figs.3 and 4 illustrate the difference
between coked HZSM-5 and HY zeolites. The broad and poorly
resolved band at 130 ppm is usually attributed either to aromatic
compounds or to polyenic chains. In addition, with both types of
zeolite signals in the range of paraffinic carbons (-CH3,-C2H5)
bonded to the aromatic rings are observed as follows from the
high-field-shifted value with a maximum at 19.8 ppm. HZSM-5
zeolite differs from HY in a clearly separated broad signal at 154
ppm, which has also been observed by other authors on coked
zeolites (refs.19-21). However, the interpretation of this signal
is not yet clear: some authors assigned it to carbocations
344

20 0 100 0 PPm

Fig.3. 13C CPMAS NMR spectra of coke deposits after acetone

reaction on Y-type zeolites at 50.32 MHz : (a) 28 w.% of
coke on H,NaY 70 zeolite, (b) 16.0 w.% of coke on HY
dealuminated zeolite, NS=8000, (c) 13.9 w.% of coke after
pyrolysis of the sample (b) at 600°C for 2h, NS=8000.
(normalized spectra as in Fig.1.)

K130*8 19,8

Fig.4. 13C CPMAS NMR spectra of coke deposits after acetone

reaction on HZSM-5 zeolite at 50.32 MHz: (a) 1.0 w.% of
coke after acetone-1,2,3-13C(lO%) reaction, NS=240,
(b)sample as ad (a) after partial oxidation at 200°C ,
( c ) sample (b) after pyrolysis at 600°C for 2h, NS=7000.
 345

(ref.l9), others to olefines (ref.20). In order to solve this

problem, we have carried out a number of experiments on the
chemical treatment of coke deposits. Partial oxidation (see
spectra in Fig.3,4) at temperatures higher than 5OO0C did not
lead to any change in the spectrum. Therefore, the creation of
carbocations does not seem probable. .
The easy addition of bromine to olefinic bonds led us to
perform bromination experiments with bromine vapours at 25 and
100°C. As the effective radius of bromine permits its adsorption
in the microporous structure and no significant effect of
bromination in the NMR spectra was observed, we concluded that the
mentioned signal cannot be associated with olefins. The
pyrolysis of the deposits in vacuum at 6OO0C yielded only evidence
that the dealkylation took place (the signal at 19.8 ppm
disappeared) but did not lead to any change inthe signalat 154
ppm. We assume (on the basis of its resistance to chemical
treatments) that this signal could be associated with carbons
belonging to an aromatic ring bonded to oxygen, as is true of
phenols, cresols or ethers (ref.l7).We suggest that phenoxy
groups are formed on the surface of HZSM-5 zeolites, analogous to
the surface methoxy groups (ref.22-26). For the wide pore Y
zeolite, the condensation of the aromatic rings is preferred, as
is indicated by the relatively strong shoulder at 140 ppm, whereas
the signal at 154 ppm is almost indistiguishable from that of
HZSM-5.

CONCLUSIONS
The 1 3 C CPMAS NMR represents a significant contribution to the
solution of problems connected with less mobile chemisorbed
species which can participate as intermediates in the
transformation of acetone. In combination with chemical treatment
of catalysts with deposits the NMR spectroscopy can help
considerably in elucidating problems in the formation and analysis
of coke residues on zeolites.

REFERENCES

1 C.D. Chang and A.J. Silvestri, J.Cata1. 47 1977) 249.

2 C.D. Chang, W.H. Lang and W.K. Bell, in: W.R. Moser (Ed.),
Catalysis in Organic Reactions, M. Dekker, New York,
1981,p.73.
3 Y. Servotte, J. Jacobs and P.A. Jacobs, in: Proc. Int. Symp.
on Zeolite Catalysis, Siofok 1985, Acta Physica et Chimica
Szegediensis, Szeged, 1985, p. 609.
346

4 J. Novakova, L. Kubelkova and Z. Dolejsek, J. Molec. Catal.,

39 (1987) 195.
5 L. Kubelkova, J. Cejka, J. Novakova, V. Bosacek, I. Jirka
and P. Jiru, in: P.A. Jacobs and R.A. van Santen (Eds.),
Zeolites, Facts, Figures, Future, Elsevier, Amsterdam, 1989,
p. 1203.
V. Bosacek and L. Kubelkova, Zeolites 10 (1990) 64.
L.M. Baigrie et al., J. Am. Chem. SOC., 107 (1985) 3640.
H. Pfeifer, W. Meiler and D. Deininger, Annual Rep. NMR
Spectroscopy, 15 (1983) 291.
G. Engelhardt and D. Michel, High Resolution Solid State NMR
of Zeolites and Related Systems, J.Wiley & Sons, 1987, Chap.7.
10 D. Freude, in: Advances in Interface Sci., Elsevier, 23 (1985)
21
11 M.W. Anderson and J. Klinowski, J. Am. Chem. SOC., 112 (1990)
10.
12 L. Kubelkova, J. Cejka and J. Novakova, Zeolites, in press.
13 T. Bernstein, D. Michel and H. Pfeifer, J. Coll. Interfaces
Sci., 84 (1981) 310.
14 G.A. Olah and A.M. White, J. Am. Chem. SOC., 90 (1968) 1884.
15 G.A. Olah and D.J. Donovan, J. Org. Chem., 43 (1978) 860.
16 Z. Dolejsek, J. Novakova, V. Bosacek and L. Kubelkova,
Zeolites, in press.
17 H.O. Kalinowski, S. Berger and S. Braun, 13C NMR
Spektroskopie, G. Thieme Verlag, 1984.
18 C.E. Snape, D.E. Axelson, R.E. Botto, J.J. Delpuech, P.
Tekely, B.G. Gerstein, M. Pruski, G.E. Maciel and M.A. Wilson,
Fuel, 68 (1989) 547.
19 J.P. Lange, A. Gutsze, J. Allgeier and H.G. Karge, Appl.
Catal., 45 (1988) 345. .
20 E.A. Lombardo, J.M. Dereppe, G. Marcelin and W.K. Hall, J.
Catal., 114 (1988) 167.
21 L. Carlton, R.G. Coppertwhite, G.J. Hutchings and F.C.
Raynhardt, J. Chem. SOC. Chem. Commun., (1986) 1008.
22 V. Bosacek and Z. Tvaruzkova, Coll. Czech. Chem. Commun., 36
(1971) 551.
23 P. Salvador and J.J. Fripiat, J. Phys. Chem., 79 (1975) 1842.
24 P. Salvador and W. Kladnig, J.C.S. Faraday Trans.1, 73 (1977)
1153.
25 G. Senkyr and H. Noller, J.C.S. Faraday Trans.I.,71 (1975)
997.
26 L. Kubelkova, J. Novakova and K. Nedomova, J. Catal., 124
(1990) 441.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 341
0 1991 Elsevier Science PublishersB.V., Amsterdam

ISOPROPYLATION OF BENZENE OVER LARGE PORE ZEOLITES

A.R. PRADHAN, B.S. RAO and V.P. SHIRALKAR

Catalysis Group, National Chemical Laboratory, Pune 411 008
(India)

ABSTRACT
Isopropylation reaction of benzene is carried out over
large pore zeolites with characteristic structural differences
(namely La-H-Y, H-mordenite and H-ZSM-12). The activity
and deactivation pattern are correlated with structural and
acidic properties. The deactivation of La-H-Y is due to
blocking of active sites while that o f H-mordenite is due
to blocking of channels. The stable activity and selective
nature o f H-ZSM-12 for cumene can be attributed to siliceous
nature, lower acidity and presence of non-interpenetrating
channels.

INTRODUCTION
Isopropylation o f benzene using solid phosphoric acid
(SPA) catalyst and Fridel-Crafts catalysts (refs. 1-3) for
the production of cumene is an industrially important reaction.
The drawbacks suffered by these processes (environmental
and corrosion) can be overcome by using solid acid catalysts
like zeolites. Major side products formed in this reaction
are isomeric diisopropylbenzenes (DIPB) and at higher temp-
eratures n-propylbenzene (nPB). Even though the medium pore
zeolite ZSM-5 is reported (ref. 4) a s a potential catalyst
for this reaction, better stability and selectivity were
observed over large pore zeolites (ref. 5).
In view of this, isopropylation of benzene was carried
out over large pore zeolites with characteristic structural
differences, like (1) La-H-Y with cubic crystal symmetry
and three directional channel system having pore opening of
7.4 k , (2) mordenite with orthorhombic structure and unidirect-
ional dual pore system with 6.7 X 7.0 (12 MR) and 2.9 X
5.7 (8 MR) connected via side pockets of 2.9 i, ( 3 ) ZSM-
12 with monoclinic symmetry and linear non-interpenetrating
channels o f 5.7 X 6.1 "A. The stability, selectivity and
deactivation pattern were correlated with structural, acidic
348

and sorption properties of these zeolites and the results

are reported in this communication.

EXPERIMENTAL
Materials
Benzene ( 99.98 X pure) and propylene (having 4 % propane)
were used for catalytic studies.

Catalysts
La-H-Y (SK-500) and H-mordenite (Zeolon 100) were procured
from M/s Union Carbide, USA and Norton, USA, respectively.
ZSM-12 was prepared in this laboratory following the procedure
reported (ref. 6 ) earlier in the literature. Co-crystallis-
ation of zeolite beta was avoided.

Characterisation
Crystalline phase purity and the state of aluminium in
the framework of these samples were characterised by the
techniques like XRD, IR and MASNMR spectroscopy. Acidity
of the samples was measured by the irreversibly adsorbed
ammonia. Adsorption studies were carried out at 25°C and
P/Po = 0.5 using a McBain balance with silica spring of
sensitivity of 4' 50.0 cm gm-'.

Catalytic reactions
The catalyst was pressed and crushed into 10-20 mesh binder
free self supported pellets. Prior to catalytic runs, the
catalyst was activated in a flow of dry air at 45OOC for 8
hrs. Catalytic runs were carried out in an integral, fixed
bed, down flow, silica reactor at atmospheric pressure.
Benzene was fed by a syringe pump (Sage Instruments, USA)
while propylene was metered through a mass-flow controller
(Matheson, USA). The products were analysed by gas-chromato-
graphy (Shimadzu, Model 15A) using Apiezone L column for
liquids and Poropak Q column for gaseous samples.

RESULTS AND DISCUSSION

The structural features, silicon to aluminium ratio, acidity
values in terms of irreversibly retained ammonia and equil-
ibrium sorption capacity for benzene are compared in Table 1.
TABLE 1
S t r u c t u r a l and physico-chemical p r o p e r t i e s of c a t a l y s t s .

Catalyst La-H-Y H-ZSM-12 H-mordenite

Channel Three directional Unidirectional Unidirectional

structure with interconnec- l i n e a r non-int- 8-membered i n t e r -
ting channels e r p en e t r at i n g connecting
P o r e opening 7.4 i 5 . 7 X 6.1 5.7 x 7,l 1
(12-membered 2 . 9 X 5.7 ‘A (8 MR)
ring)
Unit c e l l Cubic Monoclinic Orthorhombic
crystal symmetry
Si/Al 2.3 60.5 6.4
Acidity 1.338 0.067 0.535
m mole o f NH3/gm
Equil. sorption 20.3 13.2 9.8
capacity for
benzene (wt Z)

The total acidity is found to be in accordance with the

aluminium c o n t e n t o f t h e z e o l i t e , w h i l e t h e s o r p t i o n of b e n z e n e
does not follow the same trend due to the structural
differences.
The catalytic performance in alkylation of benzene with
propylene over all the three zeolites has been compared in
T a b l e 2.
A l l c a t a l y s t s showed high ( )99 X) propylene conversions.
But the impurities like aliphatics, toluene, C8 aromatics
and higher boiling fractions (H.B.F) are more in La-H-Y
and H-mordenite. Selectivity to cumene is very high i n the
case of H-ZSM-12 catalyst. A fast deactivation was noticed
i n La-H-Y and H-mordenite, w h i l e s t e a d y a c t i v i t y was o b s e r v e d
in H-ZSM-12 even after the reaction was performed for more
than 200 hrs (Fig. 1). Due to its steady activity, further
catalytic studies were performed over H-ZSM-12 catalyst.

Influence of temperature
In Table 3 the results on the influence of temperature
on the product distribution over H-ZSM-12 are p r e s e n t e d .
At temperatures below 200°C, the conversion of p r o p y l e n e i s
not completed. With t h e i n c r e a s e of temperature, a continuous
350

decrease i n the DIPB formation is noticed, while appreciable

q u a n t i t i e s o f nPB a r e o b s e r v e d a b o v e 230°C.

TABLE 2
I s o p r o p y l a t i o n o f benzene o v e r z e o l i t e c a t a l y s t s
R e a c t i o n t e m p e r a t u r e = 230OC; P r e s s u r e = Atmospheric;-TOS = 3 h r s ;
Benzene t o p r o p y l e n e molar r a t i o = 6 . 5 ; WHSV = 2 . 5 h r

Catalyst La-H-Y H-ZSM-12 H-mordenite

Product d i s t r i b u t i o n (wt % )
Aliphatics 0.74 0.06 0.30
Benzene 77.10 77.80 78.30
T o l u e n e t C8 a r o m a t i c s 0.97 0.04 0.27
Cumene 18.52 20.50 18.10
nPB 0.40 0.02 0.74
C9-C11 a r o m a t i c s 0.29 0.04 0.12
DIPB 1.75 1.55 1.78
H.B.F 0.18 0.01 0.26

C3 = c o n v e r s i o n 99.4 99.9 99.8

Cumene s e l e c t i v i t y 81.1 92.3 82.9
S e l e c t i v i t y (cumene t DIPB) 88.5 99.3 91.6

1./F
t,

w
h 19 a H.ZSM-I2
* H MORDENITE
rLa H Y

2 4 6

TIME ON STREAM (hra)

F i g . 1 . C a t a l y t i c p e r f o r m a n c e o f t h e wide p o r e z e o l i t e s i n t h e
i s o p r o p y l a t i o n of b e n z e n e w i t h t i m e o n s t r e a m (TOS).
R e a c t i o n temp. = 230OC; WHSV = 2 . 5 h r - 1 ;
Benzene t o p r o p y l e n e m o l a r r a t i o = 6 . 5 .
 351

The increase in selectivity to cumene with temperature

is a result of transalkylation of DIPB with benzene. Above
230°C, the selectivity towards cumene decreases on account
of the formation of nPB. Also unwanted products like
aliphatics, C9-C11 aromatics and higher boiling fractions
increase with the increase in temperature as a result of
cracking of higher alkylbenzenes (ref. 7).

TABLE 3
Influence of temperature on product distribution
Catalyst = H-ZSM-12; Benzene to propylene molar ratio = 6.8;
WHSV = 2.5 hr-1

Temperature ("C) 170 190 210 230 250 270

Product distribution (wt X )

Aliphatics 0.03 0.03 0.05 0.06 0.12 0.14
Benzene 84.42 82.38 80.65 80.00 79.71 78.87
Tol. t C8 arom. 0.07 0.26 0.11 0.18 0.22 0.23
Cumene 11.47 13.39 16.68 18.24 18.46 18.74
nPB - 0.01 0.03 0.11 0.31 0.63
C9-C11 arom. - 0.06 0.04 0.06 0.10 0.17
DIPB 4.01 3.86 2.41 1.35 1.05 1.03
H.B.F - 0.02 - 0.03 0.09

C3 = conversion 85.3 95.3 99.8 99.8 99.6 99.4

Select. to cumene 73.6 76.0 86.2 91.2 90.9 88.7
.
Select (cumene 99.4 97.8 97.1 98.0 96.2 93.4
+ DIPB)

Influence o f mole ratio

With increase in benzene to propylene molar ratio,
selectivity to cumene increases, even though the total
selectivity to cumene and DIPB remained almost constant during
present investigation (Fig. 2). This is due to high propylene
concentration at lower mole ratios, resulting in the successive
alkylations of cumene. Relative amounts of unwanted by-
products are less at higher mole ratios.
352

> 100-
t
>
F 95-
_-
-
0
w
d 90.
xCUMENE*UPB
CUMENE
v)

s 85-

5 10 IS 20

MOLE RATIO

Fig. 2. Influence of reactant mole ratio on the isopropylation

of benzene over H-ZSM-12 catalyst.
Reaction temp. = 2 3 0 ° C ; WHSV = 2 . 5 hr-l

Influence of weight hourly space velocity (WHSV)

Low space velocities are found to be favourable for
selective formation of cumene (Fig. 3). Total selectivity
to cumene and DIPB again remains constant over the entire
range of WHSV.

100 .
'
95
t
CUMENE *DIP6
t .
1 . CUMENE

:\
90
c
;
0

85.
fn
s 80

1 2 3 4 5 6 7
SPACE VELOCITY ( W H S V I h i l

F i g . 3. Influence o f weight hourly space velocity (WHSV) in

the isopropylation of benzene over H-ZSM-12 catalyst.
Reaction temp. = 2 3 0 ° C ; Benzene to propylene molar
ratio = 6 . 5 .
 353

Thus the
optimised condition for propylation of benzene
over H-ZSM-12 catalyst are at temperature 230°C, WHSV, 2.5
hr-l, and reactant mole ratio, 6-8.
As already mentioned, the ageing studies indicated faster
deactivation o f La-H-Y and H-mordenite catalysts. Whereas
H-ZSM-12 catalyst did not deactivate even after 200 hrs of
time on stream (TOS), therefore faster deacpivation was carried
out by accelarated ageing. All the three coked samples were
subjected to thermal and sorption studies to find out the
probable cause of deactivation. Fig. 4 presents the cumene
sorption kinetics on fresh and coked samples.

r I

CATALYST Lo H Y
o FRSH SAhlPLE
DEACTIVATED
SAMPLE 1
0
V , 6
n

I= -=+/
a

t
I
w
2
w l4
5u 10 f

2 r
5t
= I

10 20 30 ' 120

TIME ( min 1

Fig. 4 . Kinetics o f cumene sorpkion on fresh ( 0 ) and coked ( 0 )

zeolite catalysts at 25 C (P/P, = 0.5).
354

The equilibrium sorption capacity for cumene over fresh

and deactivated samples and the % coke formed for the
cummulative feed passed over each catalyst is presented in
Table 4 .

TABLE 4
Physico-chemical studies on fresh and coked catalyst samples

Catalyst La-H-Y H-mordenite H-ZSM-12

Equil. sorption of 17.6 4.5 12.55

cumene over fresh
sample (wt X)
Equil. sorption of 11.16 1.4 6.36
cumene over deact-
ivated sample (wt X)
X sorption capacity 63 31 51
retained
Amount of coke 14.78 7.48 5.80
formed (wt X)
Time required for 8 10 250
deactivation,hrs ( 10 X
of initial activity)
Amount of coke formed per 0.37 0.15 0.003
100 gm of catalyst per gm
of feed (gm)

Although the rate of sorption of cumene is same for fresh

and coked La-H-Y the equilibrium sorption capacities are
different. The deactivation of this catalyst may be attributed
to high acid site density (ref. 8) (as revealed by total
irreversibly adsorbed ammonia) in the three dimentional
structure wherein the reactants (especially propylene) and
product molecules are strongly adherent to the active sites.
Also due to dehydrocyclisation reaction,bulkier coke precursors
are readily formed in the large intra-zeolite cavities
(ref. 9). This results in higher amount of coke formation
(14.78 % calculated b y thermogravimetric methods) in the
case of La-H-Y catalyst. In spite o f this, the coked sample
shows more than half the void volume still available ( 6 3 % o f
 355

initial sorption capacity) for sorption of reactant molecules

without any further activity. Thus the deactivation is due
to blocking of the active sites.
The phenomenon of deactivation in H-mordenite is relatively
slower on account of lower acid site density compared to
La-H-Y (ref. 10) (Si/A1 = 6 . 4 and 0.535 m moles of irreversibly
adsorbed ammonia per gm of catalyst). However, the deact-
ivation in the unidirectional pore system of mordenite leads
to a drastic decrease in sorption capacity in the coked sample.
In fact, the sorption kinetics and equilibrium sorption
capacity in the coked mordenite (retained sorption capacity
30 X) suggest only surface adsorption indicating blocking
of the channels.
The least coking tendency is observed in the H-ZSM-12
sample (0.003 gm of coke formed per 100 gm of catalyst per
gm of feed passed) again on account of lowest acid site
density (Si/A1 = 60.5 and 0.067 m moles of irreversibly
adsorbed ammonia per gm o f catalyst). In addition, the linear
non-interpenetrating unidirectional channel system with virtual
absence of larger intra-zeolitic cages (like those in zeolite
Y) and highly siliceous nature do not favour the formation
of bulkier coke precursors. The sorption capacities exhibited
by ZSM-12 zeolite support these findings. Thus the stable
activity for prolonged period of time (more than 200 hrs)
can be explained for H-ZSM-12.

CONCLUSIONS
H-ZSM-12 is a superior and selective catalyst in the
alkylation of benzene with propylene.
The catalytic activity and stability are dependent on the
acidic and structural properties.
Coking of La-H-Y is due to acid site blocking, in
H-mordenite, it is due to channel blocking while deactivation
of H-ZSM-12 required accelarated ageing.

ACKNOWLEDGEMENT
We sincerely thank Dr. P. Ratnasamy, for his constant
encouragement throughout this investigation. We also thank
Dr. V.G. Gunjikar and Mr. S . P . Mirajkar, for helping in
356

the thermal and s o r p t i o n s t u d i e s . T h e w o r k was p a r t l y f u n d e d

by t h e UNDP.

REFERENCES
Y.C. Y e n , S t a n f o r d Res. I n s t . E c o n . R e p . , 22 A ( 1 9 7 2 )
and 22 B (1973).
2 I b i d , 49 (1969)
3 E.S. M o r t i k o v , S.R. Mirzabekova, A.G. Pogorelov, N.F.
Konov, R . F . M e r h a n o v a , A.Z. D o r o g o c h i n s k i i a n d Kh. M .
M i n a c h e v , N a f t e k h i m i y a , 16 ( 1 9 8 8 ) 7 0 1 .
4 W . W . K e a d i n g a n d R.F. H o l l a n d , J . C a t a l . , 109 ( 1 9 8 8 ) 212.
5 B.S. Rao, I. B a l a k r i s h n a n , V.R. Chumbhale, A . R . Pradhan
and P. Ratnasamy, P a p e r p r e s e n t e d a t F r i s t Tokyo C o n f e r e n c e
o n A d v a n c e d C a t a l y t i c S c i e n c e a n d T e c h n o l o g y (TOCAT l ) ,
J u l y 1-5, 1990.
6 E . J . R o s i n s k i a n d M . K . R u b i n , U.S. P a t e n t 3 , 8 3 2 , 4 4 9 ( 1 9 7 4 ) .
7 D . A . B e s t a n d B.W. W o j c i c h o w s k i , J . C a t a l . , 4 7 ( 1 9 7 7 ) 11.
8 H.G. Karge and E.P. Boldingh, Catalysis Today, 3
( 1 9 8 8 ) 53.
9 P.B. V e n u t o a n d P . S . L a n d i s , Adv. C a t a l . , 18 ( 1 9 6 8 ) 2 5 9 .
10 P.E. E b e r l y J r . a n d C.N. K i m b e r l i n J r . , I n d . Eng. Chem.
P r o d . Res. D e v . , 9 ( 1 9 7 0 ) 335.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 357
0 1991 Elsevier Science PublishersB.V., Amsterdam

EXAFS STUDY OF LOCAL STRUCTURE OF Pt-Cr CLUSTERS IN PENTASILS IN RELATION WITH

THEIR REACTIVITY IN LOWER ALKANES AROMATIZATION

R.W.
E.S. S H P I R O ~ , ~ 2 G . J . T U L ~ O V A ' . A.V. PFEOBR~IENSKY'.
JOYNER~,
O.P. TKACHENKO , T.V. VASINA , O.V. BRAGIN and Kh.M. MINACHEV
'N.D.Zelinsky Institute of Organic Chemistry, USSR Academy of Sciences, Moscow,
YSSR
The Leverhulme Centre for Innovative Catalysis, The University of Liverpool,
Liverpool, England

SUMMARY
Pt-Cr/H-ZSM-S samples were characterized by EXAFS and XPS and their catalytic
activity in ethane and methane aromatization was examined. EXAFS shows clear
evidence of Pt-Cr alloy particles formation in samples reduced at 823 K. Most of
these particles is located within zeolite structure and coordinated to zeolitic
oxygen. The changes of catalytic activity in C1-C3 alkane aromatization and
hydrogenolysis caused by chromium are related to alloying effect.

INTRODUCTION
It is well known that VIII Group metal additives play an important role in
catalysis of lower alkanes aromatization which proceeds on modified high-silica
zeolites (refs. 1-4). Among other metals platinum behavior is established rather
in details and such characteristics as dispersion and electronic state was shown
to be key factors for high catalytic performance in ethane and propane aromati-
zation (refs. 4-6). Recent EXAFS studies (ref. 7 ) proved earlier suggestion that
platinum clusters are located within zeolite structure in the proximate vicinity
t o Bronsted acidic centers and they are most probable candidates for active si-
tes in alkane dehydrogenation step (refs. 5-71. Platinum might play even greater
role in methane aromatization. This reaction was discovered (ref. 8 ) to proceed
over modified pentasils at 1023 K to yield up to 4-14% of aromatics.
In connection with aromatization reactions two features of platinum loaded H-
pentasils became important: (a) stabilization of very dispersed Pt particles at
temperatures as high as 823-1023 K; (b) reducing Pt hydrogenolysis activity and
as consequence coke formation and catalyst deactivation. To maintain these cha-
racteristics of platinum in reforming catalysis promotion by second metal (Re,
Sn, In, Ga, Cr) is widely used, chromium is definitely suppressed platinum acti-
vity in hydrogenolysis (refs. 9,101. Our previous studies (ref. 6 ) also sugges-
ted the strong influence of chromium on platinum behavior in ethane hydrogenoly-
358

sis but mechanism of this effect remained unclear.

This paper presents a study of the influence of chromium on Pt-HZSM-5 cata-
lyst where we have able to establish a detailed connection between structure and
catalytic function via EXAFS and XPS characterization of Pt-Cr/H-ZSM-5 and their
reactivity in aromatization of lower alkanes inclusive methane. To elucidate
possible alloying effects the activity of Pt-Cr/H-ZSM-5 and Pt/H-ZSM-5 in ethane
and propane hydrogenolysis was also compared.

EXPERIMENTAL
Catalyst containing 0.5 wt % Pt and different contents of chromium (0.13,
0.75 and 1.25 wt % I were prepared by simultaneous impregnation of H-ZSM-5 (Si/A1
= 16.5) with a mixture of H PtC16 and (CrO 1 solutions, 0.5% Cr/H-ZSM-5 was ob-
2 3 x
tained by impregnation with (CrO 1 and 0.75% Pt/H-ZSM-5 was prepared by ionic
3 x
exchange of [Pt(NH3l41Cl2 with NH -EM-5 (ref. 4). Samples were calcined in an
4
air at 623 K for 2 h and subsequently at 790 K for 3 h.
EXAFS measurements were performed at the Daresbury synchrotron radiation SQU-
rce and reduction of the catalyst specimen was carried out in-situ at 1 bar in
flowing hydrogen at 623 and 823 K. Data were collected for the Pt L I11 edge and
analyzed by standard methods (ref. 11). XPS analysis of the Pt-Cr/H-ZSM-5 has
been performed after in-situ reduction in 1 bar of flowing hydrogen at 823-873 K
in a specially developed cell attached directly to Kratos XSAM 800 spectrometer
and using Mg K radiation. The analysis of Pt-Cr/H-ZSM-5 samples after methane
a
aromatization reaction was performed with Kratos ES 200B spectrometer according
procedure described in (refs. 4 , 6 ) . Pt 4f + A 1 2p and Cr 2p peaks were analyzed
by using peak synthesis programme with PDP 11/03L computer. The details of peak
synthesis treatment for these particular spectra are described in (ref. 12).
Ethane and methane aromatization were tested in microcatalytic pulse reactor
in He flow at 823 K and 1023 K respectively. Propane and ethane hydrogenolysis
were performed in flow reactor at hydrocarbon/H2 ratio equal to 1/10 in diffe-
rential mode (hydrocarbon conversion does not exceed 5-7%).

RESULTS AND DISCUSSION

Characterization of the reduced catalysts
Studies of Pt/H-ZSM-5 catalysts by XPS, EXAFS and electron microscopy reveal-
ed that most of platinum in pre-calcined samples can be stabilized as very dis-
persed particles within zeolite structure (refs. 4,6,7). The lower limit of ave-
0
rage particle size, 7-8 A is close to the channel size EXAFS indicating formati-
on of one Pt-Pt shell clusters consisted of 13 5 atoms (ref. 7). Upon increase
of calcination temperature from 723 K to 793 K average particle size increased
0 + 75
up to 13 A and number of atoms in cluster up to 120 - 40. Nevertheless these
 359

particles remain to be located inside zeolite matrix (ref. 7). The particular
0
features of 7-13 A particles are 1-4% contraction of nearest Pt-Pt distance with
respect to the bulk and bonding between metal and oxygen of zeolitic framework.
XPS positive shifts of Pt 4f level observed for such particles have been inter-
preted in terms of charge transfer from metal to zeolite (refs. 4-6).
Fig.1 and Table 1 shown that main structure characteristics of Pt particles
remained eventually the same after promotion of 0.5% Pt/H-ZSM-5 with chromium

0.03 1
kX(k)/k b I
0.08 Fig. 1. Pt L I 1 1 EXAFS
for the Pt-Cr/H-
0.04 ZSM-5 catalyst
reduced at 623 K
(a) and 823 K
0.00 (b), solid line -
experiment;
0.04 dashed line -
calculated using
the parameters
0.08 given in Table 1.

0.12
360

(0.75%) and reduction at 623 K. The average coordination number for the first
0
Pt-Pt shell is equal to 5 and Pt-Pt distance is of 0.08 A shorter than for Pt-
foil. Pt-0 distance with C.N. 1.4 is also contributed to EXAFS spectrum. The
comparison of these data with those obtained for 0.5% Pt/H-ZSM-5 calcined at the
same temperature (793 K) (refs. 6,7)indicated some stabilization effect caused
by chromium.

TABLE 1
Best fit Pt L I 1 1 edge EXAFS data for 0.5% Pt-0.75% Cr/H-ZSM-5
~~

Tred,K Neighbor Interatomic Coordination Debye-Waller

0
distance, A number factor, X2

623 platinum 2.70:O. 01 5.0;1.0 0.012:O. 003

oxygen 1.94-0.03 1.4-0.5 0.017-0.005

823 platinum 2.7110.01 4.511.0 0.015:0.003

oxygen 1.97~0.03 1.8~0.5 0.016;O. 005
chromium 2.65-0.02 1.7-0.5 0.015-0.003

The increase of reduction temperature up to 823 K did not result in noticeab-

le sintering Pt particles but clear evidence of Pt-Cr distance was found from
analysis of EXAFS spectra (Fig. lb). Including a Pt-Cr interatomic distance into
the analysis decreased the fitting index by 51% and this is significant at the
excellent statistical level of < 0.5%. As was shown in (ref. 13) a significant
level of 5% is considered sufficient if a new shell of neighbors is to be accep-
ted. Preliminary analysis of EXAFS data for second series of Pt-Cr/H-ZSM-5 samp-
les (0.5%Pt-0.75% Cr and 0.5% Pt-1.25% Cr) which differs from above sample only
by Si/A1 ratio demonstrate again Pt-Cr coordination (ref. 1 4 ) . The existence of
platinum-chromium bond in the catalysts is thus well established and the observ-
0
ed distance is in the range expected for metallic bonding (2.65-2.70
A ) . It was
demonstrated that alloying of chromium with platinum decreases the lattice para-
meter, the intermetallic of Pt3Cr being often observed (ref. 10). The coordina-
tion numbers for 0.5% Pt-0.75% Cr/H-ZSM-5 suggests a Pt/Cr ratio of 3/1 for the
first series of samples and up to 1011 for second series (ref. 14). This implies
Pt3Cr and more diluted in Cr alloys are formed even in catalysts contained an
excess of chromium.
The additional information on chemical state of chromium and its distribution
over zeolite was deduced from XPS data (Table 2). In fresh sample chromium
exists as a mixture of Cr(VII and Cr(II1). the rather strong enrichment of ex-
ternal surface with Cr was observed. Both calcination and reduction lead to de-
 361

TABLE 2
XPS analysis of 0.5% Pt-0.75% Cr/H-ZSM-5

Treatment Pt ( 0 ) Pt(I1) Cr(0) Cr(II1) Cr(V1) Cr/Si

fresh 0.44a)
B.E..eV 74.0 - 577.5 579.5
% 100 74.8 25.2
air,793 K 0.033
B.E. ,eV 72.3 73.9 - 577.0 580.8
x 44.3 55.7 78.8 21.2
H2,823 K 0.032
B.E. ,eV 72.3 - 573.4 577.2 -
% 100 12.3 87.7
02,298K 0.037
B.E.,eV 72.8 577.2
x 100 100
H2,873 K 0.029
B.E. ,eV 72.2 - 573.0 577.4
% 100 16.2 83.8

a) Cr/Sibulk = 0.009

crease of Cr/Si ratio which can reflect migration of part of Cr ions into the
channels. At 623 K in hydrogen only Cr(II1) was found but increase of reduction
temperature up to 823 K gives rise new doublet in Cr 2p envelope which is
characteristic of Cr(0) (refs. 6.12). The degree of Cr(0) reduction reached to
10-15% at 823-873 K.

Catalytic activity of Pt-Cr/H-ZSM-5

(1) Hydrogenolysis reactions. Adding 0.75% Cr to Pt/H-ZSM-5 suppressed its
activity in both ethane and propane hydrogenolysis (Table 3). The difference be-
tween two hydrocarbons is that an decrease of reaction rate with C2 was observed
only at relatively low temperatures (623-648K), the activity also strongly de-
pends on chromium content. As temperature increased up to 673 K the difference
in activity of Pt- and Pt-Cr-samples becomes negligible and at higher temperatu-
res the activity of bimetallic sample even exceeds the activity of purePt/H-ZSM-
5. This is formally explained by higher activation energy observed for Pt-Cr-
samples. In contrast, with C3 the drop of reaction rate by an order of magnitude
was observed on whole temperature range (573-648K) with Pt-Cr sample and the
difference of activation energies for Pt-, and Pt-Cr-samples is smaller than
with ethane. On other hand, the main decrease of reaction rate was found for
0.5% Pt-0.75% Cr and further increase of Cr content to 1.25% only slightly
effects C hydrogenolysis.
3
362

One of the explanation of the observed difference is that zeolite could cont-
ribute to hydrogenolysis (dehydrogenation) or cracking of alkanes at higher tem-
peratures. This explanation is rather speculative because nor H-ZSM-5 neither
0.75% Cr/H-ZSM-5 shown no noticeable activity in C2H6 or C3H8 hydrogenolysis in
the temperature range studied. But we could not ruled out possible dual-
functional behavior of Pt-Cr/H-ZSM-S. Despite of complications connected with
possible zeolite-catalyzed reactions it is obvious that chromium suppressed in-
trinstic hydrogenolysis activity of platinum. This is particularly confirmed by
the fact that 0.5% Pt-0.75% Cr/H-ZSM-5 reduced at 623 K, when no metallic Cr is
formed, has the same activity as Pt/H-ZSM-5.

TABLE 3
Hydrogenolysis activities of Pt- and Pr-Cr/H-ZSM-S

Sample Ethane (Tred = 823 K)

Ea'
623K 648K 673K 698K 723K 748K kJ/mole

Reaction rate, U x 103, pmole/g s

0.SLPt 1.2 3.0 7.2 20 39 280 134

O.YLPt-0.7SLCr 0.36 1.8 9.8 40 - - 232
0.5%Pt-1.25%Cr 0.056 0.45 7.3 36 120 2100 260

Propane (Tred = 823 K)

573K 598K 623K 698K

Reaction rate, W x 104, pmole/g s

0.5%Pt 4.6 8.6 29 - 76

0.5%Pt-0.75%Cr 0.35 0.69 2.9 1.2 119
0.5%Pt-1.25%Cr 0.22 0.82 2.5 2.0 143

( i i ) Ethane and methane aromatization. The 0.5% Pt-0.75% Cr/H-ZSM-5 exhibit

higher aromatization activity with C H than pure Pt/H-ZSM-5. About 25% or BTX
26
was found on former catalyst at 823 K while 0.5% Pt/H-ZSM-5 gives only 15% of
aromatics at equal conditions. XPS studies of Pt state after different number of
C H pulses shown some increase of B.E. Pt 4f7/2 similar to observed earlier
26
with Pt/H-ZSM-5 (refs. 4.5). This means that platinum in small Pt-Cr particles
also possessed electron deficiency which is favorable for aromatization reac-
tions (refs. 4-6). In addition the increase of aromatics yield can be related to
Pt-Cr interaction in alloy particles which can modify Pt electronic state.
Fig.2 shows the dependence of yield of aromatics produced from methane at
 363

1023 K over different compositions of Pt-, Cr-, and Pt-Cr/H-pentasils. H-

pentasil is inactive but Cr, Ga, Zn/H-ZSM-5 give a few percent of aromatics. In-
cluding platinum substantially increased aromatics yield from 4 to 9%. But most
dramatic increase of aromatization activity was found when Cr was added t o 0 . 5 %
Pt/H-ZSM-5. Starting from 0.13% Cr aromatization activity jumped up to 14%. The
other important function of chromium is prolongation of catalyst life. While
Pt/H-ZSM-5 activity sharply and irreversibly declined after 10-15 pulses of me-
thane (ref. 8 ) (not shown on the figure) activity of Pt-Cr samples retained on
the maximum level especially for samples with higher Cr content (1.25% Cr). So,
chromium improved the resistance of the catalyst to deactivation.

1 2

T = 1023 K
g = 500 mg cat.

a VHe = 1.2 1 h-'

rl
6

2 0 0 ,
5 10 15 Number of cH4 pulees
Fig.2. The dependence of aromatics (B+T) yield on CH4 pulse number: 1 - 0.5%
Pt-0.75% Cr; 2 - 0.5% Pt-0.75% Cr (was studied by P S I ; 3 - 0 . 5 %
Pt-1.3% Cr; 4 - 0 . 5 % Pt-0.13%Cr; 5 - 0.5% Pt; 6 - 0.75% Cr.

Post-reaction studies
The enhancement of methane aromatization activity with Pt-Cr sample seems to
be indicative of platinum-chromium interaction rather than simple additive
effect. This interaction may appear in the course of the reaction which proceeds
at high temperature and i n purely reducing atmosphere. To verify this assumption
XPS spectra were monitored after treatment of 0 . 5 % Pt-0.75% Cr/H-ZSM-5 with He
and with 1, 3, 10 and 17 pulses of methane at 1023 K (Table 4). As was expected
(refs. 4-7) platinum was part,?lly reduced even during air calcination and its
reduction was progressing in He at 1023 K. After interaction with methane extent
of Pt reduction increased but about 1 5 2 0 % of Pt gives spectrum with higher B.E.
than for pure metal. By analogy with Pt/H-ZSM-5 treated with hydrogen or ethane
this spectrum can be assign to Pt" clusters. The lack of significant change of
364

Pt/Si ratio during reaction could suggest no severe sintering of metallic

particles. Although most of chromium is present as Cr203 the formation of a few
percent of metallic chromium and its alloying with platinum might be possible.
These results imply that structure of Pt-Cr catalysts after methane reaction
resembles the structure of reduced catalyst or sample exposed to ethane at
823 K. In latter case EXAFS suggest the formation of diluted Cr-Pt alloy
particles (ref. 14).

TABLE 4
XPS analysis of 0 . 5 % Pt-0.75% Cr/H-ZSM-5 after methane aromatization

Treatment Pt(I1) Pt(0) Cr (YI Cr(II1) Pt/Cr

air, 793 K 0.12

B.E. .eV 73.9 72.3 579.6 577.4
% 56 44 21 79

He, 1023 K 0.23

B.E. ,eV 73.8 71.9 - 576.9
% 18 82 100
CH4,1023 K,lth pulse 0.23
B.E. ,eV 72. 71.5 - 577* 5
% 14 86 100
CH4,1023 K, 3 pulses 0.56
B.E.,eV 73.44 71.4 577.0
% 23 77 100
CH4,1023 K, 10 pulses 0.27
B.E. ,eV 73.3a) 71.5 576.Sb)
% 26 74 100
CH4,1023 K, 17 pulses 0.33
B.E.,eV 73.3a) 71.6 - 577.5
% 22 78 100

a) P
t
'
+ ; b) a few Cr(Ol was found from peak synthesis

CONCLUSION
Let us discuss in conclusion some points concerning local structure of Pt-Cr
zeolites and its possible effect on catalysis. Both EXAFS and XPS data clearly
demonstrated that Cr(0) is formed during H2 treatment at 823-873 K part of which
is alloyed with platinum. Other properties of Pt particles such as dispersion,
location, crystallographic structure are rather similar to those in Pt/H-ZSM-5
(ref. 7). Thus we can neglect size effect and discuss the data in terms of Cr
promotion or poisoning. Chromium in H-ZSM-5 is present in several forms : (a)
 365

Pt-Cr alloy; (b) separate Cr(0); (c) Cr(II1) ions in channels; (d) chromia on
external surface. Higher XPS Cr(O)/Pt(O) ratios with respect to found from EXAFS
suggest that a part of chromium exist in separate phase, although there is no
indications from TEM o r XANES that big Cr(0) particles are formed. In addition
about 90% of total chromium content is not reduced and it can be located or in
the channels either on external surface. The latter is more probable when we
take into account higher Cr/Si ratios on the surface.
Size and composition of the alloy particles may be deduced from EXAFS
results. The sum of Pt-Pt and Pt-Cr nearest neighbor coordination number is 6.2,
very close to that found in 13-atom clusters which is 6 . 5 . For other samples
even less chromium is included into Pt-Cr particles (ref. 14) although chromium
content in bulk alloys can reach to 71% (ref. 15). We can therefore assume that
in diluted alloys chromium is homogeneously distributed over the particle. The
limit of chromium concentration in alloy can be explained by the fact that only
a part of chromium i s within zeolite structure. Also, Pt particles which size is
limited by channel cross-section can dissolve only a limited number of chromium
atoms. Besides, the surface of platinum particles can be decorated by chromia.
Thus, the difference in catalytic behavior of Pt/H-ZSM-5 and Pt-Cr/H-ZSM-5 is
likely to be due to platinum-chromium interaction in small platinum-chromium
particles and not so well-defined interaction between Pt particles and Cr20g. In
agreement with data (ref. 10) we ascribe the suppression of hydrogenolysis acti-
vity to alloying of Pt-Cr. The ensemble model can be proposed as simplest one to
explain, for instance, stronger poisoning of propane hydrogenolysis than ethane
one for sample 0.5% Pt-0.75% Cr/H-ZSM-5. But stronger drop of ethane hydrogeno-
lysis activity on 0.5-1.25% Cr requires more complex model. It should taken into
account platinum-chromium electronic interaction, strong hydrocarbon adsorption
on Cr sites and so on. Pt and Cr lie on opposite sides of their respective vol-
cano curves for alkane hydrogenolysis (ref. 16). Hydrocarbons are insufficiently
strongly adsorbed on Pt while adsorption is too strong on chromium for optimal
activity. This can inhibit hydrogenolysis which proceeds at relatively low tem-
peratures and on pure metallic surface (low conversions) but at the aromatiza-
tion conditions (high temperatures, coking) the situation may change in such way
that stronger hydrocarbon adsorption on Pt-Cr would play a positive role. This
is especially important for methane which activated very hardly. Taken into
account mechanism of methane oxidative coupling and thermodynamic hindrances of
direct methane aromatization (refs. 8,171 one can expect that first stage of me-
thane activation must be oxidative one and zeolite or oxide oxygen can partici-
pate in initializing reaction. But even in pulse mode the methane aromatization
does not look as simple stoichiometric reaction and it definitely involves cata-
lytic steps. For this particular system the presence of Cr203as source of mobi-
366

le oxygen is not enough to provide high activity. In contrast, the system Pt-
Cr/Cr 0 /H-ZSM-5 gives rise to maximum effect. The Cr reduction by reaction mlx-
23
ture was recently found for 0.5% Pt-1.25% Cr/H-ZSM-5. Similar activity of three
Pt-Cr samples in methane aromatlzation 1s in accordance with EXAFS data lndlca-
tlng formation Pt-Cr alloys of close composition in samples with very different
total Cr/Pt ratios (ref. 14).

REFERENCES
O.V. Bragln, T.V. Vasina, Ya.1. Isakov, N.V. Pallshklna, A.V.Preobrazhensky,
B.K. Nefedov and Kh.M. Mlnachev, Stud. Surf. Scl. Catal., 18 (1984) 31-36.
C.W.R. Engelen, J.P. Wolthulzen, J.H.C. van Hoof, H.W. Zundbergen. Proc. 7th
Int. Zeolite Conf., 1986, pp.709-716.
T. Inul, J.Maklno, F. Maganos, A. Mlymoto. Ind. Eng. Chem. Res. and
Develop., 26 (1987)647-652.
O.V. Bragln, E.S. Shplro. A.V. Preobrazhensky. S.A. Isaev. T.V. Vasina,
B.B. Dysenbina, G.V. Antoshin and Kh.M. Mlnachev, Appl.Catal., 27 (1986)
219- 231.
Kh.M. Mlnachev and E.S. Shpiro, React. Klnet. Catal. Lett., 35 (1987) 195-
206.
E.S. Shplro, G.J. Tuleuova, V.A. Zalkovskii, O.P. Tkachenko. T.V. Vasina,O.V.
Bragin and Kh.M. Minachev, in H.G. Karge and J. Weitkamp (Eds.), Zeolites as
Catalysts, Sorbents and Detergent Builders, Elsevier, Amsterdam, 1989, pp.
143-152.
E.S. Shplro, R.W. Joyner, Kh.M. Minachev and P.D.A. Pudney, J. Catal., to be
published
O.V. Bragin, T.V. Vaslna, A.V. Preobrazhensky and Kh.M. Minachev, Izv. AN
SSSR, Ser. Khlm., 1989, pp. 750-751.
K. Anders, R . Feldhaus, H.-G. Vieweg, S. Engels, H. Lausch et al., Chem.
Tech.(Lelpzlg) 37 (1985) 65.
10 S . Engels, H. Lausch, B. Peplinski, M. Wilde, W. Morke, P. Kraak, Appl.
Catal., 55 (1989)93-107.
11 S.J. Gurman, N. Blnstead, I . Ross, J. Phys. C (Solid State Phys.), 17 (1984)
143.
12 W. Grunert, E.S. Shpiro, R Feldhaus, K. Anders, G.V. Antoshln and Kh.M.
Minachev, J. Catal.,100 (1986) 138-148.
13 R.W. Joyner, K.J. Martln and P. Meehan, J. Phys. C (Solid State Phys.), 20
(1987)4005.
14 E.S. Shpiro, R.U. Joyner , unpublished results
15 M. Hansen, Constitution of Binary Alloys, 2nd edn. (Mc Graw-Hl11, New
York,1958).
16 J.H. Sinfelt, Catal. Revs. Scl. Eng., 3 (1970) 175-205.
17 Kh.M. Mlnachev, N.Ya. Usachev, V.N. Udut and Yu.S. Khodakov, Russian Chemical
Reviews, 57 (1988)385-404.
G . Ohlmann eta!. (Editors), Catalysis and Adsorption by Zeolites 367
0 1991 Elsevier Science Publishers B.V., Amsterdam

SPLITTING OF METHANE INTO THE ELEMENTS OVER NICKEL CONTAINING

ZSM-5 CATALYSTS

J. HOFFMANN. R. BAUERMEISTER. 8. HUNGER, K. HANTEL, G. ULLMANN.

K.-H. STEINBERG and H. SIEGEL'
Department of Chemistry, Karl Marx University, Leipzig. DDR-7010 (GDR)
'Chemieanlagenbau Grimma, Grimma, DDR-7240(GDR)

SUMMARY
Methane splitting was studied over nickel containing Na-ZSM-5 catalysts and at a Ni/AI,O,
catalyst for comparison The reaction took place between 673 and 1073 K The highest activity
was found between 923 and 1023 K The ZSM-5 catalyst showed the best long time behaviour
Good working conditions were only obtained in fluid bed realized by a vibration reactor. In
the temperature region between 673 and 973 K a rate equation containing a first order term
with respect to methane and a reversible second order one concerrung hydrogen best fulfilled
the experimental results

INTRODUCTION
The formation of carbon filaments (or whiskers) as a result of the decomposition of hy-
drocarbons on metal surfaces or, respectively. catalysts containing Fe. Ni or Co particles has
been known for a long time 11-31, Since this time the practical interest has been mainly di-
rected on the question how to avoid the whisker growth because it is an important reason
for the formation of carbon deposits on reactor walls and for mechanical break-down of ca-
talyst particles.
A good review about the production of filamentous carbon is given by BAKER [ 4 :I who
emphasizes that the scientific interest should be drrected not only on the prevention of car-
bon-filament formation but also on the possibilities to produce such materials for useful aims,
thus for electrodes with high surface area and electrical conductivity, for new generations of
3-D composites 141,for carbon fibres [ 5 ] and possibly as materials for adsorption processes.
As could be shown by electron microscopy the whisker consists of a tubular filament
with a co-axial channel [ 6 ] and a metal particle at the growing end of the filament. The
whisker structure is graphitic [7,81 with the basal planes parallel to the whisker axis. The
core of the whisker may be void or filled with carbon material of lower density.
It could be shown that after an induction period which is necessary for saturation of the
nickel particle with carbon the single whisker grows after a rate equation of zero order 191.
Moreover the rate of growth depends on the reciprocal root of the dlameter of the particle.
The growth can be inhibited when the leadmg face is encapsulated b y a layer of amorphous
carbon.
Whereas the whisker growth is obviously determined by the diffusion of carbon through the
metal particle leading to a concentration gradient in the metal there are different interpreta-
368

tions about the driving force of the carbon segregation.

In the case of the decomposition of alkenes and alkines it is assumed that the end of the
particle connected with the whisker is cooler than the leading face because of the exother-
mic splitting of the unsaturated hydrocarbons and therefore the solubility of carbon in the
metal is lower. But this explanation cannot be valid in case of the splitting of methane or
other alkanes because of their endothermicity.
Therefore in recent work other explanations are favourized. KOCK et al. [ 10 1 suggest
that an instable bulk carbide is formed as the intermediate phase whereas ALSTRUP [ 1 1 1
assumes the formation of a surface carbide and the splitting of methane only on (100) and
(110) nickel facets and segregation on ( 1 I 1) facets.
Whereas in literature extensive studies are published about whisker formation on metal
surfaces and on supported metal catalysts almost no results can be found regarding pssibili-
ties to lead the process of alkane splitting continuously and to use it for the production of
larger amounts of whisker carbon. With respect to this the observation made in this work
that the process can be effectively brought about for a period of some hours using a fluid-
bed reactor is of significance.

EXPERIMENTAL
Preparation of catalysts
Pellets of catalyst material consisting of 70 mass per cent of Na-ZSM-5 zeolite and of 30
mass per cent of y-A1203 were impregnated with such amounts of solutions of nickel nitrate
that the nickel content of the dry material was 20, 10 and, respectively, 5 mass per cent.
After heating in dry air for about 3 hours at 773 K the pellets were broken up and classified
to a fraction of 0.2 _..0.4 mm.
Catalvtic measureme&
For catalytic measurements a vibration reactor was used. It consists of a quartz tube
with an inner diameter of 1 cm which is elastically suspended from springs. By means of a
magnetic oscillation apparatus the reactor can vibrate with an amplitude of about 0.5 cm
and a frequency between I and 50 Hz. usually at I5 Hz.
The flow rate is controlled by a Brooks flow controller and measured at the reactor out-
let. The gaseous reaction products are analyzed by GC using a 2 m PORAPAK T column.
Catalytic experiments were carried out using 0.1 ... I g of catalyst. The catalyst was he-
ated in a stream of dry He up to 773 K and kept at this temperature for 3 hours. then cooled
down to 473 K, newly heated in a stream of hydrogen up to 673 K and reduced at this tem-
perature for 3 ... 4 hours. After having switched the gas stream to pure methane the vibrati-
on of the reactor was started and the sample was heated with a rate of 10 K per min up to
the reaction temperature.
 369

Tpr emeriments
In order to find out the optimum reduction conditions samples of the catalysts were re-
duced in a tpr apparatus consisting of a quartz reactor, a furnace controlled electronically
and a heat conductivity cell. The reducing gas mixture was argon containing 5 per cent of
hydrogen. The heating rate could be chosen between I and 20 K p e r min and was usually
10 K per min.
Evaluation of the experiments
It was assumed that because of the mechanical vibration of the reactor and of a relati-
vely high flow rate a fluid bed reactor was approached which can be kinetically described
by the model of a perfectly mixed reactor. For kinetic evaluation it must be considered that
the

-
CH, C 2 H, +

reaction is connected with a change of the mole number. In order to count the degree of
conversion X first of all the molar fractions xcH4and xH2were determined by GC.
Then the conversion degree could be expressed as

From this the momentary consumption of methane was calculated after

"CH4 = VCH4 '

(2)

(vCH; inlet flow rate of methane).

The whole amount of carbon formed until the reaction had been stopped could be cal-
culated by numerical integration:

a SVCHddt (3)

For the kinetics of methane splitting a rate equation of the following form was assumed:
370

In case of the perfectly mixed flow reactor the rate I results from

ngH4= molar flow at the reactor inlet

nCH4=molar flow at the reactor outlet
V = volume of the reactor

The partial pressures of methane and hydrogen can be written in the following manner con-
sidering the change of the mole number during reaction ( p - total pressure):

When substituting k, by k , / K it results from equation ( 4 ) :

P

ngn4(X3 + 2X2 + XI = klpV - klpV(l + 4p/Kp).X2 (7)

From equ (7) k , and Kp can easily be calculated by regression and from the rate and
equilibrium constants the activation energy EA1 and the heat of reaction ARH can be deter-
mined using the equations of Arrhenius and van t Hoff

RESULTS AND DISCUSSIGN

Studies of the methane splitting reaction were made mainly over Na-ZSM-5 zeolites con-
taining 20 mass p e r cent of nickel (0.2 NiNa-ZSM-5) because these catalysts provide the best
results with respect to activity and resistance against deactivation. For comparison same ex-
periments with NiNaX. NiNaY. Ni/A1,0, and NiNa-ZSM-5 catalysts of lower nickel content
were carried out.
As could be observed in all cases carbon formed by decomposition of methane under
fluid-bed conditions balls together to almost spherical aggregates above the catalyst bed but
still containing microscopic particles of the catalyst.
In order to study the conditions of reduction of the Ni" containing catalyst precursors
more in detail tpr experiments were carried out.
Fig. I shows a typical reductogramme of a ZSM-5 catalyst containing 20 per cent of
nickel. The heating rate was 10 K per min. The reduction seems to occur as a relatively
 371

uniform process as can be seen from the only less structured peak'with the maximum at about
690 K. Taking into account that the peak-maximum temperature decreases when the heating
rate is diminished it can be concluded that a reduction temperature of about '100 K should be

Fig. 1. Tpr spectrum of a 0.2 NiNa-ZSM-5 zeolite (heating rate 10 K per min)

H tim on stream [min]

heating period

Fig. 2. Catalytic activity in dependence on time of a 0.2 NiNa- ZSM-5 zeolite

372

sufficient. Indeed, a reduction degree of about 80 per cent could be calculated from the peak
area related to the whole amount of nickel. The measured peak-maximum temperature is in
good agreement with results of other authors who studied the reduction of NiO species [ 121.
Considering the activity of the various catalysts it can be stated that over nickel fauja-
sites only a very low amount of carbon was formed until the reaction broke down by rapid
deactivation (at 1 g of 0.45 NiNaX only 0.13 g of carbon were formed. the same amount of
0.5 NiNaY led to 0.2 g of carbon).
Na-ZSM-5 catalysts containing 5 or. respectively. 10 mass per cent of nickel showed lo-
wer activity and more rapid deactivation compared to catalysts with 2 0 per cent of nickel.
Comparison of the activity and long-time behaviour of convenient Ni/AI2O3 hydroge-
nation catalysts containing about 50 per cent of nickel with that of 0.2 NiNa-ZSM-5 catalysts
was of special interest: Whereas the catalytic activity of the N i l A1,0, catalyst is comparable
to that of the 0.2 NiNa-ZSM-5 its long-time behaviour is much worse.
Thus in an experiment with 0.2 NiNa-ZSM-5 after 7 hours of time on stream the fourfold
amount by weight of carbon related to the weight of catalyst was formed but the degree of
conversion diminished only from 0.6 to 0.4 whereas the Ni/AI,O, catalyst produced only
twice of its own weight until it deactivated dramatically.
In fig. 3 the momentary methane consumption at constant inlet flow rate of methane is
shown in dependence on temperature for the 0.2 NiNa-ZSM-5 catalyst. Catalytic activity can be
observed between 673 and 1073 K with a maximum in the 1000 . . . 1030 K region.

Fig. 3. Catalytic activity of a 0.2 NiNa-ZSM-5 catalyst depending on temperature

 373

Similar behaviour was found by other workers [6 1 which used Ni / MgU catalysts. The loss
of activity at temperatures higher than loo0 K should not be due to deactivation by carbon
deposition but by adsorption effects in a rate determining surface reaction [ 13 1. The results
obtained in this work for the Ni-ZSM-5 and Nil A1,0, catalysts are contrary to this explanation
because almost no catalytic activity was observed at temperatures beolw 1000 K when the
catalyst had worked before at temperatures over 1100 K (in the temperature region where the
reaction rate is decreasing) indicating a poisoning of the active nickel centres by deposition
of amorphous carbon. In fig. 2 the conversion is shown in dependence on time on stream. As
can be seen the conversion degree decreases in the course of 7 hours only from 0.6 to 0.4.
When carrying out the same experiment without vibration of the reactor the activity dramati-
cally decreases after short reaction times because of sticking together of the catalyst pellets.
Kinetic studies were carried out in a temperature region between 673 and 923 K. In contrast
to other authors 1141 an inhibition by hydrogen was not observed, thus a rate equation ex-
pressing the conditions for the equilibrium reaction CH, - C + 2H2 could be used (equ. (4)).
In case of the 0.2 NiNa-ZSM-5 catalyst the activation energy of the splitting was (1 13 2.2) kJ
per mole, the reaction heat ( 1 24 : I . 2 ) kJ per mole. For the Ni/A1203 catalyst a n activation
energy of ( 1 10 : 1.4) k] per mole and a heat of reaction of ( I 25.4 1.2) kJ per mole could
be calculated. These values are in good agreement with results of other authors r 151.
In figs. 4 and 5 Arrhenius and van? Hoff plots are shown for the 0.2 NiNa-ZSM-5 catalyst.
In Tab. 1 the equilibrium constants calculated from the experiments or, respectively. from
thermodynamic data are listed together with the respective equilibrium degrees of conversion.

TABLE I
Equilibrium constants and equilibrium degrees of conversion in dependence on temperature

T[Kl Kplbarl x-
theor. 0.2 NiNa-ZSM-5 Ni/AI,O, theor. 0.2 NiNa-ZSM-5
~
Ni/A1203
873 2.1 I .34 0.921 0.59 0.50 0.4 3
923 3.92 3.44 2.35 0.70 0.6 8 0.6 1
973 7.32 7.89 5.43 0.8 I 0.8 2 0.76
1023 12.35 16.70 11.6 0.8 7 0.90 0.86
1073 20.7 33.0 2 3.0 0.9 2 0.94 0.9 2

The results show that the equilibrium conversion can be higher than the value calculated
from the theoretical thermodynamic data, especially in the upper temperature region. This
can be explained by the fact that the gas phase does not contact with the pure graphitic
carbon surface but with a carbidic one at the exposed surface of the nickel partic!e (e.g.
Ni3C ).
374

Fig. 4. Arrhenius plot for a 0.2 NiNa-ZSM-5 catalyst

. _..._ _
1 ..... . . -..
'\
... . _..-.

C
b? -1
+
r;
-2 '4,
\
'

\.
-3 ,Q\,\

-4 '\

1
1.6
 375

CONCLUSIONS
The splitting of methane can be well realized on nickel containing Na-ZSM-5 zeolites.
When using a vibration reactor which allows fluid bed condtions a quick deactivation of the
system by sticking together of the catalyst pellets can be avoided.
The good activity and long-time behaviour of the NiNa-ZSM-5 catalysts could be ex-
plained:
by their high thermal stability
by their properties with respect to fluidized-bed conditions (e. g. low density)
by a favourable distribution of the nickel-particle size with respect to whisker formation (in
our case between 5 and 30 nm as could be proved by electron microscopy)
and possibly by the avoidance of formation of carbon forms other than whisker-like
Kinetics of the reaction follows a rate equation which contains the methane concentration
in a first order term and the hydrogen concentration in a second order one expressing the
reversible step. The activity of carbon does not appear in the rate equation and no inhibition
by hydrogen was observed. At the temperature which represents the region of highest activity
(about 1023 K ) a degree of conversion of nearly 0.9 can be realized (higher than the equili-
brium degree calculated from thermodynamic data).

REFERENCES

I P. A. Tesner and I.S. Rafalkes. Dokl. Akad. Nauk SSSR, 87(1952)821

2 R.T.K. Baker and P.S. Harris. J. Phys. E., 5(1970)793
3 J.R. Rostrup-Nielsen. J. Catal.. 2 7 ( 19 7 2 134 3
4 R.T.K. Baker. Carbon. 27(1989)315
5 G.G. Tibbetts. Appl. Phys. Lett.. 42(1983)666
6 J.R. Rostrup-Nielsen, Catalytic Steam Reforming, in: J.R. Anderson and M. Boudart (Ed.).
Catalysis - Science and Technology. Vol. 5, Springer Berlin, Heidelberg. New York. Tokyo,
1984. pp. 7 4 - 7 5
7 T. Baird. J.R. Fryer and 8. Grant, Carbon, I2(1974)591
8 S.D. Robertson, Carbon, 8(1970)365
9 R.T.K. Baker, P.S. Harris, R.B. Thomas and R.J. Waite. 1. Catal., 96(1985)468
10 A.J.H.M. Kock. P.K. de Bokx. E. Boellaard. W. Klop and J.W. Geus, J. Catal.. 96(1985)468
I 1 I. Alstrup. J. Catal.. 109(1988)241
I 2 N.W. Hurst. S.J. Gentry, A. Jones and B.D. McNicol. Catal. Rev. - Sci. Eng. 24(1982)2 3 3
I 3 J.R. Rostrup-Nielsen and D.L. Trimm. J. Catal.. 48 (1 977) 155
1 4 C.A. Bernardo. I. Alstrup and J.R. Rostrup-Nielsen. J. Catal.. 96 (1 9 8 5) 5 1 7
15 B.K. de Bokx. A.J.H.M. Bock, E. Boellaard. W. Klop and J.W. Geus. I. Catal.. 96(1985)454
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 377
0 1991 Elsevier Science Publishers B.V., Amsterdam

SULFUR TOLERANT Ni-Mo-Y-ZEOLITE CATALYSTS FOR WATER-GAS

SHIFT REACTION

M-LANIECKI and W.ZMIERCZAK

Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6,
60-780 Poznan (Poland)

SUMMARY
Molybdenum sulfide and nickel-molybdenum sulfide catalysts
were prepared from Mo(CO), encaged in Y and stabilized HY zeolites.
These catalysts were characterized by XRD, IR, ESR spectroscopy and
NO sorption capacity. Mo(CO& based catalysts are highly reactive
in water-gas shift reaction and this is related to the high
dispersion of molybdenum sulfide. Ni and Mo containing zeolites
indicate the existence of synergetic effect. The synergy is
confirmed by the presence of a band at 2082 cm during adsorption
of CO. Catalysts prepared from dealuminated supports show low
activity, mainly due to the limited access of molybdenum carbonyl
into the zeolite cavities. ESR spectroscopy indicates the formation
of sulfur chain biradicals after interaction of HIS with
molybdenum containing supports.

INTRODUCTION
It is known that both high-temperature and low-temperature
water-gas shift catalysts, based on iron oxides and copper-zinc
oxides respectively, are highly sensitive towards sulfur
contamination of the feed. In order to overcome this problem a new
class of catalysts, similar to the hydrodesulfurization catalysts,
based on alumina-supported Co-Mo sulfides has been prepared and
recently introduced into the market.
Literature concerning the application of zeolites either as
catalysts or as the supports in water-gas shift (WGS) reaction is
scarce (ref.1-4). The Ru-X (ref.1) and Ru-Y (ref.2) zeolites have
been reported to be active in WGS reaction, but their activity and
especially stability were relatively low. Iwamoto et al. (ref.3)
studying transition metal ion-exchanged X and Y zeolites
established that only C U * ~and Ni” containing zeolites showed good
performance in WGS and this was related to the low electro-
negativity of the exchanged transition metal. Lee and co-workers
(ref.4) studying the kinetics of WGS reaction over Ni-Mo-Y-zeolite
catalysts in the sulfided state established high reactivity in this
reaction and excellent resistance against H,S and NH,.
378

Studies performed in the previous years by different groups

(ref.5-7) and concerning molybdenum loaded zeolites indicate that
saturation with molybdenum hexacarbonyl leads towards the formation
of highly and homogenously dispersed molybdenum. This can be
subsequently transformed into highly dispersed supported molybdenum
sulfide species (ref.8,9). In contrast, molybdenum containing
zeolites prepared from ammonium heptamolybdate (AHM) form bulky,
weakly dispersed Mo sulfides.
Our recent studies (ref.9) showed that Mo(CO), loaded
Y-zeolites in the sulfided state indicate high activity in WGS
reaction. In the present study the catalytic activity in WGS
reaction over sulfided Ni-Mo-Y and Ni-Mo-USY zeolites was measured
and the characterization of these catalysts has been given.

EXPERIMENTAL
Mat er i a1s
NaY from KATALISTIKS (Si/A1=2.56) was applied as a starting
material for preparation of nickel and amonium exchanged zeolites.
The ammonium containing samples were obtained by a single or
multiple exchange with 0.25M aqueous solution of NH,C1 at 345 K.
Three series of stabilized Y-zeolites, denoted hereafter as USY-1,
USY-2 and USY-3, were prepared from NH4NaY forms, differing in the
degree of exchange, by hydrothermal treatment at 875 K for 4.5
hours under 100% steam. Nickel was introduced into the zeolites
before molybdenum by ion-exchange applying nickel nitrate solution,
both for NaY and USY series.
Molybdenum was loaded into the zeolites by saturation with
molybdenum hexacarbonyl vapours. Zeolitic supports after activation
at elevated temperatures in hydrogen were exposed to the Mo(CO),
vapours passing the support in a hydrogen stream for 10-15 hours at
room temperature. Samples completely saturated with Mo(CO), were
subsequently partially decarbonylated at 425 K for one hour in a
stream of hydrogen and next slowly exposed to the air at room
temperature with the use of leaking valve.
Each sample, before any experiment, was presulfided for two
hours at 675 K with a 10 vol.& mixture of hydrogen sulfide in
hydrogen, flowing with the rate of 2 dm3 h-'.
Chemicals a_nd Gases
Doubly sublimed Mo(CO), from Aldrich was used for saturations.
Hydrogen and helium were freed from impurities by passing through
 379

the MnO/SiO, oxygen-water scavenger (ref.10). CO and NO were from

Fluka and H,S from Intermar (The Netherlands) and were used without
further purification.
Characteri zatLog
Zeolitic supports as well as Ni and Mo containing samples were
characterized by XRD, NO sorption capacity. FTIR, ESR and MAS NMR
spectroscopy. The experimental details concerning NO adsorption and
ESR measurements are given elsewhere (ref.9).
For infrared measurements self-supporting wafers with the
-1
"thickness" of 3-5 mg cm were mounted in the infrared cell
operating under dynamic conditions. Samples after activation were
exposed for 30 minutes to the Mo(CO), vapours according to the
procedure already described in the previous section (Materials). IR
spectra were recorded applying FTIR Bruker IFS 113v spectrometer.
29 27
Si and A1 MAS NMR measurements of USY and Ni-USY were performed
for non-sulfided samples applying Bruker MSL-300 spectrometer.
Catalytic Activity Measurements
Grained samples (0.5-lmm) of zeolites weighing 0.25 or 0.59
were pleaced in a continous-flow reactor operating at atmospheric
pressure. Samples after presulfidation were purged 30 minutes with
He at 6 7 5 K and next the temperature was lowered to 6 2 5 K and the
WGS reaction started. Gas mixture introduced into the saturator was
composed from equimolar amounts of CO and H, and 2 vol.% of H,S.
Reaction was usually performed for 20 hours and the hydrogen
sulfide concentration was mantained constant during the reaction
time. H20 : CO ratio was changed in different experiments and
varied between 0 . 7 to 3.

RESULTS AND DISCUSSION

It was found previously (ref.9) that molybdenum sulfide supported
on sodium or hydrogen form of Y-zeolite indicate relatively high
activity in WGS reaction but with the tendency to the slow deacti-
vation. It was expected that certain loss of the zeolite
crystallinity can be responsible for the decrease in activity. The
XRD measurements indicated, however, negligible changes in the sup-
port crystallinity during or after the reaction.In the present stu-
dy three series of stabilized Y-zeolites have been apllied as the
supports in order to minimalize the changes in the catalysts crys-
tallinity during the reaction time as well as to study the influen-
ce of the support dealumination on the behaviour in WGS reaction.
380

TABLE 1
Characterization of Ni-, Mo- and Ni-Mo-Y zeolite catalysts

Cata 1yst Si/A1 Composition Surface NO adsorption

29 * **
AAS Si NMR (wt.%) area capacity
2 - 1
Ni Mo [m 9 I [mmol g- ‘ 1
NaY 2.56 0 10.3 900 0.184
NaN i Y 2.63 2.8 10.0 830 0.134
HNaY 2.60 0 10.3 930 0.166
HNaN i Y 2.78 1.1 8.0 840 0.121
USY-1 2.62 3.28 0 5.5 860 0.053
USY-I-Ni 2.48 3.78 1.2 5.0 - 0.136
USY-2 2.76 4.19 0 4.8 830 0.056
USY-2-Ni 2.48 4.47 1.0 4.6 - 0.145
USY-3 2.56 5.02 0 4.5 800 0.097
USY-3-Ni 2.55 5.30 0.8 4.0 780 0.154
* “BET analogous surface area” of the support activated at 675 K
* * after activation at 675 K , MO(CO)~ deposition, decarbonylation
at 425 K and sulfidation at 675 K
Table 1 shows certain properties of the catalysts prepared by
standart procedure described in the previous section. A l l supports
were activated 2 hours at 675 K before Mo(CO), admission. “BET
analogous surface area” was practically the same for sulfided or
non-sulfided molybdenum-free supports. After deposition of
tiiolybdcnum onto non-stabilized supports, followed by sulfidation,
t h e surface area was usually reduced by about 30-40%. This is
indicative of the location of molybdenum sulfide-like species
inside the zeolite porous system (ref.9). In contrast to the
non-stabilized zeolites, steam calcined samples indicate a lower
surface area, due to the dealumination process. After deposition of
molybdenum and subsequent sulfidation, ultrastable samples
indicated only minimal decrease of surface area.
High concentration of the non-framework aluminum atoms at
the zeolite surface (ref.ll), or the formation of boehmite-like
structures inside the supercages (ref.12) can cause a partial
blockage of the zeolite porous system towards nitrogen molecules
and can protect Mo(CO), molecules from entering zeolite porous
system. The lowered ability to adsorb Mo(CO), at the inital
stage of preparation for USY based catalysts seems to confirm
this suggestion. However, dealumination via steam calcination
causes changes in the acidity of the support and these changes
also influence the ability to adsorb Mo(CO), during catalyst
 381

s-' ,
30Q 34
WAVENUMBER CM-1

Fig.l.Infrared spectra of USY Fig.2.Infrared spectra of nickel

supports activated at 675 K.
HY-obtained from NH,,Y (78%
exchanged) calcined 2 hours
at 675 K.
exchanged NaY zeolites (NaNiY)
a)after activation at 675 K
b)after activation at 475 K
c)after activation at 475 K , sa-
turation with M O ( C O ) ~ ,and
decarbonylation at 425 K.

preparation (ref.7). It is known that basically one aluminum atom

in the zeolite framework of HY zeolite can give rise to one acid
group. Hence, a decrease in the intensities of OH stretching bands
at 3550 and 3650 cm-l with progresive dealumination was expected.
Fig.1. shows OH bands for the series of dealuminated Y-zeolites.
In our case, ultrastabilization practically eliminated OH groups
from the small cages (absence of the band at 3550cm-') and reduced
significantly the amount of acidic OH groups in supercages
(3650cm-I). The appearance of the OH stretching bands at 3690 and
3610 cm-', non reactive towards NH, and pyridine (ref.l3), as well
as silanol groups (at 3745 cm-') is indicative of strong
29
dealumination (compare also SiNMR results). The shoulder bands at
382

Fig.3. Infrared spectra of moly-

bdenum loaded NaNiY zeolite
a)after activation at 675 K
b)after activation at 675 K, satu-
ration with M~(CO)~.followed
by decarbonylation at 425 K
c)as b) with subsequent interac-
tion with HZS at room tempera-
ture.

A
b 1
3675 and 3590 cm-' appearing for
USY-3 can be attributed to the
hydroxyls connected with extra-
framework aluminum species (ref.
a 14). Nickel-containing ultrastabi-
BOO 170 lized samples showed additional
WAVENUMBER CM-' decrease of OH bands intensity,
similarily to the findings
presented in ref.14.
The characteristic OH bands formed upon nickel exchange with NaY
are shown in Fig.2. Here, after activation at 675 K the typical
acidic OH groups (3645 and 3554 cm-') are present. Activation at
475 K leads towards the appearance of new weak band at 3610cm-'.
This is usually ascribed to the characteristic dissociation of
water molecules over the zeolites containing divalent cations
(ref.13) with simultaneous formation of Me+(OH) species. Adsorption
of Mo(CO), at room temperature followed by thermal decomposition at
425 K yielded the subcarbonyl species with general formula cd
Mo(CO), (ref.8,15). Irrespective of the support used, after partial
decarbonylation, more or less complex infrared spectra in the
region of carbonyl groups vibrations were observed (example
presented in Fig.3.). Usually USY and HY supports give rise to the
more complex infrared spectra in the reg on of carbonyl vibrations
than for NaY or NaNiY samples. The decr ase in intensity of OH
bands for USY and NaNiY after partial decarbonylation at 425 K is
indicative of the oxidation of molybdenum by zeolite protons
(ref.5). Partially decarbonylated samples after intereaction with
H,S at room temperature show a significant reduction in the
 383

carbonyl bands quantity (2031 sh, 1984, 1946 sh, 1845 cm-') and
absorbance value (see Fig.3.). Exposition of partially
decarbonylated samples towards H,S at 425 K resulted in a complete
disappearance of carbonyl groups and further decrease in the OH
bands intensity, suggesting the formation of sulfided molybdenum
species. Interaction with H,S at 675 K additionally lowered the
intensity of OH groups vibrations.
These observations show that after decarbonylation, interaction
with H,S at room temperature leads towards Mo(CO),-SH like species
(ref.8), whereas at higher temperatures,MoSx structures are formed
(1< x <2) (ref.16). Bands at 2530 and 2570 cm-' observed earlier in
similar systems for NaY support (ref.8) in our case were always
absent. Y-zeolites with Si/A1 ratio higher than 2.5 do not adsorb
H2S dissociatively (ref.17) and the absence of the band assigned to
H2S physisorption (2570 cm-') indicates a lack of this type of
interaction.
TABLE 2
Catalytic activity of the studied samples after 2 hours in WGSR
~ ~

Support pretreatment temperature [K]

475 675 825
Cata1yY t Rate constant k [cm3 g-' min-'I
H20/C0 k H20/C0 k H20/C0 k

NaY 1 28 1 32
2 16
3 21
NaN i Y 1 355 1 245 1 105
2 204 2 203
3 213 3 240
HNaY 1 74
HNaN i Y 1 83
USY-1 1 10 0.7 29 1 8
1 14
2 9
USY-2 0.7 28 0.7 34
USY-3 0.7 52 1 6
USY-1 -Ni 0.1 80 1 27
2 29
USY-2-N i 0.7 53
USY-3-N i 0.7 44 0.7 48 1 12
-- - ~ - -
384

The calculated pseudo-first order reaction rate constants for the

WGS reaction and the series of Mo(CO), based catalysts are
presented in Table 2. The highest activity was observed for NaNiY
support, whereas an order of magnitude lower activity was found for
the series of USY supports. Depending on the degree of
dehydroxylation, the highest activity was found for the nickel
containing supports activated at 475 K. The increase of support
pretreatment temperature above 675 K always reduced catalytic
activity. It is known that mainly basic sites are responsible for
the adsorption and decomposition of Mo(CO), (ref.7.8). The decarbo-
nylation performed in the absence (Nay) or in the presence of very
much limited amount of OH groups (high temperature activation of HY
or USY) usually leads towards the formation of molybdenum species
with a low oxidation number. The subsequent interaction with H,S
produces sulfur deficient (ref.16) molybdenum species with a
relatively high dispersion but low catalytic activity.
TPDE profiles presented by Okamoto et al. (ref.15) show that
formation of subcarbonyl species of Mo(CO),ads.-type occurs at
temperatures lower than 425 K. It was found that below this
temperature of decarbonylation, subsequent sulfidation produces a
highly dispersed molybdenum sulfide-like species. The increase of
decarbonylation temperature above this level resulted in a
significant decrease of molybdenum sulfide dispersion and con-
sequently, in low catalytic activity. Our previous studies showed
that NO sorption capacity (represented here as the dispersion) is
an important factor influencing catalytic activity (ref.9).
A high activity of non-stabilized, nickel containing zeolites
is related to a high dispersion of molybdenum sulfide as well as to
the existence of synenergetic effect between Ni and Mo sulfided
species. The synergy between Ni and Mo is confirmed through IB
studies by the appearance of a band at 2082 cm-' after interaction
of Ni-Mo species with CO at room temperature. USY supports
activated at 675 K after deposition of Mo(CO), indicate an
increasing activity with the degree of dealurnination, while the
molybdenum content decreases. A comparison between the results of
activity and NO sorption capacity suggests that also in the case of
USY supports dispersion of the molybdenum sulfide plays a very
important role in catalytic activity. These results suggest also
that extra-lattice aluminum favours better dispersion of molybdenum
sulfide. On the other hand, nickel containing USY-zeolites,
 385

decreases catalytic activity with increasing amount of

extra-lattice aluminum and NO sorption capacity. The blank
experiments with molybdenum-free USY and USY-Ni supports explained
this discrepancy, indicating that significant amounts (about 50%)
of NO are irreversibly adsorbed at room temperature over sulfided
nickel species. Moreover, the presence of extra-lattice aluminum in
Ni-USY zeolites favours the NO adsorption.
It was already mentioned that all catalysts indicated slow but
constant deactivation in time. The formation of carbonaceous depo-
sits can cause the activity decay. It was assumed that application
of high steam concentration will suppress carbon deposition. For
these reasons different H,O to CO ratios were applied to study this
phenomenon. The deactivation in time was always observed apart from
steam concentration in the feed . The increase of H,O to CO ratio
always reduced catalytic activity, which suggests that adsorption
of CO (associative or dissociative), rather than adsorption of H,O,
is the rate-limiting step.

Fig.4.ESR spectra of molybdenum

loaded USY-2 zeolite after sul-
fidation at 675 K
a)USY-molybdenum free
b)USY + Mo(C0)6decomposed
at 425 K
c)Ni-exchange USY f Mo(COIg
decomposed at 425 K
d)Ni-exchanged USY - molybdenum
free .

The mechanism of WGS reaction proposed by Hou et al. (ref.18) for

sulfided Mo on alumina, in the case of zeolitic supports should be
ruled out because of the absence of Mo'~ species detectable v i a ESR
spectroscopy. Fig.4 shows only the typical ESR spectra obtained
after sulfidation of USY-2 based samples but similar results were
obtained for other studied samples.The shape of resonance lines and
g-values are characteristic of sulfur chain biradicals (see litera-
ture in ref.9). In Ni and Ni-Mo containing supports a presence of
wide resonance line with g=2.285 was additionally observed.
386

The results presented in th s paper indicate that high activity of

Ni-Mo sulfides supported on Y-zeolite certainly is related to the
high dispersion of these su fides and synenergetic effect between
Ni and Mo species. However, futher studies are required in order to
clarify the influence of support acidity, presence of sulfur chain
biradicals and other factors on catalytic behaviour.

CONCLUSIONS
(i) Mo- and Ni-Mo loaded Y-zeolites idicate high activity in
water-gas shift reaction in the presence of H,S.
( 1 1 ) Synergetic effect between Ni and Mo sulfided species for
water-gas shift reaction has been found.
( i i i ) Acidic OH groups of the support enhance catalytic activity in
water-gas shift reaction.
(iv) ESR measurements excluded the importance of M o ’ ~ ions in the
mechanism of WGS reaction over zeolitic sulfided catalysts.
REFERENCES
1 J.J. Verdonck, P.A. Jacobs and J.B. Uytterhoeven, J.Chem.Soc.
Chem.Comm., (1979) 181-182.
2 B.L. Gustafson and J.H. Lunsford, J.Catal., 74 (1982) 393-404.
3 M. Iwamoto, T. Hasuwa, H. Furukawa and S. Kaqawa, J.Cata1.
79 (1983) 291-297.
4 A.L. Lee, K.C. Wei, T.Y. Lee and J. Lee, in B.Imelik et al.
‘Eds.), Studies in Surface Science and Catalysis, -101.5,
Catalysis by Zeolites, Elsevier, Amsterdam 1980, pp.327-333.
5 S . Abdo and R.F. Howe, J.Phys.Chem., 87 (1983) 1713-1722.
6 T. Komatsu and T. Yashima, J.Mol.Catal., 40 (1987) 83-92.
7 M. Laniecki, in H.G. Karge and J. Weitkamp (Eds.), Studies in
Surface Science and Catalysis, vo1.46, Zeolites as Catalysts,
Sorbeiits and Detergent Builders, Elsevier, Amsterdam, 1989,
259-269.
8 Y. Okamoto, A. Maezawa, H. Kane and T, Imanaka, J.Mol.Cata1..
52 (1989) 337-348.
9 M. Laniecki and W. Zmierczak, Zeolites, in press.
10 R. Moseler, B. Horvath, D. Lindenau, E.G. Horvath and H.L.
Krauss, Naturforsh., Anorq.Chem.,Org.Chem. 31B (1976) 892-898.
11 J. Arribas, A. Corma, V. Fornes and F. Melo, J.Catal., 108
(1387) 135-142.
12 R.D. Shannon, K.H. Gardner, R.H. Staley, G.Berqeret. P.
Gallezot and A . Auroux, J.Phys.Chem., 89 (1985) 4778-4781.
13 P. Jacobs and J.B. Uytterhoeven, J.Catal., 22 (1971) 193-203.
14 A . Ezzamarty, E. Catherine, D. Cornet, J.F. Hemidy, A . Janin,
J.C. Lavalley, J. Leglise and P. Meriaudeau, in P.A.Jacobs
and R.A.van Santen ( E d s . ) Studies in Surface Scie ce and
Catalysis, vo1.49B, Elsevier, Amsterdam 1989, pp. 025-1034.
15 Y. Okamoto, A. Maezawa, H. Kane and T. Imanaka Proc. 9th
International Congress on Catalysis, Calgary 1988,
V O l . 1 , pp.11-18.
16 M. Laniecki and W. Zmierczak, unpublished results
17 H.G. Karqe and J. Raskd, J.Coll.Interface Sc ., 64 (1978
522-532.
18 P. Hou, D. Mekker and H. Wise, J.Catal., 80 (1983 280-285.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 381
0 1991 Elsevier Science Publishers B.V., Amsterdam

THE INFLUENCE OF CATIONS ON THE ALKYLATION OF TOLUENE WITH

ETHYLENE OVER MODIFIED ZSM-5 ZEOLITES

1
Ji!?:EEJKA, Blanka WICHTERLOVd and Gloria LLabre RAURELL
The J. Heyrovsky Institute of Physical Chemistry and Electrochem-
istry, Czechoslovak Academy of Sciences, 182 23 Prague 8 ,
(Czechoslovakia)
'Chemical Research Center Cerro, La Habana (Cuba)

ABSTRACT
It has been found that H-forms of ZSM-5 zeolites differing in
the Si/A1 ratio exhibit straightforward relationship of activity
vs. para-selectivity in toluene alkylation to para-ethyltoluene.
Addition of Na, K and A1 cations or A1 oxidic species into the
zeolite cationic sites suppresses the zeolite void volume. This
results in an increase of para-ethyltoluene selectivity in the
initial alkylation step occurring in the channel intersections
and/or in a preferential transport of para-ethyltoluene from the
zeolite channels. Zeolite deactivation by coke is supported by the
presence of cations in the zeolite due to narrowing of the
channels or eventually due to their function as strong electron
acceptor sites. The coke formed in the zeolite does not enhance
the zeolite p<ira-selectivity and, moreover, for highly coked
zeolites a considerably lower para-selectivity is observed.

INTRODUCTION
Medium pore zeolites with pentasil type structures, such as
ZSM-5, -22, -23 and - 4 0 , are intensively studied as catalysts for
the alkylation, disproportionation and isomerization reactions of
alkylated aromatic hydrocarbons [refs.1-71. They exhibit high
selectivity for the formation of para-isomers that is often much
higher than that corresponding to thermodynamic equilibrium.
Toluene (T) alkylation with ethylene to para-ethyltoluene (p-ET)
seems to be a reaction of great industrial interest, because of
expected demand for para-methylstyrene [ref. 3 1 .
It has been observed that high selectivity for p-ET (far
exceeding the thermodynamic equilibrium value) can be attained at
low conversion level without any H-ZSM-5 zeolite modification
using the appropriate reaction conditions in contrast to H-Y
zeolites providing preferentially the ortho-isomer. This indicates
that the initial alkylation step into the para-position of toluene
for H-ZSM-5 zeolites is caused by steric hindrances already in the
zeolite channel intersections [ref. 4 1 . The further mechanism
388

includes isomerization and transalkylation reactions, different

transport rates of individual isomers to the outer surface and
possibly also surface isomerization reactions [refs. 6-91.
This paper demonstrates the influence of the presence of
alkali-metal cations and extralattice aluminium species
(incorporated into the zeolite during zeolite synthesis and as
post-synthesis modifications) on the zeolite activity, selectivity
and deactivation followed during reaction time-on-stream
experiments.

EXPERIMENTAL
The parent ZSM-5 zeolites with Si/Al ratios ranging from 13.6
to 600 and oi: crystal size about 1 p m were supplied by the
Research Institute €or Oil and Hydrocarbon Gases, Czechoslovakia.
Acid forms of ZSM-5 zeolites were prepared by the ion exchange of
their N a forms with 0.5 M HN03 at ambient temperature. NaH-ZSM-5
and KH-2SI.I-5 'rlcrc prepared by ion exchange of H-ZSM-5 with 0 . 0 5 M
NaCl and 0.05 1.1 ICCl, respectively, at 350 K for 3 hours. Aluminium
was introduced into the H-ZSM-5 zeolites by ion exchange with 0.5M
Al(N03)3 (Alll-ZSM-5) or by impregnation with 1 M A1(N03)J
followed by calcination at 770 K in oxygen to provide
A1203H-ZSN-5.
The Si/Al ratio of the H-ZSM-5 zeolites used, the number of
strong acid bridqing hydroxyls and the sorption capacity for argon
f o r the 11- and modified ZSM-5 zeolites are given in the Table.
Fig. 1 depict.s the infrared (IR) spectra of the hydroxyl band
region for tt.e parent and modified zeolites. The IR spectra were
recorded on a FT-IR Nicolet MX-1E spectrometer. The zeolite void
volume was est-imated from the sorption capacity for argon measured
in a static apparatus at 13.33 kPa of argon at a temperature of 8 0
K on samples pretreated at 7 2 0 K in a vacuum of 10y4 kPa for 16
hours.
The alkylation of toluene with ethylene was carried out in a
vapour phase continuous down-flow microreactor at atmospheric
pressure and 623 K. Nitrogen as a carrier gas was saturated with
toluene at 3 3 3 K to 18.5 vol. %. The toluene to ethylene molar
ratio was 3.8. The reaction products were analyzed in on-line
arrangement by a Hewlett-Packard gas chromatograph with MS and FI
detectors using a supelcowax 10 capillary column. The toluene
conversion was normalized to 100 % of the theoretical conversion
corresponding t o a toluene to ethylene ratio 3.8. The details of
the catalytic measurements can be found in ref. 4 .
TABLE 1 Characteristics o f t h e z e o l i t e s used and t h e i r a c t i v i t i e s , p-ET s e l e c t i v i t i e s i n the
t o l u e n e a l k y l a t i o n w i t h e t h y l e n e a f t e r 15 m i n . of time-on-stream.

Zeolite Si/Al OH g r o u p s S o r p t i o n Capa- WHSV Ccriversion Selectivity

( n'mo l/g 1 c i t y (mmol Ar/) (h-l) ( %I (wt. %)

H-ZSM-5( 1 ) 22.5 0.72 4.87 20 79.8 31.3

NaH-ZSM-5( 1 ) 22.5 0.65 4.77 20 75.7 49.3

KH-ZSM-5( 1) 22.5 0.44 4.65 20 59.5 59.8

AlH-ZSM-5( 1) 22.5 0.67 4.76 20 78.6 56.6

H-ZSM-5( 2 ) 45 0.30 5.80 20 40.8 62.8

H-ZSM-5(3) 600 0 . 02a 5.92 20 13.7 88.9

H-ZSM-5( 4 ) 13.6 1.00 5.31 60 97.9 34.3

NaH-ZSM-5( 4 ) 13.6 0.62 5.12 20 79.8 36.6

H-ZSM-5( 5 ) 22.5 0.76 5.15 20 93.9 33.1

AlH-ZSM-5( 5 ) 22.5 0.73 5.11 20 92.1 34.6

A1203 H- ZSM-5 ( 5 ) 22.5 0.68 4.92 20 85 .O 54.4

a
calculated value
390

RESULTS AND DISCUSSION

The Table and Figure 2 present the dependence of the toluene
conversion and the selectivity to p-ET on the number of strong
acid bridging OH groups and the relationship of the activity vs.
para-selectivity for H-ZSM-5 zeolites differing in the Si/Al ratio
(not containinrj a significant amount of extralattice aluminium and
the content of Nn cations was lower than 0.05 wt. % ) . It follows
that the toluene conversion is proportional and the p-ET
selectivity inversely proportional to the number of bridging OH
groups.
The activity and p-ET selectivity of the H-ZSM-5(1)-(4) were
very stable in time-on-stream (T-0-S) (for H-ZSM-5 (1) see Fig.
3 ) . Only a slight decrease in toluene conversion and, on the other
hand, a slight increase in the para-selectivity were observed
(Fig. 3 ) . The modification of H-ZSM-5(1) with Na and K cations

Fig. 1 Infrared spectra of OH groups of H-ZSM-5(5) - a,

H-ZSM-5(1) - b, AlH-ZSM-5(1) - c, NaH-ZSM-5(1) - d and
KH-ZSM-5(1) -
e l zeolites.
caused a decrease in the zeolite void volume, in the number of
strong acid sites and a corresponding decrease in the toluene
conversion. The para-selectivity was slightly higher for
NaH-ZSM-5 (1) and for KH-ZSM-5 (1) than expected from the activity
vs. selectivity relationship (cf. Fig. 2). Simultaneously, zeolite
deactivation for Nall- and KH-ZSM-5(1) was a little increased
compared with the parent zeolite. The toluene conversion decrease
in T-0-S was accompanied by the p-ET selectivity increase which
followed the activity vs. para-selectivity relationship.
When Na cations were exchanged into H-ZSM-5 ( 4 ) (containing
 391

0 0.25 0.5 0.75 25 50 75 100

OH groups (mmoI/g) Conversion (70)

Fig. 2 A -Dependence of the toluene conversion ( 0 ) and the

p-ET selectivity ( 0 ) of H-ZSM-5 zeolites on the number
of 011 qroups compared with modified zeolites:
A - IfaH-ZSM-5(1), 0 -
KH-ZSM-5(1), 0 AlH-ZSM-5(1), -
o,e- AIII-ZSM-5 ( 5 ) and el@-
A1203H-ZSM-5( 5 ) .
B- Dependence of the toluene conversion vs. the p-ET
selectivity for H- and modified ZSM-5 zeolites.

100 I I 100

I AIB

15 55 95 135 175 15 55 95 135 175

T - 0 - S (min)

Fig. 3 Dependence of the toluene conversion

selectivity on T-0-S
N a l l - Z S M - 5 ( 1) ( ,A )
for: A - H-ZSM-5(1)
and
and the p-ET
(0
KH-ZSM-5 (1)( 0 ,a) B
A l H - Z S I ~ i - 5 ( 1 ) ( 0 , I ) and NaH-ZSM-5(4) (
O,.).
),
-
,.
1.00 mmol OH/q) to such a degree that NaH-ZSM-5(4) possessed
nearly the same number of bridging OH groups as NaH-ZSM-5(1), then
the initial conversion of these NaH- zeolites was practically
equal, however, the NaH-ZSM-5(4) exhibited faster deactivation due
to coke formztion even though that the parent H-ZSM-5(4) zeolite
had stable activity in T-0-S (the decrease of conversion wasfrom
97 to 9 2 % at. WHSV 60 h -', 623 K, after 300 minutes). If the
toluene conversion and p-ET selectivity is approximated to t = 0
then the resulting p-ET selectivity is again higher than that for
H-ZSM-5 zeolite.
The above results indicate that the larger radius of the Na
and K cations in comparison with the protons contribute to the
higher zeolite para-selectivity. However, it is difficult to
decide if it is a result of the higher selectivity to p-ET in the
initial alkylkation step occurring in the zeolite channel
intersections and/or a result of the increased diffusivity of the
para-isomer in comparison with the meta- and ortho-isomers.
Investigating the relationship of activity vs. selectivity on H-Y
and H-ZSM-5 (ref. 4 ) pointed out,that for the H-Y zeolites, o-ET
prevailed at low toluene conversion levels (due to the higher
reactivity of the ortho-position) and m-ET was found at higher
toluene conversion on the expense of ortho isomer. In contrast,
for H-ZSEI-5 (cf. Fig. 2 ) the para-isomer dominated at low
conversions and the meta-isomer was mainly formed at higher
conversions. This indicated that steric hindrances at the H-ZSM-5
channel intersections (in contrast to H-Y) might be important for
the initial alkylation step. Therefore, we can suggest that the
location of f l a and K cations in the channel intersections is
responsible for the higher para-selectivity in the initial
alkylation step, however, the contribution of the cation presence
to the differences in the diffusivity of ethyltoluene isomers
cannot be neglected.
As concerns an intensive deactivation of NaH-ZSM-5(4)
containing high concentration of Na cations, it cannot be caused
by an increasc in ethylene oligomerization which is not catalyzed
by Na ions. The reason of zeolite coking could be therefore seen
only in steric hindrances for aromatic molecules which cannot be
easily removed from the zeolite channel system.
It is clear that industrially prepared zeolites (and/or after
their thermal or hydrothermal treatment) can contain in some cases
extralattice aluminium species in a poorly specified form such as
isolated A 1 cations or A1 oxidic species as, alumina or
 393

silica-alumina clusters or phases. The H-ZSM-5(5) zeolite

investigated here differs in its performance in the alkylation
reaction in T-0-S and its tendency to deactivate by coking was
more pronounced than that for H-ZSM-5(1). A possible occurrence of
some isolated A 1 cations in H-ZSM-5(5) can be indicated from the
IR spectra exhibiting a low intensity IR band at 3663 cm-I of OH
groups bound to A 1 cations (Fig. 1, ref. 1 0 ) . The addition of

100 100

75 75 $

v
3
c x
U

2vl 50
L
ti
6 25
t
1 1

15
I
55
I
95
I
135 175
T - 0 - S (mid

Fig. 4 T-0-S dependence of toluene conversion and p-ET

selectivity for H-ZSM-5(5) (O), AlH-ZSM-5(5) ( 0 ) and
?.I2 03 ll-ZSM-5(5) (0) zeolites.

some A 1 cations (by ion exchange), to the H-ZSM-5(5) as well as

to the H - Z S f 4 - 5 ( 1 ) zeolites (see Fig. 1,2 and 4 and the
Table) resulted in a small decrease in the number of bridging OH
groups and led to a slight decrease in the toluene conversion and
to an increase in the p-ET selectivity. When A13+ ions were
exchanged and supported on a zeolite, thus forming besides
isolated A 1 3 + some A1 oxidic species, a much substantial decrease
in zeolite void volume and an increase of the zeolite
para-selectivity was observed (Fig.2,4, andtheTable). It follows
that A1 cations and to a greater extent A1 oxidic species in A1H-
and A120311-modified zeolites decrease a void space in the zeolite
channels and contribute to higher p-ET selectivity in the initial
alkylation step and to higher relative diffusivity of the
para-isomer. Simultaneously,the presence of A1 species increased
the zeolite deactivation by coke in T-0-S in comparison with
394

the particular parent zeolite (Fig. 4 ) . However, the expected

increase of p-ET selectivity in T-0-S did not correspond to the
activity v s . selectivity relationship (Fig. 2 ) . The increase in
the zeolite coking can be caused by greater steric hindrances
owing to extralattice aluminium species in the zeolite channel
system as for )la, K cation modified zeolites and/or by enhanced
ethylene oligomerization by A13+ cations (cf. ref.11) competed
with toluene alkylation.
It has been stated in the literature [ref. 51 that zeolite
coking leads to narrowing of the channel system and increases
differences in the diffusivities of ethyltoluene isomers and thus
enhances the zeolite para-selectivity. However, the activity and
para-selectivity data presented here in dependence on T-0-S for
all zeolites evidence that this para-selectivity enhancement is
only apparent. For "low" coked zeolites the para-selectivity
increase in T-0-S corresponded roughly to a decrease in toluene
conversion and, therefore, followed the activity vs. selectivity
relation ( e . g . for H-, NaH-, KH-ZSM-5(1) and for short T-0-S
values for othrr zeolites. On the other hand for zeolites with
higher content of coke the selectivity increase in T-0-S is much
lower than that corresponding to a decrease in toluene conversion
(e.g. for N ~ l l - ? S M - 5 ( 4 ) , €I-ZSM-5(5) and A1203H-ZSM-5(5)). It has
been found [ret. 4 1 that, in the very beginning of the reaction, a
simultancouc clccrcase in the activity, sorption capacity and
in numhcr of O H groups took place. The p-ET selectivity increase
corresponded to the activity decrease. For higher T-0-S values,
futher decrease in the activity and sorption capacity occurred
while the total number of the strong acid sites remained nearly
constant. At this stage in the reaction, the para-selectivity did
not increase to an extent that would correspond to the activity
decrease. Therefore, at the beginning of the reaction, the channel
system is open to reactant molecules: however, after longer T-0-S
some portion of the OH groups is poisoned and the zeolite channel
system is far more blocked. Accordingly, the wholezeolite channel
system cannot be utilized for the reaction and the
para-selectivity cannot be improved with increasing coke formation
in the zeolite channel system.

CONCLUSIONS
It can be summarized that the occurrence of the cations with
larger ionic radius than that of protons (Na, K, Al) in the
zeolite cationic sites as well as of some oxidic A1 phase
 395

increases the para-selectivity of H-ZSM-5 zeolite in alkylation of

toluene with ethylene owing to filling partly a zeolite void
volume. The cations or oxidic species depending on their number or
character stimulate as electron acceptor sites to some extent
zeolite deactivation by coke and/or by narrowing the diameter of
the channels enabling longer contact time and transformations of
bulkier aromatic molecules. Coke itself, in contrast to
homogeneously distributed cations in the zeolite cationic sites,
does not increase the zeolite para-selectivity. Its apparent
increase is only a result of a decrease in toluene conversion
caused by coke deposition on strong acid OH groups. Blocking of
the channels by coke at higher coke loadings and, therefore,
limiting utilization o f . the whole zeolite channel system is
reflected in the decrease of the zeolite para-selectivity.

REFERENCES
1. L.R. Young, S . A . Butler and W.W. Kaeding, J. Catal. 7 6 ,
(1982) t l 8 .
2. W.W. Kaeding, C.-C. Chu, L.B. Young, B. Weinstein and S . A .
Butler, J. Catal. 6 7 , (1981) 153.
3. G. PaDarntto. E. Moretti, G . Leofanti and F. Gatti. J. Catal.
105, j l ? C 7 ) 227.
4. J. elks, R . Wichterlovg and S . Bedna/gova/, Appl. Catal.,
~~

submittcd.
5. W.W. Kaedincj, L.B. Young and C.-C. Chu, J. Catal. 89 (1984)
267.
6. I. Wang, C.-L. Ay, B.-J. Lee and M.-H. Chen, Appl. Catal. 5 4
(1989) 257.
7. P. Hatnnsaniy and S.K. Pokhriyal, Appl. Catal., 5 5 (1989) 265
8. N.Y. -
C h e n a n d W.E. Garwood, Catal. Rev. Sci. Eng. 28 (1986)
185.
9. J. Wei, J. Catal. 76 (1982) 4 3 3 .
10. L.M. Kustov, V . B . Kazansky, L. Kubelkovi, S. Beran and P.
Jir6, J. Phys. Chem. 91 (1987) 5247.
11. B. Wichterlovd, J. Novakovfi, L. Kubelkovi and P. Jirg, Proc.
5th 1nt.Zeol.Conf. Napoli (Ed. L . V . C . Rees) p. 373, 1980.
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 397
0 1991 Elsevier Science Publishers B.V., Amsterdam

MULTINUCLEAR MAS NMR STUDIES ON COKED ZEOLITES H-ZSM-5

H.Ernst, D.Freude, M.Hunger and H.Pfeifer

Sektion Physik der Karl-Marx-Universitst Leipzig, Linn6straBe 5,

DDR-7010 Leipzig, GDR

SUMMARY
During the cracking process carbonaceous materials are
deposited on the outer or inner surface of the catalyst. These
deposits are in many cases the main cause of catalyst
deactivation. Magic angle spinning (MAS) NMR investigations and
catalytic n-hexane cracking were carried out o H-ZSM-5 zeolites
after a mild hydrothermal dealumination. By p 3 C CP MAS NMR it
could be shown that the enhanced catalytic activity does not
enhance the coke formation and that the chem’cal nature of these
deposits is essentially aromatic. From H’ MAS NMR tudies
qGrformed on shallow-bed activated sealed samples and 2$7Al and
Si MAS NMR on rehydrated samples it follows that for high coke
concentrations the catalyst deactivation is caused mainly by
blocking of Bronsted acid sites.

INTRODUCTION
The activity, selectivity and deactivation by coking have an
important influence on the industrial applicability of zeolites
(refs.1-7). In agreement with other authors (refs.9-11) in a
previous study (ref.12) using ‘HI 27Al and 29Si MAS NMR as well
as the catalytic cracking reaction of n-hexane we have found,
that a mild hydrothermal dealumination of zeolite H-ZSM-5 results
in an enhanced catalytic activity. Here we report ‘HI 13C, 27AL
and 29Si MAS NMR studies on such hydrothermal treated uncoked and
coked samples to elucidate where the carbonaceous products are
deposited. Whereas in some previous papers H-ZSM-5 was assumed to
produce coke preferentially on the external surface of the
crystallites (refs.13,14), recent studies give clear evidence of
coke formation in the interior pore system of the crystallites
(refs.15-19).

METHODS
Hvdrothermal treatment
The zeolite with a framework SifA1 ratio of 15 synthesized
without template was the same as used in ref.12. The hydrothermal
treatment of the binder free samples was carried out in a tube of
398

50mm inner diameter with a maximum bed-depth of the zeolite

material of 8mm. The temperature was increased at a rate of 10K
per min. The steaming was carried out at 540aC for 150min under a
water vapour pressure, which was adjusted by the temperature of
the water bath, through which the nitrogen was flowing.

Catalvtic reaction
Catalytic activity was determined for the n-hexane cracking
reaction in an integral flow reactor. The reactor contained 0.259
zeolite in the form of binder free pellets with diameters of 0.3-
0.4mm. The catalyst was heated at a rate of 6K per min to 450OC
and then maintained at this temperature for lh in a hydrogen
flow. Since it is known, that the deactivation of H-ZSM-5
zeolites in the n-hexane cracking (refs.6,20,21) and methanol
conversion (ref.22) proceeds only slowly with hydrogen a s a
strem gas, we have used nitrogen (T=450°C,pN2=6kPa, pn-
hexane=92kPa). During the rection time of 15h a
gaschromatographic analysis of the reaction products was carried
out. If U denotes the relative molar conversion, the reaction
rate constant k is determined by the equation
k=-ln( 1-U) .
The conditions of the hydrothermal treatment as well as values
for the relative rate constant k/ko after coking are given in
Table 1. ko denotes the rate constant extrapolated to zero time.

Table 1
Conditions of hydrothermal treatment and values for relative rate
constant k/kO after n-hexane cracking for the samples under
study.

Sample Conditions of rel. rate constants

hydrothermal treatment k/kO f15%
t(h) T(OC) Pwater(kPa)

H-ZSM-5/0 2.5 540 0 0.76

H-ZSM-5/10 2.5 540 10.7 0.58
H-ZSM-5/40 2.5 540 40 0.65

JWR measurements
13C, 27Al and 29Si MAS NMR measurements were generally carried
 399

out on rehydrated samples. For the H ' MAS NMR measurements the
samples were pretreated under shallow-bed conditions in a glass
tube of 5.5mm inner diameter and with a bed-depth of lOmm for
zeolite material. The temperature was increased at a rate of 10K
per h. The samples were kept at the final activation temperature
of 4OOOC under a pressure below lOmPa for 24h, and than cooled
and sealed. Measurements were made on a homemade spectrometer HFS
270 and on a Bruker MSL 300 spectrometer. The homemade MAS
equipment for the rotation of the fused glass ampoules (ref.23)
was carefully cleaned to avoid spurious proton signals. As a
reference for the 27Al intensity measurements, a well-
characterized sample of H-ZSM-5 with a framework Si/Al ratio of
15 was used. The total concentration of OH groups in the
activated samples was determined by comparison of the initial
value of the free-induction decay of the sample with the
corresponding value for a standard (water). As a reference for
the 13C CP NMR intensity measurements a coked sample of H-ZSM-5
characterized by chemical analysis with respect to the carbon
content and the HjC ratio was used.

RESULTS
' MAS NMR
H
The H' MAS NMR spectra of the uncoked as well as of the coked
sample H-ZSM-510 are shown in Fig.1. Four different signals can
1a)'CHL
l H MAS NMR

20 R 0 -10 Clppm 20 10 0 -10 6/ppm

Fig.1 H
' MAS NMR spectra of the sample H-ZSM-5/0 before (A) and
after (B) coking.
be seen. (i) The line (a) at 2ppm is due to non-acidic hydroxyl
groups at the outer surface of zeolite crystallites, at framework
400

defects and in the amorphous part of the sample (ref.16). (ii)

For the coked samples this first line is superimposed by a signal
of highly mobile molecules of methane, enclosed in the channels
of the zeolite. (iii) The line (b) at 4.3ppm is caused by
bridging (acidic) OH groups (ref.24). (iv) The very broad line in
the spectrum of coked samples is not affected by MAS. Therefore,
the line width is determined by proton-proton dipolar
interaction. Table 2 summarizes for the six samples under study
values for the total concentration (columns (1) and (2)) as well
as for the concentration of OH groups contributing to line (b)
(columns (3) and (4)). All concentrations are given in protons
per U.C. of the zeolite.

Table 2
Concentration of protons and of framework aluminium atoms

H-ZSM-510 7.0 14.0 6.0 4.8 6.0 5.0 4.6 5.8

H-ZSM-5/10 5.0 10.5 3.4 2.5 3.5 2.7 2.0 6.1
H-ZSM-5/40 4.0 6.5 1.6 1.6 1.6 1.6 1.0 -
cHtot.:Total concentration of protons; cH (b):Concentration of
protons contributing to the line (b); cAlfr.:Concentration of
framework aluminium atoms; cHinv.:Concentration of protons per
WMR-invisiblellsite; unc. :Uncoked; c. :Coked; # ) :Apparent value.
Concentrations in the columns (1)-(7) are given in protons per
U.C. of the zeolite.

2 9 ~ iMAS NMR
In Fig.2 29Si MAS NMR spectra are shown of the sample H-ZSM-
510 and of the hydrothermally treated sample H-ZSM-5/40 before
and after coking. A fitting procedure using the programm
lfLinesimlt yields three lines. It is well-known that the
unresolved signal of Si(OA1) groupings in zeolites ZSM-5 consists
of a peak at ca. -1llppm with a shoulder at ca. -115ppm. The line
at ca. -106ppm arises from Si(lA1) groupings (ref.25). The
framework SifAl ratio determined from the relation (ref.25)
 401

4 4
Si/Al = 4* C Si(nAl)/nSi(nA1) C
n=O n=0
where Si(nA1) denotes the intensity of the NMR signal
attributable to Si(nA1) groupings is the same for both uncoked
and coked sample and agrees very well in the case of uncoked
samples with the result of the 27Al MAS NMR measurements.
29si MAS NVR

1
h
1 . I
-100
.
-120
I .

61m
I

Fig.2 29Si MAS NMR spectra of the sample H-ZSM-510 and the
1

hydrothermally treated sample H-ZSM-5/40 before (Arc) and after

. I
-100
. I
-1m
.

Wpm
I

(B,D) coking.

MAS NMR
27~1
In Table 2 values are given for the number cAlfr. of framework
aluminium atoms per U.C. (columns ( 5 ) and ( 6 ) ) Because acid .
leaching was not performed, it is seen, that the coked samples
contain W M R invisible" aluminium.

13C CP MAS NMR

The 13C CP MAS NMR spectrum of the coked sample H-ZSM-510
shown in Fig.3A is dominated by three narrow lines due to
residual n-hexane. This signal disappears by heating the sample
up to 4 O O 0 C and after a sufficiently long accumulation time
(40.000 repetitions) the signals of the coke deposits can be
402

observed. Figs.3B,CID show the 13C CP MAS NMR spectra of the

coked sample H-ZSM-510 and of the coked samples hydrothermally
treated at 10.7 and 40kPa, respectively. The spectrum
corresponding to Fig.3B but with total sideband supression (TOSS)
is shown in Fig.3E.

13C MAS NMR

LA
Fig.3 13C CP MAS NMR
spectra of the coked samples :
( A ) H-ZSM-510 before
heating at 400'C;
c
(B,C ,D ,) H-ZSM-510,
H-ZSM-5/10 and
H-ZSM-5/40, respectively
after heating the samples
up to 4OO0C;
(E) the same as Fig.3 (B)
but after total suppression
of the spinning sidebands
(TOSS) which are denoted by
asterisks in Figs.3(BIC,D). 300 200 100 0 6 PPm

DISCUSSION
Figs.1 and 3 as well as Table 2 (columns (1)-(6)) show
considerable changes in the 'HI 13C and 27Al spectra caused by
the coke formation in the channels of the H-ZSM-5 zeolites. The
decrease of the intensity of line (b) at 4.3ppm in the H
' MAS NMR
spectra and that of the line at -106ppm in the 29Si MAS NMR
spectra with increasing water vapor pressure for the uncoked
samples is caused by the dealumination of the zeolite (ref.12).
On the other hand, coking leaves the 29Si MAS NMR spectra
unchanged. That means, that in the n-hexane cracking process no
 403

further dealumination occurs. Therefore, the differences between

the 27Al MAS NMR spectra of uncoked and coked samples (cf.
columns (5) and (6) in Table 2) must be explained by the
existence of "NMR-invisible1I framework aluminium. Such "NMR-
invisible1#framework aluminium is formed through the coverage of
Bronsted sites by carbonaceous deposits which disturb the
tetrahedral symmetry of the aluminium atoms (refs.17,26). The
same reason is responsible for the decreased intensity of the
line (b) and the appearance of the very broad line in the H' MAS
NMR spectra after coking. Both the Bronsted OH groups which are
poisoned by these deposits and the protons of the deposited
molecules are characterized by a strong homonuclear dipolar
interaction. The large difference in the H ' and 27Al MAS NMR
spectra between uncoked and coked samples is a direct proof for
the existence of carbonaceous deposits poisoning the Bronsted
acid sites inside of the crystallites of the zeolite
crystallites.
Assuming on the other hand that
'H(b) cokedz(kfkO) *CAlfr.uncoked
(ref.27) as well as
CAlfr. kO) *CAlfr.uncoked
because cAlfr.=cH (b) (ref.24) we can compare the experimental
values given in Table 2, columns ( 4 ) and (6), with the computed
values given in column (7). Their agreement is satisfying.
Since the ratio k/ko is also effected by pore blockage (ref.5)
the last values have to be generally smaller.
Furthermore, for the first two samples follows from the values
given in Table 2, columns (1)-(4), that about 6 protons are
connected with one Bronsted OH group poisoned by carbonaceous
deposits (cf. column ( 8 ) ) . Considering that the aromatic to
aliphatic ratio derived from the 13C CP MAS NMR spectra shown in
Figs.3B and C is ca. 3 we can conclude that (i) the H/C ratio of
the carbonaceous deposits is smaller than one and (ii) that the
coke content is 3_+lwt.-% for the first two samples and
0.5+0.3wt.-% for the sample 3, respectively.

CONCLUSION
It has been shown in the present paper that besides the pulsed
field gradient technique (ref.16), the 27Al MAS NMR and the 29Si
MAS NMR (ref.17) the H
' MAS NMR spectroscopy with sealed samples
404

is a suitable method to elucidate the location of carbonaceous

deposites in zeolitic catalysts.

REFERENCES
1 N. Y. Chen and T. F. Degnan, Chem. Eng. Progr., 8 4 (1988)
3241
2 S. M. Ciscsery, Zeolites, 5 (1985) 207
3 s. w. Addison, S . Carlidge, D. A. Harding and G. Mc Elliney,
Appl. Catal., 4 5 (1988) 307
4 J. Abbot, Appl. Catal., 47 (1989) 33
5 E. G. Derouane, in: B. Imelik et al. (Ed.), Catalysis by
Acids and Bases, Elsevier, Amsterdam, 1985, p. 221
6 M. Guisnet and P. Magnoux, Appl. Catal., 54 (1989) 1
7 J. Weitkamp, S. Ernst, H. Dauns and E. Gallei, Chem. Ing.
Techn., 58 (1986) 623
8 C. Mirodatos and D. Barthomeuf, J. Chem. SOC., Chem. Commun.,
(1981) 39
9 H. Kawakami, S. Yoshida and T. Yonezawa, J. Chem. SOC.,
Faraday Trans. 11, 80 (1984) 205
10 R. M. Lago, W. 0. Haag, R. J. Mikowski, D. H. Olson, S . D.
Hellring, K. D. Schmitt and G. T. Kerr, Stud. Surf. Sci.
Catal., 26 (1986) 677
11 K . A. Becker and S . Kowalak, J. Chem. SOC., Faraday Trans. I,
83 (1987) 535
12 E. Brunner, H. Ernst, D. Freude, M. Hunger, C. B. Krause, D.
Prager, W. Reschetilowski, W. Schwieger and K.-H. Bergk,
Zeolites, 9 (1989) 282
13 P. Dejafve, A. Auroux, P. C. Gravelle, J. C. Vedrine, Z.
Gabelica and E. G. Derouane, J. Catal., 70 (1981) 123
14 D. H. Olson and W. 0. Haag, ACS Symp. Ser., 248 (1984) 275
15 M. Guisnet, P. Magnoux and C. Canaff, in: Y. Murakami, A.
Jijima and J. P. Ward (Eds.), New Developments in Zeolite
Science and Technology, Proc. 7th Int. Conf. Zeolites, Tokyo,
1986, Studies in Surface Science and Catalysis, Vol. 28,
Elsevier, Amsterdam, 1986, p. 701
16 J. Volter, J. Caro, M. Bulow, B. Fahlke, J. Karger and M.
Hunger, Appl. Catal., 42 (1988) 15
17 R. H. Meinhold and D. M. Bibby, Zeolites, 10 (1990) 146
18 D. M. Bibby, N. B. Milestone, J. E. Patterson and L. P.
Aldrige, J. Catal., 97 (1986) 493
19 T. Ito, J. L. Bonardet, J. Fraissard, J. B. Nagy, C. AndrQ,
Z. Gabelica and E. G. Derouane, Appl. Catal., 43 (1988) L5
20 F. Fetting, E. Gallei and P. Kredel, Chem. Ing. Techn., 54
(1982) 606
21 U. Hammon, G. T. Kokotailo, L. Rieckert and J. Q. Zahn,
Zeolites, 8 (1988) 338
22 M. C. Barrage, F. Bauer, H. Ernst, J. Fraissard, D. Freude
and H. Pfeifer, submitted for publication
23 H. Ernst, D. Freude, M. Hunger, H. Pfeifer and B. Seiffert,
Z. phys. Chemie, Leipzig, 268 (1987) 304
24 D. Freude, M. Hunger and H. Pfeifer, Z. phys. Chem. NF, 152
(1987) 171
25 J. Klinowski, Progr. Nucl. Magn. Reson. Spectrosc., 16 (1984)
237
26 D. Freude, J. Klinowski and H. Hamdan, Chem. Phys. Lett., 149
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G. Ohlrnann et 01. (Editors), Catalysis and Adsorption by Zeolites 405
0 1991 Elsevier Science Publishers B.V., Amsterdam

COKE OXIDATION IN HZSM-5 ZEOLITES.INTERMEDIATES,FINAL PRODUCTS AND

REFORMATION OF OH GROUPS AND VOID VOLUMES

.
J NOVAKOVA and L.KUBELKOVA
I

J.Heyrovsk; Institute of Physical Chemistry and Electrochemistry,

Czechoslovak Academy of Sciences,Dolej&kova 3, 182 23 Prague 8,
Czechoslovakia

SUMMARY
HZSM-5 zeolite was completely deactivated during acetone
conversion at 35OoC as a result of the poisoning of bridging OH
groups by the coke deposit as well asobecause of pore
blocking.The coke residue was oxidized at 500 C to various degrees
and the restoration of hydroxyl groups and void volumes was
checked together with the changes in the remaining coke
deposit.The most pronounced changes in the adsorption properties
occurred when first coke layers were oxidized and the zeolite
pores were opened.The catalytic properties were renewed with the
reformation of bridging hydroxyls. During the oxidation, inter-
mediates of ketonic,carboxylate and carbonate character were
created,and decomposed yielding CO and COz.

INTRODUCTION
The coking of zeolites in catalytic reactionstwhich affects the
function of the active centers, depends on many factors, of which
the dimensions of the pores and cavities and their ordering are of
primary importance (refs.1-3) .The zeolite type has also been
found to influence the coke oxidation: in HY zeolitestthe coke was
oxidized at lower temperatures than that in HZSM-5 (refs.4,5) and
the CO,/CO ratio in the final oxidation products was higher
(ref.5). The access to coke deposits f o r the oxidizing agent and
the formation as well as the decomposition of oxygenated
intermediates probably play a decisive role in the coke
oxidation path.Consequently, the process of oxidation of coke in
a HZSM-5 zeolite was studied in more detail.

METHODS
NaZSM-5 zeolite (Si/A1=13.5) was supplied by the Research
Institute for Oil and Hydrocarbon Gases, Czechoslovakia, and was
transformed into the H-form by acid leaching (sample A).It was
406

deactivated in the conversion of acetone at 35OoC (70 vol% of

acetone in a helium ~tream,WHSV=5h-~,25g of acetone passed over lg
of zeolite) and then purged in a helium stream for 30 min (sample
No 1) .The oxidation of this sample was performed at 5OO0C in a 20%
oxygen-helium stream (600 ml h-') and the progress of the
oxidation was checked by mass spectrometry ( a Finnigan 400
quadrupole mass filter) by recording the m/z ratio 32 for
oxygen,28 for CO and 44 for C02.Water evolved during the oxidation
was frozen out and its amount as well as the amount of coke in the
zeolites were determined from weight changes. The oxidation was
interrupted in chosen stages ( samples Nos. 2-4 denoted in Fig. 1
by arrows). Samples 1-4 were also pyrolyzed in a vacuum or in a
helium stream at 6OO0C (Nos. 1'-4'). The gaseous pyrolytical
products were also analyzed by mass spectrometry. Prior to all the
experiments, the samples were pretreated either in a vacuum
Pa) or in a helium stream at 35OoC.
The hydroxyl groups and the coke composition were studied on
zeolite platelets (7 mg cm-2) using a Nicolet MX-1E Fourier
transform infrared spectrometer. The void volumes were determined
by measuring sorption capacities for Ar at -195OC and a pressure
of 13.3 kPa. Temperature programmed desorption (TPD) of ammonia
and benzene was also employed: the vapour was adsorbed on 0.19 of
the zeolite at room temperature for 30 min, excess adsorbate was
evacuated up to a pressure of Pa and the TPD curves were
measured by recording the pressure changes using a calibrated
Pirani gauge with a heating rate of 10°C min-l. The IR bands of
the hydroxyl groups, vibrating at 3610 cm-l (bridging hydroxyls) ,
were related to the values for the parent zeolite (A) and listed
in TABLE 1 together with the coke amounts (wt%) and oxidation
levels ( 0-1 for the completely coked and completely oxidized
sample, respectively).
The ability to exchange the hydrogen of hydroxyl groups and of
coke for the deuterium of perdeuterated benzene (supplied by the
Central Institute for Isotopes and Radiation Studies, Acad.
Sci.GDR, enrichment 99.9 at % ) was also studied: 0.13 g of samples
A,1, 1',2,3 and 4 were allowed to exchange their hydrogen atoms
with 0.02 mmol of C6D6 at 30OoC. The molecular peaks of the
benzenes were recorded using the mass spectrometer working at an
ionization energy of 20 ev.
The catalytic activity of the partially oxidized samples was
checked using the temperature programmed conversion (TPC) of
 407

preadsorbed acetone: 1 mmol g-lof acetone was preadsorbed at room

temperature on 0.039 of the zeolite.The weakly bonded acetone was
desorbed at the same temperature for 15 min,and then the TPC was
recorded by introducing the gaseous desorbed products directly
into the vacuum system of the mass spectrometer. The mass spectra
were scanned in 20-30°C steps and the products were normalized
with respect to the fragmentation and ionization cross sections.

RESULTS
Oxidation - coke c o m
The oxidation progress of the coked HZSM-5 (No l), yielding
partially oxidized samples N o s . 2-4, is depicted in Fig.1. The
partially oxidized sample No 2 exhibits the lowest oxidation level
and almost the same coke amount as the pyrolyzed sample 1' (TABLE

0 100 200 min

3160 2840 cml
Fig.1. (left) Progress of the oxidation of coked HZSM-5 (No 1) at
50OoC. Curves a,b and c correspond to the peaks with m/z 32
(oxygen),28 (carbon monoxide) and 44 (carbon dioxide),respective-
ly. The interruptions of the oxidation are denoted with
arrows.
Fig.2. (right) IR spectra of coked,pyrolyzed and partially
oxidized samples.Numbering as in TABLE 1.
408

TABLE 1
Characteristics of coked, pyrolyzed and partially oxidized HZSM-5
in comparison with the parent uncoked zeolite
Sample Coke,wt% Oxidation level Void vol. Bridging OH ( % )
Ar ,mmol/g

A 0 - 5.2 100
1 10.7 0 0.1 16
1’ 9.2 0 0.2 19
2 9.7 0.07 2.8 34
3 515 0.49 3,8 65
4 1.5 0.86 5.3 93

Fig. 3 . IR spectra of coked, pyrolyzed and partially oxidized

samp1es after subtraction of the zeolite spectrum. Numbering as in
TABLE 1.

1). Both the pyrolysis (during which mainly hydrogen,methane and

ethylene are released and condensation of the aromatic rings
increases,ref.(6)) and the beginning of the oxidation lead to the
 409

disappearance of the alkyl substituents on the aromatic rings as

follows from Fig. 2 (the IR bands of stretching vibrations of CH3
and CH2 groups in the wave number interval of 2740-2944
cm-1) .Bands at 1643 cm-’which correspond to residues of
intermediates of acetone conversion (Fig.3, refs.(6-8)) also
disappear. Less condensed aromatics ( bands at 1500-1541 cm-l) are
also missing in both samples 1’ and 2. However, in contrast to
the pyrolyzed sample 1’ sample No 2 still contains some of these
monoaromatics (Fig.3), and, in addition, new bands at 1730 and
1690 cm-’, which can be removed by pyrolysis (samples Nos.2 and
2’,Fig.3) with the evolution of CO and C02 and weight loss smaller
than l%.Samples Nos. 3 and 4 with a higher oxidation level
exhibit the same IR spectra for coke as sample No 2, but in a
lower intensity (Figs.2 and 3) .The concentration of free bridging
hydroxyls increases with the proceeding oxidation (TABLE 1).
Oxidation - sorption properties
The changes of the sorption properties of the test samples
are listed in TABLE 1 and depicted in Fig.4 (a) and (b).The Ar
sorption capacity, corresponding to the zeolite void volume, is
very low for the coked zeolite No 1,and increases only slightly
after pyrolysis (1’).In contrast, sample No 2 (of the lowest
oxidation level) exhibits a sharp increase in the void volume

Fig.4.TPD of ammonia (a) and benzene (b).Numbering as in TABLE 1.

410

value.The same behaviour can be seen in the values of the LTP (low
temperature peak) for ammonia desorption (Fig.4a).The LTP of
benzene also exhibits a lower value for sample No 2 (Fig.4b).
Isotope exchange
The kinetics of the isotope exchange of deuterium between
perdeuterated benzene and the hydrogens of OH groups and coke
residues is shown in Fig.5.It can be seen that a plot of the In of
the concentration vs. time obeys a first order law for samples A
and 2-4, while a strong deviation is visible for the completely
coked zeolite (1) and its pyrolyzed form (lt).Fig. 5 also shows
that the exchange rate is slower for the hydrogen atoms of coke
than for the hydroxyl groups. The number of H atoms participating
in the exchange is given in TABLE 2. The calculation was based on
the exchange equilibrium values obtained after 15 h of
reaction and the known amount of benzene employed in the exchange:
N = M * (co-coo)/coo (1)
where N is the number of H atoms participating in the exchange
with M deuterium atoms of benzeneland co and coo are the
concentrations in times to and too,respectively.

TABLE 2

Number of H atoms per zeolite g exchanged with C6D6 at 30OoC

Sample H x Sample H x sample H x i-21
A 0.63 1 3.8 11 2.1
2 1.3 3 0.78 4 0.56

Catalytic activity
The restoration of the active centers for acetone conversion
(strong Bronsted acid sitestbridging hydroxyls (refs.7,8))
exhibits different behaviour than the restoration of void
volumes. The acid centers are renewed in closer proportion to the
decrease in the coke amount (increased oxidation level) which can
be seen in TABLE 1 and Fig.4a (HTP -high temperature peak- of
ammonia desorption). The HTP of benzene seems not to reflect only
the number of strong acid centers.
The reformation of the catalytic activity of the zeolites
studied can be seen in Fig. 6. In this Fig. , the TPC curves are
shown for the parent HZSM-5 (A) and samples 1,1t,2,3 and 4. In
agreement with the above described adsorption properties, the
amount of physically adsorbed acetone (i.e. not converted,
released with maximum rate at 75OC ) is low for samples 1 and l t ,
 411

but high and almost the same for the remaining samples. However,
this is not true for the catalytic transformation of preadsorbed
acetone. It follows from Fig. 6 that the restoration of the
catalytic activity corresponds to the number of freed OH groups.

4
0 200
Fig.5. (left) Isotope exchange of C6D6 with the hydrogen of the
OH groups and of coke at 30OoC. F= (co- Ct )/(co - Coo); COfCt,
and coo are concentrations of D atoms at times toft and
too,respectively.
Fig.6.(right) TPC of preadsorbed acetone.- acetone,--isobutene,
.
. .C O ,~Iaromatics.
DISCUSSION
Effect of partial oxidation on the coke composition and zeolite
void volumes
Both the pyrolysis of the completely coked HZSM-5 and partial
oxidation result in some similar changes in the coke:in the
removal of the alkyl substituents on the aromatic rings and the
remainders of the acetone conversion intermediate as well as in
the decrease of the light aromatic coke components ( especially
after the pyrolysis). It can be concluded that the oxidation of
these three coke components proceeds more readily than the
412

oxidation of the highly condensed coke.This also follows from

the temperature programmed oxidation of coke (5).In contrast to
the pyrolysis,the initial stages of the oxidation involve
removal of the components of the coke that block the pore
openings, as the value of the void volume substantially
increases.Nevertheless, the loss of weight due to the low-level
oxidation,compared with the pyrolysis, is almost the same.This
means that the coke components blocking the pore openings
constitute only a small fraction of the total coke amount. A s the
oxidation leads to the formation of oxygenated intermediates,
their presence can misrepresent the data for the weight losses.
These oxygenated intermediates are of ketonic as well as
carboxylate- and carbonate-like character.The bands observed at
1730 and 1690 cm-l agree well with those reported in (ref.4) for
coke partially oxidized and freed from the zeolite matrix by its
dissolution in fluoric acid.The authors assigned these bands to
ketone-like compounds.Quinones as intermediates in the coke
oxidation in zeolites were also assumed on the basis of EPR
measurements (ref.g).Various oxygenated intermediates were found
in the oxidation of gaseous aromatic compounds (refs.lO,ll).The
oxidized coke components observed in our measurements are
thermally decomposed with the evolution of CO and C02:they are
most probably the source of the CO in the final oxidation
products, as was suggested in (ref.5).Their amount does not exceed
1% of the total coke amount.
The results of the isotope exchange measurements ,on one
hand,confirm the opening of the pores for oxygen at the
beginning of the oxidation ( the deviation of the first order law
in the kinetics on samples 1 and l'in contrast to samples 2-4
and sample A ) , and, on the other hand, enable us to evaluate the
number of hydrogen atoms taking part in the exchange. For the
parent zeolite ( A ) , the agreement between the number of OH groups
calculated on the basis of the chemical composition and
determined from the exchange data is very good. The number of
hydrogen atoms taking part in the exchange between coke (samples
1 and 1') and deuterated benzene constitutes only 6 0 % of the
total hydrogen amount.This could be most probably explained by
the inaccessibility of the remaining coke hydrogens for benzene
(cf. also Fig.4b).
 413

Effect of partial oxidation on restoration of active centers and

catalytic activity

There are a number of assumptions on the deactivation of

zeolites in catalytic reactions. Some authors emphasize the
blocking of pores, e.g (refs. 2-4), others the simultaneous
effect of poisoning of active centers ( refs.12-15). The results
presented here favour the latter suggestion: the catalytic
activity was clearly restored with reformation of the active
centers.Only after the opening of the pores was the oxygenated
agent able to penetrate inside the cavities and liberate the
active centers.
CONCLUSIONS
i) The oxidation of coke formed from acetone in a HZSM-5
zeolite begins at the alkyl substituents on the aromatic rings
and with unblocking of the zeolite pores. ii) The oxidation
proceeds via the formation of oxygenated intermediates which
decompose yielding CO and C02. iii) The restoration of the
catalytic activity is related to the reformation of the active
centers ( bridging hydroxyls). The opening of the pores, enabling
the access of the oxidizing agent to the coke components,is a
necessary condition for the reformation of the active centers.

REFERENCES
1 D.E. Walsh and L.D. Rollmann, Radiotracer experiments on carbon
formation in zeolites.11, J.Catal.,56 (1979) 195-197 and
references therein.
P-Magnoux, P.Cartraud, S.Mignard and M.Guisnet, Coking,aging
and regeneration of zeolites, J.Catal.,l06 (1987) 242-250.
M.Guis.net and P.Magnoux, Coking and deactivation of
zeolites,Appl. Cata1.,54 (1989) 1-27,and references therein.
P.Magnoux and M.Guisnet, Coking,ageing and regeneration of zeo-
1ites.VI. Comparison of the rates of coke oxidation on
HY,H-Mordenite and HZSM-SIAppl.Catal.,38 (1988) 341-352.
5 J.Novakova and Z.Dolejsek,A comment on the oxidation of coke
deposited on zeolites,Zeolites,lO (1990) 189-192.
6 J.Novakova,L.Kubelkova,V.Bosacek and K.Mach, Zeolites,in press.
7 J.Novakova,L.Kubelkova,P.Jiru,S.Beran and K. Nedomova, A study
of the interaction of some ketones with HZSM-5 zeolite,
Proc.Int.Symposium on Zeolite Catalysis,Siofok,Hungary,May 13-
-16,1985,Acta Physica et Chemica SzegediensisIl985,pp.56l-578.
8 L.Kubelkova,J.Cejka,J.Novakova,V.Bosacek,I.Jirka and P.Jiru,
Acetone conversion and deactivation of zeolites, in:
P.A.Jacobs and R.A.van Santen (Eds), Zeolites: Facts, Figures,
Future,Elsevier, Amsterdam,1989,pp.l203-1212.
9 H.G.Karge,E.P.Boldingh,J.-P.Lange and A.Gutsze,Studies on coke
formation on dealuminated mordenites by in-situ IR and EPR me-
asurements,Proc. Int. Symposium on Zeolite Catalysis,Siofok,
Hungary, May 13-16,1985,Acta Physica et Chemica Szegediensis,
1985,pp.639-648.
414

10 G.Rotzoll,Molecular beam sampling. Mass spectrometric study Of

high-temperature benzene oxidation, 1nt.J. Chem. Kinet., 17
(1985) 637-653.
11 E.A. Stemmler and M.V.Buchanan,Negative ions generated by
reactions with oxygen in the chemical ionization source, Org.
Mass Spectrometry,24 (1989) 94-104.
12 E.C. Derouane,Factors affecting the deactivation of zeolites by
coking, in: B.Imelik et al.(Eds.),Catalysis by Acids and Bases,
Elsevier,Amsterdam,1985,pp.221-240.
13 D.M. Bibby,N.B. Milestone,J.E. Patterson and L.P. Aldridge,Coke
formation in zeolite ZSM-5,J.Catal. 97 (1986) 493-502.
14 L.M. Parker and D.M. Bibby,Effects of coke formation on the
acidity of ZSM-5,J.Catal. 99 (1986) 486-491.
15 K.S. Tsakalis,T.T. Tsotsis and G.J. Stiegel, Deactivation
phenomena by site poisoning and pore blockage.The effect of ca-
talyst size,pore size and pore distribution, J.Cata1. 88 (1984)
188-202.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 415
0 1991 Elsevier Science Publishers B.V., Amsterdam

INFLUENCE OF THE CONDITIONS OF DEALUMINATION AND THE EFFECT OF

PARTIAL EXIRACTION OF NON-FRAMEWORK ALUMINIUM ON THE CATALYTIC
PROPERTIES OF ZSM-5 CATALYSTS

G.oHLMANN1, H . G . J ~ R S C H K E W I T Z ~ , G-LISCHKEI, R.ECKELT1, T.GROSS',

B.PARLITZ1, I.SCHULZ1, K.WEHNERz and D.TIMM2

l C e n t r a 1 I n s t i t u t e o f P h y s i c a l Chemistry o f t h e Academy
o f Sciences
zLeuna-Werke AG, 4220 Leuna 3

SUMMARY
Samples o t P-modified LSM-5 t y p e z e o l i t e p r e v i o u s l y d e a l u m i n a t e d
by steaming a t d i f f e r e n t temperatures were used as c a t a l y t i c a l l y
a c t i v e components i n t h e c o n v e r s i o n o f methanol t o l o w e r o l e f i n s
a t 5bO"C. R e s u l t s show t h a t d e a l u m i n a t i o n a t 400°C f o l l o w e d by
t r e a t m e n t w i t h 2 N n i t r i c a c i d a l l o w s h i g h e s t degrees o f p a r t i a l
e x t r a c t i o n o f non-framework aluminium and o f f e r s b e s t r e s u l t s w i t h
r e s p e c t t o s e l e c t i v i t y o f C z / C 4 - o l e f i n s and c a t a l y s t s t a b i l i t y .

INTRODUCTION
LSM-5 t y p e z e o l i t e s a r e a p p r o p r i a t e c a t a l y s t s f o r t h e methanol-
to-olefin conversion (1-5). Cz/C4-olefins reach s a t i s t y i n g
s e l e c t i v i t i e s , P r o v i d e d t h a t t h e ~ l / A l F r - a r n e ~ ~( ~S -i /kA l F ) r a t i o i s
sufficiently h i g h . S e l e c t i v i t y o f o l e f i n s can be i n c r e a s e d
a d d i t i o n a l l y by t r e a t i n g t h e samples w i t h p h o s p h o r i c a c i d ( 6 - 1 0 ) .
Even w i t h those P-modified z e o l i t e s , h i g h v a l u e s o f t h e S i / A l F
r a t i o e x e r t a p o s i t i v e e f f e c t on t h e f o r m a t i o n o f t h e d e s i r e d
olef ins.
Besides by a p p r o p r i a t e a d a p t a t i o n o f t h e c o n d i t i o n s o f s y n t h e s i s
i t s e l f , aluminium d e f i c i e n t z e o l i t e s can be o b t a i n e d by h i g h tem-
p e r a t u r e c a l c i n a t i o n o r steaming o f samples which o r i g i n a l l y con-
t a i n a h i g h e r f r a c t i o n o f aluminium (11). The degree o f dealuniinu-
t i o n s t r o n g l y depends on t h e e x p e r i m e n t a l c o n d i t i o n s under which
t h e steaming o t t h e sample Proceeds. BY v a r i a t i o n o f t e m p e r a t u r e
416

and time, a broad range o f t h e S i / A l F r a t 1 0 1s e x p e r i m e n t a l l y ac-

c e s s i b l e , On t h e o t h e r hand a z e o l i t e w i t h a d e s i r e d S i / A l F v a l u e
can be generated by v a r i o u s c o m b i n a t i o n s o f t h e two mentioned
e x p e r i m e n t a l parameters.
D e a l u m i n a t i o n o f aluminium r i c h z e o l i t e s , w h i c h seems e c o n o m i c a l l y
attractive, i s n e c e s s a r i l y accompanied by t h e f o r m a t i o n o f a l u m i -
nium s p e c i e s i n non-framework p o s i t i o n s ( 1 2 ) . I t i s o f i n t e r e s t
whether aluminium d e f i c i e n t z e o l i t e s w i t h i d e n t i c c o n t e n t s o f
aluminium i o n s i n t h e framework o f s i l i c a , which, however, a r e
o b t a i n e d by d e a l u m i n a t i o n o f an aluminium r i c h p a r e n t sample under
d i f f e r e n t experimental conditions, d i f f e r with respect
t o t h e e x t r a c t a b i l i t y o f t h e non-framework aluminium and t o t h e i r
catalytic Properties.
I n t h e p r e s e n t Paper t h e i n f l u e n c e o f t h e d u r a t i o n o f dealumina-
t i o n on t h e c a t a l y t i c b e h a v i o u r i s s t u d i e d w i t h emphasis on t h e
e x t r a c t i b i l i t y o f non-framework aluminium ( A l n ~ ) and on s t a b i l i t y
and s e l e c t i v i t y i n t h e c o n v e r s i o n o f m e t h a n o l . A d d i t i o n a l l y some
o f t h e samples were c h a r a c t e r i z e d by p h o t o e l e c t r o n s p e c t r o s c o p y
(XPS), by temperature programmed d e s o r p t i o n o f ammonia (NHs-TPD)
and by d e t e r m i n a t i o n o f t h e coke d e p o s i t s on t h e spend c a t a l y s t .

EXPERIMENTAL

PrePara.tiPc! . . o ~ f s n m f l ~ .
P e n t a s i l t y p e ZSM-5 z e o l i t e (HS-30, Si/A1=19, Chemie AG B i t t e r -
f e l d ) i s c o n v e r t e d i n t o t h e H+-form by a f o u r t i m e s r e p e a t e d
t r e a t m e n t w i t h a 0 . 2 N s o l u t i o n o f HNOs i n a s i m p l e b a t c h p r o -
cedure. F o r d e a l u m j n a t i o n , t h r e e s e p a r a t e samples o f t h e Hi-form
a r e exposed t o a stream o f a i r and steam (pweter=90 kPa) a t 400,
470 and 700OC. To a c h i e v e a p p r o x i m a t e l y i d e n t i c S i / A l F r a t i o s ,
t i m e o f steaming was 70. 6 and 0.25 hours, r e s p . Framework a l u m i -
nium o f each sample was d e t e r m i n e d u s i n g t h e ammonium exchange
methode (11). Subsequently P a r t o f each o f t h e samples was t r e a t e d
w i t h 2 N HN03 a t 103°C f o r p a r t i a l e x t r a c t i o n o f non-framework
aluminium formed d u r i n g d e a l u m i n a t i o n . E x t r a c t e d aluminium was
determined a n a l y t i c a l l y i n t h e s o l u t i o n o f t h e e x t r a c t i n g a g e n t .
C a t a l y s t p a r t i c l e s were p r e p a r e d by m i x i n g t h e HS-30 samples w i t h
A e r o s i l - 2 0 0 and water and subsequent e x t r u d i n g , t h e ready made
e x t r u d a t e s (6 = 1 t o 2 mm) c o n t a i n i n g 65% by w e i g h t o f z e o l i t e . P-
m o d i f i c a t i o n was c a r r i e d o u t by i m p r e g n a t i o n w i t h aqueous phospho-
r i c a c i d . The c o n t e n t o f phosphorus f o r c a t a l y s t s based upon
 417

extracted HS-30 was held somewhat lower taking into consideration

their diminished contents of total aluminium. Finally catalyst
samples were conditioned by steaming at 700°C for 1 hour.

(;o.tnlY 51s
Catalytic experiments were carried out in a tubular fixed bed
reactor ($ = 12 mm) using a mixture of methanol/Nz (molecular
ratio= 1 : l ) as reaction feed (conditions o f reaction see table 1).
Products were analyzed by an on-line operated gaschromatographic
device. Calculation o f the concentration from analytical data is
based on individual calibration of the components.

TABLE 1: Parameters of reaction

t einpera t u r e : 560°C
concentration of methanol: 50 Vol-%
catalyst volume: 10 ml
catalyst mass: 5.0
feed rate (mixture): 3.33 ml/s (STP)
c h.at-a
GHSV(mixture) : 1200 ml/mlcataivst*h
LHSV(methano1): 1 ml/mlcata~ystffh
.. .- . . . . ~~~ . . . . .. .. . -. . . . . .

Photoelectron spectrosc.oPr
XPS investigations were carried out with an AEI ES200B electron
spectrometer, using MgKd radiation. Resulting signal intensities
required a spectra accumulation based on the PDP8e/DS800 data
system. Ine analyzer system ot the spectrometer was calibrated
according to Anthony and Seah ( 1 3 ) . Evaluation of XPS intensity
ratios to derive atomic ratios on the surface was based on the
model of homogeneous distribution (14).

Temperature programmed dessrc~tiso.~Lammonia

Atter cleaning zeolite samples by heating to 500°C in a He gas
stream for 1 hour, ammonia is adsorbed at 1 2 O O C from a gas stream
contuining 3 Vol-% of NH3. After flushing by Pure He at 120°C for
two nours, desorption of ammonia UP to 5OOOC i s started (heat rate
1L OC/min). The concentration of NH3 in the exit gas is determined
using a thermoconductivity cell. The curve o f the desorptogramm is
418

r ecorded by a c o n v e n t i o n a l d e v i c e .

Temperature Programmed o x i d a t i o n
Carbonaceous d e p o s i t s formed d u r i n g r e a c t i o n on t h e c a t a l y s t
were det ermin e d by te mp e ra tu re Programmed o x i d a t i o n . Coke was
burned oft i n a stream o t d r y a i r i n t h e t e m p e r a t u r e range between
200 and 700 OC, t h e heat r a t e b e i n g 5 " C h i n . T h i s p r o c e s s was
monit ored c o n t i n e o u s l y by r e c o r d i n g c a r b o n monoxide and d i o x i d e .
The o x i d e s were s e p a ra te d by a Cekatron 5 column and d e t e r m i n e d
g aschromot ogr a p h i c a l l y a f t e r c o n v e r s i o n t o methane. Carbon ( m c )
was c a l c u l a t e d from t h e t o t a l amounts o f t h e o x i d e s .

RESULTS
Experiment al r e s u l t s o f methanol c o n v e r s i o n w i t h t h e s i x c a t a -
lysts based on HS-30 samples o f d i f f e r e n t P r e p a r a t i o n a r e r e p r e -
sented i n t a b l e s 2 and 3 . Values o f p r o d u c t s e l e c t i v i t y a r e r e l a -
t e d to t h e p o r t i o n s o f carbon o f fe d methanol w h i c h a r e c o n t a i n e d
i n t h e g i v e n component o f t h e p r o d u c t :

vr = nuinber o f carbon atoms Per m o l e c u l e o f p r o d u c t

hl = molor- amount o f p r o d u c t formed Per t i m e u n i t
IL .- molar amount o f methanol c o n v e r t e d Per t i m e u n i t

Data r e p o r t e d i n t h e t a b l e s a r e v a l u e s averaged over t h e whole

r e a c t i o n o e r i o d . The t i m e on stream when methanol f i r s t appears i n
t h e e x i t a n s o f t h e r e a c t o r i s denoted as t i m e o f d e a c t i v a t i o n .
D u r i n g record e d times o f experiment no d i m e t h y l e t h e r was d e t e c -
t a b l e among t h e p r o d u c t s o f r e a c t i o n .
A l l c a t a l y s t s c o n t a i n i n g n o n -e x tra c t e d z e o l i t e samples ( T a b l e 2 )
g i v e r a t h e r h i g h s e l e c t i v i t y values f o r t h e d e s i r e d products - the
lower o l e f i n s . Propene e x h i b i t s t h e h i g h e s t p o r t i o n among them. By
v a r i a t i o n o f conditions o f dealumination o n l y gradual d i f f e r e n c e s
a r e observed w i t h i n t h e d i s t r i b u t i o n o f p r o d u c t s . Values o f t i m e
on stream a r e r e l a t i v e l y low, w i t h medium c o n d i t i o n s g i v i n g a
maximum ,
 419

TABLE 2: E f f e c t o f steam d e a l u m i n a t i o n on p r o d u c t s e l e c t i v i t i e s
and c a t a l y s t s t a b i l i t y
Non-extracted HS-30 z e o l i t e
Content o f phosphorus 1 . 5 w t - %

catalyst D93P1.5 D76P1.5 DS6P1.0

temperature o f steaming " C 400 470 700

ti me o f steaming h 70 6 0,25
molar S i / A l F r a t i o 93 76 86
- - - -- -_-~- - ~ _ _ _ - ~ __
product s e l e c t i v i t i e s _ %
ethene 17,O 17,O 17,3
Propene 36,2 36,2 37,O
b u t enes 23,4 24,2 23,2

Ca/C4 olefins 76,6 77.8 77,s

- _ _ _ _ _ _ _ _ _ _ - - - - - - - - - - -
met hone 1,s 1,9 2,4
ethane 0,18 0,16 0,22
Propane 1,5 1,6 1,7
i - b u t one 1.3 1,6 1,3
n-butane 0,78 0,57 0,51
- - - - - - - - - - - - - - - - -
Ca-a1 i p ha t i c s 10,8 8,6 10,o
_ _ _ _ _ _ _ _ _ _ _ _ _ _ - - _
benzene 0,17 0,19 0,20
toluene 0,86 1,o 1,l
xvlenes 2,2 2,3 2.6
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
BTX aromat ics 3,2 3,s 3,9
- - - - - - - - - - - - - - - - -
t i m e o f d e a c t i v a t i o n (h ) 47 58 25

The amount o f e x t r a c t e d non-framework aluminium ( Ta b l e 3) i n c r e a -

ses as d u r a t i o n o f d e a l u m i n a t i o n i s i n c r e a s e d . C a t a l y s t s t a b i l i t y
- expressed i n terms o f ti m e on stream - i s i n c r e a s e d by e x t r a c -
t i o n i n any case. The s t r o n g e s t e f f e c t i s a c h i e v e d i f dealumina-
t i o n proceeded under l o n g t i m e c o n d i t i o n s : The v a l u e f o r t i m e on
stream i s r a i s e d f o r loo%, as compared w i t h t h e n o n - e x t r a c t e d
sample.
420

TABLE 3: E f f e c t o f steam d e a l u m i n a t i o n on p r o d u c t s e l e c t i v i t i e s
and c a t a l y s t s t a b i l i t y
E x t r a c t e d HS-30 z e o l i t e , c o n t e n t o f phosphorus 1.1 w t - %

catalvs t D93EP1. CI Di-eEPi, n De6EPi. 5

temperature o f steaming * C 400 470 700

t i m e o f steaming h 70 6 0,25
m olar S i / A l F r a t i o 93 76 86
degree o f e x t r a c t i o n o f A l n ~ 22 15 6
~ ~- - _ .

p roduct s e l e c t i v i t i e s X
e t hene 17,O 18,9 19,5
Propene 37,6 30,6 27,9
b u t enes 25,l 18,5 16,9
- - - - - - - _ - - - - - - - - - - - - - - - - _ - - - - - - - _
CZ/& olefins 79,7 68,O 64,4

methane 2,8 3,4 6,3

ethane 0,19 0,34 0,47
propane l,4 2.4 2,8
i - b ut ane 1,6 1,6 1,9
n-butane 0,48 0,57 0,86

Cs-aliphatics 7,l 6,4 7,2

_ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - - - -
benzene 0,25 0,41 0,62
toluene 1,1 1,7 2,6
xylenes 2,2 3,l 4,8

BTX aromat ics 3,5 5,2 8,O

ti me o f d e a c t i v a t i o n ( h ) 96 68 33
- . ... -

The i n f l u e n c e o f P a r t i a l removal o f non-framework a l u m i n i u m on

c a t a l y s i s c l e a r l y depends on t h e c o n d i t i o n s o f d e a l u m i n a t i o n o f
t h e z e o l i t e . T h i s can be concluded from t h e comparison o f any o f
the e x t r a c t e d w i t h t h e c o rre s p o n d i n g n o n - e x t r a c t e d samples.
Whereas a f t e r l o n g t i m e d e a l u mi n a t i o n , e x t r a c t i o n r e s u l t s i n a
s l i g h t increase o f o l e f i n s e l e c t i v i t y , d i s t i n c t losses o f t h e i r
p o r t i o n among t h e p r o d u c t s a r e found w i t h t h e two o t h e r c a t a l y s t s .
The decrease o f t o t a l s e l e c t i v i t y i s caused by ProPene and t h e
 421

butenes. S e l e c t i v i t y o f ethene i s n o t n e g a t i v e l y i n f l u e n c e d as
t i m e o f d e a l u m i n a t i o n i s decreased: I n c o n t r a s t t o Propene and t h e
butenes i t s v a l u e s l i g h t l y i n c r e a s e s w i t h d e c r e a s i n g t i m e o f stea-
ming. I t i s w o r t h m e n ti o n i n g t h a t e x t r a c t i o n o f non-framework a l u -
minium f avou rs t h e f o r m a t i o n o f methane, b u t s l i g h t l y suppresses
t h e accumulati o n o f C s - a l i p h a t e s .
F or p r a c t i c a l purposes o f t h e methanol c o n v e r s i o n , a c a t a l y s t ba-
sed on an e x t r a c t e d , P-modified ZSM-5 z e o l i t e p r e v i o u s l y dealumi-
nat ed by steaming a t temperatures i n t h e r e g i o n o f 4000C s h o u l d be
P r e f e r e d . S e l e c t i v i t y o f l o w e r o l e f i n s and c a t a l y s t s t a b i l i t y
a chieve a t t r a c t i v e v a l u e s .
D e t e r m i n a t i o n o f coke on spend c a t a l y s t s ( Ta b l e 4) r e v e a l s t h a t
t h e r a t e o f coke d e p o s i t i o n i s h i g h e r w i t h t h e n o n - e x t r a c t e d sam-
p l e s . These c a t a l y s t s , a l t h o u g h performed o v e r a d e f i n i t e l y
s h o r t e r t i m e th a n t h e i r e x t r a c t e d c o u n t e r p a r t s , show p r a c t i c a l l y
i d e n t i c amounts o f coke. The s u p p re s s i o n o f t h e d e p o s i t i o n o f coke
i s o b v i o u s l y due t o t h e removal o f non-framework aluminium,
because t h e e f f e c t i s found w i t h b o t h P-modified and P - f r e e
catalysts.

TABLE 4: E f f e c t o f p a r t i a l e x t r a c t i o n o f non-framework aluminium

on c a t a l y s t d e a c t i v a t i o n and d e p o s i t i o n o f coke

ti m e o f d e c t i v a t i o n amount o f coke d e p o s i t e d
Catalyst I hours ) (mgcoke/gzeoli te)

31,5
35,8

8 119,4
10 126,s
12 114,3
26 110,6

The e v a l u a t i o n o f XPS d a t a (T a b l e 5) r e v e a l s t h a t w i t h t h e p a r e n t
HS-30 z e o l i t e t h e S i / A l r a t i o on t h e s u r f a c e i s h i g h e r t h a n t h e
average S i / A l v a l u e d e r i v e d from NHe+-exchange d a t a . D i s t r i b u t i o n
o f aluminium over t h e c r y s t a l i s s l i g h t l y inhomogeneous. W i t h t h e
dealuminated samples, d i f f e r e n c e s between t h e s u r f a c e and t h e
422

TABLE 5 : XPS i n v e s t i g a t i o n , r e l a t i v e X P S i n t e n s i t i e s
( d e v i a t i o n f 10%). Hs-30

ratio of Al/Si ratio Si/A1 ratio Si/A1 ratio

sample intensities XPS XPS NH4 +-exchange
IAIZP/ISIZP (surface) (bulk)

n on-t reat ed 0,021 0,031 32 18

steamed f o r 0,038 0,056 18 86
Wh a t 700°C
steamed f o r 0,143 0,213 4,7 93
72h a t 400°C

average S i / A 1 r a t i o a r e c o n s i d e r a b l e . S u r f a c e v a l u e s a r e c l e a r l y
s h i f t e d i n fa v o u r o f t h e a c c u m u l a ti o n o f a l u m i n i u m . B o t h samples
have n e a r l y i d e n t i c S i / A l F r a t i o s and t h e r e f o r e do n o t d i f f e r i n
t h e i r t o t a l amounts o f non-framework a l u m i n i u m . The s t r o n g d e v i a -
t i o n s o f t h e r e l a t i v e X P S i n t e n s i t i e s between t h e two d e a l u m i n a t e d
samples show t h a t d i s t r i b u t i o n s o f non-framework a l u m i n i u m a r e
d i f f e r e n t . I t can be assumed t h a t d e p o s i t i o n o f a l u m i n i u m on non-
microporous s u r f a c e areas, i . e . i n t h e system o f mesopores o r on
t h e e x t e r n a l s u r f a c e area, i s fa v o u re d by l o n g t i m e steaming.
The t o t a l number
of acid sites i s
i n c r e a s e d by ex-
traction. This >
can be seen from
the results o f
I

:,
(

$
temperat ure p r o - 3
srammed desorp- :.
t i o n o f ammonia i
o f the P-f r e e
zeolite (Fig.1). 7"
lhe amount o f
ammonia adsorbed 2& jw h c o
-
,oo T / '2 200 100 .:OO 5W

-F-i g_ .- -1: Te_mmp_er_at_ur_e _pr_os_amm_eed_~e.s_ollPJi~n- o_f -a&m-n_ii_a

1
D93 dealuminated HS-30 ( S i / A 1 ~ = 9 3 ) Dealurnination
D93E d e a l u mi n a te d e x t r a c t e d Hs-30 a t 4000 C
(degree o f e x t r a c t i o n
- - - - - - - - - - - - - - - - - - - ._ f o r 70 h
I
= 22%)
D e e dealuminated HS-30 ( S i / A 1 ~ = 8 6 ) Dealumination
D e 6 E dealuminated e x t r a c t e d HS-30 a t 7000C
(degree o f e x t r a c t i o n = 6%) for 0 2 5 h
 423

on places o f s t r o n g i n t e r a c t i o n (maximum o f t h e c u r v e o f desorp-

t i o n a t about 400°C) achieves h i g h e r v a l u e s w i t h b o t h e x t r a c t e d
samples. I t is obvious t h a t t h e g ro w th o f a c i d i t y is more s t r o n g l y
Inarked w i t n t h e i o n s t i m e dealuminated z e o l i t e .

DiSCbSSlUN
.The e x p u l s i o n o t t e t r a h e d r a l aluminium from s u b s t i t u t i o n a l P o s i -
t i o n s i n t h e framework o f s i l i c a g i v e s r i s e t o t h e f o r m a t i o n o f
non-framework aluminium o f v a r i o u s c h e m i c a l n a t u r e ( 1 2 ) . Aluminiiiin
species w i t h t e t r a h e d r a l l y and o c t a h e d r a l l y c o o r d i n a t e d c e n t r a l
i o n s ( 1 s ) o f d i f f e r e n t degrees o i a g g r e g a t i o n a r e d e p o s i t e d i n t h e
z e o l i t e channels and channel i n t e r s e c t i o n s . M i g r a t i o n t o t n e
e x t e r n a l s u r f a c e i s p o s s i b l e . I t can be assumed t h a t P a r t i a l
b l o c k i n g o f pores by a e p o s i t s can cause a h i n d r a n c e o f t h e d i f f u -
s i o n o f t h e p r i m a r y p r o d u c t s o u t o f t h e p o r e system t h u s i n c r e a -
s i n g the p r o b a b i l i t y o f f u r t h e r undesired reactions o f the
o l e f i n s . Besides, i t cannot be excluded t h a t non-framework a l u m i -
nium i t s e l f o r - as i n o u r case - aluminium phosphates formed by
i n t e r a c t i o n w i t h t h e p h o s p h o ri c a c i d a r e c a t a l y t i c a l l y a c t i v e ,
P o s s i b l y e n a b l i n g h y d r i d e t r a n s f e r w i t h t h e o l e f i n s o r any o t h e r
b y - r e a c t i o n s o f t h e feed component.
C a t a l y t i c r e s u l t s show t h a t w i t h n o n - e x t r a c t e d samples t h e v a r i a -
t i o n o f t h e c o n d i t i o n s o f d e a l u m i n a t i o n has no s i g n i f i c a n t e f f e c t
on t h e d i s t r i b u t i o n o f p r o d u c t s . D i f f e r e n c e s w i t h r e s p e c t t o Pore
t r a n s p o r t phenomena and t o o t h e r i n f l u e n c e s o f t h e non-framework
alumina on t h e f o r m a t i o n o f a n a l y t i c a l l y determined p r o d u c t s a r e
n e g l i g i b l e . i t i s , however, e v i d e n t t h a t t h e f o r m a t i o n o f h i g h l y
condensed compounds (carbonaceous d e p o s i t s . coke) i s a f f e c t e d by
t h e n a t u r e o f non-framework aluminium. Dealuminated z e o l i t e s
o b t a i n e d by s h o r t ti me steaming undergo t h e most r a p i d d e a c t i v a -
t i o n , as i s shown by t h e v a l u e s o f t i m e on stream and c o n f i r m e d by
t h e d e t e r m i n a t i o n o f d e p o s i t e d coke.
The dependence o f t h e degree o f e x t r a c t i o n o f non-framework a l u m i -
nium on t h e c o n d i t i o n s o f d e a l u m i n a t i o n c l e a r l y shows t h a t l o n g
ti me steaming o t t h e z e o l i t e d u r i n g d e a l u m i n a t i o n f a v o u r s deposi-
t i o n o t aluminium i n Places o f good a c c e s s i b i l i t y t o l i q u i d
a g ent s. With growing t i m e o f d e a l u m i n a t i o n t h e f r a c t i o n o f non-
framework aluminium whicn can m i g r a t e i n t o t h e r e g i o n o f pore-
mouths o r t o t h e e x t e r n a l s u r f a c e a re a i s r a i s e d . T h i s assumption
Is supported by t h e r e s u l t s o f p h o t o e l e c t r o n spectroscopy ( X P S ) .
l h e h i g h e s t Al/Si r a t i o on t h e e x t e r n a l s u r f a c e i s found w i t h t h e
sample steamed Tor 72 h o u r s .
424

Removal o t non-framework aluminium can improve c a t a l y t i c Proper-

t i e s , I n any case c a t a l y s t s t a b i l i t y , expressed i n terms o f t i m e
o f deactivation, i s i n c r e a s e d . A p o s i t i v e i n f l u e n c e on p r o d u c t
d i s t r i b u t i o n i s found w i t h t h e l o n g t i m e d e a l u m i n a t e d sample o n l y .
where t o t a l olef1.n s e l e c t i v i t v i s s l i g h t l y i n c r e a s e d . W i t h t h e
r e m a i n i n g two c a t a l y s t s , total selectivity of olefins i s clearlv
decreased i n f a v o u r o f t h e p r o d u c t s o f h v d r i d e t r a n s f e r ( l o w e r
alkanes and BTX a r o m a t i c s ) . These l o s s e s o f t o t a l s e l e c t i v i t y o f
olefins, t h e s h i f t o f d i s t r i b u t i o n w i t h i n the lower o l e f i n s i n
favour o f ethene, and t h e decrease o f s e l e c t i v i t y o t CS a l i p h a t i c s
i n d i c a t e t h a t w i t h d e c r e a s i n g t i m e o f dealurninat i o n , suhseauent
e x t r a c t i o n o f non-framework aluminium, which i s l e s s e f f e c t i v e
w i t h t h e soinole dealuminated f o r 1 5 m i n u t e s o n l v , i s riccomponied
by t h e appearance o f a d d i t i o n a l s t r o n g o c i d s i t e s . l h e v m i a h t be
c r e a t e d by t h e removal o f aluminium i o n s from non--tramework Phos-
phate d e p o s i t s . I h e i n c r e a s e o f t h e number o t s t r o n g a c i d s i t e s ,
which a r e m a i n l y r e s p o n s i b l e for c a t a l y t i c a c t i v i t y , a f t e r e x t r u c -
t i o n w i t h n i t r i c a c i d i s proved by t h e r e s u l t s o f NH3-IP1).

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2 C.D.Chang, C a t a l . R e v . - S c i . E n g . 2 6 , 3 / 4 . 223(1984)
3 V.Ducarme. J . C . V k d r i n e . A ~ ~ l . C a t a l . 1 7175-84(1985)
.
4 N.Y.Chan, W.E.Gorwood, C a t a l . K e v . - S c i . E n g . 2 8 , 185-264(1986)
S P.Jarlagadda, C.F.R.Lund, E . R u c k e n s t e i n , A p p l . C a t . 5 4 , 135(1989)
6 L.B.Young, S . A . B u t t e r . W.W.Kaeding, J.Cata.L.76, 418-432(1982)
i J . C.Vedrine, A . Auroux, P . D e J a i t r e , V . I)ucarire, n . H O S e r , 5 . Lliou
J . C a t a 1 . 7 3 , 147-160(1982)
8 L.W . Z a t o r s k y , P . r . Wierzchowski. A . A . Cichowtas. 61111. P o l i s h
Acad.Sciences, Chemistry, 32, 217-222(1984)
9 .J . A . I - e r c h e r . G . R~JmolmflVr. H .N o l l e r - . Acto Pbvs. Cheni. 5 1 , 71(1(485)
10 S h i g e r u I k a i , Manabu Okomoto. A u p l . C a t . 4 9 . '143(1989)
11 G.ohlaann, H.-G.Jerschkewitz, G.Lischke, b . P o r l i t z , K . t c k e l t ,
M . H i c h t e r , L . t.Cheinie 28, 5, 161-168 (1988)
1 2 J .Scherzer i n C a t a l y t i c M a t e r i a l s , ACS SYinposiuni S e r i e s 248,
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1 3 M.T.Anthony, M.P.Seah. S u r f . I n t e r f a c e A n a l . 6 . 95(1984)
14 M.P.Seah, i n P r a c t i c a l S u r f a c e A n a l y s i s ( t d s . D . B r i g g s . M . P .
Seoh). W i l e y . 1983. ChaD.5
1 5 A.Samoson, E.Lipmaa, G . t n g e l h a r d t , U.Lohse, H . - G . J e r s c h k e w i t z
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G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 425
0 1991 Elsevier Science Publishers B.V., Amsterdam

SPECTROSCOPIC AND ChTALYTIC INVESTIGATIONS OF HYDROTHERMALLY

DEALUMINATED ZSM-5

E. LOFFLER 1 , L.M. KUSTOV', V.L. ZHOLOBENKO~, CH. P E U K E R ~ ,

n
u. LOME', V.B. K A Z A N S K Y ~ , G.OHLMANN'
'Central Institute of Physical Chemistry, Academy of Sciences of
the GDR, Berlin-1199

2N.D.2elinsky Institute of Organic Chemistry, Academy of Sciences

of t h e USSR, Moscow

ABSTRACT
The influence of different hydrothermal treatment conditions of
HZSM-5 on the n-hexan cracking activity wa5 studied. The Bronsted
and Lewis acid sites were characterized by diffuse reflectance IR
spectroscopy using various probe molecules. The spectroscopic and
catalytic results were discussed with t h e emphasis to t h e role of
Lewis sites in the activity enhancement after steaming and in the
mechanism o f t h e paraffin cracking.

INTHODUCTION
The influence of hydrothermal treatment on the properties of
zeolites is of particular interest from the point of view of
preparation of cracking catalysts with high activity, selectivity
and stability. Recently, an effect of a considerable enhancement
of t h e cracking activity for HZSM-5 zeolites pretreated under mild
steaming conditions was reported (refs. 1-3). It was explained
(ref. 1 ) b y a strengthening of acidic properties of a part of
bridged OH groups. However, hydroxyl groups exhibiting acidic
properties stronger than OH groups of t h e initial zeolite have not
been detected (refs. 1-3). In the present work the nature and
properties of Bronsted and Lewis acidic sites in HZSM-5 zeolites
deal urn1 nated under mi 1 d o r severe hydrothermal condi ti o n s are
studied by the highly sensitive method of diffuse reflectance IR
spectroscopy. Different probe molecules ( H2 , CH4, CH3CN) a r e used
t o characterize the Lewis acidic sites.

EXPERIMENTAL
The H Z S I I - 5 zeolite (Si/A1=18) was treated with water vapour
under mild (T = 810 K , pHz0 = 1.3*104 Pa,t = 10-150 min) or severe
426

5
conditions (T = 770 K, pH = 10 Pa, t = 1.5 - 24 h). Before
2
spectroscopic or catalytic measurements the samples were
pretreated at 690 - 770 K for 4 h in vacuum or in He stream.
Diffuse reflectance IR spectra were measured using Perkin Elmer
580 B and Beckman Acta M V I I spectrophotometers according to the
procedure described by Kazansky et al. (ref. 4). Transmission
measurements were carried out on an IR spectrometer SPECORD M80
(Carl-Zeiss-Jena GmbH). For identification of Lewis acid sites t h e
low temperature adsorption of molecular hydrogen (ref. 4) a s well
a s the adsorption o f methane (re+. 5 ) and acetonitrile (ref. 6 ) at
300 K were used. The catalytic data were obtained using a flow
reactor with on-line GC-analysis of t h e products. Mixtures of
n-hexane and I-hexene were used as feeds with olefin
concentrations varying from to 10 vol %. The reaction
temperature ranged from 670 t o 770 K.

RESULTS AND DISCUSSION

In accordance with t h e data obtained by Lago et al. (ref.1) t h e
catalytic activity of the samples under investigation in n-hexane
cracking is strongly depending on t h e steaming conditions, i.e. on
t h e time of steam treatment.

kt'ko I
*i

0 40 80 120 160 1440

tlmln

Fig. 1. The dependence of t h e kt/kO ratio on t h e time of steaming

pretreatment of HZSM-5: 1-cracking of pure n-hexane, 2-cracking of
t h e mixture containing 99% of n-hexane and 1X of 1-hexene.
 427

Fig.1 shows t h e ratio kt/ko characterizing the enhancement of

the cracking activity of t h e zeolites dealuminated for t minutes
a s cornpared with t h e initial sample, as a function of t h e t i m e of
steaming. It follows from these data that at the initial stages of
mild dealumination t h e catalytic activity increase6:at t = 40 min
it is almost 7 times higher than that of the starting material.
Further dealumination leads to a progressive decline of the
activity. A prolonged hydrothermal treatment in severe conditions
(t = 24 h) results in a decrease of t h e activity a s compared with
t h e initial sample. On t h e other hand, the product distribution
a s well a s the values of the apparent activation energy of
50 kJ/mol are practically the same for t h e initial zeolite and for
the samples dealuminated under mild steaming conditions For
strongly dealuminated zeolites this energy is 67 kJ/mol.

361 0
3665 I

3610
I

3700 3600
-3/cm-1
3500 3700
-3600 3500
3 / c m -1

Fig. 2. Diffuse reflectance IR spectra of OH groups of HZSM-5

zeolites measured before ( 1 ) and after stearning under mild
conditions: ( 2 ) t = 20 min, (3) t = 150 rnin and severe conditions:
(4) t = 1.5 t i , (5) t = 24 h.

In order t o explain the catalytic data the active sites in

hydrothermally dealuminated HZSM-5 were studied by diffuse
428

r e f l e c t a n c e I R spectroscopy. I n Fig.2 t h e I R s p e c t r a o f OH groups

i n t h e o r i g i n a l and dealuminated z e o l i t e s a r e presented. In the
spectrum o f t h e unsteamed sample two narrow bands w i t h maxima at
3610 and 3740 cm-l belonging t o t h e s t r e t c h i n g v i b r a t i o n s of the
a c i d i c bridged h y d r o x y l s and t e r m i n a l S i O H groups are observed.
Short steaming ( t < 30 m i n ) under m i l d conditions results in a
decrease o f t h e band i n t e n s i t y o f a c i d i c h y d r o x y l s as w e l l as in
t h e appearance o f two new bands a t 3780 and 3665 cm-'. After 150
min of steaming t h e i n t e n s i t y o f t h e band a t 3780 cm-l starts to
d i m i n i s h and t h a t o f t h e band a t 3665 cm-' continues t o increase.
Fig.2 shows dl50 t h e I R s p e c t r a of OH groups i n hydrothermally
dealuminated samples treated under severe conditions. The
i n t e n s i t y CC t h e band a t 3610 cm-l s t r o n g l y decreases and t h a t of
t h e band a t 3665 cm-l increases as compared with the other
samples.
The above data show t h a t i n HZSM-5 z e o l i t e s t r e a t e d i n stearning
conditions there are d i f f e r e n t kinds o f OH groups. The band at
3780 cm-l appears a f t e r a s h o r t t i m e o f hydrother.!nal pretreatment ,
i.e. a t t h e i n i t i a l stages of dealurnination. Its imiensity first
increases and then decreases w i t h steaming timeas well as after
e x t r a c t i o n o f non-framework A1 ( r e f . 7 ) . These OH groups are able
only t o a weak i n t e r a c t i o n w i t h benzene molecules and hence their
a c i d i c p r o p e r t i e s a r e n e a r l y t h e same as those o f s i l a n o l s . On t h e
bases o f L:hec-e data t h e band a t 3780 cn-l may be assigned to
t e r m i n a l d l O F ! groups probably i n O=Al-OH species ( r e f .7).
U n l i k e t h e band a t 3780 cm-l t h e I n t e n s i t y od t h e narrow band
a t 3665 g r a d u a l l y increases witn incressiog time of mild
dealumination and i s n o t i n f l u e n c e d bv t h e a c j d leaching (ref.7).
These OH groups exhibit relatively stronq acidic properties
comparable tr. those of bridged hydrox!/le in zeolite X. In our
o p i n i o n t h i s band corresponds t o the Ft-otoi:rj Eompensating A104
t e t r a h e d r b where t h e aluminium atom is s t i l l connected with the
z e o l i t e framework by csne or two remaining chsmical bonds ( r e f . 7 ) .
The a c i d i t y o f t h e OH groups formed a f t e r steaming ranges from
that of s i l a n o l s t o that of bridged OH groups. No superacid
Bronsted G i t o s stronger than the bridged OH groups of HZSM-5
z e o l i t e were found. Therefore, t h e e f f r c t of the enhancement of
t h e c a t a l y t i c a c t i v i t y o f HZSM-5 z e o l i t e a f t e r stearning c o u l d not
be explainer! b.; a eariation of the Bronstod acidity and
p a r t i c u l a r l y by an enhancement o f t h e s t r e n g t h o f OH groups. Thus
we may suppose t h a t t h e observed c a t a l y t i c e f f e c t s a r e caused by a
 429

change of Lewis acidity of zeolites after mild steaming.

For the investigation of Lewis acid sites in t h e zeolites under
study CH3CN, H2 or CH4 molecules were used a s probes.

2 308
I

\
-
2400

-
2300 2200

31cm-1
Fig. 3. Transmission IR spectra of
CH3CN adsorbed on t h e fresh HZSM-5
zeolite (1) and on zeolites steamed
under mild conditions: (2) t = 10 min
and (3) t = 150 min.

Fig.3 shows t h e transmission IR spectra of adsorbed CH3CN in

the region of CN stretching vibrations. The band at 2280 cm-' is
due t o CH3CN molecules interacting with OH groups (ref. 8 ) whereas
the band at 2330 cm-l is caused by CH3CN molecules interacting
with Lewis acid sites (ref. 6). In the untreated sample Lewis
sites are not detected, but they are created already after 10 min
under mild steaming conditions.
In IR spectra of H2 adsorbed on t h e steamed zeolites (fig.4~1)
bands at 4110 and 4135 cm-l are observed which are assigned to
complexes with t h e bridged O H groups and silanols, respectively.
The low intensive line at 4070 cm-' according t o our previous data
(ref-4) corresponds t o H2 complexes with Lewis sites containing
non-framework aluminium.
In fig.4b IR spectra of CHq adsorbed on the initial and
steamed zeolites are shown. The bands at 3010 cm-' and 2895 cm-'
are attributed t o physically adsorbed CH4 (ref- 5 ) . An additional
line at 2860 cm-' appears in the spectra of stearned zeolites
430

previously assigned t o methane polarized by Lewis acid sites

connected with t h e non-framework aluminium. T h e intensities

3010
3080 I
&110
I
hOB0 4035

4150 4100 4050 4000 3100 3000 2900 2800

- d

Slcrn-1 ---v/cm
-, -1

Fig. 4. Diffuse reflectance IR spectra of Hz (a) and CH4 (b)

adsorbed on t h e fresh HZSM-5 zeolite ( 1 ) and on zeolites steamed
under mild conditions: (2) t=ZO min and (3) t i 6 0 min.

of both of these lines and of t h e band at 4070 cm-l in t h e spectra

o+ adsorbed Hz rapidly increase at t h e initial stages of stearning
and saturate after some time.
Thus ,a hydrothermal treatment o f HZSM-5 zeolite leads t o the
formation of Lewis acidic sites capable to polarize paraffin
molecules. We assume that they are responsible for the
enhancement of the catalytic activity of HZSM-5 zeolite in
n-hexane cracking and probably participate in the stage of
initiation occurring via alkane dehydrogenation.
The formation of Carbenium ions is considered in t h e literature
a s t h e rate controlled step in alkane cracking. Olefins a r e known
t o b e much more reactive in cracking than paraffins and may be
protonated easier than alkanes. Then oleiin addition to the
reactant should lead to an increase of t h e cracking activity of
t h e non-steamed sample and should have n o significant influence on
t h e activity of mildly steamed zeolites.
In fig.1 the ratio kt/ko is plotted versus the time of
 431

steaming. This dependence was obtained f o r c r a c k i n g b o t h of pure

n-hexane (curve 1) and of the mixture of n-hexane (99x) and
1-hexene ( 1 % ) (curve 2 ) . I n t h e case o f pure n-hexane one could
observe a sharp maximum at k /k =7. For t h e cracking of the
t o
m i x t u r e t h e character of t h i s dependence becomes smoothed as
compared w i t h pure hexane.

'10 o f C6H12

Fig. 5. T h e dependence of t h e r a c k i n g r a t e constant k from t h e

concentration o f 1-hexene i n t h e feed: (1) the i n i t i a l HZSM-5
z e o l i t e , ( 2 ) t h e HZSM-5 z e o l i t e treated under m i l d steaming
c o n d i t i o n f o r 30 min.

I n fig.5 t h e r e l a t i o n s h i p between t h e cracking rate constant

and t h e o l e f i n concentration i n t h e r e a c t i o n m i x t u r e i s presented
f o r t h e i n i t i a l HZSM-5 z e o l i t e s and f o r the sample steamed for
30 min. The presence of 1-hexene in concentrations lower than
lo-'% practically does not influence the activity of both
zeolites. However a t concentrations o f 1-hexene ranging from 0.1
t o 10% t h e a c t i v i t y o f t h e f r e s h z e o l i t e shows a maximum a t about
1%o f I-hexene added whereas t h e a c t i v i t y o f t h e steamed zeolite
g r a d u a l l y decreases. I n our o p i n i o n t h i s seems t o result from a
competition betneen a c c e l e r a t i o n of the formation of carbenium
ions formation due to addition of the reactive olefin and
i n h i b i t i o n o f cracking a t aconsiderable concentration of 1-hexene
because of blocking of a c t i v e sites.
I t was e s t a b l i s h e d t h a t i n t h e case o f pure n-hexane cracking
432

t h e H /C ratio in t h e reaction products on stearned zeolites is

2 3
about 1.5 times higher a s compared with t h e initial HZSM-5. In t h e
presence of 0.5-2.5% of 1-hexene t h e H2Z/C3 ratio becomes almost
equal for both samples. It is known that hydrogen may b e formed a s
a product of different reactions such as coke formation,
dehydrocyclization, etc. Nevertheless, in our opinion the
discussed difference in H2 yields for the fresh and steamed
zeolites is connected with t h e production of H2 at the stage of
initiation of cracking because there are no changes in
distribution of other products and in deactivation rates for the
investigated samples. Moreover, in accordance with (ref.2) the
coke formation decreases for HZSM-5 zeolites steamed in mild
hydrothermal conditions.

CONCLUSION
Depending on t h e conditions of hydrothermal treatment different
acid sites appear in HZSM-5 zeolites due to the formation of
non-framework aluminium. Most of these species are hydroxylated
fragments with acidic properties weaker than those of bridged
OH-groups. Only a small part of non-framework A1 exhibits the
properties of Lewis acid sites.
In our opinion Lewis acidic sites connected with non-framework
aluminium which are capable to polarize C-H-bond in alkane
molecules a r e t h e active s i t e s responsible for t h e acceleration of
t h e initial stage of cracking via alkane dehydrogenation or
demethanation. The optimum in t h e cracking activity observed for
HZSM-5 zeolites dealuminated under mild steaming conditions could
b e interpreted in terms of t w o competitive tendencies:
i ) acceleration of t h e rate-determining step of initiation due
t o an increasing concentration of non-framework Lewis acid sites
and
i i ) inhibition o f cracking via the disappearance of Bronsted
acid sites during steaming pretreatment which a r e also involved
into t h e reaction. In our opinion these s i t e s take part in the
cracking process a s centres responsible for t h e transformation of
formed olefinr via t h e classical carbenium ion mechanism.
T h u s t h e former trend results in an increase of activity at t h e
very beginning of dealumination whereas t h e latter trend which is
well-pronounced at t h e middle o r final stages of steaming leads t o
a loss of activity. Therefore, t h e highest catalytic activity and
t h e best cracking performance of HZSM-5 zeolites could be reached
 433

via optimization of the ratio between Lewis and Bronsted acidity.

REFERENCES
1 R.M. Lago, W. 0.Haag, R. J. Mi kovsky, D. H. Olson, S. D. He1 Iring,
K.D.Schmitt, G.T.Kerr, Proc. 7th Int. Conf. on Zeolites,
1986, Tokyo , p.677.
E. Brunner, H.Ernst, D.Freude, T.Froh1 ich, M. Hunger, H. Pf eif er,
Stud. Surf. Sci. Catal., 1989 , v.49 , part CI ,p.623.
V.L. Zholobenko, L. M. Kustov, V. B. Kazansky, E. Loef f ler, U.
Lohse, Ch. Peuker, G. Oehlmann, Zeolites, 10 (1990) 304-306.
V.B.Kazansky, V.Yu.Borovkov, L.M.Kustov, Proc. 8th Int. Congr.
on Catalysis , West Berlin , 1984 , v.3 , p.3.
V.L.Zholobenko, L.M.Kustov, V.B.Kazansky, Dokl. CIN SSSR, 300
( 1988), 384-388.
E. A.Paukshtis, R. J. Sol tanov, E. N. Yurchenko, React. Ki net.
Catal. Lett., 23 (1983) 339-342.
E.Loeffler, U.Lohse, Ch.Peuker, G.Oehlmann, L.M.Kustov,
V.L.Zholobenko, V.B.Kazansky, Zeolites, 10 (1990) 266 - 271
H-Kriegsmann, A-Reklat, E.Loffler, Th.Steiger, Z. phys. Chemie,
Leipzig, 271 (1990) 61-67
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 435
0 1991 Elsevier Science PublishersB.V., Amsterdam

COMPUTER MODELLING OF P-XYLENE SORPTION IN ZSM-5/SILICALITE-l

K.-P. SCHRBDER
Central Institute of Physical Chemistry, Academy of Sciences of the GDR,
DDR-1199 Berlin-Adlersliof (GDR)

ABSTRACT
The method of molecular mechanics is used to model pxylene sorption in
ZSM-5/silicalite-l on the basis of empirical atom-atom potentials. The
experimental atomic coordinates of both monoclinic and highly gxylene-loaded
orthorhombic ZSM-5 were taken into account. Considerable differences with
respect to the sorption properties were found. It is concluded that the
framework structure is locally changing already at very small amounts of sorbed
yxylene. There exist two types of pxylene molecules at maximal loading. The
XYLl molecule is highly mobile with respect to diffusion along the straight
channel, whereas the mobility of the XYLZ molecule in the sinusoidal channel is
significantly more restricted.

INTRODUCTION
The three-dimensional pore system of the silicon-rich zeolite ZSM-5 consists
of straight channels parallel to [ O l O l interconnected by sinusoidal channels in
[loo] direction, both built of ten-membered rings. The pore diameters are of a
size similar to the kinetic diameters of aromatic molecules such as benzene and
xylene. Thus the mobility of aromatic molecules in ZSM-5 is restricted (refs.
1-41 and a complicated dependence of the differential heats of sorption on pore
filling is observed (refs. 5-8).
One of the most interesting features of ISM-5 is its reversible
transformation between monoclinic and orthorhombic crystal structures.
As-synthesized ZSM-5 including template is orthorhombic with Pnma space group
(ref. 9). H-ZSM-5 and its aluminium-free form silicalite-1 are monoclinic. A
transformation to orthorhombic symmetry occurs on increasing the temperature up
to 320 - 360 K (refs. 10-13) or on loading with various molecules (refs.
9,14,15) including aromatics.
This change of crystal structure has been neglected in previous computer
modelling studies (refs. 8,16-23) of sorption and diffusion of aromatic
molecules in ZSM-5/silicalite-l, which assumed rigid frameworks.
A theoretical study of the packing arrangement of pxylene in a ZSM-5 type
framework has been performed by Reischman et al. (ref. 2 0 ) . The atomic
coordinates of Olson et al. (ref. 2 4 ) with Pnma space group were used. On the
basis of an empirical atom-atom potential due to Williams and Starr (ref. 25)
the interaction energies of a pxylene molecule with the framework in the
436

different regions of the pore system were calculated. A significant energetic

preference for the channel intersection was found. Eor a full occupation of all
intersections by one molecule an adsorption energy of -82 kJ.mo1-I was
calculated. The energies due to occupation of the straight and the sinusoidal
channels were - 4 8 and -30 kJ.mol-', respectively. Packing arrangements for high
pxylene loading (eight molecules per unit cell) were also considered. An
occupation of each intersection and each segment of the sinusoidal channel both
by one molecule is most favoured. The average interaction energy per molecule is
-57 kJ.mol-I. This means a decrease of the adsorption energy with increasing
amount of sorbed pxylene which is not observed (refs. 8,26,27). It seenis that
the interaction energy is underestimated for the channel segments. This leads
also to values for the activation energy of diffusjon of more than 50 kJ.rno1-l
(ref. 28) in contrast to the value of about 25 kJ.mol-I suggested by sorption
uptake measurement (ref. 3 ) .
Therefore, the empirical atom-atom potential of Kiselev et al. (ref. 29) was
adopted in a recent study (ref. 22) of benzene and gxvlene sorption in
ZSM-5/silicalite-l. The atomic coordinates of Olson et al. (ref. 2 4 ) were used
again. The framework structure was assumed as rigid, but the methvl groups of
pxylene were considered as free rotors. This decreases the interaction energy
by 1 - - 3 kJ.mol-I. Only a single molecule was used as a probe, no sorbate-sorbate
interaction was taken into account. The adsorption energies for optimized
structures were -82.6 kJ.mol-' in the straight channel, -79.3 kJ.mol-I in the
sinusoidal channel, and -81.9 kJ.mol-' in the channel intersection.
Very recently detailed crystal structures of monoclinic (MONO) and hiqhly
pxylene-loaded orthorhombic HZSM-5 (PARA) have become available from single
crystal XRD analyses (ref. 3 0 , 3 1 ) . The present study is the first attcnipt to
model the sorption of aromatics in ZSM-5/silicalite-l considering different
framework structure. Packing arrangements for low and high coverages of p-sylene
are studied.

CALCIJLATIONS
Stable sorbate structures correspond to minima of the potential energy
surface for the interaction between the zeolite framework and sorbed molecules.
The interaction energy is represented in this study by a pairwise additive
atos-atom potential function. The energy for the sorbent-sorbate interaction is
calculated using a Lennard-Jones type potential,

AE = r (-A
at?
r -.6. + Bap r -12
I J
, ,) ,
I J
i j

and that for the interaction between pxylene molecules using a Buckingham type
potential,
 437

The index i runs over all atoms in the framework cut-out, indices j and k over
all atoms in different pxylene molecules, r . is the interatomic distance. The
11
empirical parameters AaS, BaB and C characterizing the interaction between
aB
atoms of the type a and p are taken from Kiselev et al. (ref. 29) for the
Lennard-Jones type potential and from Williams and Starr (ref. 25) for the
Buckingham type potential (see Table 1). The minimization was performed by the
PENOPT-2 program (ref. 32) using a quasi-Newton method. Energy gradients were
calculated analytically.
The following restrictions and approximations were made:
(i) 'The geometries of the framework (MONO and PARA) and of the pxylene
molecules are fixed and not affected by sorption. Only the methyl groups of
pxylene are permitted to rotate freely.
(ii) No electrostatic interaction is taken into account. The pairwise summation
is performed only over the oxygen atoms of the framework, not over silicon or
aluminium sites. No cations or protons are considered, so that the interaction
with silicalite-1 rather than ZSM--5 is studied.
(iii) The zeolite framework is represented by a cut-out of the size 1.5a x 1 . 5 b
x 212, where a, b and c are the unit cell parameters. In the high-coverage
calculations the interaction of the two pxylene molecules with 16 pairs in the
neighbourhood was considered.
As previously demonstrated (refs. 8 , 2 1 , 2 2 ) the occupation of sorption sites

'TABLE 1
Potential parameters

sorbent - sorbate (ref. 29)

A B
(kJ ..k6 .mol (kJ * A" .tool-
0 - H 5.3781 .lo2 1.5028 .lo5
2.1623~10~ 1.4478.106
1.7041 .lo3 1.1410*106

sorbate - sorbate (ref. 25)

c-c 3.6725 . l o 5 3.60 2414

C - H 6.5485.10' 3.67 573
H - H 1.1677 -10' 3.14 136
438

is sensitive t o temperature changes. A simple model is adopted to take

temperature etfects into consideration. The sorbate complexes are treated
analogously to gas phase complexes within the rigid rotor, harmonic oscillator,
and ideal gas approximation (ref. 21.33). The over-all thermodynamic functions
are obtained as weighted sums of the contributions from the individual
preferential sorption sites (ref. 22). The knowledge of the frequencies of
intermolecular vibrations (librations and hindered translations) and of
low-frequency torsional motions of the methyl groups is prerequisite, but all
other intramolecular modes are not expected to contribute. The frequencies are
computed by a recently developed efficient method (ref. 34).

RESULTS AND DISCUSSION

Low-coverage sorbate structures
The MONO and PARA frameworks were probed by a single p-xylene molecule. This
actually corresponds to zero loading. For the MONO structure ten sites for the
sorption of psylene with an interaction energy lower than -80 kJ.mol-1 were
detected. Five of them with energies between -80.6 and -83.2 kJ.mol-I are
located at the channel intersection. The energetically most favoured sorption
site (-86.7 kJ.rnol-I) was found in the straight channel in the mid between two
intersections. In the sinusoidal channel an adsorption energy of -85.5 kJ.mol-'
is reached. Under the common assumption, that the framework was not deformed at
low loadings, the first pxylene molecule would be sorbed in the straight
channel at temperatures below 100 ti. Above this temperature the position at the
channel intersection would be thermodynamically more favoured since the mobility
of the pxylene molecule is larger at the intersection than in the narrow pores.
The sorption heat at 300 K , calculated taking the average over all ten sorption
sites, is -74.5 kJ.mol-I.
The shape of the pores changes significantly, when the MONO structure of
ZSM-5/silicalite-l is transformed into the PARA structure. The limiting ports of
the straight channel 10-rings become from 5.78 A x 5.18 A and 5.83 A x 5.27 A to
6.06 -4 x 5.07 .4 and 6.18 .4 x 4.80 .4 (ref.30). Similar changes are reported for
the sinusoidal channel (ref. 30). The effect of these structural changes on the
energy of pxylene sorption is remarkable. The interaction energy clearly
decreases in all regions of the pore system compared to the MONO structure (see
'Table 2 ) . The energy is particularly lowered for the sorption sites in the
sinusoidal channel. At 300 ti the calculated over-all sorption heat of a single
psylene molecule in a PARA structure amounts to 90.7 kJamol-'. Thus the
difference to the value f o r MONO is about 16 kJ.mol-l. Comparing this with the
enthalpy change of 3.7*0.5 kJ.mo1-l connected with the temperature-induced
transformation from the monoclinic t o the orthorhombic structure of ZSM-5 as
found by differential scanning calorimetry (ref. 1 2 ) it is concluded that the
 439

TABLE 3
Interaction energy (kJ.mo1-I) of a single pxylene molecule with the rigid
framework at different sorption sites

MONO PARA
channel intersection -83.2 -86.6
straight channel -86.7 -91.8
sinusoidal channel -85.2 -98.5

assumption of framework rigidity at low loadings of pxylene is not valid. The

pxylene molecule is able t o induce a local change of the framework structure.
29
This result is consistent with those from XRD (refs. 35,361 and Si MAS NMR
spectroscopic experiments (ref. 37), which show, that already a small amount of
sorbed pxylene changes the structure and symmetry of the ZSM-5/silicalite-l
framework.

High-coveraqe sorbate structure

The pxylene sorption capacity of ZSM-5/silicalite-l was reported to be near
8 mol./u.c. (ref. 27) at room temperature. This corresponds to a loading of two
molecules per intersection. Since the straight channel segment and the channel
intersection cannot be occupied simultaneously, it is concluded, that one
molecule (XYL2) is located in the sinusoidal channel. In order to search for the
preferential site of the second molecule (XYL1) the energy profile along the
straight channel was calculated f o r a dense packing of 8 mol./u.c. (see Fig. 1).
Periodic boundary conditions were used. The XYLl molecule was shifted in [OlO]
direction through the straight channel passing the intersection with the
sinusoidal one. The y coordinate of the centre of the molecule was fixed after

-90-
b a c
0
0 0
0 0
-100- 0 0 0 O 0 0 0
0 0
oooooo 0 0 0
0 0
0 0 0 ooooo
I I I I I I I I I I I

Fig.1. Energy profile (see text) along the straight channel ([OlO]) at high
loading (8 mol./u.c.) beginning at the mid of the channel intersection (y/b =
0.25), minimum a: XYLla, b: XYLlb, c: XYLlc
440

Fig.?. Energy profile (see text) along the sinusoidal channel ([loo]) at high
loading ( 8 mol./u.c.) beginning at the intersection with the straight channel
(x/a = 0.5). XYLl on site XYLla ( 4 , XYLlb ( 0 ) or XYLlc (+)

steps of 0 . 3 A and the remaining 15 coordinates corresponding to the locations

and orientations of both molecules and their rotable methyl groups were fully
optimized. It is surprising, how flat the energy profile is (see Fig. 1). Thus a
hiqh diffusional mobility of the XYLl molecule can be expected. In contrast, the
energy profile for shifting the pxylene molecule through the sinusoidal channel
(Fig. 2) shows, that the diffusion of the XYL2 molecule is much more hindered.
The authors of a deuterium solid-state NMR study (ref. 4 ) reached the same
conclusion.
While there is one clearly preferred sorption site in the sinusoidal channel
there are several minima of about the same interaction energy corresponding t o
favourable sorption sites in the straight channel. An analysis of the
vibrational frequencies shows, that the sites XYLla and XYLlb are not only
energetically but also entropically favoured over the others.It is, however, not
possible to decide on the basis of our calculations, which of the two sites is
preferred. It seems that both are occupied to some extent, what may be the
reason, why the theoretical sorption capacity of 8 mol./u.c. is not reached in
practice. In both possible packing arrangements the sorbate-sorbate interaction
plays an important role in stabilizing the structure. Neither XYLla nor XYLlb
(see Fig. 3 , Table 3 ) represents the global framework-sorbate interaction energy
minimum inside the straight channel, The atomic coordinates of the XYLla
 44 1

4- +-h
-0-

b -0-

Fig.). High-coverage packing arrangements XYLa (left) and XYLb (right); top:
view down [OlO]; bottom: view down [OOl]; for purposes of clarity hydrogen atoms
(and at the bottom also zeolite atoms) were left out

molecule are almost identical to those reported by van Ronigsveld et al.

(ref. 31) on the basis of their XRD study. Similar packing arrangements were
suggested by Mentzen (ref. 3 8 ) and Reischmnn et al. (ref. 2 0 ) .

CONCLUSIONS
'The transformation of the ZSM-5/silicalite-l framework induced by pxylene
sorption provides a considerable gain of sorption heat. A single pxylene
molecule should be able to effect in its neighbourhood a local structural change
from the monoclinic t o an orthorhombic space group. At high coverage the
sinusoidal channels are fully occupied. Inside the straight channels the
p-xylene molecules are highly mobile with respect to translation in the channel
direction. At least two distinct sites may be occupied. One of them coincides
with experimental findings.
442

TABLE 3
Fractional coordinates ( ) ( l o 4 ) of pxylene molecules for the two high-coverage
packing arrangements XYLa and XYLb

XYLla XYLlb

atom X Y Z X Y 2

c1 5268 3296 -208 5155 1739 105

C2 4801 3164 540 4716 1547 862
c3 4663 2497 816 4520 872 951
c4 4992 1963 345 4763 389 284
c5 5459 2095 -403 5203 581 -472
C6 5597 2762 -679 5399 1256 -561
c7 5416 4015 -505 5366 2467 8
C8 4843 1244 642 4552 -339 381
H2 4547 3576 903 4528 1920 1376
H3 4303 2395 1392 4181 124 1535
H5 5713 1683 -766 5391 208 -986
H6 5957 2864 -1255 5738 1404 .1145
H7a 5015 4206 -971 5405 2600 -777
H7b 5882 4031 -920 5848 2537 367
H7c 5460 4321 160 4999 2791 366
H8a 4477 1242 1240 4284 -408 1079
H8b 5298 1002 899 4990 -662 373
H8c 4648 970 3 4229 -~472 -239

XYL2a XYL2b
~-
atom X Y 2 X Y 2

c1 1659 2429 -1164 I754 2428 -1161

c2 1872 2828 -1962 1967 2820 -1967
c3 2552 2925 -2130 2647 2913 -2140
c4 3019 2623 -1500 3114 2614 -1507
c5 2806 2223 -702 2902 2221 -701
C6 2126 2126 -534 2222 2128 -529
c7 926 2324 -982 1021 2327 -975
C8 3752 2727 -1682 3848 2714 -1693
H2 1511 3062 -2447 1606 3051 -2455
H3 2716 3233 -2745 2811 3216 -2761
H5 3167 1990 216 3262 1990 -213
H6 1962 1818 82 1058 1825 93
H7a 662 7798 -1101 758 2800 1106
H7b 848 2156 -219 944 2168 -207
H7c 737 1944 -1495 830 1941 -1471
H8a 3934 3132 -1204 4060 3016 -1095
H8b 3833 2862 -2459 3918 2974 -2401
H8c 4020 2263 -1513 4095 2225 -1718

ACKNOWLEDGEMENT
Part of this work was done during a stay at the Institute of Inorganic
Chemistry of the Slovak Academy of Sciences at Bratislava. The author thanks dr.
J . Noga for hospitality. Thanks are a l s o directed t o dr. J. Sauer (Berlin) for
numerous helpful discussions.
 443

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G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 445
0 1991 Elsevier Science Publishers B.V., Amsterdam

MICRODYNAMICS O F GUEST MOLECULES IN ZEOLITES STUDIED BY OUASI-

ELASTIC NEUTRON SCATTERING AND NMR PULSED FIELD GRCIDIENT TECHNIQUE

Her& Jobicl, Marc B&e 2, Jiirgen Caro3 , Martin Bulow 3 ,

Jorg k'Brger4 and Harry Pfeifer4

'Institut de Recherche5 sur la Catalyse, 2 avenue CI. Einstein,

69626 Villeurbanne, France.
'Laboratoire d e SpectromGtrie Physique, Universite Joseph
Fourier, ,78402 St. Martin d'H&res, France.
3Zentralinstit~~tfiir physikal ische Chemie der AdW der DDR,
Rudower Chaussee 5, 1199 Berlin, G.D.R.
4Sektion Physik der Universitat Leipzig
Linnestr. 5, 7010 Leipzig, G.D.R.

SUMMARY
Application of the quasi-elastic neutron scattering and NMR
pulsed field gradient technique to molecular self diffusion studies
of hydrocarbons in zeolites ZSM-5 and NaX leads to coinciding
results in both the absolute values, the concentration dependence
and activation energy of the intracrystalline self-diffusion co-
efficients. Further agreement between the neutron and NMR diffusion
data is obtained by comparing the mean molecular jump lengths which
by both techniques are found to be of the order of 1.2...0.25 nm,
slightly decreasing with increasing loading. Due to the different
time scales o f the two experimental methods applied, the mean
diffusion paths followed are of different magnitude: in neutron
scattering experiments molecular translation is measured up to 6
nm; in the NMR pulsed field gradient technique the mean molecular
displacements amount to some pm. However, in both methods, long-
range self-diffusion is detected.

INTRODUCTION
The investigation of molecular migration of sorbate and reactant
molecules in zeolites of different structures has become an impor-
tant topic in both fundamental research and industrial application.
As a most spectacular result obtained about 10 years ago, the
application of the NMR pulsed field gradient technique (cf. /1-.3/)
to the study of hydrocarbon diffusion in A type zeolites gave
evidence that for a number of systems the self-diffusion coeffi-
cients determined by the up-to-date sorption uptake methods have
been erroneous by up to five orders of magnitude /4,5/. Since this
time, the clarification of the correct order of magnitude of the
translational mobility of molecules in zeolites is one of the most
controversially discussed topics in zeolite research. The analysis
of the possible reasons for this discrepancy led to a critical
reconsideration of both the sorption measuring techniques and the
models of intracrystalline molecular transport in zeolites /6-8/.
446

However, recent d i f f u s i o n data o f l i g h t hydrocarbons on Z S M - 5 also

vary over orders o f magnitude 19-141.
Besides the NMR, t h e o n l y o t h e r experimental technique that
measures molecular s e l f - d i f f u s i o n a t s o r p t i o n e q u i l i b r i u m i s quasi-
e l a s t i c neutron s c a t t e r i n g (QENS). Up t o now, l i t t l e d i f f u s i o n data
for molecules sorbed i n porous media such as z e o l i t e s /12-19/ have
been obtained by QENS. Therefore, t h e two experimental techniques
which measure self-diffusion on a microscopic scale in adsor-
bate/adsorbent systems have been applied: quasi-elastic neutron
s c a t t e r i n g (QENS) and NMH pulsed f i e l d g r a d i e n t technique (PFGT).

EXPERIMENTAL
a) Q u a s i - e l a s t i c neutron s c a t t e r i n g
The zeolite samples were heated i n a g l a s s r e a c t o r a t 720 Y
-7
under f l o w i n g oxygen and outgassed t o a f i n a l pressure o f 10 Pa
at the same temperature. I n s i d e a glovebox, the crystals were
transferred into a slab-shaped aluminium container of circular
geometry (diameter 50 mm). The mass o f the activated zeolite
amounted t o about 5 9, thus ensuring a h i g h neutrcsn transmission.
The c e l l was connected t o a gas i n l e t system a l l o w i n g t o load the
sample w i t h the hydrocarbons a t d i f f e r e n t pressures and tempera-
t u r e s d u r i n g the neutron experiment.
The neutron r e s u l t s were obtained a t the I n s t i t u t Laue-Langevin,
Grenoble, using t h e t i m e - o f - f l i g h t spectrometer IN5 w i t h incident
wavelengths o f 0.8 and 0.9 nm and e l a s t i c r e s o l u t i o n s o f ca. 25
and 1 9 peV, respectively. Because o f the l a r g e incoherent cross
section o f hydrogen, the s c a t t e r i n g from hydrocarbon molecules i s
largely incoherent. The coherent S c a t t e r i n g from the zeolite is
avoided as much as p o s s i b l e by t a k i n g s e l e c t e d groupings of the
d e t e c t o r s between t h e Bragq peaks o f t h e z e o l i t e .

b ) NMH pulsed f i e l d q r a d i e n t technique

The zeolite samples were heated i n V~CLIO up t o 670 K until a
pressure < Pa was maintained. The z e o l i t e s were loaded w i t h
hydrocarbons immediately aft.er sample activation. The sorbed
amounts of hydrocarbons were c o n t r o l l e d b o t h volumetrically and
gravimetrically. The g l a s s tubes were then sealed o f f .
The self-diffusion c o e f f i c i e n t s o f the sorbed molecules were
measured on the home-made NMR p u l s e spectrometer FEGRIS operating
a t a proton frequency o f 60 MHz a t t h e Department o f Physics o f the
Universitat Leipzig.
 441

THEORY
a) Quasi-elastic neutron scattering
The long-range translational motion of a molecule can be derived
from the broadening of the elastic peak a s a function of the momen-
tum transfer. For hydrocarbons in zeolites, only incoherent scatte-
ring has to be considered because of the large incoherent cross
section of hydrogen. The intensity scattered by the sample i s then
proportional to the incoherent scattering law Sinc(Q,o), which i s
related to the self-motion of protons (-0 and nu denote t h e neutron
momentum transfer and the neutron energy transfer, respectively).
The broadening values obtained for methane diffusing in zeolites
can be fitted to a model of a diffusion process proceeding via
molecular jumps with a Gaussian distribution of j u m p lengths / 2 0 / .
Thus, the scattering law becomes a Lorentzian,

S(Q,o) = _1_ .
&(Q)

n w2 + CaO(Q)12 '
whose half-width at half maximum (HWHM)

is determined by both the mean jump rate r ( t h e inverse of r gives

the mean time T between two succeeding jumps) and the mean-square
jump length (1 2 >.
At small 0 values, using the relationship between continuous
and jump diffusion, D = <12>/67,the HWHM becomes equal to h ( Q=)
DO2. Clt high (1 values, the half-width approaches t h e mean j u m p rate
r.
The broadening values obtained for ethane and benzene in NaX
were fitted with the jump diffusion model of Singwi and Sjolander
/21/. When the molecule spends more time in i t s oscillary state
than diffusing, the shape of the quasi-elastic peak i s still a
Lorentzian, but the HWHM i s given by

This model w a s used for ethane and benzene in NaX because the
broadening curves converged more slowly towards their asymptotic
values at high Q than for methane in NaZSM-5.

b) NMH pulsed field gradient technique

In pulsed field gradient NMR, spin echo attenuation W d u e to
diffusion in an isotropic system such a s zeolite X with a self-
diffusion coefficient D follows the relation /3/
448

with the parameters o f t h e s p i n echo experiment g, 6: and fl deno-

ting, respectively, the i n t e n s i t y , t h e w i d t h and t h e separation o f
the f i e l d g r a d i e n t pulses. Y stands f o r t h e gyromagnetic r a t i o o f
the n u c l e i under study, which a r e i n the given case t h e protons o f
the hydrocarbon molecules. The measurements a r e based on t h e n / Z -
n - echo pulse sequence.
For a n i s o t r o p i c systems l i k e d i f f u s i o n i n Z S M - J / s i l calite eq .
( 4 ) has t o be replaced /3,22/ by
+
-b 2 2-*--+
Pr(g,S,A) = exp I-Y 6 g D g ( A - 6/3)3 (5
-b
with
+
D
+
and g denoting t h e d i f f u s i o n tensor and t h e f i e l d gradient
vector, respectively, i n s t e a d o f the s c a l a r q u a n t i t i e s D and 9.
I t has been found, however, t h a t f o r methane i n ZSM-5 there i s
no significant d i f f e r e n c e between t h e values of the individual
p r i n c i p a l elements o f the d i f f u s i o n tensor /22/, so t h a t the expe-
r i m e n t a l data are c o r r e c t l y described by eq. ( 4 ) w i t h a mean s e l f -
diffusion c o e f f i c i e n t D = 1/3 (Dxx + D + D Z Z ) denoting one t h i r d
YY
o f t h e t r a c e o f t h e d i f f u s i o n tensor /3, 22/.

RESULTS
a ) Methane d i f f u s i o n i n ZSM-5
The results obtained i n the QENS f o r t h e broadening of the
elastic peak versus Q2 a t 200 K a r e shown i n F i g . 1 for different
loadings.

Fig. 1
Elastic peak broadening versus GI2
for CH i n ZSM-5 a t 2OOK for the
loadings
8 CH4 per U.C.
(A)
2, ( I4, )and (v)
I t f o l l o w 5 from Fig.1 t h a t i n the
QENS experiments the broadening of
2
the e l a s t i c peak as a f u n c t i o n o f Q
deviates from a straight line so
that a jump d i f f u s i o n model w i t h a
Gaussian distribution o f the jump
l e n g t h s has t o be considered. This
interpretation i m p l i e s t h a t molecu-
l a r jumps w i t h v a r y i n g jump lengths
may occur w i t h i n t h e channel seg-
ments a s w e l l as across the indi-
vidual channel intersections. The
s e l f - d i f f u s i o n c o e f f i c i e n t s obtained
a r e presented i n Table 1.

O oI2 0:4 ' 6.6 a

 449

These data yield an energy of activation for t h e self-diffusion

o f methane in NaZSM-5 o f the order of 4...5 kJ mol-l. The mean jump
lengths are found to be larger at small loading and high tempera-
tures /12,14/. For methane in NaZSM-5, the mean jump lengths calcu-
lated for small and high loadings at 200 K amount to 1.04 and 0.87
nm, respectively.
For the NMR PFGT experiments, Fig. 2 represents the spin echo
attenuation due to molecular self-diffusion of methane in the
NaZSM-5 at 250 K at different sorbate concentrations. In complete
agreement with the behaviour predicted by eq.(4), the plots of 1nPc
y2 92 &#2
VS. ( A - 1/3 6 ) provide straight lines, whose slopes
should coincide with the intracrystalline diffusivities. Cornparing
the slopes of the spin echo attenuations and using eq. (41, the
mean diffusion coefficients D = 1/3 ( D x x + Dyy + D Z z ) are found t o
decrease slightly with increasing sorbate concentration from 6.3 x
10-5 cmzs-l ( 4 CH4/u.c.) to 4.5 x 10-5cm2~-1 ( 1 2 CH4/u.c.). The
diffusivities thus obtained are shown in Table 1. From the Arrhe-
nius plots of the NMR self-diffusion coefficients of methane 1251,
the energy o f activation for the intracrystalline self-diffusion of
methane in NaZSM-5 amounts to (4.7 f 0.7) kJ mole-' being in good
agreement with the QENS data of Ed. In addition to the values of D
and Ed, a further agreement between P E N S and NMR PFGT i s found by
comparing the individual molecular j u m p lengths. In neutron scatte-
ring experiments /12,14/ a s well a s in a previous NMH study /25/
dealing with the microdynamics of hydrocarbons in ZSM-5 type zeo-
lites, it has been shown that the mean jump lengths of light paraf-
fins decrease from 1...1.2 nm at low sorbate concentration to a
value of 0.7...0.8 nm for high loadings.

Fig.2
Spin echo attenuations d u e
100 to intracrystalline self-
80 diffusion of CH4 in NaZSM-5
m
60 at 250 K for the loadings
c
C ( 0 ) 4 ; (.)8and ( 0 )
-=!a 12 molecules per u.c., re-
2
.-.
* spectively. For calibration,
the echo attenuations for
I *O neat water (
ammonia (A v
) ,
) and liquid
whose self-
10 diffusion coefficients taken
1 3 4 5 6 7 8 9 10
-2 $ g 2 6 * ( A - + & I / re\.units
from literature amount t o
2.3 x loF5 cm2s-' /23/ and
1.5 x cm2s-' /24/,
respectively, are included.
450

TABLE 1 Intracrystalline self-diffusion coefficient of methane

in NaZSM-5 measured by QENS and NMR PFGT

loading/ T = 200 K T = 250 I(

CH4iu. c . D ~ ~ D ~ ~ ~~ /~ D / ~ ~ D~ ~ ~ ~ /~ /

<: 1 0 ~ ~ ~ ~ . - ~ x 1o5cm2s-'
1.5 5.0
2 2.8
2.8 5.9
4 2.5 3.7 6.3
8 2.9 2.8 5.2
12 2.5 4.5

b ) Ethane self-diffusion in NaX

Fig.3 shows a comparison of experimental and calculated energy
spectra for ethane in NaX at different P values. Table 2 contains
the molecular mobility data determined by QENS.

Frg.3
Energy spectra for
ethane in NaX at
different Q values
-
3
(253 K-, 4.3 CZH6
p e r supercage) .
-.
0'

- 0 4 -02 0 02 04 06 08 hw(meV)

1 oad ing/ D/ T/ <12>1'2

CZH& Per 105cm2s-1 % 10% nm
supercage
1.3 5.4 1.36 0.66
4.3 2.5 1.48 0.47
5.8 1.5 2.22 0.44
 451

In Fig.4, the self-diffusion coefficients obtained by QENS

(cf.Tab. 2 ) are compared with the corresponding NMR PFGT data. A
complete agreement both in the absolute value and the concentration
dependence of the self-diffusion coefficient is observed. Further-
more, a very similar trend in the decrease of the mean molecular
jump lengths with increasing sorbate concentration a s shown for the
QENS results of ethane/NaX in Tab. 2 has been found in previous NMR
self-diffusion and NMH relaxation studies for propane/NaX /25/. At
135 K , the mean jump lengths were found t o decrease from 0.78 nm
(1.5 C3HB per supercage) to 0.25 nm (5.5 C3H8 per supercage) 1 2 5 1 .

I Fig .4
Comparison of the self-dif-
, fusion coefficients of
ethane in NaX at 253 K mea-
sured by QENS ( A this
study) and the NMR PFGT
,1261)-

1
(

‘“:I
.“-5!

1
,

2 3
,

4
, ,

5
n

Loading /C2H6 per supercoge

0 ,

6 7

c ) Benzene self-diffusion in NaX

Taking account of the influences of external heat and mass
transfer resistances in limiting the sorption rates, in many
instances reasonable agreement between sorption and NMR data could
be obtained /4,11,27-29/. However, there is also a number of well-
documented experimental studies showing differences of up to two
orders of magnitude /10,28/. An especially large number o f investi-
gations were concentrated on the study of benzene in zeolite NaX.
For this system, sorption uptake measurements by different research
groups revealed both agreement /13,30,31,34/ and disagreement
/10,32/ with the NMR data.
Table 3 gives a summary of the QENS self-diffusion coefficients,
mean jump lengths and correlation times at 458 K for different
sorbate concentrations. In Fig.5, these diffusivities are compared
with the results of previous NMR PFGT measurements and the results
of adsorption/desorption experiments.
452

loading/ D/ <12>1/2/ T/
6 2 -1
C6H6 per supercage x 1 0 cm s nm x 1d1s

0.8 7 0.46 5.0

1.3 4 0.35 5.1
2.0 1.9 0.24 5.0

Fig. 5
Comparison of the self-
diffusion coefficients of
N
benzene i n NaX a t 458 K
5
\
directly determined by b o t h
n the NMH PFGT ( 0 0 / 3 3 / and
10-6 /28/) and QENS ( A , / 1 3 / )
n with the corresponding d i f -
0 fusivities determined
non-equilibrium measurements
piezometric/30/;
from

+,
10.~ :e?b 'Length Column method
/32/;n,frequency response
and s i n g l e s t e p frequency
response technique /31f-.) as
w e l l as deduced from NMH
10-8 l i n e shape a n a l y s i s ./rS4/.
The r e g i o n o f the r e s u l t s o f
gravimetric measurements
with different specimens
/28/ is indicated by a
10-9 hatched area. Asterisked
0 1 2 3 1 5 symbols represent data which
Loading / C6H6 per supercoge have been obtained by e x t r a -
p o l a t i o n from lower tempera-
tures.

It appears from Fig.5 t h a t i n both the absolute values and the

trends in t h e c o n c e n t r a t i o n dependence, the neutron scattering
data, the NMR r e s u l t s and the data derived from sophisticated
uptake experiments applying t h e piezometric o r single-step fre-
quency response techniques agree. Nevertheless, disagreement w i t h
some s o r p t i o n r e s u l t s has t o be stated.
Once again, the decrease i n t h e mean jump l e n g t h s w i t h increa-
sing sorbate concentration (cf. Tab.3 i s i n agreement with the
result of previous NMR d i f f u s i o n and NMR r e l a x a t i o n studies of
hydrocarbons i n NaX / 2 5 , 2 6 / , where t h e decrease i n t h e t r a n s l a t i o -
nal m o b i l i t i e s could be shown t o be ma n l y due t o a reduction of
the mean jump l e n g t h s r a t h e r than t o i n c r e a s i n g mean residence
times between succeeding jumps.
 453

DISCUSSION
B o t h QENS and NMR PFGT, a r e methods enabling t h e investigation
o f molecular self-diffusion, i.e. t h e n e t effect o f a succession o f
consecutive elementary s t e p s o f m a s s transfer a t sorption equili-
brium. However, d u e to the different t i m e s c a l e s o f t h e t w o
methods, the mean diffusion paths followed a r e o f different magni-
tude: while in QENS, molecular translation i s measured u p t o 6 nm,
in NMR P F G T t h e mean molecular displacements may amount t o several
pm. Nevertheless, for t h e three adsorbate-adsorbent s y s t e m s under
study, the self-diffusion coefficients measured independently by
neutron scattering and NMR a r e in very good agreement.
However, in the c a s e o f the methane diffusion in ZSM-5, the
self-diffusion coefficients given in T a b l e 1 a r e by about s i x
o r d e r s of magnitude larger than t h o s e determined by gas-chromato-
graphy /35/, t w o o r d e r s of magnitude larger than t h e diffusion
coefficients determined by using a permeation method with a zeolite
membrane /36/ and by a factor o f 5 larger than diffusion coeffi-
c i e n t s measured by means of t h e frequency-response s i n g l e s t e p
analysis Ill/. Also for t h e benzene diffusion in NaX, d i f f e r e n c e s
of t w o o r d e r s of magnitude a r e still open f o r explanation / l O / -
T h e s e strong differences cannot be explained by theory. Following
the formalism o f irreversible thermodynamics, t h e diffusion coeffi-
cient determined under non-equilibrium sorption c o n d i t i o n s should
be expected t o be either equal ( i n t h e c a s e o f a linear sorption
isotherm, Henry's law) o r larger ( f o r convex shaped isotherms s u c h
a s those o f t h e Langmuir type) than t h e self-diffusion coefficient
measured at sorption equilibrium /37/. While in t h e Q E N S and NMR
P F G T experiments intrinsic intracrystalline self-diffusivities are
measured, diffusion coefficients derived from adsorption/desorption
experiments can be affected, additionally, by intercrystalline
diffusion (bed d e p t h ) influences, sorption heat release processes
and/or by transport resistances near t h e crystal s u r f a c e ( s u r f a c e
barriers).

CDNCLUSIUNS
(1) T h e joint application of Q E N S and NMR PFGT t o t h e adsorbate-
adsorbent s y s t e m s CH4/NaZSM-5. C2H6/Nal( and C6H6/NaX leads t o
coinciding results in both t h e absolute values o f t h e intra-
crystalline self-diffusion coefficients, their concentration
dependence, t h e e n e r g i e s o f activation o f self-diffusion, t h e
mean molecular j u m p lengths and t h e correlation t i m e s o f
molecular motions.
454

(ii) By both QENS and NMR PFGT, the intracrystalline self-diffu-

sion coefficient of methane in ZSM-5 was found in a tempera-
tcire region of 2 0 0 K - 2 5 0 K to be . cm s . By both
methods, the activation energy was determined to be 4...5
kJmol-l. A coinciding value o f ca. 1 nm was obtained f o r the
mean molecular jump lengths.

(iii) The self-diffusion coefficient of ethane in zeolite NaX w a s

found to decrease with increasing sorbate concentration.
Dependent on the loading, self-diffusion coefficients between
0.5...5 x 10-5cm2cm-1 at 253K were measured by both QENS and
NMR PFGT. Mean jump lengths between 0.7 nm and 0.4 nm were
found .
(iv) Also the comparison of the self-diffusion data of benzene in
NaX at 458K gave coinciding values o f 7 x and 2 x
cm2s-' at low and elevated sorbate concentrations, respec-
tively. By both techniques it was found that it is a decre-
asing mean molecular jump length rather than an increasing
mean residence time between succeeding jumps that causes this
reduction of the self-diffusion coeffitient. Whereas the cor-
relation time of the molecular motions turned out t o be 5 x
10-"s independent of the sorbate concentration, the mean
molecular jump lengths decrease from initially 0.46 nm (1
benzene per supercage) to 0.24 nm ( 2 benzene per cage).

ACKNOWLEDGEMENT
The authors thank Dr. G . J . Kearley (Grenoble) f o r his help in
performing the neutron experiments at the Institut Laue-Langevin
Grenoble and Dr. W . Heink (Leipzig) for the development of the NMR
spectrometer FEGHIS.
 455

LITERATURE
/1/ J.E. Tanner and E.O. Stejskal, J. Chem. Phys., 49 (1968) 1768.
/2/ J. Klrger and H. Pfeifer, Zeolites, 7 (1987) 90.
/ 3 / J. K a r g e r , H. Pfeifer and W. Heink, in Rdvances in Magnetic
Resonance, ed. J.S. Waugh, 12(1988) 1.
/4/ J. Karger and J. Caro,
J. Chem. Soc., Faraday Trans. I, 73 (1977) 1363.
/5/ J. Karger, H. Pfeifer and W. Heink, Proc. 6 t h Int. Conf.
Zeolites, Reno, 1983, Butherworths, 1984, p,104.
/6/ M. Bulow, J. Karger, M. KoEiFik and A. Voloscuk,
Z. Chem., 2 1 (1981) 175.
/7/ D.M. Ruthven, L.-K. Lee and H. Yucel,
AIChE J., 26 (1980) 16.
/8/ H.-J.Doelle and L. Riekert, Angew. Chem., 9 1 (1979) 309.
/9/ J. Caro, M. Biilow and J. Karger,
Chem. Engng. Sci., 40 (1985) 2169.
/10/ J. Karger and D.M. Ruthven, Zeolites, 9 (1989) 267.
/11/ N. Van-Den-Begin, L.V.C. Rees, J. Caro and M. Eiilow,
Zeolites, 9 (1989) 287.
/12/ H. Jobic, M. B6e, J. Caro, M. Bulow and J. Karger,
J. Chem. SOC, Faraday Trans. I, 85 (1989) 4201.
/13/ H. Jobic, M. Ebe, J. Karger, H. Pfeifer and J. Caro,
J. Chem. S o c . , Chem. Commun., 1990, 341.
/14/ H. Jobic, M. Bee and G.J. Kearley, Zeolites, 9 (1989) 312.
1151 H. Jobic, A. Renouprez, M. Bee and C. Poinsignon,
J. Phys. Chem, 90 (1986) 1059.
1161 H. Jobic, M. Bee and A. Renouprez,
Surface Sci., 140 (1984) 307.
/17/ E. Cohen d e Lara, R . Kahn and F . Mezei,
J. Chem Soc., Faraday Trans. I, 79 (1983) 1911.
/18/ R. Stockmeyer, Zeolites, 4 (1984) 81.
1191 C.J. Wright and C. Riekel, Molec. Phys. 36 (1978) 695.
/ 2 0 / P.C. Hall and D.K. Ross, Mol. Phys., 42 (1981) 673.
/21/ K.S. Singwi and A. Sjolander, Phys. Rev., 119 (196Q) 863.
1221 E . Zibrowius, J. Caro and J. Karger,
Z. phys. Chemie (Leipzig), 269 (1988) 1101.
1231 H. Weingartner, Z. phys. Chemie, N.F., 132 (1982) 129.
/24/ Landolt-Bornstein, Zahlenwerte und Funktionen, Vol. 5a,
Transportphanomene I, p.583, Springer Verlag Berlin, 1969.
/25/ J. Caro, M. Biilow, W. Schirmer, J. Karger, W . Heink, H.
Pfeifer and S.P. rdanov,
J. Chem. SOC., Faraday Trans. I, 81 (1985) 2541.
1261 J. Karger, H. Pfeifer, M. Rauscher and A. Walter,
J. Chem. S O C . , Faraday Trans. I, 76 (1980) 717,".
1271 M. Bulow, J. Karger, M. KoEiFik and A. M. Voloscuk,
Z. Chem., 2 1 (1981) 175.
/28/ J. Karger and D.M. Ruthven,
J. Chem. S o c . , Faraday Trans. I, 77 (1981) 1485.
/29/ N.6. Van-Den-Begin and L.V.C. Rees, in "Zeolites:Facts,
Figures, Future", eds. P.A. Jacobs and R.A. van Santen,
Elsevier, Amsterdam, 1989, p. 915.
/ S O / M. Bulow, W . Mietk, P. Struve and P. Lorenz,
J. Chem. S O C . , Faraday Trans. I, 79 (1983) 2457.
/31/ Dongmin Shen and L.V.C. Rees, unpublished results.
/32/ M. Eic, N.V. Goddard and D.M. Ruthven, Zeolites, 8 (1988) 327.
/33/ A. Germanus, J. Karger, H. Pfeifer, N.N. Samulevic" and
S.P. tdanov, Zeolites, 5 (1985) 91.
/34/ B. Boddenberg and R. Burmeister, Zeolites, 8 (1988) 488.
/35/ R.S. Chiang, A.G. Dixon and Y.H. Ma,
Chem. Engng. Sci., 39 (1984) 1461.
1361 D.T. Hayhurst and A.R. Paravar, Zeolites, 8 (19881 27.
/37/ D.M. Ruthven, Principles of Adsorption and Adsorption
Processes, Wiley-Interscience Publ., New York, 1984.
This Page Intentionally Left Blank
G.Ohlrnann et al. (Editors), Catalysis and Adsorption by Zeolites 457
1991 Elsevier Science PublishersB.V.. Amsterdam

PERMEABILITY STUDIES ON A SILICALITE SINGLE CRYSTAL MEMBRANE MODEL

E.R. Geusl, A.E. Jansen', J.C. Jansen', J. Schoonmanl, and H. van Bekkum'
Delft University of Technology, Laboratory of Applied Chemistry,
Julianalaan 136, 2628 BL Delft, The Netherlands
TNO-MT, Utrechtseweg 48, 3704 HE Zeist, The Netherlands

SUMMARY
Permeation experiments on large silicalite single crystals (MFI type),
embedded in an epoxy resin were performed, using permanent gases and small
alkanes. A scaling-up from initially a one zeolite crystal membrane to a
multi zeolite crystal membrane is presented. Differences in permeability were
small and attributed to a sorption-diffusion mechanism, in qualitative
agreement with theory. As permeation may vary within different regimes,
maximum selectivities are expected in the Henry region. Some boundary
conditions in the preparation of (ceramic) zeolite membranes are formulated.

INTRODUCTION
Zeolite membranes may open new horizons in both separation technology and
reaction engineering. At present, most gas separation membrane processes are
operated using polymer membranes. Ceramic membranes can be used at higher
temperatures, which allows regeneration and catalytic application (ref. 1).
The sol-gel technique has been used successfully in the preparation of
ceramic membranes (refs. 2-5). Alumina gas separation membranes can be
produced on a semi-industrial scale with relative ease (ref. 6). Zeolite
membranes in an all-ceramic system are expected to exhibit significantly
higher selectivities due to the zeolite's molecular sieve characteristics.
In the development and use of zeolite membranes it is essential to obtain
information on the mass transport through zeolite crystals. Recently an
extensive mathematical model for the permeation through porous crystal
membranes has been proposed by Barrer (ref. 7).
In the experimental field Hayhurst and Paravar (refs. 8 - 9 ) reported on the
determination of the diffusivity of alkanes by means of a zeolite membrane
configuration. These experiments, however, were performed on a twinned
silicalite crystal at low feed pressures. Recently this work was extended by
similar experiments on benzene passage through a silicalite single crystal
(ref. 10). Wernick and Osterhuber (refs. 11-12) reported on the permeation
through a NaX single crystal. Significantly higher feed pressures were used
in these experiments, and the permeation characteristics in time were
emphasized.
According to patent literature ceramic zeolite membranes have been prepared
by crystallizing zeolites in situ either in (ref. 13), or on (refs. 14-18) a
macroporous support. Alternatively, small zeolite crystallites together with
458

a ceramic binder are said to cover a macroporous support completely (ref,

19), or result in an unsupported film (ref. 2 0 ) . Recently Bein et al. (ref.
21) reported on the preparation of inorganic thin films, containing zeolite
crystals (type Y and chabazite).
In the above cited patent literature it is emphasized that the size of the
zeolite crystals (i.e. the membrane thickness) should be minimalized to
realize sufficiently high permeabilities. On the other hand, large zeolite
crystals are expected to be most practical in the preparation of zeolite
membranes (ref. 2 2 ) . and in the authors' opinion especially on a laboratory
scale.
In this work the permeation of permanent gases and linear alkanes through
silicalite single crystals in a membrane configuration has been subjected to
a first scaling-up. To that end several crystals were embedded into an epoxy
resin matrix on a perforated metal layer, preliminary to all-ceramic
membranes which are in preparation.
This study also intends to improve knowledge on (i) pitfalls in the
preparation of zeolite membranes, and (ii) the operation under practical
conditions (e.g. high feed pressures). In addition, unexpected behaviour of
zeolite membranes (caused by e.g. cracking of zeolite crystals or fouling)
could be diagnosed.

THEORY
Barrer (ref. 7) recently proposed a permeation model for systems obeying
Langmuir's isotherm in which activated intracrystalline diffusion takes
place. In addition external surface effects on both feed and permeate side
were included, resulting in a five step process. In this work we will focus
on the overall permeability, which is expected to be governed by a sorption-
diffusion mechanism.
A convenient way to define the permeation rate of a membrane makes use of
the permeability ( @ ) (ref. 23). which can be derived from Fick's first law of
diffusion:

in which Qmor denotes the steady state flow, A,,, the surface area of the
membrane, 1, the membrane thickness (in this work the crystal size in the b-
direction), and Ap the pressure difference over the membrane. The
permeability should be considered a phenomenological parameter of the
membrane, resulting from specific conditions (i.e. pressure, temperature,
feed composition, degree of fouling). Formula [l] will be used to calculate
the permeability from the permeation rate at steady state.
According to Barrer's model, maximum permeation will occur when the mass
transport is only governed by intracrystalline diffusion. This holds if
sorption processes on both sides of the membrane are much faster than
 459

intracrystalline diffusion:

'mo1,max Dintra,diff * %
/
'
m *
I --
in which Acmax denotes the maximum concentration difference over the
membrane. Acmax can be derived from sorption isotherms (assuming equilibrium
between gas and adsorbed phase). Dintra,diff can be obtained from NMR data,
referring to the intracrystalline self-diffusivity (Dself). The PFG NMR
technique measures DSelf directly, albeit only for rapid processes (ref. 2 4 ) .
The Darken equation enables one to calculate the intracrystalline Fickian
diffusivity (ref. 2 5 ) :

Dintra,diff = Dself *
For the Langmuir isotherm, equation [ 3 ] may be written as:

Dintra,diff = Dself * - 6') [41

in which 6' denotes the fraction of sites occupied. NMR results (ref. 2 6 ) have
shown that for small alkanes (C1-C3) DSelf decreases for increasing carbon
number, due to the diminished molecular free volume. For sufficiently high 6'.
this effect is overruled by the increase of 1/(1 - 6') (ref. 2 5 ) .
During permeation a concentration profile will exist over the zeolite
crystals, which will remain constant at steady state. As 6' varies over the
membrane, an average diffusivity can be found by integrating over the total
membrane. Finally, equation [ 2 ] is rewritten as:

@mol,max (Dintra,diff)av * m'I% * r51

When 6' is high over the whole membrane, the Fickian Dintra,diff will be
significantly higher than the NMR DSelf. Thus, the sorption equilibrium will
influence the permeability of a species, and both sorption and diffusion
should be considered in evaluating the permeability through a zeolite
membrane.

EXPERIMENTAL
Large. flat silicalite single crystals were synthesized as described by
Jansen et al. (ref. 2 7 ) . The Si/Al ratio (> 3 0 0 ) was determined by ICP
analysis on large crystals from a single batch. Selected crystals of about
equal size (a.b,c = 200*100*350 p n ) were carefully calcined at 500' C
(heating rate 1" C/min).
In a preliminary experiment one large silicalite crystal was mounted in an
epoxy resin film (bisphenol A glycidyl ether/poly amine; Araldit, Ciba-
Geigy). As this procedure was rather time consuming and complex, a more
460

practical procedure was developed.

Thin copper platelets (thickness 50 fim) were provided with up to 20 holes
(diameter 150 pm). Any remaining o i l was removed by cleaning the plate in
boiling acetone, and drying in air. The components of the epoxy resin were
homogeneously mixed and carefully spread around each hole. A silicalite
single crystal was positioned on each hole. The epoxy resin showed good
adhesion towards both the zeolite surface and the copper. The starting
viscosity of the epoxy upon mixing is very low. This resulted in an epoxy
film over the total crystal surface facing the copper plate (b-direction).
After 1-2 hours, the viscosity of the epoxy had increased strongly. The
adhesion to the zeolite material is still excellent. Therefore, the zeolite
crystals are preferably placed on the platelet at this stage of the hardening
of the epoxy resin. The epoxy resin had hardened within 24 hours completely.
Table 1 gives characteristics of the various membranes.

TABLE 1: Zeolite-epoxy-on copper composites studied in this work

Code 'N A,' (m2) 1, (m) Remarks

M1 o 1.2*10-~ l.0*10-4 epoxy resin film in a perforated

platelet
c1 1 1.68*10-' 9.0*10-5 as-synthesized single crystal,
containing Pr4N+ template
MES-21 1 3.0*10-' 1.0*10-4 initial preparation method
5ZH-1 5 4.48*10-' l.0*10-4 measurements at 30" and 120" C
LPZ- 1 10 1.36*10-7 9.0*10-' measurements at 30" C
LPZ-3a,b,c 8 1.10*10-7 9.0*10-5 sequence of measurements at 300,
130", and 30' C ; LPZ-1 after repair

')number of crystals embedded

')effective surface area, determined by light microscopy

Figure 1 shows an embedded zeolite crystal in epoxy on a copper plate. The

zeolite membranes were inspected by means of light microscopy. Figure 2
demonstrates the determination of the effective surface area of an embedded
zeolite crystal. In addition, the integrity of each embedded zeolite crystal
was checked by microscope FTIR-spectroscopy.
The experimental set-up is described elsewhere (ref. 28). Permanent gases
(H2 (99.5%), N2 (99.999%). and O2 (99.9951)). small alkanes (methane (99.5%),
ethane (99.9%), and n-butane (99.0%)), and carbon dioxide (99.7%) were used
as permeate feeds. Measurements were performed at permeation periods of 2-10
minutes. Feed pressures were within 1-2 bar. Permeate pressures always
started at approximately 2-4 Pa, and never exceeded 100 Pa, except for
hydrogen (< 250 Pa). As some inleak occurred (approximately 0.01 Pa/s)
permeation rates could not be determined at too low a pressure rise. By
embedding several silicalite crystals in one membrane the accuracy of the
measurements was increased.
 461

Fig. 1. Silicalite crystal, embedded Fig. 2 . Determination of free area

in epoxy resin (lighter area in the centre
of the zeolite crystal)

RESULTS
Some preliminary experiments were performed as to make sure that only
transport through the zeolite crystals was to take place. To double check,
experiments were carried out several times, using different membranes.
The non-permeability of the epoxy resin was checked by membrane M1. Up to
200" C no permeation could be detected, establishing that the epoxy resin
meets the requirements.
On an as-synthesized crystal (still containing the template molecules;
membrane Cl), embedded in a similar way, no permeation could be detected. The
expected permeation rate (related from measurements on LPZ-3b at similar
conditions) should have been significantly higher than the accuracy of the
apparatus. Thus, it was concluded that zeolite crystals could be embedded
properly by means of the present procedure.
Membrane MES-21 is the initial one crystal composite. For all gases very
high permeabilities were found (cf. Table 2 ) . resulting in Knudsen diffusion
selectivity. Inspection by scanning electron microscopy revealed a large
crack in the zeolite crystal. The high permeability and Knudsen selectivity
are attributed to the presence of this crack.
Permeation results on membrane LPZ-1 are listed in Table 2 as well. The
permeability for each gas seemed to increase slightly after repeated
experiments. For this reason LPZ-1 was removed from the cell for inspection.
Two out of ten crystals appeared to be cracked, and subsequently these
crystals were completely covered by fresh epoxy resin.
Permeation rates through the thus repaired membrane (LPZ-3; Figure 3) were
462

nearly two orders of magnitude lower than for LPZ-1 (cf. Table 2). This
change in permeability can not be accounted for by the loss of free surface
area, which is only 20%. It can be seen from Table 2 that no high
selectivities for the various gases were found. The permeability for n-
butane at 30" C (LPZ-3a) was higher than for other gases tested.

TABLE 2: Experimental permeabilities for permanent gases and alkanes on

zeolite-epoxy composites

Permeability (nmol .m/m2.s . Pa)

Membrane MES-21 LPZ - 1 LPZ-3a LPZ-3b LPZ-3c

T ('C) 25 30 30 130 30
AP (bar) 1-2 1.6-1.8 1.6 1.6 1.6

Gas

H2 780 0.69 0.0095 0.0234 0.0430

N2 170 0.24 0.0046 0.0058 0.0134
02 200 0.33 0.0057 0.0120
COP 170 0.20 0.0052
CH4 250 0.32 0.0037 0.0082 0.0182
'ZH6 0.37 0.0027 0.0065 0.0158
n-C4H10 120 0.42 0.0145 0.0056

Fig. 3. Membrane LPZ-3; the two

cracked crystals are
completely covered by
epoxy resin

As the temperature was raised to 130' C (LPZ-3b). permeabilities of all

gases slightly increased, except for n-butane (decrease of 70%). Again,
selectivities were found to be rather small. The measurements on LPZ-3a and
LPZ-3b were highly reproducible.
Upon cooling to 30" C (LPZ-3c) again, all permeabilities were found to be
much higher compared to LPZ-3a. In contrast to the previous experiments,
these experiments were not very reproducible. Upon inspection it was indeed
 463

found that some crystals were cracked, so the increased permeability is not
an effect of the activation at higher temperature.
During the first few experiments on LPZ-3a (at 30' C) the zeolite pores
proved to be obstructed by adsorbed vater. FTIR-spectra (Figure 4) of
calcined silicalite crystals reveal a considerable amount of adsorbed vater
under ambient conditions. As the phenomenon vanished after some experiments,
the adsorbed water is apparently induced to desorb by the permeating gas.

Fig. 4. FTIR-spectrum of embedded silicalite crystal

The above-mentioned phenomenon was also observed during experiments on

membrane 5ZH-1 at room temperature. Only few experiments were performed at
30' C, after which the temperature was raised to 90' C. The permeability
decreased at this high temperature, and finally the membrane was completely
impermeable. Inspection of the zeolite crystals by microscope FTIR-
spectroscopy revealed C-H-vibrations (Figure 5). As these vibrations do not
refer to the zeolite framevork it was concluded that some obstructing guest
molecule was stabilized within the zeolite framework at high temperature.

1.8

I . 35

0.9

0. a 5

0.e 4 I t
4000 3528 3000 z m 2000 ism iaaa
YAVENUMBERS C H - 1

Fig. 5. FTIR-spectrum of non-permeable silicalite crystal due to fouling

464

DISCUSSION
In Table 3 the calculation of the maximum flow according to equation [5] is
shown for the linear alkanes C1-C4 at 30", assuming a linear concentration
profile. Unfortunately, the required data on sorption (ref. 29) and diffusion
(ref. 26) were rather incomplete. The effect of sorption on DFickaV is only
demonstrated qualitatively.

TABLE 3: Maximum theoretical flows of linear alkanes C1-C4 for membrane LPZ-
3 , calculated from equation [ 5 ]

T = 30" C; Ap = 1.5 bar; pressure on permeate side: 100 Pa

CH4$ 3600 0.63 0.00 1.2*10-8 1.48*10-8 65.3 3.56*10-1°

C2H6 3472 0.67 0.02 7.5*10-' 5.Ol*lO-' 21.2 1.16*10-1°
0.81 0.07 6.O*lO-lo 4.14*10-' 16.0 8 . 71*10-11
0.83 0.53 5 . 0*1O-l1 6.31*10-1° 0.84 4.55*10-12

')fract .ion of sites occupied on feed (F) and permeate (P) side (equilibrium)
$ ) data extrapolated from sorption data (ref. 29). cf. text
I)data extrapolated from diffusion data (ref. 26), cf. text
The intracrystalline self-diffusivity of n-butane can not be determined by
the PFG NMR technique (ref. 30). and was estimated from data on methane,
ethane, and propane. The correlation of the intracrystalline diffusivity to
the carbon number for n-alkanes, found by Eic and Ruthven with the ZLC method
(ref. 30) was used. The sorption data on methane were estimated from sorption
isotherms of ethane, propane, and n-butane (ref. 29).
Because of lack of sufficient data, permeabilities of permanent gases (H2,
N2, and 02) and carbon dioxide were not calculated. The sorption behaviour of
nitrogen and to a lesser extent carbon dioxide has been shown (ref. 31) to
obey Henry's law up to high temperatures (70" C), and high pressures (up to 1
bar). In contrast to the alkanes, no sorption effect is expected for
permanent gases, as (aln p/aln c) remains constant.
In contrast to theory (Table 3), small differences in permeability are
measured (Table 2 ) . Permeabilities are considerably smaller (methane, ethane)
than the maximum flows, or of the same magnitude (n-butane) . This implicates
that other processes (e.g. sorption to and from the zeolite pores) than
intracrystalline diffusion govern the permeation.
Applying l o w feed pressures (up to 1.8 kPa), Hayhurst and Paravar have
found high selectivities (ref. 9). In their experiments however, permeation
occurred through the c-direction (ref. 32). resulting in a high tortuosity
factor. Permeation may therefore be hindered, especially for higher alkanes.
Negligible selectivity was also found by Wernick and Osterhuber (ref. 11)
on binary and ternary mixtures of various alkanes (NaX crystal). The reported
 465

rapid and slow permeation regime transition may be (partly) explained by the
sorption effect on intracrystalline diffusion, as high feed pressures (1 bar)
were applied (permeate pressure < 133 Pa). In the rapid permeation regime the
factor (aln p/ah c) will be high, due to high site occupation. This rapid
regime was found to be metastable for higher temperatures (65°-1000 C).
Sorption experiments by Stach et al. (ref. 33) have shown that sorption on
permeate side (13.3-133 Pa) decreases strongly in this temperature region.
From these studies it is concluded that the highest selectivities will be
realized in the Henry regime. Table 3 indicates that at equal conditions the
difference between DSelfmaX and DFickaV will be larger for higher alkanes. As
sorption is small in the Henry region, the permeation is governed by the
intrinsic diffusivity only. In order to achieve high permeabilities, the
Henry regime is favourably reached by an increase of temperature.

CONCLUSION
Large silicalite single crystals have been found to be permeable for
permanent gases and small alkanes. A scaling-up of the mass transfer was
achieved by embedding several zeolite crystals into one membrane.
Permeation through zeolite membranes may occur within different regimes.
Maximum selectivity is expected to be realized in the Henry region, in which
the intracrystalline diffusivity is hardly affected by sorption.
The application of large zeolite crystals in preparing zeolite membranes is
to be preferred from a preparative point of view. Draw-backs, however, may be
the sensitivity to high feed pressures, and relatively low permeabilities. As
zeolite membranes have to be (re)-activated, all-ceramic membrane
configurations are strongly recommended.

ACKNOWLEDGEMENT
E.R. Geus is very grateful to Prof. R.M. Barrer for a stimulating
discussion on zeolites as membranes.

REFERENCES
H.P. Hsieh, Inorganic Membrane Reactors - A Review, AIChE Symposium Series
5 , 8 5 , no. 268, (1989), 53-67;
A. Larbot, A. Julbe, C. Guizard, L . Cot, J.Membr.Sci., 93, (1989), 289-
303 ;
A. Larbot, J.P. Fabre, C. Guizard. L. Cot, J.Am.Ceram.Soc., 72, (1989),
257-61;
W.A. Zeltner, M.A. Anderson, ‘Chemical Control over Ceramic Membrane
Processing: Promises, Problems and Prospects’, in: Proc. 1st
Int.Conf.Inorg.Membr., (eds. J. Charpin, L . Cot), Montpellier, France,
July 3-6, 1989, 213-223;
A. Leenaars, Preparation, Structure and Separation Characteristics of
Ceramic Alumina Membranes, thesis, University of Twente, Netherlands,
(1984) ;
H.M. van Veen, R.A. Terpstra, J.P.B.M. Tol, H.J. Veringa, ’Three-Layer
Ceramic Alumina Membrane for High Temperature Gas Separation
Applications’, in: Proc. 1st Int.Conf.Inorg.Membr., (eds. J. Charpin, L.
Cot), Montpellier, France July 3-6, 1989, 329-335;
466

7 R.M. Barrer, J.Chem.Soc.Faraday Trans., 86(7), (1990). 1123-1130;

8 A.R. Paravar, D.T. Hayhurst, 'Direct Measurement of Diffusivity for Butane
Across a Single Large Silicalite Crystal', 6th Int.Zeol.Conf., (Eds. D.
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9 D.T. Hayhurst, A.R. Paravar, Zeolites, !3, (1988), 27-29;
10 V.V. Nesarikar, D.B. Shah, D.T. Hayhurst, poster on BZA meeting,
Chislehurst, England, July 15-20, 1990;
11 D.L. Wernick, E.J. Osterhuber, 'Diffusional Transition in Zeolite NaX: 1.
Single Crystal Gas Permeation Studies', 6th Int.Zeol.Conf., (Eds. D.
Olson, A. Bisio), Reno, USA, July 10-15, 1983, 122-130;
12 D.L. Wernick, E.J. Osterhuber, J.Membr.Sci., 22, (1985). 137-146;
13 H. Suzuki, European Patent Application 180,200, (1985) to H. Suzuki;
14 M. Oyama, Japanese Patent 63,291,809. (1988) to Idemitsu Kosan Co.Ltd.;
15 H. Suzuki, US Patent 4,699,892, (1987) to H. Suzuki;
16 I.M. Lachman, M.D. Patil, US Patent 4,800,187, (1989) to Corning Glass
Works ;
17 H. Suzuki. European Patent Application 135,069, (1986) to H. Suzuki;
18 S. Satoshi, N. Tagaya, T. Maeshima, T. Isoda, Canadian Patent 1,235,684,
(1988) to Toa Nenryo Kogyo Kabushiki Kaisha;
19 K. Miyazaki. Japanese Patent 60,129,119, (1985) to Matsushita Denki Sangyo
K.K. ;
20 G. Bellussi, F. Buonomo. A. Esposito, M. Clerici, U. Romano, European
Patent Application 265,018 (1988) to Eniricerche, Snamprogetti, Enichem
Synthesis ;
21 T. Bein, K. Brown, C.J. Brinker, 'Molecular Sieve Films from Zeolite-
Silica Microcomposites', Stud.Surf.Sci.Catal., 49, (1989). 887-896;
22 U. Muller, A. Reich, K.K. Unger, Stud.Surf.Sci.Cata1, 5 2 , (1989), 241-
251;
23 K. Kammermeyer, Gas and Vapor Separations by Means of Membranes, Progress
in Separation and Purification, Vol. 1, (Ed. E.S. Perry), Wiley, (1968).
335-372;
24 J. KBrger, D.M. Ruthven, Zeolites, 9, (1989), 267-281;
25 J. KBrger, S.P. Shdanov, A. Walter, Z.phys.Chemie, Leipzig 256, (1975).
319-329;
26 J. Caro, M. Btllow, W. Schirmer, J . KBrger, W. Heink, H. Pfeifer, S.P.
Zdanov, J.Chem.Soc.Faraday Trans., 6 l , (1985). 2541-2550;
27 J.C. Jansen, E. Biron, H. van Bekkum. Stud.Surf.Sci.Cata1.. 37 (1988).
133-141 ;
28 H.C.W.M. Buys, A. van Elven, A.E. Jansen, A.H.A. Tinnemans,
J.Appl.Pol.Sci., in press;
29 R.E. Richards, L.V.C. Rees, Langmuir, 3 , (1987). 335-340;
30 M. Eic, D.M. Ruthven, Stud.Surf.Sci.Cata1.. 49, (1989), 897-905;
31 P. Graham, A.D. Hughes, L.V.C. Rees, Gas Sep.Purif., 3 , (1989), 56-64;
32 D.T. Hayhurst, private communication;
33 H. Stach, S.P. Shdanov, K. Fiedler, W. Schirmer, N.N. Samulevic,
Z.phys.Chemie, Leipzig. &SO, (1979). 455-464.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 461
0 1991 Elsevier Science Publishers B.V., Amsterdam

THE ADSORPTIVE AND THE CATALYTIC DIFFUSION OF 2,3-DIMETHYLBUTANE I N LARGE

CRYSTALS OF (ALUMINATED) SILICALITE

P. VOOGD and H. VAN BEKKUM

Department o f A p p l i e d Chemistry and Chemical Technology, D e l f t U n i v e r s i t y o f
Technology, J u l i a n a l a a n 136, 2628 BL D e l f t (The Net herlands)

SUMMARY
The a d s o r p t i v e d i f f u s i v i t y o f 2,3-dimethylbutane (2,3-DMB) i n s i l i c a l i t e
(373-473 K) o b t a i n e d by t h e v o l u m e t r i c method has been compared w i t h t h a t
o b t a i n e d f ro m c r a c k i n g r e a c t i o n s o v e r l a r g e aluminat ed s i l i c a l i t e c r y s t a l s
(673-773 K) i n a f i x e d - b e d c o n t i n u o u s - f l o w r e a c t o r .
A n a l y s i s o f 2,3-dimethylbutane c r a c k i n g r a t e s w i t h T h i e l e ’ s model r e s u l t s i n
experiment a l r e a c t i o n e f f e c t i v e n e s s f a c t o r s which a r e c l o s e l y f o l l o w e d by
t h e o r y . The a c t i v a t i o n energy o f t h e r e a c t i o n l i m i t i n g d i f f u s i v i t y o f 2,3-
di met h y lbut a ne i n aluminated s i l i c a l i t e i s found t o be much h i g h e r t h a n t h e
a c t i v a t i o n energy o f t h e c o r r e s p o n d i n g a d s o r p t i v e d i f f u s i v i t y . T h i s phenomenon
i s shown t o be c h a r a c t e r i s t i c f o r t h e c a t a l y s t sample.

INTRODUCTION
D e s p i t e numerous i n v e s t i g a t i o n s t o d e t e r m i ne i n t r i n s i c and s e l f - d i f f u s i v i t i e s
o f adsorbates i n z e o l i t e channels and c a v i t i e s , e s t i m a t i o n s o f t hese parameters
from catalytic experiments ( a t h i g h t e m p erat ures) a r e scarce (1,Z). It i s o f
high interest to compare diffusion data determined under i n e r t c o n d i t i o n s
(adsorptive d i f f u s i v i t i e s ) w i t h t h e s e ‘ c a t a l y t i c ’ d i f f u s i v i t i e s . As i t i s n o t
p o s s i b l e t o do b o t h t y p e s o f experiments a t t h e same t emperat ure, comparison
can o n l y be made t h r o u g h t h e a c t i v a t i o n energy o f d i f f u s i o n , assuming t h a t t h e
ze ol it i c d i f f u s i v i t y i n c r e a s e s exponenti a1 l y w i t h temperature.
Zeolite ZSM-5 offers an attractive o p p o r t u n i t y t o compare c a t a l y t i c and
adsorptive d i f f u s i o n r a t e s o f hydrocarbons, f o r i t i s a h i g h l y a c t i v e c a t a l y s t
and can be synthesised i n crystals large enough f o r a d s o r p t i v e d i f f u s i o n
experiments ( 3 ) . U n f o r t u n a t e l y , d i r e c t l y s y n t hesised ZSM-5 c r y s t a l s i n v a r i a b l y
have been found c o n t a i n more aluminium a t t h e i r r i m t h a n a t t h e i r core.
to
Since such a aluminium g r a d i e n t and i t s c o n comit ant heterogeneous d i s t r i b u t i o n
in catalytically active s i t e s impedes t h e successf ul a p p l i c a t i o n o f T h i e l e ’ s
t h e o r y t o ’ c a t a l y t i c ’ d i f f u s i o n , h e r e we r e p o r t on l a r g e ZSM-5 c r y s t a l s
o b t a i n e d by a l u m i n a t i o n o f p u r e l y s i l i c e o u s ZSM-5 frameworks ( s i l i c a l i t e ) . 2,3-
Dimethylbutane i s used as probe molecule because i t ’ s k i n e t i c d i a m e t e r i s
comparable t o t h a t o f t h e ZSM-5 channels and t h u s w i l l r e n d e r e x t e r n a l h e a t and
m a s s - t r a n s f e r r e s i s t a n c e n e g l i g i b l e i n a d s o r p t i v e methods.
468

EXPERIMENTAL
D i r e c t s v n t h e s i s and c h a r a c t e r i s a t i o n o f s i l i c a l i t e and o f ZSM-5
Two batches o f l a r g e s i l i c a l i t e c r y s t a l s ( S i l l and Si12) were prepared
by an a l k a l i n e - f r e e s y n t h e s i s method o f Ghamami e t a l . ( 5 ) . A t h i r d s i l i c a l i t e
sample (Si13) was s y n t h e s i s e d a c c o r d i n g t o p a t e n t l i t e r a t u r e ( 6 ) . Elemental,
s t r u c t u r a l and a d s o r p t i v e c h a r a c t e r i s a t i o n methods as w e l l as methods t o
de t ermine c r y s t a l morphologies and c r y s t a l s i z e d i s t r i b u t i o n s have p r e v i o u s l y
been d e s c r i b e d ( 3 ) .
I n T a ble 1 a summary o f t h e samples’ c h a r a c t e r i s t i c s i s g i v e n . S i l i c a l i t e was
dealuminated w i t h H20/HC1 a t 1073 K a c c o r d i n g t o a st andard method (7), l e a d i n g
to samples S i l l d , S i l L d and S i l 3 d . X - r a y powder d i f f r a c t i o n (XRD) and i n f r a r e d
spectroscopy (IR) showed that the p a r t i a l dealumination d i d n o t a f f e c t the
crystallinity o f t h e samples. Dealuminated samples were used i n t h e a d s o r p t i v e
d i f f u s i o n experiments.

TABLE 1
C h a r a c t e r i s a t i o n o f (dealuminated) s i l i c a l i t e samples

Sample Sill Si12 Si13

Mean c r y s t a l l e n g t h ,
c - d i r e c t i o n (pm) 34.9 89.3 5&
Mean c r y s t a1 he ig ht
#
a- o r b - d i r e c t i o n (pm) 11.4, 8 . 4 39.7
S i 1 i c o n - t o - a 1 umi n i um r a t i o6 503/600* 400/ 500* 150/400*
Occurrence o f c r y s t a l
agglomerates r10 Yes Yes
n-Hexane ads. (wt%) 10.09/10.19* 10.75/10.72* 10.66/10.83*

&) As determined f r o m SEM photographs.

#) Crystal bre a d t h s ( a - a x i s ) were equal t o h e i g h t s ( b - a x i s ) , except f o r S i l l
f o r which s i z e s i n a - and b - d i r e c t i o n a r e g i v e n (a, b ) .
* ) As d et e rmined w i t h ICP-AES.
*
) As-synthesised/after dealumination.

A ZSM-5 sample was s y n t h e s i s e d (8), c a l c i n e d a t 823 K ( 1 K/min) and

r e p e a t e d l y ion-exchanged w i t h NH4C1 (1M) f o l l o w e d by a f i n a l c a l c i n a t i o n . X-ray
d i f f r a c t i o n and I R proved t h e sample t o be h i g h l y c r y s t a l l i n e ZSM-5. According
t o elemental a n a l y s i s i t s s i l i c o n - t o - a l u m i n i u m r a t i o was 86.
 469

A1 umination o f s i l i c a l it e
S i l i c a l i t e S i l l and Si12 were aluminated a t 773 K w i t h A1C13 according t o
Yamagishi e t a l . (9), followed by a repeated ammonium exchange. The aluminated
samples are denoted S i l A l l and SilA12, r e s p e c t i v e l y .
The aluminium d i s t r i b u t i o n in SilA12 c r y s t a l s was determined by Electron-
Probe Microanalysis (EPMA) .
AdsorDtive d i f f u s i o n and adsorDtion constants
The d i f f u s i v i t y o f 2,3-dimethylbutane (2,3-DMB) i n t h e s i l i c a l i t e samples was
determined i n a constant volume v a r i a b l e pressure system as described e a r l i e r
(10)-
The experimental parameters of diffusion measurements performed w i t h
Silld and S i l 2 d were: pressure = 50 - 700 Pa a t 373 K and 1000 - 10000 Pa a t
473 K; amount sorbed = 1.3*10-3 - 7*10-3 mmol/g per uptake run a t both
temperatures. Adsorption c a p a c i t i e s were 0.60 and 0.24 mmol/g a t 373 K and 473
K, respectively. I n addition 2,3-DMB adsorption isotherms were obtained on
silicalite Sil3d at
373, 473 and 523 K. Adsorption data on S i l 3 d above 673 K
were determined by gas chromatography as described e a r l i e r (3).

Catalvsis
Cracking reactions were performed in a fixed-bed continuous f l o w glass
microreactor, (3), w i t h 6% 2,3-DMB (>99 %), 6% 3-methylpentane (>99.5%) o r 2%
n-butane (>99.5 %) i n d r y helium a t 101 kPa. The products o f t h e cracking
reactions were gaschromatographical l y analysed.
Apparent first order r a t e constants, kaPP, were determined according t o
conventional equations (3).

RESULTS AND DISCUSSION

Characteri sation
Scanning e l e c t r o n microscopy (SEM) of Sill and Si12 revealed t h a t these
crystals are invariably twinned. No gel phase i s detected. The batches each
show a narrow p a r t i c l e s i z e d i s t r i b u t i o n . Sample Si12 does c o n t a i n a c e r t a i n
fraction o f agglomerates. SEM o f Si13 shows s p h e r u l i t i c c r y s t a l l i n e m a t e r i a l 5
pm i n size. The ZSM-5 sample consists o f smaller s p h e r u l i t e s (0.1-1 pm). From
the silicon-to-aluminium ratios i n Table 1 it i s clear that true Al-free
470

silicalite is n o t r e a l i s e d i n the a l k a l i n e - f r e e synthesis g e l , mainly because

of the i m p u r i t y of the s i l i c a source (Ludox AS40/Dupont, 100 ppm A l ) .

A1 uminat i o n
Alumination of Sill and Si12 has r e s u l t e d i n a s u b s t a n t i a l increase o f the
aluminium content (Table 2) whereas t h e adsorptive p r o p e r t i e s f o r n-hexane have
remained unchanged. Results of the elemental analysis reveal

TABLE 2
Characterisation o f aluminated s i l i c a l i t e samples

Sample SilAll SilA12

Si/A1 (before NHi-exchange)* 31 46

Si/A1 ( a f t e r NH; -exchange)* 70 85
n-Hexane ads. (wt%) 9.98 10.09

t h a t ammonium removes between 20 and 30 % o f t h e deposited aluminium from the

sample. This l o s s o f aluminium can be explained w i t h t h e r e a c t i o n scheme
proposed by Chang e t a l . ( l l ) , e.g. an i n s e r t i o n o f aluminium i n t o t h e z e o l i t e
framework w i t h a concomitant formation o f counter c a t i o n i c aluminium.
In Figure 1 the s i l i c o n and aluminium d i s t r i b u t i o n across an a- ( b - ) section
of a polished c r y s t a l o f sample SilA12 are shown. The A l - l e v e l does n o t vary
significantly over the major part of the polished crystal surface.
Nevertheless, some Al-zoning seems t o e x i s t over a very small distance, v i z . 2 -
3 pm as i n d i c a t e d by t h e i n t e r v a l o f t h e step advancement.

Adsorot ive d i f f u s i on
An analysis o f adsorption isotherms o f 2,3-DMB revealed t h a t t h e r e are no
serious deviations in adsorptive p r o p e r t i e s o f t h e (dealuminated) s i l i c a l i t e
samples. Thus a comparison of data on diffusion obtained w i t h d i f f e r e n t
adsorbent samples i s j u s t i f i e d as the adsorption c h a r a c t e r i s t i c s are comparable
f o r each sample.
In Figures 2 and 3 uptake curves are shown f o r 2,3-DMB d i f f u s i o n a t low
coverage (maximum 3.5 molec. 2,3-DMB/u.c.) i n a volumetric system a t 373 K and
 471

--: 5 0 0 0 .
L A
SI

4000
.r
b %

c
3000. Al

1.2 1.4 1.6

10'/T, K"

b-dlractlon (mlcron)

FIg. 4: Tamprraturr rffoct on k- for

Flg. 1: SI- an Al-dlstrlbutlon across an
2,3-dlmothylbutano crocklng on
alurnlnotrd crystal of SIIAIZ.
sarnplrs SIIAll. A and SllA12,
and on H-ZSM-5, 0 .

r;
1.0'I 1.0
Y Y
0.8 0.8
I

0.6 0.6

0.4 0.4

0.2 0.2
*
0.0 1 J 0.0 4
0 100 200 300 400 0 1000 2000 3000

t,

Flg. 2: Uptako of 2.3-dlmrthylbutana In FIg. 3: As Flguro 2. T=473 K

Slldl, 0 and SlldZ, at 373 K. + Sorb. covorago=0.15 maloc./u.c.
Sorb. covrragr= 0.5 molrc./u.c.
472

473 K , respectively. It is clear that the theoretical curve follows the data
reasonably well up to high relative uptake.

TABLE 3
Apparent and intrinsic diffusivity of 2,3-DMB in dealuminated silicalite
samples Silld and Sil2d at 373 K and 473 K

Sil Id Sil2d Si 1 Id Si 12d

373 4.i*io-16 1.0*10-15 2.8*10-16 5.5*10-16

473 1 .5*10-14 1 .4*10-14 1 .7*10-14 1 .6*10-14

In Table 3 results are given o f the curve fitting procedures. Apparent

together with intrinsic diffusivities are given, the latter being obtained by
calculating Darken’s correction factor from the respective isotherms (10).
Furthermore, for each silicalite sample a specific diffusion length is given,
taken t o be half the breadth o f a crystal. From the diffusivities obtained at
373 K and at 473 K an activation energy o f diffusion is calculated o f about 52
kJ/mol e .
Both the diffusivities and the activation energy compare well with data
obtained (using other techniques) on diffusion o f other hydrocarbons in
silicalite/ZSM-5 at other temperatures. The diffusivity o f 2,3-DMB is, after
extrapolation t o corresponding temperatures, substantially lower than that of
3-methylpentane in ZSM-5, viz. by a factor o f 100 (10). Contrarily, compared to
2,2-dimethylbutane (Deff= 6.5*10-19 m2/s) the migration rate o f 2,3-DMB is
enhanced by a factor o f about 500 (2).

’Catalytic’ diffusion
First order rate constants have been determined for the 2,3-DMB cracking
reaction over the directly synthesised H-ZSM-5 sample and over the aluminated
silicalite samples SilAll and SilA12. The rate constants relate t o steady state
situations. Figure 4 shows an Arrhenius plot revealing that the apparent
activation energy of reaction is highly dependent on the size o f the zeolite
 473

c r y s t a l s . I f t h e c o n c e n t r a t i o n s o f a c t i v e s i t e s i n t h e d i f f e r e n t samples do n o t
diverge t o a l a r g e e x t e n t t h i s phenomenon i s i n d i c a t i v e o f a r e a c t i o n which i s
l i m i t e d by the diffusional r a t e o f r e a c t a n t and/or p r o d u c t molecules i n t h e
zeolite channels. As 2,3-DMB i s a f a r more b u l k i e r molecule t h a n i t s c r a c k i n g
pro duc t s i t i s presumed t h a t t h e r e a c t i o n i s l i m i t e d by r e a c t a n t d i f f u s i o n . The
r e a c t i o n ov er t h e ZSM-5 sample has t h e h i g h e s t a c t i v a t i o n energy o f w e l l over
100 kJ/mole. T h i s i s i n d i c a t i v e o f a c o n v e r sion n o t l i m i t e d by i n t r a c r y s t a l l i n e
2,3-DMB d i f f u s i o n .
The use o f t h e Thiele theory i n determining t h e d i f f u s i v i t y o f t h e reactant
requires knowledge o f t h e i n t r i n s i c a c t i v i t i e s o f t h e z e o l i t e samples. We have
determined intrinsic activities by employing a reference reaction, viz. n-
butane c r a c k i n g . T h i s r e a c t i o n i s expected t o occur w i t h o u t any i n t e r f e r e n c e o f
diffusion i n t h e ZSM-5 c r y s t a l s because t h e k i n e t i c d i a m e t e r o f n-but ane ( 0 . 4 9
nm) i s l o w e r t h a n t h a t o f 2,3-DMB (0.56 nm).
F i r s t o r d e r r a t e c o n s t a n t s f o r t h e n-butane c r a c k i n g r e a c t i o n over t h e H-ZSM-
5 sample and ov e r t h e a l u m i n a t e d s i l i c a l i t e s a r e again present ed i n t h e f orm o f
an A r r h e n i u s p l o t i n F i g u r e 5. From t h e r e s p e c t i v e a c t i v a t i o n e n e r g i e s i t can
be concluded t h a t a l l c o n v e r s i o n s o c c u r w i t h an e f f e c t i v e n e s s f a c t o r (0) equal
to unity and that the cracking rate is therefore not retarded by
i n t r a c r y s t a l l i n e n-butane d i f f u s i o n .
I f t h e c a t a l y s t p a r t i c l e i s c o n s i d e r e d t o be o f p l a t e geometry, permeable f o r
reactant molecules i n one direction only, the effectiveness factor is
t h e o r e t i c a l l y g i v e n by:

4 i s t h e T h i e l e modulus:

R i s equal t o h a l f t h e b r e a d t h o f a twinned c r y s t a l . The a d s o r p t i o n c o n s t a n t Kc

is incorporated i n o r d e r t o r e l a t e t h e d i f f u s i v i t y t o t h e adsorbat e
concentration inside the zeolite c r y s t a l s . kintr can be c a l c u l a t e d f rom t h e
r e s p e c t i v e apparent f i r s t o r d e r r a t e c o n s t a n t s u s i n g t h e n-but ane r e a c t i o n
da t a . I t i s assumed t h a t t h e c r a c k i n g o f 2,3-DMB proceeds u n r e t a r d e d over t h e
H-ZSM-5 sample.
474

I n Figure 6 T h i e l e p l o t s are given. I t can be seen t h a t a p e r f e c t f i t r e s u l t s

of evaluated data w i t h theory (eq. 1) which i s a marked improvement compared
with results obtained e a r l i e r using d i r e c t l y synthesised ZSM-5 (3). Thus the
improved homogeneity of the distribution of active sites throughout the
aluminated c r y s t a l s now j u s t i f i e s t h e use o f t h e simple T h i e l e theory.
Thiele analysis resulted i n an e f f e c t i v e d i f f u s i v i t y times a dimensionless
adsorption constant, e.g. Deff*Kc. I n order t o c a l c u l a t e t h e t r u e Deff the
adsorption constant, based on the 2,3-DMB concentration i n a z e o l i t e c r y s t a l ,
has t o be determined. Two types o f adsorption experiments have been performed.
A t temperatures below 523 K the volumetric method was used. Above 523 K the
adsorption constant was determined gaschromatographically from n e t t o r e t e n t i o n
times using conventional r e l a t i o n s h i p s . I n both experiments sample Si13 was
used. I t was assumed t h a t adsorption c h a r a c t e r i s t i c s o f s i l i c a l i t e do n o t
d i f f e r s i g n i f i c a n t l y from t h a t o f the aluminated samples used i n c a t a l y t i c
experiments. The r e s u l t s showed t h a t a good c o r r e l a t i o n e x i s t s between the
experimental data from both methods, and t h e Van’t H o f f equation:

Kc=Ko*exp( -AH/RT) (3)

with the pre-exponential factor, KO, equal t o 1 .8*10-4 and the adsorption
enthalpy, (-AH), equal t o 57 kJ/mol.

TABLE 4
Reaction l i m i t i n g d i f f u s i v i t i e s o f 2,3-DMB i n aluminated s i l i c a l i t e .

673 2.8*10 - 4.8 5. 8 * d 3

7 23 7. 2.4 3.0*10-12
748 9.o*10-l2 1.7 5.3*10-12
773 1 .3*10-11 1.3 1.0*10 -

Table 4 shows the r e s u l t s o f estimations o f 2,3-DMB d i f f u s i v i t i e s a t

d i f f e r e n t temperatures. I n Fig. 7 an Arrhenius p l o t i s given i n which both
adsorptive and ’ c a t a l y t i c ’ 2,3-DMB d i f f u s i v i t i e s are p l o t t e d i n dealuminated
and aluminated s i l i c a 1 i t e , r e s p e c t i v e l y . The c o r r e l a t i o n a f t e r e x t r a p o l a t i o n o f
 475

1=723 K
-4 D,~'K, = 7.3. m2/s
k. s-'
1.00

0.10
P

1=773 K
0.0 1
1.2 1.4 1.6 DeffK, = 1 . 2 6 lo-'' m 2 / s

lO'/T, K-'

Fig. 5:

A s Fig. 4 for n-butane cracking.

0

Fig. 6: Effectiveness f a c t o r as a function

of Thiele modulus. 2.3-dimethyl-
butane cracklng at 7 2 3 K and
a t 773 K.

Def f

10-14
10-15
.. 1
I -

1.00 1.45 1.90 2.35 2.80 1.2 1.4 1.6

10'/T, K-' 10-'/T, K-'

Fig. 7:
Adsorptive ( m ) ond 'catalytic'( 0 ) Fig. 8: As Fig. 4 f o r
3-methylpentane cracklng.
dlffuslvltles of 2,3-dlmethyl-
bulane In (olumlnoted) slllcallte.
476

a d s o r p t i v e d i f f u s i v i t i e s t o l o w e r r e c i p r o c a l t emperat ures i s w i t h i n an o r d e r o f
magnitude. However, t h e a c t i v a t i o n e n e r g i e s o f d i f f u s i o n , ED, d e v i a t e , v i z . 121
kJ/mole f o r t h e ' c a t a l y t i c ' and 52 kJ/mole f o r t h e a d s o r p t i v e d i f f u s i v i t y .
I n o r d e r t o f i n d o u t whether t h i s d e v i a t i o n o r i g i n a t e s f r o m t h e p r o p e r t i e s o f
t h e r e a c t a n t molecule, 2,3-DMB, o r t h e c a t a l y s t , we have repeat ed t h e c r a c k i n g
experiments u s i n g 3-methylpentane. U s i n g d i r e c t l y s y n t h e s i s e d l a r g e ZSM-5
crystals we have determined d i f f u s i v i t i e s a t 723 K and a t 811 K which, a f t e r
extrapolation, corresponded satisfactorily with 1 ow-temperature adsorptive
d i f f u s i v i t i e s (3).
An Arrhenius plot of t h e r e s u l t s ( F i g . 8) shows t h a t , c o n t r a r y t o 2,3-DMB
cracking, the 3-methylpentane conversion is diffusion l i m i t e d o v e r sample
S ilA 12 only. Using the same method as i n t h e 2,3-DMB case t h e ' c a t a l y t i c '
d i f f u s i v i t y o f 3-methylpentane i n a l u m i n a t ed s i l i c a l i t e has been determined.
A d s o r p t i o n d a t a r e p o r t e d e a r l i e r ( 3 ) have been used t o c a l c u l a t e t h e t r u e Deff
from Deff*Kc. I n Table 5 t h e r e s u l t s o f t h e e s t i m a t i o n s a r e compared w i t h d a t a

TABLE 5
Reac t io n l i m i t i n g d i f f u s i v i t i e s o f 3-methylpentane i n aluminat ed s i l i c a l i t e and
i n ZSM-5. Data on ZSM-5 and a d s o r p t i o n c o n s t a n t s a r e t a k e n f r o m r e f . 3.

A1 uminated 723 1.0*10- lo 4.2 2 . 4*10-11

Silica1 i t e 773 1.4*10-1° 2.3 6. 1*10-l1
81 1 2.3*10-1° 1. 5 1. 5*10-1°

ZSM-5 723 5.6*10- lo 4.2 1. 3*10-1°

811 4.6*10- lo 1.5 3. 1 * 1 0 - l o

on 3-methylpentane diffusion i n d i r e c t l y s y n t h e s i s e d ZSM-5 ( 3 ) . I t i s c l e a r

that correspondence exists within an order of magnitude. However, the
r e s p e c t i v e a c t i v a t i o n e n e r g i e s o f d i f f u s i o n a r e h i g h l y d e v i a t e , v i z . 48 kJ/mole
versus 100 kJ/mole.
I t can be concluded t h a t t h e l a r g e d i s c r e p a n c i e s i n a c t i v a t i o n e n e r g i e s o f
diffusion between d i r e c t l y s y n t h e s i s e d ZSM-5 and aluminat ed s i l i c a l i t e a r e due
 471

t o t h e c a t a l y s t . I n f a c t , a discrepancy e x i s t s because t h e a c t i v a t i o n energy o f

the cracking r e a c t i o n over aluminated s i l i c a l i t e does n o t decrease sharply
enough to result i n an a c t i v a t i o n energy o f d i f f u s i o n which i s comparable t o
that of the adsorptive diffusivity. This is an important d i f f e r e n c e w i t h
r e s u l t s obtained by Voogd e t a l . ( 3 ) on ZSM-5 samples where a c t i v a t i o n energies
of r e a c t i o n on the largest crystals amounted t o about h a l f t h e i n t r i n s i c
a c t i v a t i o n energy. This d i f f e r e n c e i n c a t a l y s t behaviour between ZSM-5 and
aluminated s i l i c a l i t e i s as y e t unclear.
Some insight into this problem might be gained by i n v e s t i g a t i n g t h e basic
features of countersorption behaviour i n submicroporous systems. Studies on
countersorption o f l i q u i d hydrocarbons i n f a u j a s i t e type z e o l i t e s and i n
mordenite have been reported (12-15). The r a t e o f countersorption was observed
to be considerably lower than the sorption r a t e o f these sorbates i n the gas
phase. Although experimental difficulties can be rather tedious, it is
recommended t o study co- and countersorption behaviour o f gaseous adsorbates i n
p e n t a s i l z e o l i t e systems. Results from experiments l i k e t h i s w i l l undoubtedly
shed more l i g h t on p e c u l i a r i t i e s o f ’ c a t a l y t i c ’ d i f f u s i o n .

CONCLUSIONS
I n t h i s study 2,3-DMB has been chosen as probe hydrocarbon species i n
d i f f u s i o n experiments w i t h (aluminated) s i l i c a l i t e c r y s t a l s . The uptake o f t h i s
compound in adsorption experiments at 373 K and a t 473 K was c o n t r o l l e d by
i n t r a c r y s t a l line diffusion, not influenced by external heat and/or mass
t r a n s f e r resistances.
Cracking experiments were performed w i t h t h e probe hydrocarbon a t 673-773 K
using large crystals of aluminated s i l i c a l i t e . Reactions were l i m i t e d by
intracrystalline diffusion o f 2,3-DMB. It was found that aluminium was
deposited randomly through a large silicalite crystal. Also an n-butane
cracking activity of aluminated silicalite equal to that of directly
synthesised H-ZSM-5 ( o f comparable s i l i c o n - t o - a l u m i n i u m r a t i o ) was found. As
the a c t i v e s i t e s were d i s t r i b u t e d homogeneously throughout t h e z e o l i t e c r y s t a l
the rates o f diffusion and o f r e a c t i o n were equal a t any l o c a t i o n w i t h i n a
crystal. Therefore an important condition for using Thiele’s model i n i t s
simple form was f u l f i l l e d . ’ C a t a l y t i c ’ d i f f u s i v i t i e s were estimated between 673
K and 713 K.
478

I t was found t h a t a l a r g e discrepancy e x i s t s between t h e a c t i v a t i o n energy o f

diffusion o f 2,3-DMB determined by adsorption k i n e t i c s and by performing
cracking experiments. Experiments w i t h 3-methylpentane l e a d t o t h e conclusion
t h a t t h i s discrepancy i s caused by t h e a p p l i e d c a t a l y s t r a t h e r than t h e probe
molecule.

ACKNOWLEDGEMENTS
The authors w u l d l i k e t o thank M r . E.J.A. van Dam, M r . J.F. van Lent and D r .
W.G. S l o o f o f t h e Laboratory o f M e t a l l u r g y f o r Electron-Probe Microanalysis,
SEM and X-ray d f f r a c t i o n analyses as w e l l as f o r discussions. M r . J. Padmos i s
thanked f o r the AAS analyses.

REFERENCES
1. W.O. Haag, R.M. Lago and P.B. Weisz, Faraday Discuss. Chem. SOC., 72
(1981) 317.
2. M.F.M: Post, J. van Amstel and H.W. Kouwenhoven, i n "Proceedings, 6 t h
I n t e r n a t i o n a l Z e o l i t e Conference" (D.H. Olson and A. B i s i o , Eds.), p. 517.
Butterworths, Guildford, 1983.
3. P. Voogd and H. van Bekkum, Appl. Catal. 59 (1990) 311.
4. D.B. Shah, D.T. Hayhurst, G. Evanina and C.J. Guo, AIChE J. 34 (1988) 1713.
5. M. Ghamami and L.B. Sand, Z e o l i t e s , 3 (1983) 155.
6. R.W. Grow and E.M. Flanigen, U.S. Patent 4,061,724, (1977).
7. C.A. Fyfe, J.H. O'Brien and H. S t r o b l , Nature 326 (1987) 281.
8. R.J. Argauer and G.R. Landolt, U.S. Patent 3,702,886, (1972).
9. K. Yamagishi, S. Namba and T. Yashima, J. Catal., 121 (1990) 47.
10. P. Voogd and H. van Bekkum, i n "Proceedings o f an I n t e r n a t i o n a l Symposium
on Z e o l i t e s as Catalysts, Sorbents and Detergent B u i l d e r s " , (H.G. Karge
and J. Weitkamp, Eds.), p. 519, E l s e v i e r , Amsterdam, 1989.
11. C.D. Chang, C.T.-W. Chu, J.N. Miale, R.F. Bridget- and R.B. C a l v e r t , J. Am.
Chem. SOC., 106 (1984) 8143.
12. C.N. S a t t e r f i e l d , J.R. Katzer and W.R. Vieth, Ind. Eng. Chem., Fundam., 10
(1971) 478.
13. R.M. Moore and J.R. Katzer, AIChE J., 18 (1972) 816.
14. C.N. S a t t e r f i e l d and J.R. Katzer, Adv. Chem. Ser., 102 (1971) 193.
15. C.N. S a t t e r f i e l d and C.S. Cheng, AIChE J., 18 (1972) 724.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 479
0 1991 Elsevier Science Publishers B.V., Amsterdam

T R A N S P O R T PHENOMENA AND R E A C T I O N S I N 13X T Y P E ZEOLITES

M. BULOWl, W . HILGERT2 a n d G . EMIG3

' C e n t r a l I n s t i t u t e o f P h y s i c a l C h e m i s t r y , Academy o f S c i e n c e s o f
t h e G.D.R., B e r l i n - A d l e r s h o f , DOR-1199 (German Dem. R e p . )
2 1 n s t i t u t e o f T e c h n i c a l C h e m i s t r y I,U n i v e r s i t y o f E r l a n g e n - N u r e m -
b e r g , E g e r l a n d s t r . 3, 0 - 8 5 2 0 E r l a n g e n ( F e d . Rep. o f Germany)
3 1 n s t i t u t e o f Chemical Technology, U n i v e r s i t y o f K a r l s r u h e , K a i s e r -
s t r a a e 1 2 , 0 - 7 5 0 0 K a r l s r u h e 1 ( F e d . Rep. o f Germany)

SUMMARY
I n f o r m a t i o n a b o u t Inass t r a n s f e r p r o c e s s e s d u r i n g h e t e r o g e n e o u s
c a t a l y t i c r e a c t i o n s on m i c r o p o r o u s s o l i d s h a s become o f s p e c i a l
i m p o r t a n c e . To i n v e s t i g a t e b o t h s o r p t i o n a n d k i n e t i c s o f t r a n s p o r t
and r e a c t i o n o f e d u c t s and p r o d u c t s , e s p e c i a l l y o f t h e d i s p r o p o r -
t i o n a t i o n o f e t h y l b e n z e n e o n 13X z e o l i t e s , a h i g h p r e s s u r e a p p a -
r a t u s with a B e r t y r e c y c l e r e a c t o r i s described. D i f f u s i o n c o e f f i -
c i e n t s o f a r o m a t i c h y d r o c a r b o n s i n 13X t y p e z e o l i t e s a r e m e a s u r e d
as dependences o n t e m p e r a t u r e and c o n c e n t r a t i o n i n t h e n o n - r e a c -
t i o n s o r p t i o n r e g i o n b y means o f b o t h t h e h i g h - p r e s s u r e c h r o m a t o -
g r a p h i c t e c h n i q u e and t h e p i e z o m e t r i c method. I n p a r t i c u l a r , a
comparative study o f the transport parameters f o r the p - d i e t h y l -
b e n z e n e / l 3 X z e o l i t e s y s t e m i s c a r r i e d o u t . The d a t a o b t a i n e d a r e
i n g o o d a g r e e m e n t , e s p e c i a l l y i n t h e h i g h t e m p e r a t u r e r e g i o n . They
complement each o t h e r w i t h r e s p e c t t o t e m p e r a t u r e and c o n c e n t r a -
tion.

INTRODUCTION
I n t h i s work i t i s a t t e m p t e d t o d e t e r m i n e t h e c o e f f i c i e n t s o f
d i f f u s i o n a n d s o r p t i o n o f v a r i o u s a r o m a t i c h y d r o c a r b o n s o n 13X
t y p e z e o l i t e s b y means o f t h e h i g h p r e s s u r e c h r o m a t o g r a p h i c ( G C )
and t h e s o r p t i o n u p t a k e (SU) methods i n o r d e r t o a p p l y t h e r e s u l t s
t o t h e m o d e l l i n g and i n t e r p r e t a t i o n o f c o n t i n u o u s d i s p r o p o r t i o n a -
t i o n o f e t h y l b e n z e n e on a p p r o p r i a t e m o l e c u l a r s i e v e ( M S ) cata-
lysts. I n t h e GC (SU) s t u d y t h e t e m p e r a t u r e r a n g e i s 373 ...6 8 3 K
(373 ... 563 K ) a n d t h e p r e s s u r e r a n g e s f r o m v a l u e s less t h a n 1 T o r r
i n vacuo (SU) t o a b o u t 140 b a r ( G C ) . The t r a n s a l k y l a t i o n r e a c t i o n
w i l l b e p e r f o r m e d w i t h i n t h e same t e m p e r a t u r e r a n g e , b u t p r e s s u -
res t o b e u s e d w i l l b e h i g h e r t h a n 400 b a r i n o r d e r t o e x c e e d t h e
Besides the s o r p t i o n study, p r e l i m i n a r y explo-
c r i t i c a l point.
r a t i o n s a r e needed t o f i n d a most a c t i v e and s t a b l e c a t a l y s t f o r
the disproportionation reaction.
480

EXPERIMENTAL
The e x p e r i m e n t a l t e c h n i q u e s t o m e a s u r e m a s s f l u x e s o f s o r b i n g
s p e c i e s i n m i c r o p o r o u s c a t a l y s t s , e . g . MS c r y s t a l s , a r e c o n f r o n t e d
with t h e f o l l o w i n g problems:

- n o n - i s o t h e r m i c i t y of t h e s o r p t i o n p r o c e s s ;
- v e r y s m a l l p a r t i c l e (MS c r y s t a l ) s i z e s ;
- i n t e r p l a y between i n t r a c r y s t a l l i n e and i n t e r c r y s t a l l i n e t r a n s -
p o r t f o r p e l l e t s o r p a c k i n g s o f MS c r y s t a l s .

B e s i d e s t h e c l a s s i c a l SU m e t h o d , t h e G C e x p e r i m e n t s h a v e e v o l v e d
a s a major source f o r r e l i a b l e diffusionhon-equi1ibrium)data f o r
MS s y s t e m s . I n a d d i t i o n , t h e N M R t e c h n i q u e s h a v e e x t e n s i v e l y b e e n
u t i l i z e d t o determine s e l f - d i f f u s i o n c o e f f i c i e n t s (equilibrium
d a t a ) . U n f o r t u n a t e l y , one f r e q u e n t l y e n c o u n t e r s l a r g e d i s c r e p a n -
cies between v a r i o u s t y p e s of e x p e r i m e n t a l r a t e p a r a m e t e r s ,
e s p e c i a l l y f o r h i g h l y m o b i l e systems, e . g . f o r h y d r o c a r b o n s i n
13X t y p e z e o l i t e s . O f t e n t h i s f l a w i s b e i n g a t t r i b u t e d t o u n -
s a t i s f a c t o r y d e s i g n of experiments or improper measurement c o n d i -
t i o n s , c f . t h e reviews ( r e f s . 1-3). Therefore, i n t h i s investiga-
t i o n t h e i n f o r m a t i o n o n m o l e c u l a r t r a n s p o r t i s o b t a i n e d by t w o
i n d e p e n d e n t e x p e r i m e n t a l m e t h o d s , i . e . t h e GC a n d t h e SU
techniques.

Chromatographic method
I f o n e uses u n p e l l e t i z e d MS c r y s t a l s a s s o r b e n t , t h e d i s t r i b u -
t i o n o f c o n c e n t r a t i o n of a s o r b i n g m o l e c u l a r s p e c i e s b e t w e e n t h e
g a s e o u s a n d s o r p t i o n ( p a r t i c l e ) p h a s e s c a n b e d e s c r i b e d by t h e
following equations:
gaseous phase:

with

p a r t i c l e phase:
 481

The required measurements of transport rate without any chemi-

cal reaction were performed by the experimental setup shown in
Fig. 1 schematically. The GC column is filled with zeolite

Fig. 1. Flow
diagram for
GC measure-
ments at high
pressures.

bl
chrornslopraphlc
column I

' U
-
- -- hsnlsd llnes

nmpllllsr recorder

crystals (without binder) diluted by inert material to reduce the

retention times in actual GC experiments. This arrangement ensures
a more uniform gas flow than in the case of the Zero Length
Column method (ref. 4). The carrier gas velocity was always high
enough to guarantee a quasi-isothermic sorption-diffusion process
and to exclude limiting external transport resistance at the
particle-gas interface. In addition, the influence of axial dis-
persion on chromatograms is eliminated by high gas velocities. The
pressure drop along the column axis is accounted for by the trans-
port model of the column (Blake-Kozeny equation). A very similar
model for GC experiments with zeolite crystals was proposed by
Chiang et al. (ref. 5).
It is most essential for further use o f the experimental data
that the concentration dependence of the coefficients of diffusion
and sorption is determined. For this purpose, the carrier gas
nitrogen was loaded with the corresponding aromatic in a saturator
and a peak is injected on top of the elevated base-line. All
measurements were performed at different temperatures. Therefore,
it i s possible to calculate both the activation energy and sorp-
tion heat for the systems under study. Fig. 2 shows the depen-
dences of diffusion coefficients on temperature for various
482

a r o m a t i c h y d r o c a r b o n s on NaX t y p e z e o l i t e ( c r y s t a l s i z e 1...2 pm).

The d i f f u s i o n c o e f f i c i e n t s a r e t a k e n f r o m t h e r e g i o n w h e r e t h e y

F i g . 2. A r r h e n i u s p l o t s
f o r v a r i o u s systems
aromatic hydrocarbon/
NaX t y p e z e o l i t e
(values 0 obtained by
t h e GC t e c h n i q u e ; Do...
c o r r e c t e d by t h e
Darken eqn. benzene
( E / k J mol-1; 0 5 ) ; A t o -
lu8ne ( 6 9 ) ; O e t h y l b e n -
z e n e (72); a m - x y l e n e
(81).

1.5 1.6 1.7 1.8

1 / T [lo3 K - ' I
remain unchanged w i t h c h a n g i n g c o n c e n t r a t i o n a f t e r a p p l y i n g t h e
D a r k e n e q u a t i o n t o t h e p r i m a r y d a t a . An e x a m p l e o f t h e c o n c e n t r a -
t i o n dependence o f d i f f u s i o n c o e f f i c i e n t s i s g i v e n i n F i g . 3 f o r
t h e p-diethylbenzene/NaX z e o l i t e system.

-U
0)
ul
N
\

-5
Y

c
.-aJ
10-8
A
.-U
.c
Y -

g A
U
C
.-0
ul
3
Y-
'c
u ,040

1 2 3 I

concentration [ m o l e c u l e s / cage]

F i g . 3 . C o n c e n t r a t i o n dependence o f t h e d i f f u s i o n c o e f f i -
c i e n t o f p - d i e t h y l b e n z e n e o n NaX z e o l i t e a t 6 9 3 K ( o b -
t a i n e d by t h e GC t e c h n i q u e ) .
 483

A second apparatus was built in order to

- decide if the results obtained by the GC technique are trans-
ferable to the disproportionation of ethylbenzene (ref. 6 ) ;
- derive a kinetic model f o r prediction o f selectivities and
conversions on various MS catalysts at different temperatures,
pressures and residence times.
The corresponding experimental setup is shown in Fig. 4. I n the
recycle reactor, pressures up to 400 bar and temperatures up to
770 K can be maintained, so that measurements at the critical

I-7-
--
- I

, t

Fig. 4. Flow diagram of the experimental setup f o r kinetic measure-

ments in the supercritical region,

point and in the supercritical region are feasible. The experi-

mental principle prevents pulsations in both the gaseous and the
liquid phases. First investigations indicate a lower coking ten-
dency at supercritical conditions (refs. 7 - 9 ) . Fig. 5 shows an
Arrhenius plot of diffusion data (corrected by the Darken equation)
f o r the p-diethylbenzene/NaX zeolite system investigated by both
484

t h e G C ( c r y s t a l s i z e 1...2 pm) a n d t h e p i e z o m e t r i c S U ( c r y s t a l
s i z e 8 0 pm) m e t h o d s . The r e s u l t s f r o m b o t h t e c h n i q u e s c o m p l e m e n t
e a c h o t h e r on t h e temoerature scale.

F i g . 5 . Compa-
r i s o n o f GC
( c i r c l e s ) and
SU ( s q u a r e s )
d i f f u s i o n data
f o r p-diethyl-
benzene on
NaX t y p e z e o l i -
tes.

S o r p t i o n method
I n t h e SU e x p e r i m e n t s a c o n s t a n t v o l u m e - v a r i a b l e p r e s s u r e
system w i t h v a l v e - e f f e c t c o r r e c t i o n s as d e s c r i b e d i n ( r e f s . 10,ll)
was e m p l o y e d . The v a l v e - e f f e c t c o r r e c t i o n s r e l a t e t o d e a d - t i m e
moments o f t h e a p p a r a t u s a m o u n t i n g t o s 0.2 s . To a v o i d t h e i n -
f l u e n c e o f i n t e r c r y s t a l l i n e d i f f u s i o n on t h e u p t a k e r a t e and t o
r e a l i z e quasi-isothermic conditions, SU was m e a s u r e d u s i n g ,
r e s p e c t i v e l y , a monolayer o f s i n g l e c r y s t a l s and f a v o u r a b l e e x t e r -
n a l temperature conditions ( i . e . , To< T v where t h e s u b s c r i p t s
o and v i n d i c a t e t h e dosed gas and z e o l i t e c r y s t a l phases, respec-
tively) (ref. 12). To e v a l u a t e d i f f u s i o n c o e f f i c i e n t s , the for-
m u l a s o f t h e s t a t i s t i c a l moments t h e o r y a s g i v e n p r e v i o u s l y ( r e f .
1 0 ) a r e u s e d . As i n t h e c a s e o f t h e GC d i f f u s i o n d a t a , the diffu-
s i o n c o e f f i c i e n t s t h u s d e r i v e d a r e t r e a t e d by t h e Darken e q u a t i o n
(ref. 3).
I n t h e p i e z o m e t r i c SU e x p e r i m e n t s t h r e e d i f f e r e n t l y s i z e d
samples o f l a b o r a t o r y - s y n t h e s i z e d 13X z e o l i t e a r e u s e d :
NaX ... 6 0 pm; 8 0 pm; NaKX ... 1 2 0 pm, 80% K+. The s i z e p a r a m e t e r s
given denote the diameter o f spheres c i r c u m s c r i b i n g t h e c r y s t a l s .
 485

The standard deviations of crystal sizes are l e s s than 10% for

each sample. Therefore, no size distribution function is needed
for calculating the diffusion coefficients.
The use of NaKX zeolite in S U experiments is due to its larger
crystal size compared to that o f the NaX spezimens. Thus, SU
measurements at temperatures approaching those of the GC investi-
gation became possible.
By the above experimental conditions it is presumed that the
diffusion coefficients characterize the intracrystalline molecular
mobility of p-diethylbenzene in 13X zeolite. A final decision can
only be done by their comparison with the independently deter-
mined GC data and by variation of crystal sizes in the investiga-
tion.

RESULTS
Fig. 6 shows concentration dependences of diffusion coefficients
for p-diethylbenzene on both NaX and NaKX in the temperature region
323 . . . 373 K. The following main results are evident:
- the diffusion coefficients coincide for both 13X specimens(with
different crystal sizes) except the data for lower loadings at
higher temperature, whereat the mobility o f p-diethylbenzene in
the NaX crystals seems to be lowered;
- the molecular mobility decreases strongly with increasing con-
centration in the intraccystalline void volume (this result
corresponds with the behaviour of other hydrocarbon/NaX type
systems (refs. 1 1 , 1 3 , 1 4 ) ) .
To provide further information on the behaviour of the p-diethyl-
benzene/NaX zeolite system at low concentration, a treatment of
corresponding SU rate curves by means of the computer programme
Z E U S (ref. 15) was carried out. An example is given in Fig. 7.
At least the conclusion can be drawn that with sufficiently low
concentration the molecular mobility of p-diethylbenzene in NaX
zeolite decreases most probably. This finding should be connected
with the comparatively strong interaction between aromatic molecu-
les and Na' cations. On the other hand, the decrease of diffusion
coefficients in the high concentration region can be explained by
increasing mutual interaction of molecules sorbed and by a reduced
free volume in the micropores (ref. 1 3 ) . As follows from Fig. 8
wherein a r e given the concentration dependences o f diffusion
coefficients of p-diethylbenzene on NaKX zeolite a t various tempe-
486

F i g . 6. Comparison o f
c o n c e n t r a t i o n dependen-
ces o f d i f f u s i o n c o e f f i -
c i e n t s o f p-diethylben-
z e n e o n NaX a n d NaKX
1 o.8 type zeolites a t various
temperatures
(SU experiments).

ro-'O

0.1 1.0
concentration [rnmol/g]

r a t u r e s up t o 5 6 3 K, t h i s e f f e c t becomes s u p p r e s s e d a t h i g h t e m p e -
r a t u r e s due t o i n c r e a s i n g k i n e t i c e n e r g y o f m o l e c u l e s s o r b e d i n

F i g . 7. S i -
mulation o f
a SU c u r v e
o f p-di-
ethylbenze-
n e o n NaX
zeolite at
3 7 3 K and
0.04 -1
mmol g
( + ) by t h e
software
ZEUS ( s o l i d
line).
 487

the high concentration range. In addition to above conclusions,

the following findings are significant:
- at temperatures above 560 K the diffusion coefficient remains
nearly constant within a wide concentration range;
- the piezometric SU rate data become comparable with the high
pressure GC data.
The latter conclusion can be drawn especially from the Arrhenius
plot at high concentration ( n 2 0.8 mmol 9-l) shown in Fig. 9 .

lo- r Fig. 8. Concentration

dependences of diffusion
coefficients of p-di-
ethylbenzene on NaKX
zeolite at various tempe-
ratures.

03 1.o
concentration [mmol/g]

The difference in diffusion coefficients from SU and GC experi-

ments amounts to a half order of magnitude, only. Taking into
account well-known problems connected with such comparisons
(ref. 3 ) and the presence of K + cations in one of the zeolites
considered, this result is quite satisfactory. The activation
energy derived from the SU data amounts to 40 kJ mol-l, a value
indicating the intracrystalline character of the underlying mole-
cular transport. It exceeds the well-established value for benzene
in NaX zeolite amounting t o % 2 5 kJ mol-' (ref. 14) due to the
488

Fig. 9 . Arrhe-
nius plot of GC
(empty symbols)
and SU (full
symbols) data
for p-diethyl-
benzene on NaX
and NaKX type
zeolites, r e -
spect ively.

E, N 40 ItJ/rnol
at n N 0.8 rnrnol/g

10-'O F
more complex molecular structure of p-diethylbenzene.
If one takes into account that the GC measurements were carried
out in a temperature region where the diffusion coefficients r e -
main practically constant over a wide concentration region and,
on the other hand, this result is also confirmed by the SU measu-
rements, a good agreement can be stated for the data from both
methods. The SU method complements the GC technique at low tempe-
rature contributing information about an increasing influence of
concentration on intracrystalline molecular mobility. The low dif-
fusion coefficients of p-diethylbenzene at very low micropore
fillings of the NaX zeolite - as shown by the GC technique - is
suggested by the SU results as well.
The molecular mobility data described will serve as reliable
information on intracrystalline transport for further considera-
tion of reaction kinetics.

CONCLUSIONS
The principle of an experimental high pressure chromatographic
system with a Berty recycle reactor to study sorption,diffusion
and reaction on columns with crystals of molecular sieves is
described.
 489

By means of this technique at pre-catalytic conditions, coeffi-

cients of sorption and diffusion of benzene, ethylbenzene and di-
ethylbenzene isomers on NaX crystals with different sizes are ob-
tained as dependences on concentration approaching values up to
4 molecules per supercage and on temperature as well.
A comparative study of diffusion of p-diethylbenzene on various
13X molecular sieves by means of the piezometric sorption uptake
method leads to good agreement between diffusivities obtained by
both this technique and the high pressure G C method, especially
in the high temperature region. The data derived from the measure-
ments by both methods complement each other with respect to tempe-
rature and concentration.
The diffusion coefficients of p-diethylbenzene in NaX and NaKX
zeolites characterize the molecular mobility in the intracrystal-
line zeolitic void volume.
The comparison of intracrystalline molecular mobility data re-
ported here with those from literature for other aromatics in 13X
type zeolites shows the sequence:
benzene > p-xylene > p-diethylbenzene.

ACKNOWLEOGEMENTS
W.H. and G . E . thank the Oeutsche Forschungsgemeinschaft for
financial support. M.B. thanks the Akademie der Wissenschaften der
D D R for the possibility to work on diffusion phenomena in molecu-
lar sieve systems.

NOTATIONS
D diffusion coefficient
?3x
coefficient of axial dispersion
K constant of sorption equilibrium
L column length cm
mass flux density across the m m o l cm
-2 s -1
NRc zeolite crystal interface (cf.eqn.2)
RC
external r a d i u s of zeolite crystals cm
C gaseous phase concentration mmol cm-3
9
CT total sorbate concentration in mmol cm-3
gaseous phase
C
* = Kc , sorbate concentration in mmol cm-3
intrgcrystalline void volume o f
zeolite
r radial coordinate of zeolite crystal cm
t time S
490

-1
V l i n e a r gas v e l o c i t y cm s
X molar f r a c t i o n -

' i n t e r p a r t i c l e v o i d volume of
column p a c k i n g (volume f r a c t i o n )
-

7 = r/Rc, dimensionless radius -

of zeolite crystal
5 dimensionless a x i a l coordinate -

REFERENCES

1 J . K a r g e r a n d D.M. R u t h v e n , Z e o l i t e s , 9 ( 1 9 8 9 ) 2 6 7 - 2 8 1 .
2 H.W. H a y n e s , J r . , C a t a l . Rev. - S c i . E n g . , 30 ( 1 9 8 8 ) 5 6 3 - 6 2 7 .
3 M. B u l o w , J . K a r g e r , M . K o z i r f k a n d A . M . V o l o g z u k , Z . Chem.,
L e i p z i g , 2 1 (1981) 175-182.
4 D.M. Ruthven and M. E i c , Z e o l i t e s , 8 (1988) 40-45.
5 A . S . C h i a n g , A . G . D i x o n a n d Y . M . Ma, Chem. Eng. S c i . , 3 9 (1984)
1451-1459.
6 W.J. Thomas a n d U . U l l a h , Chem. Eng. Res. D e v . , 6 6 ( 1 9 8 8 ) 138-
146.
7 N . A . C o l l i n s , P . G . O e b e n e d e t t i a n d 5. S u n d a r e s a n , A I C h E J . , 3 4
(1988) 1211-1214.
8 G . Manos, Ph. 0 . T h e s i s " U n t e r s u c h u n g e n d e r V e r k o k u n g v o n
Z e o l i t h e n und i h r e r R e a k t i v i e r u n g m i t u b e r k r i t i s c h e n F l u i d e n "
U n i v e r s i t a t E r l a n g e n - Nurnberg, 1989.
9 H . S c h a f e r , Ph. 0 . T h e s i s " U n t e r s u c h u n g e n z u r K i n e t i k d e r Des-
a k t i v i e r u n g und R e a k t i v i e r u n g p o r o s e r K o n t a k t e m i t u n t e r - bzw.
u b e r k r i t i s c h e n R e a k t i o n s g e m i s c h e n " U n i v e r s i t a t E r l a n g e n - Nurn-
b e r g , 1990.
10 P . S t r u v e , M . KoEi??<k, M. Bulow, A . Z i k a n o v a a n d A . G . B e z u s ,
Z . p h y s . Chem., L e i p z i g , 264 ( 1 9 8 3 ) 4 9 - 6 0 .
11 M. Bulow, P. L o r e n z , W. M i e t k , P . S t r u v e and N.N. S a m u l e v i x ,
J . Chem. S O C . , F a r a d a y T r a n s . I , 7 9 ( 1 9 8 3 ) 1 0 9 9 - 1 1 0 8 .
12 M. B u l o w , P . S t r u v e a n d W . M i e t k , Z . p h y s . Chem., L e i p z i g ,
267 ( 1 9 8 6 ) 6 1 3 - 6 1 6 .
13 J . K a r g e r , H. P f e i f e r , M. R a u s c h e r a n d A . W a l t e r , J . Chem. S O C . ,
Faraday Trans. I , 7 6 (1980) 717-729.
14 M . B u l o w , W . M i e t k , P . S t r u v e a n d P . L o r e n z , J . Chem. S o c . , F a r a -
day T r a n s . I,79 ( 1 9 8 3 ) 2 4 5 7 - 2 4 6 6 .
15 M . B u l o w a n d A . M i c k e , K a t a l y s e , D e c h e m a - M o n o g r a p h i e Ed. 1 1 8 ,
VCH V e r l a g s a n s t a l t , F r a n k f u r t / M . , 1989, p. 349-355.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 491
0 1991 Elsevier Science Publishers B.V., Amsterdam

THE EFFECT OF VARIOUS PHYSICAL AND CHEMICAL PARAMETERS

ON THE SYNTHESIS OF ZSM-5 FOR PROPENE OLIGOMERIZATION

C.T. O’Connor, S. Schwarz and M. Kojima

Department o f Chemical Engineering, U n i v e r s i t y o f Cape Town,

P r i v a t e Bag, Rondebosch 7700, SOUTH AFRICA

ABSTRACT
I n t h e p r e s e n t s t u d y i t has been shown t h a t t h e propene igomerization a c t i v i t y
o f ZSM-5 a t 5MPa and 220-290°C i s m a i n l y dependent on t h e aluminium c o n t e n t and
c r y s t a l s i z e o f t h e c a t a l y s t . Optimum a c t i v i t i e s and l i f e t i m e s were o b t a i n e d
w i t h Si/A1 = 40, c r y s t a l s i z e < lpm and a s y n t h e s i s t i m e o f 3 days. T his
y i e l d e d under optimum r e a c t i o n c o n d i t i o n s a c a t a l y s t u t i l i z a t i o n v a l u e o f 1100
g.liq/g.cat. E x t r u d i n g t h e c a t a l y s t u s i n g alumina as a b i n d e r d i d n o t a d v e r s e l y
affect the activity, selectivity or lifetime o f the catalyst. Pelletizing
reduced t h e a c t i v i t y o f t h e c a t a l y s t . A m e c h a n i c a l l y - s t i r r e d autoclave l e d
t o a decrease i n t h e t h e average c r y s t a l s i z e and a narrower s i z e d i s t r i b u t i o n .
A number o f t e mp l a t e s were used i n t h e s y n t h e s i s o f ZSM-5 and 1,6-hexanediamine
and 1,2-cyclohexanediamine produced c a t a l y s t s w i t h s i m i l a r c a t a l y t i c p r o p e r t i e s
t o t h o s e prepared u s i n g tetrapropylammonium bromide.

INTRODUCTION
ZSM-5 has been shown t o be an e x c e l l e n t c a t a l y s t f o r t h e c o n v e r s i o n o f
l i g h t o l e f i n s t o l i q u i d f u e l s ( r e f s . 1 - 4 ) . I n general t h e a c t i v i t y i s r e l a t e d t o
t h e A1 c o n t e n t ( r e f s . 5-7). The c r y s t a l s i z e a l s o increases as Si/A1 ratio
inc re as es ( r e f . 8 ) . The a c t i v i t y o f v a r i o u s c a t a l y t i c r e a c t i o n s i n c r e a s e s as
c r y s t a l s i z e decreases ( r e f s . 9-10). The need t o f orm e x t r u d a t e s and p e l l e t s
fro m t h e powder can a l s o s t r o n g l y i n f l u e n c e t h e s e l e c t i v i t y and a c t i v i t y o f t h e
c a t a l y s t ( r e f s . 11-14). Longer c r y s t a l 1 i z a t i o n t imes enhance t h e c o n c e n t r a t i o n
o f A1 on t h e e x t e r n a l s u r f a c e sometimes r e s u l t i n g i n a s h o r t e r c a t a l y s t l i f e
( r e f . 15). The use o f a l t e r n a t i v e templates i n t h e s y n t h e s i s o f ZSM-5 has a l s o
been e x t e n s i v e l y s t u d i e d ( r e f s . 16-20).
T h i s paper p r e s e n t s r e s u l t s o b t a i n e d i n a s t u d y o f t h e e f f e c t o f S i / A l
r a t i o , s y n t h e s i s t i m e , t e m p l a t e s and s t i r r i n g mechanism on t h e c h a r a c t e r i s t i c s
o f ZSM-5 and on i t s a c t i v i t y , s e l e c t i v i t y and l i f e t i m e f o r t h e o l i g o m e r i z a t i o n
o f propene i n a h i g h p r e s s u r e f i x e d bed r e a c t o r . Powdered c a t a l y s t samples were
a l s o e x t ruded and p e l l e t i z e d u s i n g v a r i o u s b i n d e r s and t h e e f f e c t s o f t h i s
t r e a t m e n t on l i f e t i m e and s e l e c t i v i t y was s t u d ied.

EXPERIMENTAL
Samples o f ZSM-5 were s y n t h e s i z e d a c cording t h e method o f Argauer and
L a n d o l t ( r e f . 21) u s i n g b o t h m e c h a n i c a l l y and m a g n e t i c a l l y s t i r r e d a u t o c l a v e s .
492

D e t a i l s o f the method are given elsewhere ( r e f s . 22,23). The samples used are
r e f e r r e d t o as (A)-Z-X-Y where A = template (tetrapropylammonium bromide unless
otherwise stated), Z = ZSM-5, X = S i / A l r a t i o and Y = synthesis time. Three
types of templates were used, viz. tetra-alkylammonium ions, amines and
alcohols. The f i r s t category included methyl (TMA), e t h y l (TEA), propyl (TPA)
and b u t y l (TBA) ammonium bromide. The amines used were 1,2 ethanediamine (1,2
ED), 1,2 propenediamine (1,2 PD), 1 butylamine (1 BA), 1 hexylamine (1 HA), 1,6
hexanediamine (1,6 HD) and 1,2 cyclohexanediamine (1,2 CHD). A number o f
alcohols were a l s o used. The c a t a l y s t s were characterized using SEM, EDX, XRD,
ammonia TPD and, i n some cases, MASNMR.

A l l the samples prepared were t e s t e d f o r t h e i r a c t i v i t y and s e l e c t i v i t y

f o r propene o l i g o m e r i z a t i o n and d e t a i l s o f t h e r e a c t o r system used as w e l l as
the methods used t o analyse t h e r e a c t i o n products are described elsewhere ( r e f s .
22,23). Reactions were c a r r i e d out a t 5MPa, WHSV = 12 h-' and, i n general,
r e a c t i o n temperatures between 220 and 290°C. I n some cases t h e l i q u i d product
was hydrogenated over a Pd/C c a t a l y s t and t h e 'H-NMR spectrum used t o estimate
cetane numbers. The amount o f coke deposited on t h e c a t a l y s t was determined
using thermogravimetri c anal ys is .
RESULTS
All samples o f c a t a l y s t prepared had X-ray d i f f r a c t i o n p a t t e r n s and
ammonia TPD spectra c h a r a c t e r i s t i c o f ZSM-5 ( r e f . 23). Tables 1 and 2 show the
effect of Si/Al ratio, synthesis time and s t i r r i n g procedure on the number
average c r y s t a l size.

TABLE 1

E f f e c t o f S i / A l r a t i o and synthesis t i m e on average c r y s t a l s i z e

(Temp1a t e TPABr)

Si/Al Synthesis Average c r y s t a l

time (days) s i z e (pm)

18 1 1.8
44 1 0.8
64 1 1.1
131 1 1.4
197 1 1.8
487 1 4.7
48 3 1.1
43 6 1.2
45 10 1.2
19 3 2.9
26 6 3.0
 493

TABLE 2
E f f e c t o f s t i r r i n g on average c r y s t a l Size
(Synthesis time = 3 days)

S i / A l Temp1 a t e Type o f Average c r y s t a l

Stirring size (p)

46 TPA none 2.4

41 TPA mechanical 0.9
31 1,6 HD mechanical 0.4
44 TPA magnetic 1.1
32 1,6 HD magnetic 1.3
38 T PA mechani cal 0.7
487* TPA magnetic 4.7

* Synthesis time = 1 day

1 Catalyst u t i l i z a t i o n value = g l i q / g cat

As expected the c r y s t a l s i z e i n general decreased as t h e A1 content

increased. When t h e s l u r r y was mechanically s t i r r e d smaller c r y s t a l s w i t h a
r e l a t i v e l y narrower s i z e d i s t r i b u t i o n than f o r the magnetically s t i r r e d samples
was obtained. The c r y s t a l s i z e o f samples synthesized using a v a r i e t y o f
tetraalkylammonium bromides, amines and alcohols as templates was also
determined. TBA, TPA, lHA, 1,6-HD and 1,2-CHD a l l produced ZSM-5 w i t h c r y s t a l s
-1 pm. The other amines y i e l d e d c r y s t a l sizes o f > 3 pm and t h e alcohols c r y s t a l
sizes > 4 pm.

Fig. 1 shows the r e l a t i v e e f f e c t o f aluminium content on propene

conversion t o l i q u i d products. An unusually h i g h r e a c t i o n temperature o f 300°C
was used t o ensure t h a t 2-487-1 would show s u f f i c i e n t a c t i v i t y . When samples
were prepared w i t h S i / A l r a t i o o f 48 and 64 r e s p e c t i v e l y and c r y s t a l s i z e o f
-1.1 pm i n both cases, the aluminium content was more s i g n i f i c a n t than c r y s t a l
s i z e f o r propene oligomerization a c t i v i t y . Fig. 2 shows t h e c a t a l y s t
u t i l i z a t i o n values obtained throughout t h i s study f o r d i f f e r e n t c r y s t a l sizes
i r r e s p e c t i v e o f the method o f synthesis used o r aluminium content. The c r i t i c a l
importance o f the c r y s t a l size i s c l e a r l y evident f r o m t h i s f i g u r e .

The best c a t a l y s t u t i l i z a t i o n values (CUV = g.liq/g.cat) were obtained

using samples w i t h c r y s t a l sizes < lpm and Si/A1 = 40. C r y s t a l s o f 2.4 pm
showed very poor oligomerization a c t i v i t y (CUV = 110 g/g). The CUV values f o r
the 1,6 HD and TPA based samples ( m x h a n i c a l l y s t i r r e d ; Si/A1 = 40) were 409 and
494

100
C
0
n
V
e 80
r
0
I
0
n 80

0
I
40
P
r
0
P
n
e
x 0'
0 2 4 6 8 10 12 14 16 18
Time on stream (hrs)

Fig. 1 E f f e c t o f A1 content on propene o l i g o m e r i z a t i o n a c t i v i t y ( P = 5

MPa, T = 3OO0C, WHSV = 12 h-')

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6

Crystal size (urn)

Fig. 2 E f f e c t o f c r y s t a l s i z e on c a t a l y s t u t i l i z a t i o n value.
 495

385 g/g and t h e i r magnetically s t i r r e d equivalents were 286 and 258 g/g
r e s p e c t i v e l y . Their c r y s t a l sizes are shown i n Table 2.

A t a constant Si/A1 r a t i o o f about 40 i t was found t h a t an optimum CUV =

520 g/g was obtained f o r a synthesis t i m e o f 3 days. For a Si/A1 r a t i o o f about
20 t h e optimum CUV (380 g/g) was obtained f o r a synthesis time o f 1 day. The
former optimum corresponded t o t h e highest concentration o f strong a c i d s i t e s as
determined by TPD, v i z . 0.40 mmol/g, whereas the l a t t e r optimum corresponded t o
the smallest c r y s t a l size. I n a l l these runs the r e a c t i o n temperature was
increased g r a d u a l l y from 220 - 290°C over t h e e n t i r e run o f about 40h and the
r e p r o d u c i b i l i t y was found t o be very good.

The f o l l o w i n g general propene oligomerization a c t i v i t y sequence was

observed when d i f f e r e n t templates were used: TPA, TBA, C, diamines > C, amines >
Cp,3,4 amines and diamines > alcohols. The f i r s t mentioned group all had
comparable CUVs o f -300 g/g.

When samples o f ZSM-5 (TPA-Z-41-3) were extruded w i t h s i l i c a o r alumina i t

was found t h a t t h e r e was no change i n the CUV o f t h e c a t a l y s t which was found t o
be 400 and 375 g/g r e s p e c t i v e l y as opposed t o 385 g/g f o r t h e powder. When
s i l i c a - a l u m i n a was used as a binder the CUV increased from 409 t o 497 g/g. Fig.
3 shows c l e a r l y t h a t the a c t i v i t y and l i f e t i m e o f t h e c a t a l y s t decreased
s i g n i f i c a n t l y when p e l l e t s were used, the CUV dropping from 380 g/g for
extrudates o f TPA-Z-38-3 t o 60 g/g f o r 10 ton p e l l e t s o f t h e same sample.

Fig. 4 shows the l i q u i d product analysis obtained from t h e o l i g o m e r i z a t i o n

o f propene using powder and extrudates. The values obtained f o r t h e powder are
representative o f those f o r almost a l l runs i n t h i s work. High r e a c t i o n
temperatures l e d t o a s h i f t t o l i g h t e r products l a r g e l y because o f t h e increased
e x t e n t o f cracking a t these temperatures. This f i g u r e shows a d i s t i n c t t r e n d t o
heavier products i n the case o f the extruded c a t a l y s t independent o f t h e binder
used. Gautier's c o r r e l a t i o n ( r e f . 24) was used t o c a l c u l a t e cetane numbers from
the 'H-NMR spectra o f hydrogenated l i q u i d samples. The values obtained were i n
the range 39-52 f o r both powder and extrudates. The best c a t a l y s t t e s t e d was
alumina-bound extrudates o f (TPA)-Z-38-3 (mechanically s t i r r e d ) which had a CUV
o f 1100 g/g and a product cetane number o f 44.

A g r a v i m e t r i c analysis o f the carbonaceous deposit on t h e c a t a l y s t a t the

end o f a run showed t h a t i n the case o f extrudates bound w i t h alumina t h e t o t a l
mass o f these deposits, v i z . " g r a p h i t i c " material p l u s h i g h b o i l i n g p o i n t
hydrocarbons, was 15% o f the t o t a l mass o f deactivated c a t a l y s t . This was about
496

Conversion of orooene (a)

2 Ton9
5 Tons

0 5 10 15 20 25 30 35 40 45
Time on stream (hr)

Fig. 3 Effect of extrusion and pelletizing on propene oligomerization

activity (P = 5 MPa, T = 250"C, WHSV = 12 h- )

40
Mass%

30

20

10

0
Dlmer Trimer Tetramer Pentamer Hexamer,

Oligomer Group
Powder @ Silica extrudates 0Alumina Extrudetes
Fig. 4 Liquid Product Analysis
 497

half that found in the case of powdered, silica or silica-alumina bound

extrudates.

DISCUSSI ON
The number average crystal sizes of 2-18-1, 2-19-3 and 2-26-6 were larger
than what was expected from the trend observed by Van der Gaag et a1 .(ref. 25)
and Jacobs and Martens (ref. 13). For the 6-day catalyst this may be due to
amorphous material being deposited on the zeolite surface. The increase in
crystal size (2-19-3 and 2-26-6 larger than 2-18-1) has been observed by other
workers (ref. 26). Mechanical stirring is expected to cause more attrition than
a magnetic stirrer bar in a synthesis mixture and hence as observed in the
present study should cause a decrease in crystal size. The narrow size
distributions obtained with mechanical stirring could be a result of more
effective agitation throughout the autoclave and a more even distribution of
stress on the crystals. This is distinctly advantageous with respect to the
propene oligomerization activity. When different templates were used it was
found that 1 BA, 1,2 ED, 1,2 PD as well as the alcohol-based samples produced
larger crystal sizes than TPA-ZSM-5. This may happen if the formation of the
template-silicate complex is difficult resulting in the formation of only a few
nuclei which then grow to a larger size.

The activity for propene 01 igomerization increased with decreasing Si/A1

ratio. TPD studies indicated a high concentration of Bronsted sites (refs. 23-
26). Moreover little dehydroxylation appeared to have taken place. The
relationship between aluminium content and activity is thus probably indicative
of a relationship between activity and Bronsted acidity for propene
ol igomerization. Calcination temperatures less than 500°C however do not favour
optimum catalytic performance (ref. 22,23).

The synthesis used in this study was similar to type ‘A’ of Gabelica et
al. (ref. 27), who reported an aluminium rich outer layer for this synthesis
procedure. Aluminium zoning of this nature was reported by Von Ballmoos and
Meier (ref. 28). Suzuki et al. (ref. 29) also confirmed this finding and
observed a decrease in activity for methanol conversion as synthesis time
increased once maximum crystal1 inity was attained. They attributed the decrease
in activity to increased coking on the catalyst surface. The results of the
present study support these observati ons.

This work has shown that a decrease in crystal size enhances lifetime and
activity for propene ol igomerization as has been reported for methanol
498

conversion (ref. 3 0 ) , xylene isomerisation (ref. 31) and propene oligomer sation
using N i - and Zn-impregnated ZSM-5 (ref. 3 2 ) .

The improved performance of small crystals may be related to coking This

has been found by Behrsing et al. (ref. 3 3 ) who compared ZSM-5 crystals of
differing crystal sizes using methanol conversion. They observed that ZSM-5
with a crystal size < 1 pm had the longest lifetime for methanol conversion,
even though it contained more coke than the other catalysts. The long lifetime
of small ZSM-5 crystals may also be attributed to higher pore volumes, higher
external surface areas and more external acid sites when compared to large
crystals. Higher pore volumes will increase resistance to coking and more
external acid sites ensure that a large fraction of the total acid sites are
easily available for reaction. In larger crystals, with a lower ratio of
external to internal surface area, many acid sites may not be accessible for
reaction due to excessively long diffusional pathways. Moreover heavier
hydrocarbons produced inside a large crystal may not be able to diffuse out of
the crystal and will therefore block the passage of other molecules further into
the crystal. This would decrease the amount of acid sites available for
reaction and cause quicker deactivation than in small crystals.

The low crystallinities and primarily the large crystal sizes of the
alcohol-based ZSM-5 samples were probably responsible for their low activities
and short lifetimes. Surprisingly extrusion did not decrease the activity for
propene ol igomerization although the high conversions involved may have masked
any difference in activity between powdered and extruded catalysts. Attempts to
verify this observation at low conversions were difficult due to temperature
runaway problems. The observed decrease in lifetime and activity with
increasing pelletisation pressure is probably due to increased diffusional
resistance in the intercrystalline pores and blockage of the ZSM-5 micropores by
binder particles.

The activity and lifetime of catalysts synthesized using different amine

templates increased in the order: 1 , 2 ED = 1,2 PD < 1 BA < 1 HA (crystal size
= 3 . 4 prn, 4 . 7 pm, 2 . 9 pm and 1 . 0 pm respectively). At larger crystal sizes this
trend became indistinct. No reference has been made to the importance which
different morphologies may have on the catalytic properties and this has been
considered el sewhere (ref. 2 3 ) . Temperature control for extruded catalysts was
much easier than for powdered catalysts due to the dilution effect of the binder
and the void spaces between individual extrudates in the catalyst bed. Although
it may have been expected that the lighter products would thus be produced by
powdered ZSM-5 due to cracking at hotspot temperatures, it was observed that
 499

p e l l e t s y i e l d e d t h e l i g h t e s t l i q u i d products. T h i s was p o s s i b l y due t o t h e

lo we r c o nv ers io n s .

S i l i c a - a l u m i n a e x t r u d a t e s produced more coke t h a n t h e o t h e r e x t r u d a t e s

i n v e s t i g a t e d and t h i s may be due t o t h e a c t i v i t y o f t h e b i n d e r f o r propene
01 i g o m e r i s a t i o n . T h i s i n c r e a s e d i d not, however, adversely a f f e c t t h e 1 i f e t i m e
o f these extrudates. The l o w coke c o n t e n t o f t h e alumina-bound e x t r u d a t e s (-
1/2 o f t h e coke c o n t e n t o f t h e s i l i c a e x t r u d a t e s ) did not result i n any
d i f f e r e n c e i n l i f e t i m e o r a c t i v i t y when compared t o t h e s i l i c a e x t r u d a t e s . The
o b s e r v a t i o n t h a t 1 i g h t l y coked e x t r u d a t e s d i d n o t c o n t a i n g r a p h i t i c coke, w h i l e
t h e h e a v i l y coked e x t r u d a t e s d i d , seemed t o i m p l y t h a t d e a c t i v a t i o n would o n l y
occ ur once h i g h q u a n t i t i e s o f g r a p h i t i c coke were deposit ed.

CONCLUSION
T h i s s t udy has shown t h a t a t Si/A1 r a t i o s o f about 40, t h e c r y s t a l s i z e o f
ZSM-5 has a c r i t i c a l e f f e c t on propene o l i g o m e r i z a t i o n a c t i v i t y . S m a l l e r s i z e
and narrow er c r y s t a l s i z e d i s t r i b u t i o n s a r e o b t a i n e d when u s i n g m e c h a n i c a l l y
s t i r r e d a ut o c lav e s . When t h e powder i s e x t r uded t h e r e i s no adverse e f f e c t on
o l i g o m e r i z a t i o n a c t i v i t y and when alumina i s used as a b i n d e r b e t t e r q u a l i t y
distillate fuel i s produced. P e l l e t i z i n g t h e powder reduces a c t i v i t y in
p r o p o r t i o n t o t h e p r e s s u r e s used. Other t e m plat es such as 1,6 hexanediamine and
1,2 cyclohexanediamine produce ZSM-5 o f s i m i l a r a c t i v i t y t o TPA-based ZSM-5 b u t
o t h e r amines and a l l a l c o h o l s t e s t e d produced poor o l i g o m e r i z a t i o n c a t a l y s t s .
ACKNOWLEDGEMENT
The a ut h or s w i s h t o acknowledge f i n a n c i a l support f r o m t h e U n i v e r s i t y o f
Cape Town, N a t i o n a l Energy Council and Sasol .
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01991 Elsevier Science PublishersB.V., Amsterdam

ON CONTROLLED GROWTH OF SAPO-5 MOLECULAR SIEVE CRYSTALS

OF DIFFERENT SIZES AND SHAPES

G. FINGER, .J. KORNATOWSKI~,J. RICHTER-MENDAU, K. JANCKE, M. RIJLOW,

and M. ROZWADOWSKIl
Central Institute of Physical Chemistry, Academy of Sciences of the G.D.R.,
Berlin (German Democratic Republic)
‘Institute of Chemistry, Nicolaus Copernicus University, Toruh (Poland)

SUMMARY
Systematic studies of the SAPO-5 system have been performed. Roth the
crystal size and shape as well as the phase purity can be controlled by the
reacting gel composition and also by the duration and/or temperature of crys-
tallization. Evidence is given for the interdependence between the shape of
crystals and their sorption properties.

INTRODUCTION
Porous silicoaluminophosphates (ref. 1) are promising materials for numer-
ous scientific and potential practical applications. However, thoroughly re-
fined applications require materials of strictly defined physical featiires,
e.g. crystal size and shape. Unfortunately, the control of these parameters in
the case of zeolitic materials did not represent a field of major interest un-
til now, except for the tailoring of type A zeolites for washing powder produc-
tion (refs. 2 , 3 cited in ref. 4) and for the growing of MFI type crystals
(refs. 5-10). Obviously, the growth of tailored crystals requires the knowledge
of both the kinetics of the process and the conditions enabling the formation
of larger crystals. The latter problem has been solved for both the AlPO4-5
(refs. 11-16) and the SAPO-5 molecular sieves ( r e f s . 17-19). Recently, the
kinetics of SAPO-5 crystallization has been investigated in detail (ref. 2 0 )
but not with respect t o the size of the crystals.
We aim at a better understanding of the SAPO-5 crystallization process and
at getting control of size and shape of the crystals. The paper presents a num-
ber of results and conclusions regarding these goals.

EXPERIMENTAL
SAPO-5 molecular sieve crystals were synthesized hydrothennally in teflon-
lined steel autoclaves in air-heated w e n s at 4 5 3 to 473 K from gels of the
formal molar composition
 a A1203 * b P2O5 - c TEA d Si02 e H20 * x H2SO4 (1)
with a = 1, b = 1 t o 2.4, c = 1.5 t o 12, d = 0.05 t o 1 , e = 300 t o 2000, x ? 0.
F i r s t , g e l s were formed by mising a s t a b i l i z e d aluminiumoxidehydrate
s o l ( p u r c h a s e d from CTA SAURESCHUTZ, B e r l i n ) w i t h s i l i c a s o l (LUDOX AS 40 from
DUPONT/Germany). Next, a s o l u t j o n of 85% p h o s p h o r i c a c i d and t r i e t h y l a m i n e / T E A /
(Merck) i n t w i c e d i s t i l l e d w a t e r was added under v i g o r o u s s t i r r i n g . Varioiis
amounts o f H3PO4, TEA, and w a t e r were admixed a c c o r d i n g t o t h e g e l rompr~siticln
s t u d i e d . A t t h e same t i m e , s u l f u r i c a c i d was added, i f n e c e s s a r y , t o a d j u s t t h e
pH v a l u e t o 3 , 3 + 0 , 2 . A s e r i e s of r u n s was made a t d = 0 t o grow AlP04-5 c r y s -
t a l s a s r e f e r e n c e samples.
These g e l s were p u t i n t o t h e a u t o c l a v e s and exposed t o t h e c r y s t a l l i z a t i o n
t e m p e r a t u r e . A f t e r a p p r o p r i a t e time p e r i o d s , t h e v e s s e l s were c o o l e d down, t h e
samples were washed, s e p a r a t e d from b y p r o d u c t s , i f n e c e s s a r y , by d e c a n t a t i o n
( o b v i o u s l y , a number of smaller SAPO-5 c r y s t a l s were l o s t a t t h e same t j m e ) ,
and d r i e d a t 3 7 3 K. Furthermore, s e l e c t e d samples were c a l c i n e d under s t a t i c
a i r atmosphere a t about 1050 K f o r 24 h r s .
The p r o d u c t s were c h a r a c t e r i z e d by XRD ( G u i n i e r t e c h n i q u e ) , MAS NMR, I R
s p e c t r o s c o p y , a d s o r p t i o n , and SEM. The c o n t e n t of c r y s t a l s i n t h e samples was
e s t i m a t e d and t h e c r y s t a l dimensions were measured by l i g h t microscopy accor-d-
i n s t o t h e methods d e s c r i b e d i n d e t a i l e l s e w h e r e ( r e f . 2 1 ) .

RESUILTS
The procedure e l a b o r a t e d ( r e f s . 17-19) i s a r e l i a b l e r c c j p e € o r t h e syn-
t h e s i s of l a r g e hexagonal SAPO-5 p r i s m s , though sometimes i n a broad p a r t i c l e
s i z e d i s t - r i b u t i o n . I n comparison w i t h t h e similar p r o c e d u r e t o grow A1P04-5
m o l e c u l a r s i e v e s ( r e f s . 13-16), t h e SAPO-5 s y s t e m is more complex. However, t h e
c r y s t a l s o b t a i n e d i n a l l e x p e r i m e n t s e x h i b i t X-ray p a t t e r n s c o r r e s p o n d j n g t o
t h e A F I topology and MAS NMR measurements prove s i l i c o n i n c o r p o r a t i o n i n t o t h e
framework.
The c r y s t a l l i z a t i o n was s t u d i e d w i t h i n t h e range of t e m p e r a t u r e from 423
t o 4 7 3 K and p e r i o d s up t o 10 days. Whereas a t t h e lower l i m i t of t.emperature
f o r e i g n phases a r e formed, t h e c r y s t a l l i z a t i o n of SAPO-5 is a c c e l e r a t e d w i t h
r i s i n g t e m p e r a t u r e . T h i s l e a d s t o y i e l d s of SAPO-5 up t o 100 p e r c e n t depending
on t h e g e l composit.ion. A t 463 K , t h e l a r g e s t c r y s t a l s were obt.ained. There-
f o r e , we r e p o r t o n l y about t h e e x p e r i m e n t s a t t h i s t e m p e r a t u r e ,
The g e l c o m p o s i t i o n r e p r e s e n t s t h e most i m p o r t a n t f a c t o r f o r t h e c o n t r o l
of b o t h c r y s t a l s i z e and s h a p e . To t h e d e g r e e t o which t h e r o l e of s j l i c o n can
be n e g l e c t e d , i . e . a t s u f f i c i e n t l y low s i l i c a c o n c e n t r a t i o n i n t h e gel, t h e
e f f e c t s of c o n t e n t s of H 2 0 , TEA, and P2O5 are s i m i l a r t o t h o s e which govern t h e
n u c l e a t i o n and growth of AlPO-5 c r y s t a l s ( r e f . 1 6 ) . The i n f l u e n c e s of b o t h t h e
c o n t e n t of H 2 0 ( F i g . 1 ) and t h e c o n t e n t of TEA o r TEA and P2O5 t o g e t h e r ( F i g . 2 )
 503

have been chosen as representative illustrations of the system, The maximum

length of the hexagonal prism grown from gels of various compositions are
depicted in a graph (Fig. 3 ) .
Dilution of the reacting gel results always in the growth of larger crys-
tals (Fig. 1). However, this is accompanied by a rising content of a byproduct
and a considerable prolongation of the crystallization time (more than one week
for the most diluted gels). Occasionally, a new nucleation of hexagonal prisms
occurs in the bulk volume of the gel and on the surface of crystals already
formed. A water content 750 < e c 1000 seems t o be an advant.ageous compromise.
Then, the largest crystals can grow up to a length of 580 pm (Fig. 4D1 and the
yield of the SAPO-5 phase (regardless of the size distribution) can amount up
to 80 per cent.

Fig. 1. SAPO-5 crystals (after decantation) synthesized from gels with rising
water content (a:b:c:d = 1:1:1.55:0.2):
( A ) e = 300, (B) e = 450, ( C ) e= 600, (D) e = 750.
504

Fig. 2. SAPO-5 crystals (after decantation) synthesized from gels with constant
water content (e = 300 H20, d = 0 . 2 Si02):
( A ) b = 1 , c = 1.55; ( B ) b = I , c = 3.1,; ( C ) b = 1, c = 6 . 2 ; (D) b = 2, c =
3.1.

6 00- I
/
0 1.55 0.2 +,
1 3.1 0.2
E 400- 1 6.2 0.2

-2
E
-.
-
2 3.1 0.2 0

200-

I I
I I I I I
400 600 800 H20ImoLe
Fig. 3. Maximum length of AFI hexagonal prisms depending on the gel
composition.
 505

F i g . 4 . Various c r y s t a l morphology i n SAPO-5 s y n t h e s i s

Gel composition a b c d e
(A) vicinal faces 1 1 3.1 0.2 450
( B ) growth aggregate 1 2 3.1 0.2 300
(C) byproduc t
(D) SAPO-5 c r y s t a l s 1 1 1.55 0.3 750
(E) d i s t o r t e d c r y s t a l s 1 1 1.55 1.0 300
( F ) secondary n u c l e a t i o n 1 1 1.55 0.4 300
 For AlPO-5, recrystallization of AFI type crystals into tridymite and/or
crystobalite type phases have been reported (ref. 2 2 ) . We could not observe
this even in runs of one week duration (optimum period for the largest crystals
growth). Small contents of a tridymite phase can be observed with SAPO-5 grown
from gels with an overabundance of phosphorus, i.e. b:a = 2.4 (ref. 2 3 ) . Simi-
lar results have been already reported (ref. 20).
At a fixed water content in the gel, the crystal size can be influenced by
the content of template or template and phosphoric acid toget.her (Fig, 2).
Their excess can result in the formation of smaller crystals with a higher
yield and in a decreasing crystallization period. Distortions of the cr-ystals
or rose-like looking vicinal faces start to occur (Fig. 4A). This behaviour
underlines the role of the template in the process of the molecular sieve for-
mation and its significance for the nucleation stage in particular.
An excess of both P2O5 and TEA leads to the strongest effect on the mor-
phology of the product and, at low water content., even polycrystalline growth
aggregates are formed (Fig. 48). On the other hand, the samples do not contain
any byproduct and the crystallization is completed within 24 hrs.
Depending on the gel composition, small spherulitic particles can be
formed together with the SAPO-5 crystals (Fig. 4C). According to an MAS NMR
investigation (ref. 24), this byproduct represents an aluminophosphate which we
failed to identify until now. Its occurrence is correlated with HzO/TEA 2 100
(molar ratio), i.e. just with the conditions to synthesize the large SAPO-5
crystals. However, using the differences in s i z e , both phases can be separated,
e.g. by decantation. Occasionally, a small number of rhombohedric crystals have
been observed in the samples, too (Fig. 4C).
Concerning the silicon incorporation into the AFI framework, it is gene-
rally accepted that only small amounts can substitute phosphorus atoms esclu-
sively (ref. 2 5 ) . As it was stated for the system investigated, even the smal-
lest content of silica in the gel (i.e. d = 0.05) seems to hitlder the crystals
to grow so large as in the AlP04-5 system. With increasing silicon content up
to about d = 0.25 the system remains almost insensitive with regard to the
crystal size and shape. Surprisingly, the largest crystals ( u p to about 580 pm
long) can be synthesized at d = 0.3 (Fig. 4D), whereas at higher d values, only
crystals as illustrated in Figs. 4E and 4F are formed. A similar appearance
(Fig. 4F) was observed in the FAPO-5 system and attributed to secondary 11uc1ea-
tion (ref. 26). Unquestionably, this behaviour of the system should be attrihu-
ted to the presence of heteroatoms. This is underlined by the absence of simi-
lar findings in the systems forming large AlP04-5 crystals (ref. 1 6 ) .
Up to the same composition limit ( d = 0.31, silicon replaces almost esclu-
sively phosphorus atoms in the framework of the crystals in this study. This
 507

i s proved by 29S1 MAS NMR ( r e f . 24) and I R measurements a r e c o n s i s t e n t w i t h

t h i s s t a t e m e n t a s w e l l ( r e f . 2 4 ) . I n r e f . 20, a similar l e v e l of s i l i c a c o n t e n t
in t h e g e l ( d = 0 . 4 ) h a s been s u g g e s t e d as a c r i t i c a l v a l u e € o r t h e s i l i c o n i n -
c o r p o r a t i o n i n t o t h e A F I framework and f o r t h e optimum c r y s t a l l i z a t i o n of g e l s
c o n t a i n i n g n-tripropylamine.

1 I I I 1 I I I

-2 .4 .6 .8 PIP,

F i g . 5 . Adsorption i s o t h e r m s of n-hexane on SAPO-5 m o l e c u l a r s i e v e c r y s t a l s of

d i f f e r e n t morphology ( T = 298 K):
1-hexagonal p r i s m s ; 2-growth a g g r e g a t e s ; 3 - d i s t o r t e d c r y s t a l s .

The a d s o r p t i o n behaviour of t h e v a r i o u s SAPO-5 m o l e c u l a r s i e v e s a m p l e s

d i f f e r s depending on t h e c r y s t a l morphology ( F i g . 5 ) . A t h i g h r e l a t i v e a d s o r -
b a t e p r e s s u r e ( p / p s ) , o n l y t h e well-formed hexagonal prisms e x h i b i t t h e i d e n -
t i c a l a d s o r p t i o n and d e s o r p t i o n i s o t h e r m s , whereas b o t h t h e d i s t o r t e d c r y s t a l s
and t h e growth a g g r e g a t e s show a n a d s o r p t i o n h y s t e r e s i s o c c u r r i n g most p r o b a b l y
i n t h e secondary p o r e systems. I € t h e l a t t e r p o r e system is assumed as s e r v i n g
a s a channel f o r t r a n s p o r t , t h e a d s o r p t i o n k i n e t i c s might b e a c c e l e r a t e d , b u t
i n t h e s e p a r a t i o n p r o c e s s e s , t h e a d s o r p t i o n h y s t e r e s i s would be a draw back due
t o r e d u c t i o n of t h e a d s o r b e n t - a d s o r b a t e i n t e r a c t i o n .
The d i f f e r e n c e s i n t h e amounts adsorbed i n comparison t o t h e f i n d i n g s i n
r e f . 27 can be a t t r i b u t e d t o t h e n o t optimized c a l c i n a t i o n c o n d i t i o n s i n t h e
present case.

CONCLUSIONS
The s t u d i e s performed have shown t h e c o n d i t i o n s € o r t a i l o r i n g t h e c r y s t a l s
of t h e SAPO-5 molecular s i e v e w i t h c r y s t a l s i z e s r a n g i n g from 25 t o 580 pm i n
508

l e n g t h . P a r t i c u l a r a t t e n t i o n h a s been p a i d t o t h e c o n d i t i o n s i n f l u e n c i n g c r y s -
t a l morphology.
The f o r m a t i o n and growth of t h e c r y s t a l s a r e i n f l u e n c e d by t h e c o n t e n t of
a l l components i n t h e g e l . D i l u t i o n of t h e s y s t e m enhances t h e growth a l o n g t h e
c-axis l e a d i n g t o t h e f o r m a t i o n of l a r g e hexagonal p r i s m s . On t h e o t h e r h a n d ,
an e x c e s s of amine o r amine and p h o s p h o r i c a c i d t o g e t h e r r e s t r i c t s t h e c r y s t a l
growth v i a an a c c e l e r a t i o n of t h e n u c l e a t i o n r a t e . Then, t h e d i s t o i . t e d c r y s t a l s
o r even growth a g g r e g a t e s a r e formed.
The s i l i c o n c o n t e n t r e p r e s e n t s a n a d d i t i o n a l v a r i a b l e i n f l u e n c i n g t h e
c r y s t a l shape. The e u h e d r a l hexagonal p r i s m s c a n c r y s t r a l l i z e o n l y from g e l s
c o n t a i n i n g up t n about 0 . 3 s i l i c o n ( m o l a r r a t i o ) which is incorporat.ed i n t o t h e
s t r u c t u r e a l m o s t o n l y on phosphorus-T-sites.
The f o r m a t i o n of t h e p u r e SAPO-5 phase is c o r r e l a t e d w i t h t h e c o n d i t i o n
H?O/TEA < I 0 0 ( m o l a r r a t i o ) . T h e r e f o r e , l a r g e hexagonal SAPO-5 prisms a r e always
accompanied by s m a l l p a r t i c l e s of an u n i d e n t i f i e d aluminophosphate which can be
s e p a r a t e d , i n p r i n c i p l e , because of t h e l a r g e d i f f e r e n c e s i n t h e s i z e of t.he
particles.
The shape of t h e c r y s t a l s i n f l u e n c e s c o n s i d e r a b l y t h e i r s o r p t i o n
properties.

ACKNOWLEDGEMENTS
The authoi i a r e i n d e b t e d t o Dr. Janchen f o r a d s o r p t i o n measurements and t o
D I . M . Hndnn f o r h e l p f u l d i s c u s s i o n s . Thr work was p a r t i a l l y s u p p o r t e d by Leuna
WilrkF' AG. by t h e fund of t h e P r e s i d e n t of t h e Academy of S c i e n c e s of tht, GDR,
and by t h e P o l i s h M i n i s t r y of N a t i o n a l Education w i t h i n t h e P r o j e c t CPBP 01.06.

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G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 511
1991 Elsevier Science Publishers B.V., Amsterdam

APPROXIMATE ASSIGNMENT OF VIBRATIONAL FREQUENCIES OF THE NaX

FRAl.iEI.VORK

E. GEIOEL', H. 9uHLIG2, CH. PEUKER' and W. PILZ'

' C e n t r a l I n s t i t u t e o f P h y s i c a l C h e m i s t r y , Academy o f S c i e n c e s ,
Rudower Chaussee 5, B e r l i n - 1 1 9 9 (GDR)

2Department o f C h e m i s t r y , K a r l - M a r x - U n i v e r s i t y Leipzig,
T a l s t r a R e 35, L e i p z i g - 7 0 1 0 (GDR)

SUMMARY
O n t h e b a s i s o f s y s t e m a t i c a l l y d e v e l o p e d s u b u n i t c l u s t e r mod-
e l s o f NaX z e o l i t e framework n o r m a l c o o r d i n a t e a n a l y s e s h a v e
been c a r r i e d o u t by means o f WILSON'S GF m a t r i x method i n t e n d i n g
t o u n d e r s t a n d t h e c o r r e s p o n d i n g e x p e r i m e n t a l v i b r a t i o n a l spec-
t r a . An a p p r o x i m a t e a s s i g n m e n t o f v i b r a t i o n a l f r e q u e n c i e s o f t h e
NaX z e o l i t e framework i s g i v e n o n t h e b a s i s o f c a l c u l a t e d e i g e n -
v a l u e s , p o t e n t i a l e n e r g y d i s t r i b u t i o n s and e i g e n v e c t o r s . The r e -
s u l t s a r e d i s c u s s e d i n c o n n e c t i o n w i t h t h e FLANIGEN c o n c e p t i o n
o f i n t e r n a l and e x t e r n a l v i b r a t i o n s .

INTRODUCTION
Z e o l i t e s have been w i d e l y used f o r i o n exchange, s e l e c t i v e
a d s o r p t i o n and c a t a l y s i s . Related t o t h a t r e s u l t s o f a great
number o f e m p i r i c a l s t u d i e s o f i n f r a r e d and Raman s p e c t r a have
been p u b l i s h e d m a i n l y c o n c e r n i n g w i t h OH s t r e t c h i n g v i b r a t i o n s
and more r e c e n t l y c o n s i d e r i n g t h e v i b r a t i o n s o f t h e z e o l i t e
framework on t h e b a s i s o f FLANIGEN c o n c e p t i o n ( r e f . 1). I n t h e
most c a s e s t h e r e a r e d i f f i c u l t i e s w i t h r e s p e c t t o t h e i n t e r p r e -
t a t i o n o f v i b r a t i o n a l s p e c t r a because o f t h e c o m p l i c a t e d c r y s t a l
s t r u c t u r e on one s i d e and t h e s t r o n g l y o v e r l a p p e d bands i n t h e
z e o l i t e s p e c t r a on t h e o t h e r s i d e . Beside t h a t i t i s i n s u f f i -
c i e n t l y known t h e i n f l u e n c e o f c a t i o n s , s t r u c t u r a l OH g r o u p s ,
a d s o r b e d w a t e r and o t h e r m o l e c u l e s on t h e v i b r a t i o n a l spectrum.
F u r t h e r d i f f i c u l t i e s a r i s e w i t h i n a more t h e o r e t i c a l t r e a t -
ment o f v i b r a t i o n a l b e h a v i o u r o f z e o l i t e s c o n n e c t i n g w i t h t h e
l a r g e u n i t c e l l s and t h e i n s u f f i c i e n t l y known f o r c e r e l a t i o n s
between t h e l a t t i c e atoms and i o n s . The n o r m a l c o o r d i n a t e a n a l y -
s i s a s a r o u t i n e method c a n be u s e d t o i n t e r p r e t v i b r a t i o n a l
spectra, but i s r e s t r i c t e d t o the s o l u t i o n o f d i r e c t eigenvalue
p r o b l e m s because o f t h e l a c k o f e x p e r i m e n t a l d a t a f i t t i n g t h e
model f o r c e c o n s t a n t s . So f a r some n o r m a l c o o r d i n a t e a n a l y s e s
512

have been c a r r i e d o u t on t h e b a s i s of s u b u n i t cluster models

( r e f s . 2 , 3 ) a s s u m i n g t h e d e c o u p l i n g p o s t u l a t e o f 6LACICI”IELL
( r e f . 3 ) and s i m p l i f i c a t i o n s w i t h i n t h e p s e u d o - l a t t i c e method
( r e f s . 4 - 6 ) , r e s p e c t i v e l y . R e c e n t l y t h e m e t h o d s of m o l e c u l a r
m e c h a n i c s h a v e b e e n u s e d , t o o ( r e f s , 6-8).
I n t h i s s t u d y , n o r m a l mode c a l c u l a t i o n s were d o n e f o r some
s y s t e m a t i c a l l y s e l e c t e d s u b u n i t c l u s t e r models on t h e b a s i s of a
simplified force f i e l d for understanding the vibrational spectra
o f NaX z e o l i t e framework.

SUBUNIT CLUSTER MODELS AND CALCULATIONS

T h e s u b u n i t c l u s t e r m o d e l s o f NaX z e o l i t e f r a m e w o r k h a v e b e e n
s e l e c t e d f o r t h e normal c o o r d i n a t e t r e a t m e n t s u s i n g a t e t r a h e d -
r a l s u r r o u n d i n g o f T ( T = S i , A l ) atoms a n d a s s u m i n g t h e v a l i d i t y
o f LOEWENSTEIN r u l e ( r e f . 9 ) . G e o m e t r i c a l p a r a m e t e r s h a v e b e e n
t a k e n from OLSON‘S X-ray d i f f r a c t i o n s t u d y o f h y d r a t e d N a X zeo-
l i t e ( r e f . 10). The s e l e c t e d c l u s t e r m o d e l s t o g e t h e r w i t h t h e i r
p o i n t g r o u p s y m m e t r i e s , t h e d i s t r i b u t i o n o f norrnal v i b r a t i o n s t o
t h e i r r e d u c i b l e r e p r e s e n t a t i o n s a n d t h e number o f i n f r a r e d a n d
Raman a c t i v e m o d e l v i b r a t i o n s a r e shown i n T a b l e 1. T h e r e s u l t
of a n u c l e a r s i t e group a n a l y s i s f o r t h e complete u n i t c e l l o f
NaX z e o l i t e b a s e d o n Fd3 s p a c e g r o u p symmetry a n d s u b t r a c t i n g
t h e m o t i o n s o f Na’ c a t i o n s i s g i v e n i n t h e l a s t r o w . MARONI
( r e f . 1 1 ) a n d GODBER a n d OZIN ( r e f . 1 2 ) o b t a i n e d an o t h e r r e s u l t
o n t h e b a s i s o f Fd3m s p a c e g r o u p s y m m e t r y . W i t h t h e e x c e p t i o n o f
S i 0 4 ( A 1 0 3 ) 4 a n d A 1 0 4 ( S i 0 3 ) 4 A l g t h e number o f i n f r a r e d a n d Raman
a c t i v e model v i b r a t i o n s i s a l w a y s smaller t h a n t h e c o r r e s p o n d i n g
number o f o p t i c a l a c t i v e v i b r a t i o n s o f t h e u n i t c e l l . T h e n o r m a l
mode c a l c u l a t i o n s were d o n e by m c a n s o f t h e GF m a t r i x m e t h o d o f
WILSON ( r e f . 1 3 ) o n t h e b a s i s o f t h e JONES p r o g r a m ( r e f . 1 4 )
u s i n g i n t e r n a l c o o r d i n a t e s i n t h e u s u a l way w i t h e x c e p t i o n o f
t o r s i o n a l o n e s w h i c h were c h o i c e d t o t a k e i n t o c o n s i d e r a t i o n
o n l y o n e d i h e d r a l a n g l e b e n d i n g f o r o n e n o n - t e r m i n a l bond.
A c c o r d i n g t o BLACKWELL ( r e f . 3 ) we h a v e u s e d t h e s o - c a l l e d bond
l e n g t h s c a l e d f o r c e f i e l d o n t h e b a s i s o f t h e BADGER r u l e
(BLSF-BR) .
 513

TABLE 1
D i s t r i b u t i o n o f n o r m a l v i b r a t i o n s o n t h e symmetry s p e c i e s o f
d i f f e r e n t z e o l i t e c l u s t e r models

C l u s t e r models; D i s t r i b u t i o n o f normal u(1R) u(RA)

/ p o i n t o r space group/ vibrations

S i 0 4 , A104 9 9
O3 S i -0 ( i) -A103 21 21
4R(hP), 4R(S)- 42 42
6 R ( h P ) ; /C3/ r=22a+22e 44 44
06R; /S6/ r=20au t 2oa + 20eu+20e 40 40
9 9
Si04(A1)4 r=21a 21 21
Si04 (A103)4 r=57a 57 57
A104 P i 0 3 14 ( A 1 19 r=84a 84 84
A124Si24096 ; /Fd3, (Th 4 ) / r=18A +18Au+18E +18Eu+ 53
90
9 9
54 Fa+53F,

( u ( 1 R ) number o f i n f r a r e d and u(RA) number o f Raman a c t i v e m o d e l

v i b r a t i o n s ; i = 1 - 4 ; 4R(hP) 4 - r i n g i n t h e h e x a g o n a l p r i s m ; 4R(S)
4 - r i n g i n t h e s o d a l i t e u n i t : 6R(hP) 6 - r i n g i n t h e h e x a g o n a l
p r i s m ; D6R d o u b l e - 6 - r i n g )

RESULTS AND DISCUSSION

The r e s u l t s o f o u r c a l c u l a t i o n s f o r some s e l e c t e d s u b u n i t
c l u s t e r models a r e r e p r e s e n t e d i n F i g . 1 and compared w i t h t h e
e x p e r i m e n t a l i n f r a r e d s p e c t r u m o f NaX z e o l i t e framework t a k e n
f r o m MIECZNIKOWSKI and HANUZA ( r e f . 1 5 ) . Whereas t h e o b s e r v e d
spectrum i s g i v e n i n t r a n s m i s s i o n u n i t s t h e c a l c u l a t e d frequen-
c i e s a r e p l o t t e d a g a i n s t t h e number o f f r e q u e n c i e s p e r f r e q u e n c y
interval i n arbitrary units. I t c a n be seen t h a t an i n c r e a s e o f
s u b u n i t c l u s t e r s i z e l e a d s t o i n c r e a s i n g d e n s i t y o f bands p e r
f r e q u e n c y i n t e r v a l . The A10 and SiO s t r e t c h i n g v i b r a t i o n s a b s o r b
i n c l e a r l y d i f f e r e n t f r e q u e n c y r e g i o n s whereas OAlO and O S i O
b e n d i n g ones appear i n t h e same r e g i o n what i s shown i n r e p r e s e n -
t a t i o n (b). T h e r e f o r e t h e l a t t e r v i b r a t i o n s a r e d e n o t e d by OTO
bendings. T h i s p r i n c i p a l d i f f e r e n c e remains v a l i d a l s o i n t h e
o t h e r s u b u n i t c l u s t e r s m o d i f i e d , however, by c o m p l i c a t e d coup-
lings.
I f t e r m i n a l bonds e x i s t i n t h e c l u s t e r models as i n t h e c a s e s
(b)-(e) t h e c a l c u l a t e d h i g h f r e q u e n c y A10 s t r e t c h i n g v i b r a t i o n s
f a l l i n t h e e x p e r i m e n t a l f r e q u e n c y gap (780-850 cm"). Lacking
t e r m i n a l bonds ( f ) t h e above m e n t i o n e d v i b r a t i o n s a r e s h i f t e d t o
514
I I

600 400

1200 1000 800 600

krn-11 -
400
 515

l o w e r f r e q u e n c i e s by s t r o n g c o u p l i n g s . T h i s r e s u l t i s supported
by FLANIGEN's i n f r a r e d s t u d i e s o f sodium a l u m o s i l i c a t e s i n d i f -
ferent crystallization states (ref. 16). Increasing the crystal-
l i z a t i o n degree and t h u s d e c r e a s i n g t h e number o f t e r m i n a l bonds
i n t h e m i x t u r e l e a d s t o d i s a p p e a r a n c e o f an a b s o r p t i o n band a t
850 cm" c h a r a c t e r i z i n g t e r m i n a l A 1 0 bonds.
The c a l c u l a t e d f r e q u e n c y r e g i o n s o f s t r e t c h i n g and OTO bend-
ing vibrations, t o g e t h e r w i t h an a p p r o x i m a t e c l a s s i f i c a t i o n o f
t h e model v i b r a t i o n s a r e c o l l e c t e d i n t h e T a b l e s 2 and 3. The
TOT b e n d i n g s and t o r s i o n a l v i b r a t i o n s a p p e a r i n g i n t h e f a r i n -
f r a r e d r e g i o n a r e n o t s u b j e c t o f t h i s s t u d y . V i b r a t i o n a l modes
o f t h e s u b u n i t c l u s t e r models d e t e r m i n e d by t h e p o t e n t i a l e n e r g y
d i s t r i b u t i o n and t h e e i g e n v e c t o r s show a c o m p l i c a t e d p i c t u r e .
I t c a n be d i s t i n g u i s h e d between 3 t y p e s o f s t r e t c h i n g v i b r a -
tions: terminal, bridging ( w i t h regard t o linkages connecting 2
t e t r a h e d r o n s ) and t e t r a h e d r a l v i b r e t i o n s , a l l o f t h e s e c a n be
f u r t h e r d i v i d e d i n s y m m e t r i c and a s y m m e t r i c ones. I n addition t o
t h i s t h e p o t e n t i a l e n e r g y can be d i s t r i b u t e d i n a d i f f e r e n t way.
T h i s statement i s v a l i d i n p r i n c i p a l f o r t h e bending v i b r a t i o n s ,
too,
The b r i d g i n g and t h e t e t r a h e d r a l t y p e v i b r a t i o n s o f t h e sub-
u n i t c l u s t e r models c a n be u s e d t o i n t e r p r e t t h e v i b r a t i o n a l
s p e c t r a o f an a c t u a l z e o l i t e . The a p p r o x i m a t e a s s i g n m e n t t h u s
o b t a i n e d i s shown i n T a b l e 4. So t h e h i g h f r e q u e n c y framework
a b s o r p t i o n s can be a s s i g n e d t o a s y m m e t r i c b r i d g i n g s t r e t c h i n g
vibrations. The m a i n p a r t o f p o t e n t i a l e n e r g y o f t h e s e i s l o -
c a t e d i n t h e S i O bonds. Then f o l l o w a s y m m e t r i c b r i d g i n g s t r e t c h -
i n g v i b r a t i o n s w i t h dominant A 1 0 c h a r a c t e r ( S i O c h a r a c t e r less
t h a n 10%). Symmetric b r i d g i n g and t e t r a h e d r a l v i b r a t i o n s a p p e a r
a t l o w e r f r e q u e n c i e s . The d o u b l e r i n g and p o r e o p e n i n g modes
m e n t i o n e d i n T a b l e 4 have been d e s c r i b e d i n d e t a i l e l s e w h e r e
(ref. 1 7 ) . The a b s o r p t i o n s between 510 cm" and 408 cm" c a n be

Fig. 1. Observed IR s p e c t r u m and c a l c u l a t e d v i b r a t i o n a l f r e q u e n -

c i e s o f NaX z e o l i t e framework ( T = t r a n s m i s s i o n , nf=number o f f r e -
quencies per frequency i n t e r v a l ; ( a ) e x p e r i m e n t a l IR s p e c t r u m o f
NaX z e o l i t e (Si/A1=1.12) a c c o r d i n g t o MIECZNIKOWSKI and HANUZA
(ref. 15), ( b ) S i 0 4 ( f u l l l i n e ) and A104 ( d o t t e d l i n e ) c l u s t e r ,
( c ) 03Si-0(1)-A103 cluster, (d) 6 - r i n g c l u s t e r i n t h e hexagonal
prism, ( e ) double-6-ring cluster, ( f ) A104(Si0,)4(A1)9 cluster).
TABLE 2
C a l c u l a t e d f r e q u e n c y r e g i o n s and a p p r o x i m a t e a s s i g n m e n t s f o r t h e s t r e t c h i n g v i b r a t i o n s o f
s e l e c t e d z e o l i t e c l u s t e r models

Cluster C a l c u l a t e d f r e q u e n c y r e g i o n and a p p r o x i m a t e a s s i g n m e n t
Si04 / A104 1011-978 828-805 720 574
V (SiO) Ztt,as(AIO) Vt,s(SiO) 2r (A10)
t,as t.s
03S i - C ( i ) - A 1 0 3 1086-1041 1C16-982 845-811 820-803
Y
b, a s
(Si0,AlO) 5 ,a s ( S i O ) yt ,as (A10) 4, ( S i o ,A10) 5,705-690
( s i o Ale)
8

571-559 239-231
v (A10) Y (A10,SiO)
T, s b, S
6R(hP) 1082-1052 991 866-864 827 785 756
b, a s ( S i O . A l 0 ) Y,as(SiO) v, %,as (A1O) 5,a s (A1o) vb, as (A1O)

732 669 564-561 347,233

‘V (Al0,SiO) (SiO.Al0) Y (A10) vb,s(AIO,SiO)
t.S b,s T,s
D6 R 1095-1065 1039-1027 902-894 814-803 800-791 812,779
b.as ( S i 0 , A l O ) % ?,as uT, as ( *b, a (
889,768 744-682 687-682 609-604 569,365,260
Y ( A 10, Si C ) vb, ( SiO ,A 10 ) “;-, ( Si0 ) VT, ( A10 ) vb, ( A 1 0 , S i O )
t,s
1098-1045,936-901 789-721,694-595 534-523 584-539
vb, as ( Si0 , A 10 ) V (A10,SiO) VT,s(A1O)
yb, a s ( T,s

(wave numbers i n cm-’; d i s p l a c e m e n t s o f t e r m i n a l , o f b r i d g i n g and o f t h e bonds o f a c o m p l e t e

t e t r a h e d r o n a r e d e n o t e d by t , b and T, r e s p e c t i v e l y ; s and a s d e n o t e s y m m e t r i c a l ( t h e same
s i g n ) and a s y m m e t r i c a l ( o p p o s i t e s i g n ) di s pl ac ement s , r e s p e c t i v e l y ; m c h a r a c t e r i z e s m ixed
v i b r a t i o n a l modes; S i O a n d A10 d e n o t e t h e m a i n p a r t o f p o t e n t i a l e n e r g y w i t h i n t h e p o t e n t i a l
energy d i s t r i b u t i o n )
 TABLE 3
C a l c u l a t e d f r e q u e n c y r e g i o n s and a p p r o x i m a t e a s s i g n m e n t s f o r t h e OTO-bending v i b r a t i o n s o f
s e l e c t e d z e o l i t e c l u s t e r models

C a l c u l a t e d f requenc y r e g i o n and approx i mat e assignment

Si04 / A104 304-376 363-356 362-357

, a s (Oslo 1
t t393-381
if Jt * a s ( O A l O 1 Jt * (Oslo 1 dt * ( O M 01

I 03Si-0 ( i)-A103 544-443

&tb.
410-404
m
'
381-376
dtt (OT0
276- 27 1
'tb, a s

I 6R(hP)
06 R
.
590-549
dbb (OT0)
219,136-114
524-503
dtb, (OT0)
481-397
am
353-351.214-162
Jm
325-222
atb, a s

abb. a s

I
( t t * t b and bb c h a r a c t e r i z e a n g l e d e f o r m a t i o n s . i f t h e a n g l e c o n s i s t s o f two t e r m i n a l ( t t ) .
o f a t e r m i n a l a n d a b r i d g i n g ( t b ) a n d of two b r i d g i n g bonds ( b b ) ; s and a s d e n o t e symmet-
r i c a l and a s y m m e t r i c a l d e f o r m a t i o n s , respectively; OTO=OA10, O S i O ; m c h a r a c t e r i z e s mixed
v i b r a t i o n a l nodes)
518

a s s i g n e d t o OTO b e n d i n g s . I t s h o u l d be n o t e d t h a t so f a r an ex-
p l a n a t i o n o f t h e e x p e r i m e n t a l s p e c t r a c a n be o b t a i n e d o n l y by
c o n s i d e r i n g t h e v i b r a t i o n a l b e h a v i o u r o f some d i f f e r e n t s u b u n i t
c l u s t e r models,

TABLE 4
Approximate assignment o f observed v i b r a t i o n a l f r e q u e n c i e s o f
NaX z e o l i t e ( S i / A l = l . l 2 )

cm-' Assignment a )
obs.
IF! b, RA

1082 m
1078 sh
985 m
975 ve
800 w
(A10)
752 m b,as

700 m ub, ( S i 0 , A l O )
612 vw vl-s(AIO)
562 m d o u b l e r i n g mode
510 vs 'bb,
461 S
$( OTO )
408 W

375 m
p o r e o p e n i n g mode
364 m

( s h s h o u l d e r , w weak, v w v e r y weak, m medium, s strong, vs very

strong)
')notation see t a b l e s 2 and 3
b ) t a k e n f r o m MIECZNIKOWSKI and HANUZA ( r e f . 15)
measurements

As a r e s u l t t h e FLANIGEN c o n c e p t i o n o f e x t e r n a l and i n t e r n a l
t e t r a h e d r a l v i b r a t i o n s h a s t o be m o d i f i e d because o f t h e s t r o n g
c o u p l i n g between t h e z e o l i t e framework v i b r a t i o n s . Each bond has
b r i d g i n g and i n t e r n a l t e t r a h e d r a l c h a r a c t e r s i m u l t a n e o u s l y . Si-
m i l a r c c n c l u s i o n s have been drawn by WALTHER ( r e f s . 18,19) from
c o r r e s p o n d i n g c a l c u l a t i o n s f o r ZSM-5 z e o l i t e s u b u n i t c l u s t e r
models. The c o u p l i n g between t h e t e t r a h e d r o n s d o m i n a t e s t h e
c o u p l i n g w i t h i n t h e t e t r a h e d r o n s . T h e r e f o r e we p r e f e r t o d i s -
 519

t i n g u i s h between l o c a l i z e d and d e l o c a l i z e d v i b r a t i o n s ( s e e
ref. 20) t h a n between i n t e r n a l and e x t e r n a l ones.
CONCLUDING REMARKS
Z e o l i t e s r e p r e s e n t an e x t r a o r d i n a r y c h a l l e n g e f o r t h e v i b r a -
t i o n a l s p e c t r o s c o p y because o f t h e i r l a r g e u n i t c e l l s . They a r e
c o n n e c t e d w i t h a l a r g e number o f v i b r a t i o n a l modes l y i n g c l o s e l y
t o g e t h e r i n a s m a l l frequency region. Vibrational calculations
o f z e o l i t e s u b u n i t c l u s t e r models c a n be a c c o u n t e d f o r an i n t e r -
mediate step i n t r e a t i n g t h e complete s p e c t r o s c o p i c a l l y s i g n i f i -
cant u n i t c e l l . I f t h e c l u s t e r p r o b l e m w i l l be s o l v e d , the
q u e s t i o n f o r a p p r o p r i a t e f o r c e f i e l d s r e m a i n s open. In a d d i t i o n
t o t h i s methods f o r t h e e s t i m a t i o n o f v i b r a t i o n a l i n t e n s i t i e s o f
z e o l i t e s seem t o be n e c e s s a r y e x p l a i n i n g c o m p l e t e l y t h e e x p e r i -
m e n t a l s p e c t r a . W i t h r e s p e c t t o b o t h t h e problems mentioned
above quantum c h e m i c a l methods have t o c o n t r i b u t e c o n s i d e r a b l y .

REFERENCES

1 E.M. F l a n i g e n , H. K h a t a m i and H.A. Szymanski, Adv. Chem.

Ser. 101 (1971) 201
2 Y.S. Kong, M.S. 3hon and K.T. No, B u l l . Kor. Chem. SOC.
6 (1985) 57
3 C.S. B l a c k w e l l , 3. Phys. Chem. 83 (1979) 3251, 3257
4 K.T. No and M.S. Jhon, J. Phys. Chem. 8 7 (1983) 226
5 K.T. No, O.H. Bae and M.S. ahon, J. Phys. Chem. 90 (1986)
1772
6 K.T. No, B.H. Seo, 3.M. Park and M.S. Jhon, J. Phys. Chem.
9 2 (1988) 6783
7 K.T. No, Y.Y. Huh and M.S. Jhon, 3. Phys. Chem. 93 (1989)
6413
8 K.T. No, B.H. Seo and M.S. Jhon, Theor. Chim. A c t a 75 (1Y89)
307
9 K.T. No, H. Chon, T. Ree and M.S. Jhon, 3 . Phys. Chem, 85
(1981) 2065
10 D.H. Olson, 3. Phys. Chem. 74 (1970) 2758
11 V.A. M a r o n i , A p p l . S p e c t r o s c . 4 2 (1988) 487
12 J. Godber and G.A. Ozin, J. Phys. Chem. 9 2 (1988) 2841
13 E.B.Wilson, jr., J.C. D e c i u s and P.C. Cross, M o l e c u l a r
V i b r a t i o n s , M c G r a w - H i l l Book Company, Inc., New York, 1955
14 R.N. 301188, Computer Programs f o r I n f r a r e d S p e c t r o p h o t o m e t r y
-Normal C o o r d i n a t e A n a l y s i s
Canada, 1976
- N.R.C.C. B u l l e t i n No. 15,

15 A. M i e c z n i k o w s k i and J. Hanuza, Z e o l i t e s 5 (1985) 188

16 E.M. F l a n i g e n , S t r u c t u r a l A n a l y s i s by I n f r a r e d S p e c t r o s c o p y ,
ACS Monograph No. 171, Z e o l i t e C h e m i s t r y and C a t a l y s i s , 1976,
chap. 2, pp. 80-117
17 E. G e i d e l , H. B o h l i g , Ch. Peuker and W. P i l z , Z. CIiem. 28
(1985) 155
18 P. W a l t h e r , 2. Chem. 26 (1986) 189, 222
19 P. W a l t h e r , Z. phys. Chem. L e i p z i g , 269 (1988) 809
20 R.A. v a n S a n t e n and D.L. Vogel, L a t t i c e Dynamics o f Z e o l i t e s ,
Advances i n S o l i d S t a t e C h e m i s t r y , V o l . 1, JAI P r e s s Inc.,
1989, pp. 151-224
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 521
0 1991 Elsevier Science Publishers B.V., Amsterdam

THE TOPOLOGICAL STRUCTURE REPRESENTATION OF ZEOLITES

B. MULLER
I n s t i t u t f u r P h y s i k a l i s c h e Chemie, Friedrich-Schiller-Universitat
Jena. LessingstraRe 10, 0-6900 Jena, BRD

SUMMARY
I t i s shown t h a t z e o l i t e s can be c h a r a c t e r i z e d and c l a s s i f i e d
by means o f t o p o l o g i c a l s t r u c t u r e a n a l y s i s . The t o p o l o g y used i s a
non-metrical geometry. The advantage o f u s i n g t h e s e t o p o l o g i c a l
s t r u c t u r e d e s c r i p t i o n i s t h a t t h e general s t r u c t u r a l p r o p e r t i e s
r e p r e s e n t i n g t h e frame f o r t h e p h y s i c s and c h e m i s t r y o f m a t e r i a l s
can be d e c l a r e d w i t h s i m p l e numbers o f t h e t o p o l o g i c a l parameters
Nk1. The l o c a l r e c i p r o c a l curves o f t h e c e l l u l a r c o n f i g u r a t i o n
b31/l11, expressed i n t h e t o p o l o g i c a l parameters, a r e measures f o r
both t h e compactness and t h e c a t a l y t i c a l p r o p e r t i e s o f z e o l i t e s .
The general s t r u c t u r e f u n c t i o n N 2 1 = N21(NS2,NO',N12) o f t h e
independent t o p o l o g i c a l parameters N k 1 i s deduced f r o m t h e t h e o r y
of c e l l u l a r configurations. The d i s t r i b u t i o n f u n c t i o n s g21i and
9 3 2 1 o f t h e f a c e s and polyhedra, r e s p e c t i v e l y , which may b u i l d up
t h e v a r i e t y o f z e o l i t e c o n f i g u r a t i o n s , a r e given.

INTRODUCTION
The simplest, but a l s o t h e most e s s e n t i a l relations between
e 1ement s of spatial systems a r e o f a topological nature. The
topo 1ogy obtains the connective s t r u c t u r e relations which are
i n v a r i a n t a t continuos transformations (ref. l), therefore, the
topo 1ogy s non-metrical. The problem o f s p a t i a l t o p o l o g i c a l s t r u c -
ture ana y s i s consists i n the determination of both intrinsic
t o p o l o g i c a l s t r u c t u r e elements and i n t h e corresponding connective
relations between those c o n s t r a i n e d t h e structure configurations
(refs. 2,3). Atomic condensed systems such as z e o l i t e s may be
uniquely mapped into space-filling cellular configurations
(ref .4).
One k-celloid of t h e dimension k correponds inquely to one
structure element o f t h e concrete zeolite. These homomorphisms
make it p o s s i b l e f o r t h e t o p o l o g i c a l parameters o f the cellular
configurations space t o u n i q u e l y r e p r e s e n t , as w e l l as classify,
t h e t o p o l o g i c a l s t r u c t u r e o f atomic condensed system ( r e f . 5). The
topological parameters Nk1 and t h e i r d i s t r i b u t i o n functions gkli
constrain n o t o n l y t h e s p a t i a l c o n f i g u r a t i o n and arrangement but
also the s p a t i a l e x i s t e n c e and s t a b i l i t y i n every cellular-con-
nected system represented b y t h e z e o l i t e s ( r e f . 6 ) .
522

TOPOLOGICAL STRUCTURE CONFIGURATIONS

The topological s t r u c t u r e elements o f zeolite configurations
can be r e a l i z e d by k - c e l l o i d s w i t h d i f f e r e n t dimensions k (k =
0,1,2.3) on a 4-dimensional c o n f i g u r a t i o n space. Each o f the k-
celloids represent one k-dimensional f i g u r e bounded a t least k+l
(k-l)-celloids (k>O). These f i g u r e s can be r e a l i z e d as k-dimensio-
n a l polyhedra e x h i b i t i n g a t l e a s t k + l v e r t i c e s ( r e f . 5 ) .
0-celloids mOp (p = 1.2. ...,N o ) : I n our case of crystalline
zeolites, both the Si- and t h e A l - t e t r a h e d r a represent the 0-
celloid, which i s a l s o r e f e r r e d t o as the v e r t i c e s . Atoms o r i o n s
with single (dangling-bonds) o r two chemical bonds (as the 0-
atoms) do n o t represent O - c e l l o i d s because o f the general pro-
p e r t i e s o f connected c e l l u l a r systems.
1-celloids mlq (q = 1,2,. . . .N1 1: The "bonds" e x i s t i n g between
neighbouring Si- o r A l - t e t r a h e d r a by means o f t h e i n c l u s i o n 0-ion
represent t h e 7 - c e l l o i d s o f t h e z e o l i t e c o n f i g u r a t i o n s .
2 - c e l l o i d s nPr ( r = 1,2, ...,Nz): The 7 - c e l l o i d s which a r e also
c a l l e d the edges o f the c e l l u l a r c o n f i g u r a t i o n may be b u i l t cycles
or rings. Only t h e r i n g s which seperate two neighbouring polyhedra
are 2 - c e l l o i d s , i.e., the 2-celloids depict c o r r e la t io n d i s t r i b u -
tions of the third-order. This i s a condition o f the homotopic
invariance o f c e l l u l a r c o n f i g u r a t i o n s ( r e f . 6 ) .
3-celloids nP. (s = 1 , 2 , , . . , N a ) : The polyhedra belonging to
either the same o r d i f f e r e n t classes cover compactly over the 3-
dimensional c o n f i g u r a t i o n space. The 3 - c e l l o i d s (the polyhedra)
are formed by t h e 2 - c e l l o i d s and represent spatial correlation
d i s t r i b u t i o n s o f the fourth-order, The polyhedra o f c e l l u l a r con-
figurations do n o t agreed w i t h the conventional co-ordinate poly-
hedra o f s t r u c t u r e chemistry ( r e f , 7 ) .

CONNECTIVE STRUCTURE RELATIONS

The simplest structure relations i n the set M (&p: k =
O,l, . . . ,d: p = 1,2, ...,N k ) o f k - c e l l o i d s can be produced by means
of the i n t e r s e c t i o n between a l l elements. The k - c e l l o i d mkp is
then, and only then, t h e border o f t h e 1 - c e l l o i d mrq, if the
result of the i n t e r s e c t i o n between both i s the k-celloid &p.

Thouse second-order limboide connective s t r u c t u r e r e l a t i o n s can be

mapped t o t h e connective r e l a t i o n m a t r i x Mk1 g i v i n g each connecti-
ve s t r u c t u r e r e l a t i o n a m a t r i x element mklpO w i t h t h e values
 523

1 i f mkp n ml0 = rnkp

mklpq = I
0 o t h e r wise

he mean v a l u e Nk1 which i s a l s o c a l l e d t h e t o p o l o g i c a l parame-

t e r c h a r a c t e r i z e s t h e number o f l i m b o i d e connective r e l a t i o n s o f a
typ cal k - c e l l o i d i n regard t o i t s 7 - c e l l o i d s . The m a t r i x Nk1 of
the topological parameters Nk1 represents t h e g l o b a l as well as
the typical topological structure invariants o f a given atomic
condensed system. The d i s t r i b u t i o n f u n c t i o n gkli obtains types
n k l i of t h e limboide connections between t h e k- and t h e 7-celloids
(ref. 7 ) .

TOPOLOGICAL STRUCTURE CONSTRAINTS

Three-dimensional c e l l u l a r s t r u c t u r e s must be c h a r a c t e r i z e d by
three o f t h e f o u r independent t o p o l o g i c a l parameters No1,N12,N21,
and N32 (ref. 7). The general g l o b a l s t r u c t u r e f u n c t i o n o f such a
c o n f i g u r a t i o n i s given by equation ( 2 ) :

The topological structure function ( 2 ) constrains not only the

spatial configuration and arrangement b u t a l s o t h e spatial exi-
stence and s t a b i l i t y i n every c e l l u l a r connected system represen-
ted by the zeolites. I t i s d e r i v e d from the topological group
theory that the t o p o l o g i c a l parameters Nk1 are related to the
o r d e r s o f t h e f a c t o r groups as w e l l as t o t h e o r b i t l e n g t h s o f the
permutation group i n t h e c o n f i g u r a t i o n space (eqn. (3) and r e f . 7 ) .

N3 and No a r e t h e d e n s i t y numbers o f t h e 3- and 0-celloids,

respectively, which a r e i n v a r i a n t i n regard t o b o t h homeomorphic
and permutative t r a n s f o r m a t i o n s .
The distribution function g k l i gives the types nkli of the
limboide connections of the k-celloids i n respect to the 1-
celloids. The d i s t r i b u t i o n f u n c t i o n s g k l i a r e dependent on each
o t h e r as a d d i t i o n a l , d i f f e r e n t r e l a t i o n s e x i s t between t h e subma-
trizes Mk1 (ref. 7). Especially, they y i e l d the following rela-
tions between t h e d i s t r i b u t i o n f u n c t i o n 9211 and the topological
524

Parameters N Z 1 and N 3 2 (eqns. ( 4 ) - ( 7 ) , ref. 7):

i=l i=l

This i s t h e p h y s i c a l and chemical reason why different atomic

and bonding p r o p e r t i e s g i v e d i f f e r e n t s o r t s o f c o n f i g u r a t i o n s and
evolutions. The i n t e r a c t i o n o f l o c a l energy m i n i m a z a t i o n and topo-
logy produces complex t h r e e - d i m e n s i o n a l c e l l u l a r configurations of
zeol it e s .

TOPOLOGICAL CURVATURE MEASURE

The s p e c i f i c t o p o l o g i c a l c u r v a t u r e measures b ’ * k / v 1 1 1 determine
both the s t a b i l i t y , t h e compactness and a d s o r p t i o n p r o p e r t i e s of
the zeolites ( r e f . 7). These measures have t h e i n t e r e s t i n g geome-
trical property that they a r e t h e u n i t d i s t a n c e of a parallel
surface. A p a r a l l e l s u r f a c e i s formed by t r a n s f o r m i n g each p o i n t a
c o n s t a n t d i s t a n c e a l o n g t h e s u r f a c e normal a t t h e p o i n t .
A z e o l i t e c r y s t a l c o n f i g u r a t i o n can be d e s c r i b e d as consisting
o f a number o f d i f f e r e n t t y p e s o f p o l y h e d r a whose r e c i p r o c a l unit,
c u r v a t u r e , i s o n l y g i v e n by t h e t o p o l o g i c a l parameters ( r e f . 7).

COMPUTING METHODS OF THE TOPOLOGICAL PARAMETERS

A complete e v a l u a t i o n o f a l l t o p o l o g i c a l parameters i s i n this
case possible, if t h e s e t o f atomic c o o r d i n a t e s i s know as are
those in c r y s t a l l i n e z e o l i t e structures. The algorithm of our
computational program NWS i s as f o l l o w s ( r e f . 8 ) :

1. Generate t h e s e t o f atomic c o o r d i n a t e s i n t o a f i n i t e structu-

r e model o f c r y s t a l l i n e z e o l i t e .
2. Determinate the c o n n e c t i v e m a t r i x Mo1 by means of metrical
 525

distance r e l a t i o n s between t h e g i v e n model coordinate poly-

hedra.
3. Search t h e c o n f i g u r a t i o n r i n g s and d i s c r i m i n e between their
faces ( r e f . 9).
4. Evalute both the topological d i s t r i b u t i o n functions gk’i and
t h e t o p o l o g i c a l parameters N k l .
5. Correct the t o p o l o g i c a l p a r a m e t e r s Nkl w i t h regard to the
model s i z e e f f e c t ( r e f . 10).

TOPOLOGICAL STRUCTURES OF ZEOLITES

The t o p o l o g i c a l p a r a m e t e r s N 0 1 1 N 1 2 , N 2 1 , and N32 o f most o f the
z e o l i t e s a r e shown i n t a b l e 1 .

TABLE 1
The t o p o l o g i c a l p a r a m e t e r s o f t h e z e o l i t e s

: Zeol it e 1 NO1 NZ1 N32 b 3 * 1 / ~ 1 * 1 N3/N0 P/1000 132 121 !

1
-~ ~ -1

1Afghanite 1 4 3 5.08 .182 2.89 2 2 1

Li-A ; 4 3.5 5.6 10 3.0 .25 4.75 1 3 1
1Bikitait.e 1 4 4 6 8 3.0 .333 6.73 1 3 1
1Chabazite 1 4 3 5.2 16 3.5 .143 2.09 2 3 1
1Deca dodecasil 1 4 3 5.14 14 3.0 .166 2.92 3 3 1
1Dodecasil 1H 1 4 3 5.14 14 3.0 ,166 3.07 2 3 1
1 TMA-E( AB) 1 4 3 5.2 15 3.25 .154 2.37 3 3 :
IEdlngtonIte 1 4 4 6 8 3.0 .333 5.53 2 2 1
1 Ericnite 1 4 3 5.2 15 3.25 .154 2.40 3 3 1
; Faujasite 1 4 3 5.25 16 3.5 .143 1.82 3 3 1
1Ferrierite 1 4 3 5.4 20 4.5 .111 1.96 2 4 1
1Gismondine 1 4 3.5 5.6 10 3.0 .25 3.85 1 2 1
1Gmenilite 1 4 3.4 5.66 12 3.5 .2 2.92 3 4 1
1Heulandite 1 4 5 6.67 6 3.0 .5 8.5 2 6 1
1 Levyne 1 4 3 5.14 14 3.0 .166 2.52 2 3 1
1Liottite 1 4 3 5.2 16 3.5 .143 2.17 3 2 1
1 Losod 1 4 3 5.25 15 3.25 .154 2.43 2 2 1
1 L inde-A 1 4 3 5.22 15.33 3.3 .150 1.93 3 3 1
1 L inde-N ; 4 3 5.19 14.8 3.2 .156 2.37 5 3 1
1 L inde-W 1 4 3.28 5.41 11.33 3.0 .214 3.42 3 3 1
1Mordenite 1 4 3.72 5.63 8.25 2.68 .32 5.50 4 4 1
1Natrolite 1 4 4 5.82 7.33 2.67 .375 6.67 2 2 1
1Phillipsite 1 4 3 5.33 18 4.0 .125 1.95 1 2 1
1 RHO 1 4 3 5.33 18 4.0 .125 1.78 2 3 1
1Sodalite 1 4 3 5.14 14 3.0 .166 2.86 1 2 :
1Thomsonite 1 4 3.5 5.6 10 3.0 .33 6.56 2 3 1
1 ZK-5 : 4 3 5.2 15 3.25 .154 2.26 4 3 1
!Quartz 1 4 9 6 3 1.75 2 53.0 1 1 :
1Cristobalit.e 1 4 6 6 4 2.0 1 23.2 1 1 1
1 T r 1dymit e 1 4 5 6 5 2.25 .667 15.11 1 1 :
!Random Voronoi 1 4 3 5.23 15.5 3.39 .148 ? ? ? 1

Moreover, t h i s t a b l e 1 a l s o shows t h e t o p o l o g i c a l i n t r i n s i c r a t i o
between t h e numbers o f p o l y h e d r a end v e r t i c e s N 3 / N 0 , the recipro-
526

cal topological u n i t curvature b3,l/v1,1, t h e polyhedron density,

P / I O O o g i v e s t h e number o f polyhedron per 1000 AS, and t h e number
of b o t h t h e p o l y h e d r a t y p e s 132 and f a c e s t y p e s 121, respectively.
In order t o compare w i t h t h e r e l a t e d parameters of zeolites,
t h e t o p o l o g i c a l q u a n t i t i e s o f some S i O z m o d i f i c a t i o n s as w e l l as a
random Voronoi c o n f i g u r a t i o n a r e a l s o shown i n t a b l e 1.

Topological. c o n s t r a _ i n t s of_t h e ZeOl.ite c o n f i w r a t i o n s

The value o f t h e t o p o l o g i c a l parameter N O 1 i s equal four for
each one c o n f i g u r a t i o n o b t a i n e d i n t a b l e 1. This typical vertex
with four i n c i d e n t edges r e p r e s e n t s t h e S i O 4 1 z - and the A10412-

tetrahedra, respectively, o f the z e o l i t e configurations.

The t o p o l o g i c a l mean v a l u e parameters N O 1 , N 1 2 , N Z 1 , and N 3 2 o f
each zeolite c o n f i g u r a t i o n (and a l s o o f each SiOz-modification)
realize the topological structure equation (eqn. 2), i.e., the
z e o l i t e c o n f i g u r a t i o n s a r e t o p o l o c a l l y determined. Each topologi-
c a l parameter NR1 depends on each o t h e r .

TABLE 2
P o s s i b l e face d i s t r i b u t i o n s F Z 1 1 o f a t y p i c a l p o l y h e d r o n w i t h N j 2
= 10 f o r t h e t o p o l o g i c a l parameters NO1 4, N1z = 3, and N21 =
4.8, r e s p e c t i v e l y
_ _
;F21i\n21i 1 3 4 5 6 7 8 9 10 1
I
I \ 1 - 1
I

1 1 1 0 2 8 0 0 0 0 0 1
1 2 : 1 0 9 0 0 0 0 0 1
; 3 1 0 3 6 1 0 0 0 0 1
I
1 4 I 1 1 7 1 0 0 0 0 1
1 5 1 0 4 4 2 0 0 0 0 :
1 6 1 1 2 5 2 0 0 0 0 1
1 7 I 2 0 6 2 0 0 0 0 1
1 8 1 0 5 2 3 0 0 0 0 1
I
! 9 I 1 3 3 3 0 0 0 0 :
f 10 1 2 1 4 3 0 0 0 0 1
1 11 1 0 6 0 4 0 0 0 0 1
: 12 1 1 4 1 4 0 0 0 0 1
1 13 1 2 2 2 4 0 0 0 0 1
1 14 1 3 0 3 4 0 0 0 0 1
1 15 : 2 3 0 5 0 0 0 0 :
1 16 1 3 1 1 5 0 0 0 0 1
:
I
17 : 4 0 0 6 0 0 0 0 :
I
I I

Because o f the topological constraints f o r c e l l u l a r configura-

tion spaces w i t h NO1 = 4, t h e mean number o f edges p e r face can
only be i n t h e range 5 < N21 < 7 (ref. 7). These constraints
affect the zeolite c o n f i g u r a t i o n so t h a t distributions of the
f a c e s 9211 must e x i s t .
 527

For example i n t a b l e 1, the c r y s t a l l i n e SiO2 modifications are

unique, one having o n l y one f a c e t y p e w i t h n 2 l i 6. The dis-
t r i b u t i o n o f t h e faces 921, i s g i v e n by t h e e q u a t i o n s ( 4 ) - ( 7 ) .
I n table 2, an example o f t h e p o s s i b l e f a c e d i s t r i b u t i o n s Fzli
of a t y p i c a l polyhedron w i t h N3z = 10 f o r t h e t o p o l o g i c a l parame-
t e r s No' = 4, N 1 2 = 3 , and N Z 1 = 4 . 8 i s shown ( r e f . 7 ) .
The polyhedron shape i s s i m i l a r t o t h a t o f a cage having more
faces with $11 < 6 than faces w i t h n21i > 6. Atoms and small
molecules can o n l y pass r i n g s w i t h n 2 1 i > 6.
The d i s t r i b u t i o n o f faces f o r g i v e n mean v a l u e NZ1, determined
by equations ( 4 ) - ( 7 ) , can o n l y be r e a l i z e d i n most cases by means
o f s e v e r a l polyhedron types 1 3 2 > 1. Exclusively, the zeolites L i -
A, Gismondine, Phillipsite, and S o d a l i t h e have o n l y one single
polyhedron t y p e ( t a b l e 1 ) .
The t o p o l o g i c a l s t r u c t u r e f u n c t i o n ( 2 ) as w e l l as o t h e r a d d i t i o -
nal topological constraints ( r e f . 7 ) imply t h a t t h e v a l u e o f the
t o p o l o g i c a l parameter must be N12 > 3 f o r a l l cellular configurati-
ons with N32 < 13. The z e o l i t e s w i t h Nl2 = 3 are called simple-
connected.

Toml-ogicpl curvatures o f z e o l i t e c o n f i g u r a t i o n s
The mean topological reciprocal u n i t curvature b311/vl i 1 is
characteristic o f the adsorption properties o f the zeolites.
The mean reciprocal configuration curvature i s found in the
range 2.667 <. b311/v1,1 < 4.5 (table 1 ) . I n t h e case of single
polyhedra, the range i s g r e a t e r 1.0 < bJ*l/vl.l 4.5 (table 11,
as f o r F a u j a s i t e .
The g r e a t e r t h e polyhedron v a l u e o f b3*l/vlpl, t h e more e a s i l y
l a r g e molecules can be adsorbed a t t h e polyhedra. The s m a l l e r the
configuration value of bJ.l/vl.l the better a force-field of
curvature i s g i v e n which can be bent and can break t h e molecules.
The c a t a l y t i c a l p r o p e r t i e s of t h e z e o l i t e s e s s e n t i a l l y give rise
to both t h e mean r e c i p r o c a l u n i t c u r v a t u r e o f the configuration
and those o f t h e s i n g l e polyhedra.
The value of bJ.l/vl ~1 for zeolite configurations must be
g r e a t e r than 8/3. Those i s a measure f o r t h e d i s c r i m i n a t i o n o f t h e
zeolites. The m o d i f i c a t i o n s o f b o t h S i O z and f e l s p a r s have values
f o r r e c i p r o c a l c u r v a t u r e s l e s s t h a n 8/3.
The p o s s i b l e polyhedron d i s t r i b u t i o n n32i o f z e o l i t e configura-
t i o n s are given i n r e f . 7 .
The number o f polyhedra per v e r t e x N3/N0 i s also characteristic
528

of the c e l l u l a r zeolite configurations. A zeolite configuration

y i e l d s N3/N0 < 0.5. I n t a b l e 1 t h e v a l u e s o f N3/N0 a r e shown. The
functional relations between NJ/NO and bJ-l/v1.1 are given in
ref. 7.
The polyhedron d e n s i t y P/1000 As ( f o r t h e z e o l i t e s see t a b l e 1)
arranges t h e r e l a t i o n s h i p between t h e m e t r i c a l q u a n t i t i e s of the
z e o l i t e c o n f i g u r a t i o n s and t h e t o p o l o g i c a l parameters. The c o r r e l a -
t i o n between t h e polyhedron d e n s i t y P/1000 ( r e f . 11) and t h e mean
reciprocal curvature b3~7/v1.1 i s b e t t e r than t h a t between the
t e t r a h e d r o n d e n s i t y T / l O O O and b3 8 l /v1 I ( r e f . 7 1.

REFERENCES
1 H . S . M . Coxeter, Unvergangliche Geometrie, B i r k h b u s e r , Base1 1982
2 F. Yonezawa, T . Ninomiya ( E d s . ) , T o p o l o g i c a l D i s o r d e r i n Conden-
sed M a t t e r , S p r i n g e r , B e r l i n , 1983
3 N.J. T u r r o , Angew. Chem., 98 (1986) 872-879
4 8 . Mullet-. Exper. Tech. Phys., 36 (1988) 121-134
5 B. M u l l e r , The t o p o l o g i c a l c h a r a c t e r i z a t i o n o f amorphous s t r u c -
t u r e s , i n P h y s i c a l Research, Akademie-Verlag, B e r l i n 1990
6 D. Stoyan, W.S. K e n d a l l . R . Mecke, S t o c h a s t i c Geometry, Akade-
mie-Verlag, B e r l i n 1987
7 B. M u l l e r , The t o p o l o g i c a l f o u n d a t i o n s o f s t r u c t u r e c h e m i s t r y ,
submitted f o r p u b l i c a t i o n
8 R. Schubert, B. M i l l l e r , Computing Program NWS, Computer Centre
o f Friedrich-Schiller-Unioversity Jena, 1987
9 0. M u l l e r , R . Schubert. Exper. Tech. Phys. 36 (1988) 135-144
10 B. Moller, R . Schubert, Wiss. Z e i t s c h r . F r i e d r . - S c h i l l e r - U n i v .
Jena, i n p r e s s
11 W.W. Meier, D.H. Olsen, A t l a s o f Z e o l i t e S t r u c t u r e Types,
B u t t e r w o r t h s , London, 1987
C,. Ohlrnann et nl. (Editors),Culalysk and Adsorption by Zeolites 529
1991 Elsevier Science PublishersR.V.,
Amsterdam

STUDIES OF SECONDARY SYNTHESIS ON MODIFIED PENTASIL ZEOLITES

W. RESCHETILOWSKI’, W.-D. EINICKE

1 t B. MEIER 1 E. BRUNNER2 and
H. ERN ST^
‘Department of Chemistry, Karl Marx University, Liebigstr. 18,
DDR-7010 Leipzig, German Democratic Republic
’Department of Physics, Karl Marx University, Linnbstr. S , DDR-
7010 Leipzig, German Democratic Republic

SUMMARY
The secondary synthesis on modified pentasil zeolites and Its
influence on the properties of these zeolites was investiga-
ted. It is shown by X-ray diffractiontZ7Al MAS NMR and nitrogen
adsorption that a high degree of dealumination and a high pH
value of the synthesis mixture led to a favourable insertion of
aluminium into the ZSM-5 framework.

INTRODUCTION
In connection with the industrlal application of zeolites a
rapid development in the processes of chemical conversion, sepa-
ration and cleaning can be observed. Unmistakable is the increa-
sing importance of new zeolitic molecular sieves with adapted
pore systems and defined surface-chemical properties.
one way for the production of such zeolites is the isomor-
phous substitution of aluminium and/or silicon in the framework
through other elements with the condltions of the hydrothermal
crystallization. A high variation concerning the multitude of
various elements was observed for the pentasil zeolites (ref.
1). However, the information about the state of these elements
In the zeolitic framework is limited.
The actual investigations have shown that such materlals are
also available as a result of the secondary synthesis using alu-
minosilicates (refs. 2 , 3 ) . The secondary synthesis is a new and
almost unknown procedure for the postsynthetic zeol te modifice-
tion. This procedure allows the reversion of the dealuminina-
tion of zeolltes, observed during their use, by a s mple method
(ref. 4 ) .
 The aim of this paper is to show the systematical investiga-
tions of the secondary synthesis of modified pentasils to get
informations concerning the influence of the conditions of syn-
thesis on the structural, surface-chemical and adsorptional pro-
perties of the resulting zeolites.

EXPERIMENTAL
Materials and Methods
The starting material ZSM-5 (Si/A1=50) synthesized with or-
ganic template (ref. 5) was calcinated f o r 6 hours at 700 " C t
800 Oc and 900 OC. One part of the these samples was transrered
into the H-form, where 25 g of the freshly calcinated zeolite
powder was ion exchanged wlth 1 1 of 0.5 M aqueous solution of
ammonium nitrate ( 3 hrs, 80 "C) and deammoniated ( 4 hrs, 500
0
C) .
For the secondary synthesis with aluminium insertion alumini-
um sulphate was contacted with the zeolite and an aqueous solu-
tion of 2 N NaOH where the atomic ratio of aluminium between the
zeollte and the suspension was varied. The reaction mixture with
pH 10 to 12 was stirred for 3 hours at 70 O C , filtered and
washed carefully. The resulting products were dried and charac-
terized by various analytical methods.
The determination of the Si/A1 ratios (ref. 6) of the samples
was carried out at a NMR pulse spectrometer designed at the KMU
Leipzig at a resonance rrequency of 70 MHz. The chemical shltt
against [A1(H20)6]3+ was obtained with an accuracy of 2 ppm.
The identification of the crystalline phases and the crystal-
linity of the samples were determined by means or a goniometer
HZG 4 in the 20 region from 5 to 70 '. For comparlson the crys-
tallinity of the Leuna-ZSM-5 standard was used. The volumes of
the unit cells of some zeolites were obtained from the difreren-
ces of the angel positions of 5 references in the 20 range from
23.00 to 25.70 in comparison to the references of a-A1203.
The adsorption properties were investigated by the measure-
o
ments of the nitrogen isotherms at - 196 C on a Sartorius ba-
lance.
The designation, the conditions of the secondary synthesis,
the aluminium content per unit cell. the Sl/Al ratios, the crys-
tallinity, the volume of the unit cell from X-ray data and the
nitrogen adsorption capacity at 0.1 MPa are shown in table 1.
 531

TABLE 1
Characterization of the ZSM-5 zeolites investigated

Nr. prepar. conditions Al/u.c. Si/A1 cryst. V/u.c.

T/OC pH Al-supply % nm mg g

1 700 - - 1.96 48 84 - 94.1

2 800 - - 1.29 73 88 - 124.5
3 900 - - 0.91 104 48 5.3428 51.0
4 700 12 1:l 1.86 52 76 - 98.0
5 800 12 1:l 2.91 32 77 - 111.4
6 900 12 1:l 2.91 32 93 - 128.4
7 700 12 1:8 12.31 6.8 38 - 45.7
8 800 12 1:8 9.80 8.8 68 5.3933 129.6
9 900 12 1:8 10.79 7.9 64 5.3958 129.0
10 800 10 1:l 1.71 55 91 - 124.7
11 800 11 1:l 1.86 51 85 5.3743 116.3
12 800 10 1:8 0.98 97 62 - 70.4
13 800 11 1:8 4.00 23 67 5.3803 118.7
14* 900 - - 0.40 239 82 - 132.1
15** 900 12 1:l 7.27 12.2 93 5.3743 134.6
* HZSM-5, proton form of starting material
* * Sample was prepared by secondary synthesis from sample 14

RESULTS AND DISCUSSION

x-ray diffraction
The results of the qualitative analysis of crystalline phases
have shown that the samples produced by our procedure have a
ZSM-5 structure. For all samples a varying content of a-quartz
was detected. A s can be seen from table 1 the crystallinities
0
maintained during the calcination of the samples at 700 C and
800 OC (samples 1 and 2, crystallinity of the starting material
85 % ) . The calcination at 900 OC (sample 3 ) led to a decrease of
the crystallinity which is be due to a dissolution of the zeoli-
tic framework connected with a further dealumlnation.
In the case of the secondary synthesis with realumination and
a low alumlnium supply (samples 4 , 5 , 10, 11) the crystallinity
of the samples calcinated at 700 OC and 800 OC was remained al-
most unchanged. The increase in the content of aluminium in the
synthesis mixture obviously led also to the increased insertion
of aluminium into Si framework positlons. The silicon species
obtained during the substitution procedure can combine to
a-quartz and therefore they should be the reason for the de-
crease of the crystallinity (sample 7, 8, 12, 13). In the case
of the realumination of a sample with a lower crystallinity cal-
cinated at 900 OC, i t seems that as well a s the realumination a
reinsertion of silicon species occurs which led to the recon-
struction of the lattice and the increase of the crystallinity
(samples 6 and 15). A higher content of aluminium in the synthe-
sis mixture (sample 9) has a negative influence on the crystal-
linity, because the increased insertion of aluminium prevents
the insertion of silicon species.
Due to the differences in the ionic radii of A1 (r=0.051 nm)
and si (r=0.042 nm) the increased insertion of aluminium into
the framework should change the lattice parameters which is con-
nected with the lncrease of the volume of the unit cell. As can
be seen from table 1 there is a relation between the Si/A1 ra-
tios which are determined by 27Al MAS NMR and the volume of the
unit cell. The higher the aluminium content of the framework the
higher the volume of the unit cell. This behaviour seems to be
indirect evidence for the realumination of the zeolite frame-
work.

2 7 ~ 1MAS N M R
Dealuminated samples
The sharp signal in the 27Al MAS NMR spectra at 53 ppm was
assigned to the tetrahedrically coordinated aluminium in frame-
work positions. The higher the calcination temperature the lower
the intensity of the signal which is due to the dealumination of
the framework. In fig. 1 the change of the amount of aluminium

2.0 .
u t
Fig. 1 Change of the
? 1.6-
A

amount of aluminium
6
1.2 - per unit cell in de-
pendence on the cal-
0.8 - cination temperature
0.1, - (A:NaZSM-5, B:HZSM-5)

700 800 - 9 0 0
T("C1
per unit cell is demonstrated by the dependence on the calcina-
tion temperature. It is shown that in the case of HZSM-5 zeoli-
tes the dealumination of the framework with higher temperatures
becomes advantageous in comparison with NaZSM-5 zeolltes.

Realuminated samples
The results of the realumination of the calcinated NaZSM-5 zeo-
lltes are shown in fig. 2. In all cases the pH of the aqueous

A
Fig. 2 Realumination in
dependence on the calci-
nation temperature and
the Al-Supply at pH=12
( theor. max. values A :

17.1 and €3: 3 . 8 Al/u.c.)

I
700 800 -900
T ("C 1

suspension was 12 and the ratio of aluminium in the framework to

aluminium in the suspension varied from 1:l to 1:8. From the sum
of all aluminium atoms in the solid and in the suspension a
theoretical value for the highest insertion possible for alumi-
nium was calculated. While in the case of a 1:l ratio this value
is 3.8 Al/u.c. for the 1:8 ratio the value increases to 17.1 All
u.c.. From fig. 2 i t is shown that the aluminium insertion de-
pends strongly on the aluminium supply of the suspension. For
the 1:l ratio with calcination temperatures of 800 OC and 900 OC
the realumination was possible up to 75 percent of the theore-
tical maximal value. The increase of the aluminium supply led to
the highest increase of insertion which also about 70 percent of
the theoretical value was reached. It seems that with the men-
tioned reaction conditions a barrier for the aluminium insertion
can not be crossed.
A purposeful variation of the reaction conditions has shown
that a constant pH value during the secondary synthesls is the
main factor for a sucessful realumination. The influence of the
pH value on the realumination is demonstrated in fig. 3 for
NaZSM-5 zeolite calcinated at 800 OC. The higher the pH of the
aqueous suspension the higher the amount of aluminium Inserted
into the framework positions corresponding to the aluminium sup-
Ply.

10-
u t
< 8-
d
6-
L-

2-

10 11 -
PH
12 150- 50
d(PPm1
-50

Fig. 3 Realumination in depen- Fig. 4 27~1 MAS NMR-

dence on the pH at Al-supply of spectra of samples, pre-
1:8 (A) and 1:l (6) pared at pH=12 (A), pH=
11 (B) and pH=lO (C)

Prom the 27Al MAS NMR spectra of the realuminated zeolites in

fig. 4 it becomes clear that in the case of a lower pH value the
content of the octahedrically coordinated extra-framework alumi-
nium increased. The lncrease of the pH value led to a decrease
of these aluminium species, which do not appear in the case of
pH=12.

Nitrogen Adsorption
Now we should focus our attention on the influence of the
chemical reactions of the solid on the pore system of the post-
synthezised zeolites. The investigations have shown that in all
 535

cases a typical and an almost identical nitrogen adsorption iso-

therm appeared. Differences in the limiting values of nitrogen
adsorption caused by the different crystalline content of the
zeolites as shown in table 1.
Contrary to the adsorption investigation on realuminated pen-
tasils dealuminated at 540 C' in a water stream (refs. 4 1 7 ) no
formation of a secondary Pore system was found. Therefore the
different aluminium distributions for the pentasils synthesized
with and without organic templates should be the reason. It
seems that for the pentasils synthesized without organic tem-
plate a stronger aluminium and silicon gradient exist which can
not be maintained after the dealumination and the following re-
alumination. The reconstruction of the structural defects in
such products is connected with the insertion of the tetrahed-
rically coordinated positions by silicon and the formation of a
secondary pore system with a narrow distribution of the pore
radi 1 .

ACKNOWLEDGEMENTS
The authors thank Dr. P. Kraak and K. Heimbach for supplying
the X-ray data and Prof. D. Freude and Dr. K. Becker for helpful
support.

REFERENCES
M . Tielen, M . Geelen and P.A. Jacobs, Proc. Intern. Symp.
Zeolite Catal., szeged 1985, Acta Phys. Chem. Szeged., 1985,
P. 1
G.W. Skeels and E.M. Flanigen, ACS Symposium series ( M . L .
Ocelli and H. E. Robson, Eds.) 398 (1989) 420
B. Sulikowskl and J. Klinowski. ACS Symposioum Series ( M . L .
Ocelli and H.E. Robson, Eds.) 398 (1989) 393
I

W. Reschetilowski, W.-D. Einicke, M . Juaek, R. SchOllner, D.

Freude, M . Hunger and J. Klinowski, Appl. Catal. 56 (1989)
L 15
DD-WP 207 186 (1984)
D.R. Corbin, B.F. Burgess jr., A.J. Vega and R.D. Farlee,
Anal. Chem. 59 (1987) 2722
W.-0. Einicke, W. Reschetilowski, M. Heuchel, M.
v.Szombathely, M . Jusek, H.-R. Poosch, P. BrMuer, W.
Schwieger and K.-H. Bergk, Chem. Techn. 42 (1990), 215
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 537
0 1991 Elsevier Science Publishers B.V., Amsterdam

INCORPORATION OF S I L I C O N I N T O THE FRAMEWORK OF SAPO-5 S T U D I E D BY

NMR AND I R SPECTROSCOPY

1 1 1 3
BI Z j b r o w i u s , E. Loffler , G. Finger , E. Sonntag', M. Hunger
4
and J . Kornatowski
' C e n t r a l I n s t i t u t e o f P h y s i c a l Chemistry and 'Central I n s t i t u t e o f
I n o r g a n i c Chemistry o f t h e Academy o f Sciences o f t h e GDR,
Rudower Chaussee 5, B e r l i n , DDR-1199 (German Democratic R e p u b l i c )
'Department o f Physics, K a r l - M a r x - U n i v e r s i t y L e i p z i g , L i n n s s t r . 5,
L e i p z i g , DDR-7010 (German Democratic R e p u b l i c )
4 1 n s t i t u t e o f Chemistry, N i c o l a u s Copernicus U n i v e r s t y , Gagarina
7 , 87-100 Torun (Poland)

SUMMARY
SAPO-5 was s y n t h e s i z e d from s t a r t i n g g e l s COVI - r i n g a broad
range o f composition. The i n c o r p o r a t i o n o f s i l i c o n i n t o t h e A F I
framework was s t u d i e d by m u l t i n u c l e a r MAS NMR and I R spectroscopy.
I t was found t h a t t h e g e l composition determines t h e morphology o f
t h e c r y s t a l s , b u t o n l y s l i g h t l y i n f l u e n c e s t h e amount o f s i l i c o n
i n c o r p o r a t e d . An upper l i m i t f o r t h e i n c o r p o r a t i o n o f i s o l a t e d
s i l i c o n atoms can be expected.

INTRODUCTION
C r y s t a l l i n e s i l i c o a l u m i n o p h o s p h a t e m o l e c u l a r s i e v e s (SAPOs) a r e
novel microporous s o l i d s which can be considered as derivatives
from t h e corresponding alurninophosphates by isomorphous s u b s t i t u -
tion (ref. 1). D i f f e r e n t mechanisms f o r t h i s s u b s t i t u t i o n a r e d i s -
cussed. Only i n t h e case o f an i n c o r p o r a t i o n o f monomeric s i l i c o n
on phosphorus s i t e s ( i . e . t h e s i l i c o n atoms a r e bonded v i a oxygen
to four adjacent aluminium atoms), the calcination of the as-
synthesized SAP0 generates one Bronsted a c i d i c s i t e per one s i l i -
con atom incorporated. Therefore, not only the o v e r a l l content,
b u t a l s o t h e t y p e o f s i l i c o n i n c o r p o r a t i o n determines t h e c a t a l y -
t i c a c t i v i t y o f SAPOs.
The goal o f our work was t o i n v e s t i g a t e t h e influence o f gel
composition on the final composition of the crystals and, in
p a r t i c u l a r , on t h e s i l i c o n i n c o r p o r a t i o n i n t o t h e framework o f t h e
resulting differently s i z e d and shaped SAPO-5 crystals. Further-
more, we want t o show t h a t t h e combination o f NMR and I R s p e c t r o -
538

scopy i s an a p p r o p r i a t e t o o l t o o b t a i n more d e t a i l e d information

about t h e samples. The p r e s e n t paper i s a d i r e c t c o n t i n u a t i o n o f
ref. 2. The samples were s y n t h e s i z e d f r o m s t a r t i n g g e l s w i t h i n a
broad range o f composition. The s o l i d s o b t a i n e d a f t e r c r y s t a l l i z a -
t i o n were c h a r a c t e r i z e d by XRD and scanning e l e c t r o n microscopy
and analyzed c h e m i c a l l y . To s t u d y t h e s i l i c o n i n c o r p o r a t i o n , s o l i d
s t a t e 31P, 29Si, 27Al and 'H MAS NMR as w e l l as I R spectroscopy
were appl l e d .

EXPERIMENTAL
Synthesis
0
SAPO-5 sample were s y n t h e s i z e d h y d r o t h e r m a l l y a t 190 C s t a r t i n g
from g e l s o f d i f f e r e n t molar r a t i o s o f t h e components a A1 0 .
2 3
b P205 c TEA . d Si02 . e H 2 0 ( c f . Table 2 ) . The g e l s were
formed applying an aluminiumoxydehydrate s o l (2.35 mass% A 1 0 1,
2 3
phosphoric a c i d ( 8 5 mass% H PO 1, t r i e t h y l a m i n e (TEA) a c t i n g as
3 4
template, a s i l i c a s o l ( 4 0 mass% S i O ) , and b i d i s t i l l e d w a t e r . The
2
s t a r t i n g pH value o f t h e g e l was 3.3 !: 0 . 2 r i s i n g t o about 7.0
after completion of the crystallization process. The obtained
c r y s t a l s were separated f r o m t h e mother l i q u o r and, i f necessary,
from some o c c a s i o n a l l y formed s m a l l amount o f by-products, washed
0
c a r e f u l l y and d r i e d . C a l c i n a t i o n was performed under a i r a t 750 C .
A more d e t a i l e d d e s c r i p t i o n o f t h e s y n t h e s i s i s g i v e n i n r e f . 2.

Chemical a n a l y s i s
..____~___

The d e t e r m i n a t i o n o f the chemical composition o f the SAPO-5

samples as g i v e n i n Table 2 was c a r r i e d o u t by wet chemical a n a l y -
s i s u s i n g t h e f o l l o w i n g procedures.
After calcination a t lOOO"C, the powdered m a t e r i a l was f u s e d
with sodium carbonate ( f i v e f o l d excess) followed by dissolution
i n t o hydrochloric acid. For t h e d e t e r m i n a t i o n o f silicon, poly-
e t h y l e n e o x i d e s o l u t i o n was used t o aggregate t h e s i l i c i c a c i d .
The p r e c i p i t a t e was f i l t e r e d , washed and weighed a f t e r h e a t i n g a t
1100°C. Then h y d r o f l u o r i c a c i d was added to evaporate silicon
dioxide. The q u a n t i t y o f s i l i c o n was determined on t h e b a s i s o f
w e i g h t r e d u c t i o n . The f i l t r a t e was t a k e n t o q u a n t i f y t h e r e s i d u a l
amount o f s i l i c o n d i o x i d e by means o f t h e molybdenum b l u e s p e c t r o -
photometry.

,
'..
, I
 539

The f i l t r a t e o f s i l i c i c a c i d was t a k e n t o o b t a i n t h e amounts o f

A 1 0 and P 0 Aluminium was p r e c i p i t a t e d by 8 - h y d r o x y q u i n o l i n e
2 3 2 5'
i n a weak a c e t i c a c i d s o l u t i o n (pH 6...7, 50'C). The oxyquino-
l a t e o f aluminium was f r i t t e d , washed w i t h l i t t l e c o l d water and
weighed as A1(CgH60N) a f t e r d r y i n g f o r 2 h a t 1 3 5 ' C . Phosphate
3
was p r e c i p i t a t e d as magnesium ammonium phosphate i n a two-step
procedure. The p r e c i p i t a t e was f i l t e r e d , washed and t h e paper sub-
sequently ashed. A f t e r h e a t i n g a t 1 1 O O " C , t h e r e s i d u e was weighed
as Mg P 0
2 2 7'

1-nst r ument a 1
The 27Al, 29Si and 31P MAS NMR s p e c t r a were recorded on a
Bruker MSL 400 spectrometer. The experimental conditions f o r the
NMR measurements a r e summarized i n Table 1 . A l l s p e c t r a shown i n
t h i s paper were o b t a i n e d by s i n g l e p u l s e e x c i t a t i o n . I n t h e case
o f 2 9 S i and 31P MAS NMR, high-power p r o t o n d e c o u p l i n g was a p p l i e d .
The chemical shifts reported for 27Al are not corrected for
second-order quadrupole e f f e c t s .
'H MAS NMR s p e c t r a were measured a t room temperature u s i n g a
Bruker MSL 300 spectrometer and a home-made magic-angle-spinning
equipment t h a t a l l o w s t o s p i n sealed g l a s s ampoules. The total
c o n c e n t r a t i o n o f OH groups i n t h e a c t i v a t e d samples was determined
by comparing t h e l i n e i n t e n s i t y w i t h t h a t o f a standard.

TABLE 1
Experimental c o n d i t i o n s f o r MAS NMR measurements.
____- -
nucleus resonance p u l s e flip repeti- no. o f MAS reference
frequency d u r a t i o n angle t i o n t i m e scans f r e q u .
/MH i! /us /S /kHz

1
H 300.0 4.0 7r/2 10.0 400 2.5 TMS
3+
2 7 ~ 1 104.2 0.6 T/l2 0.5 800 5.1 Al(H20)6

29s1 79.5 2.5 n/4 5.0 ,2000 4.2 TMS

31P 161.9 3.0 n/2 215.0 64 4.8 H3P04(85%)

For t h e ' H M A S NMR measurements, t h e samples were p r e t r e a t e d i n

a g l a s s tube o f 5.5 mm i n n e r diameter w i t h a 10 mm bed-depth.
S t a r t i n g a t room temperature, t h e samples were heated under vacuum
540

w i t h a r a t e o f 10 K/h. A f t e r keeping f o r 2 h a t 670 K , t h e samples

were evacuated up t o a pressure below 0 . 0 1 Pa f o r 20 h and s e a l e d
off.
The same samples were used i n DRIFT (diffuse reflectance IR
Fourier transform) i n v e s t i g a t i o n s o f OH groups. I n some cases an
anologous p r e t r e a t m e n t i n a s p e c i a l vacuum c e l l ( r e f . 3 ) was c a r -
r i e d o u t b e f o r e t h e I R measurements. The D R I F T measurements were
performed w i t h a F o u r i e r spectrometer I R F 180 ( C e n t r e o f Scien-
t i f i c I n s t r u m e n t a t i o n s o f t h e Academy o f Sciences o f t h e GDR) w i t h
-1
a r e s o l u t i o n o f 4 crn . An empty g l a s s tube o r a rough copper s u r -
face i n the vacuum cell were employed as the standard, respec-
tively.

RESULTS AND D I S C U S S I O N
By means o f XRD i t was proven t h a t all samples investigated
e x h i b i t indeed A F I s t r u c t u r e ( r e f . 4 ) . The q u i t e d i f f e r e n t morpho-
logy o f t h e t h e c r y s t a l s i s i l l u s t r a t e d in ref. 2: sample A in
Fig. lA, samples B and D i n F i g s . 2D and 4 8 and sample C i n F i g .
4E. The chemical compositions o f b o t h t h e g e l s and t h e c a l c i n e d
samples a r e g i v e n i n Table 2. Although the compositions o f the
g e l s cover a broad range, t h e composition o f t h e SAPO-5 crystals
i s nearly c o n s t a n t .

TABLE 2
Chemical compositions o f b o t h t h e g e l s and t h e c a l c i n e d and
dehydrated samples.

samp 1 e ge 1 c a l c i n e d sample
A1 0 , : P 0 : S i O : TEA: H20 A1 : P : Si Al/(P+Si)
2 3 2 5 2

*
A- 1.0 : 1 . 0 3 : 0.25: 1.55: 300 0.506: 0.458: 0.036 1.024

B 1.0 : 2.06: 0.25: 3.10: 300 0.505: 0.459: 0.036 1.020

C* 1.0 : 1.03: 1.00: 1.55: 300 0.505: 0.442: 0.053 1.021

D 1.0 : 2.06: 1.00: 3.10: 300 0.496: 0.465: 0.037 0.992

E* 1.0 : 1.10: 0.24: 1.12: 450 - - - -

F 1.0 : 2.35: 1.00: 3.43: 450 - - - -

~~~ ~ __ _~_____ ~~

*samples c o n t a i n i n g small amounts o f by-products which were sepa-

r a t e d b e f o r e t h e NMR and I R i n v e s t i g a t i o n s
 541

31P A-29.4

. . -
100 50 0 -50 0 -20 -Ul -GO
PPm PPm

F i g . 1 . 2 7 A l and 31P MAS NMR s p e c t r a o f SAPO-5 (sample A ) :

( a + d ) as-synthesized, (b+e) c a l c i n e d and dehydrated and ( c + f )
c a l c i n e d and rehydrated. S p i n n i n g sidebands a r e denoted by
asterisks.

27Al and 31P MAS NMR s p e c t r a o f sample A a r e shown i n Fig. 1.

For both n u c l e i we observe o n l y one l i n e i n the spectra o f the
c a l c i n e d and dehydrated sample c o n f i r m i n g t h e s t r i c t a l t e r n a t i o n
o f phosphorus and aluminium a t T p o s i t i o n s o f t h e aluminophosphate
framework ( r e f . 5 ) . The l i n e a t 3 5 . 4 ppm i n t h e 2 7 A l NMR spectrum
has t o be a s c r i b e d to tetrahedrally coordinated aluminium atoms
bonded v i a oxygen t o f o u r phosphorus atoms, whereas t h e line at
-30.2 ppm i n t h e 31P NMR spectrum corresponds t o phosphorus l i n k e d
w i t h f o u r A10 tetrahedra ( r e f s . 5 , 6 ) .
4
The substitution of a part of the framework T positions by
s i l i c o n i s n o t r e f l e c t e d i n t h e s p e c t r a . The s i n g l e resonance l i n e
o b t a i n e d f o r phosphorus c o r r o b o r a t e s t h a t P-0-Si bonds a r e u n l i k e -
l y t o occur ( r e f . 1). The d i f f e r e n t environments o f t h e phosphorus
n u c l e i i n t h e case o f a s i l i c o n i n c o r p o r a t i o n on h y p o t h e t i c a l a l u -
minium T sites should be detectable in 31P MAS NMR spectra.
The s p e c t r a i n F i g . 1 a l s o i n d i c a t e t h a t l a r g e changes i n t h e
542

AFI framework occur during sample c a l c i n a t i o n and rehydration.

These changes seem t o be a common f e a t u r e of many aluminophos-
phate-based m a t e r i a l s ( r e f s . 6 - 9 ) . Comparing t h e s p e c t r a i n F i g . 1
w i t h those o f A l P O - 5 , we found no i n f l u e n c e o f t h e s i l i c o n i n c o r -
4
p o r a t i o n . The 2 7 A l and 31P MAS NMR s p e c t r a o f t h e d i f f e r e n t SAPO-5
samples are almost i d e n t i c a l and agree w i t h those o f t h e s i l i c o n -
f r e e A l P O -5. Although o t h e r w i s e s t a t e d i n r e f . 10, the i n t e n s i t y
4
o f t h e l i n e due t o o c t a h e d r a l l y c o o r d i n a t e d aluminium i n t h e 2 7 A l
MAS NMR spectrum o f t h e c a l c i n e d and r e h y d r a t e d sample (-13.3 ppm
i n Fig. l c ) does n o t depend on t h e amount o f s i l i c o n i n c o r p o r a t e d .
N e i t h e r 2 7 A l nor 31P MAS NMR can be used t o d e t e c t o r t o q u a n t i f y
t h e amount o f s i l i c o n i n c o r p o r a t e d i n t o an aluminophosphate frame-
work.

'95i M A S N M R DRIFT

RL I

-60 -80 -100 -120 4

ppm

F i g . 2. 29Si MAS NMR and D R I F T s p e c t r a o f c a l c i n e d and dehydrated

SAPO-5. D e n o t a t i o n as i n Table 2 .

29Si MAS NMR i s t h e o n l y d i r e c t method t o i n v e s t i g a t e t h e t y p e

o f s i l i c o n incorporation. The *'Si NMR s p e c t r a t o g e t h e r w i t h t h e
corresponding d i f f u s e r e f l e c t a n c e I R F o u r i e r t r a n s f o r m s p e c t r a a r e
shown i n F i g . 2 . The 2 9 S i NMR l i n e s w i t h maxima between - 9 1 ppm
and - 9 6 ppm a r e a s c r i b e d t o s i l i c o n atoms bonded v i a oxygen t o
 543

f o u r aluminium atoms ( r e f s . 7 , l l - 1 5 ) . Each s i l i c o n atom i n c o r p o r a -

ted i n t h i s way should cause one Bronsted a c i d i c site. A weak
second signal at about -110 ppm can be seen in the case of
samples B, C and D. I t stems from s i l i c o n atoms bonded v i a oxygen
t o f o u r s i l i c o n . These pure s i l i c a u n i t s may be p r e s e n t i n s i l i c a
islands within the AFI structure or i n an amorphous by-product
(refs. 12,13). Since we have found t h a t the sometimes o b t a i n e d
by-product i s i n our case an aluminophosphate (vide infra), the
former e x p l a n a t i o n i s more l i k e l y . I n l i n e w i t h the findings o f
ref. 1 3 , an i n c r e a s e o f t h e o v e r a l l s i 1 i c o n c o n t e n t i n c r e a s e s t h e
r e l a t i v e i n t e n s i t y o f t h e -110 ppm l i n e , i . e . lowers t h e number o f
Bronsted a c i d i c s i t e s per s i l i c o n atom i n t h e sample.
The h y d r o x y l s generated by the silicon incorporation can be
studied by b o t h I R and ’H MAS NMR spectroscopy. The d i f f u s e
reflectance I R Fourier transform spectra i n Fig. 2 present the
r e g i o n o f fundamental OH s t r e t c h i n g v i b r a t i o n s
0-1 - Two bands a t
3625 and 3520 cm-l are observed due to Bronsted acidic sites
(SiOHAl groups). Corresponding t o literature (refs. 16,171, we
propose t h a t these d i f f e r e n t two bands c h a r a c t e r i z e undisturbed
S i O H A l groups (3625 cm-’) and S i O H A l groups i n t e r a c t i n g w i t h l a t -
t i c e oxygen ( 3 5 2 0 cm-’1. The t h r e e low intensity l i n e s a t 3785,
3745 and 3675 cm-l are caused by AlOH, SiOH and POH groups,
r e s p e c t i v e l y ( r e f . 17).

29si M A S NMR O R I FT

- 95.6
I

3625 A 3520

-
~~

-60 -80 -100 -12 0 4000 3500 3000

;/crn-’
PPm

F i g . 3 . 2 9 S i MAS NMR and D R I F T s p e c t r a o f t h e samples E ( b r o k e n

l i n e s ) and F ( s o l i d l i n e s ) .
544

As F i g . 3 shows, the s e n s i t i v i t i e s o f 29Si MAS NMR and D R I F T

a r e r a t h e r d i f f e r e n t . The samples d i f f e r s t r o n g l y i n t h e amount o f
i n c o r p o r a t e d s i l i c o n due t o a non-optimized synthesis procedure.
I n t h e case o f sample F , there i s only a weak 29Si NMR line at
-95.6 ppm c h a r a c t e r i z i n g t h e monomerically incorporated s i l i c o n ,
b u t t h e v i b r a t i o n bands o f OH groups due t o t h i s t y p e o f s i l i c o n
i n c o r p o r a t i o n are q u i t e intense. Hence, i t can be concluded t h a t
t h e D R I F T spectroscopy i s a v e r y s e n s i t i v e method t o p r o v e monome-
r i c a l l y incorporated s i l i c o n .

3.8
I

4.8
I
*

I
*
* *

1
Fig. 4. H MAS NMR spectrum o f SAPO-5 (sample A ) .

IR spectroscopy always encounters difficulties in obtaining

reliable quantitative data on the number of the different
h y d r o x y l s . T h i s problem can be s o l v e d by t h e a p p l i c a t i o n o f ' H MAS
NMR spectroscopy. The 'ti MAS NMR spectrum o f SAPO-5 consists o f
t h r e e l i n e s ( F i g . 4 ) . The l i n e s a t 4 . 8 and 3 . 8 ppm a r e caused by
b r i d g i n g S i O H A l groups and correspond t o t h e I R bands a t 3520 and
3 6 2 5 cm-l, respectively. Furthermore a broad band a t 1.9 ppm is
observed, which was a s c r i b e d t o POH groups (ref. 11). But a l s o
terminal S i O H groups can contribute to this line. The data are
summarized i n Table 3 . Except f o r sample C , t h e number o f b r i d g i n g
 545

hydroxyls agrees well with the total number of silicon atoms

p r e s e n t i n t h e samples. This f i n d i n g i n d i c a t e s an almost e x c l u -
s i v e l y monomeric i n c o r p o r a t i o n o f t h e s i l i c o n and i s t h e r e f o r e i n
accordance w i t h t h e s i l i c o n s p e c t r a shown i n F i g . 2 . From t h e -110
pprn l i n e p r e s e n t i n t h e s i l i c o n s p e c t r a , one would assume t h a t ,
except for sample A, the total number o f s i l i c o n atoms should
s l i g h t l y exceed t h e number o f b r i d g i n g h y d r o x y l s . D i s c u s s i n g these
q u a n t i t a t i v e d e t a i l s , t h e f a c t t h a t we a r e d e a l i n g w i t h v e r y small
amounts o f s i l i c o n and h y d r o x y l s has t o be considered.

TABLE 3
Concentrations o f s i l i c o n atoms and h y d r o x y l groups.
~ _ _ _ _ ~ _ _ _ _ __~ _________-__---_____--
~ ~

a
sample s i l i c o n atoms b r i d g i n g OHb n o n - a c i d i c OHC
/1O2O g-1 /1O2O g-l /1O2O g-1
~ - ._.. __ -

A 3.6 4.4 0.5

El 3.6 4.6 0.5
5.3 3.5 0.5
3.7 3.2 0.5
2.8 0.6
1.6 0.6
___ __
a from chemical a n a l y s i s
1
b from t h e i n t e n s i t h e H NMR l i n e s a t 3.8 and
4 . 8 ppm ( i O . 5 . 1 0 g
c from t h e ' n t n s i t y o f t h e ' H NMR l i n e a t 1 . 9 ppm
(LO.l.10 g
26 -7,

Since some o f the SAPO-5 samples synthesized contain by-

products ( s p h e r u l i t i c p a r t i c l e s up t o about 20 pm i n d i a m e t e r ) ,
one c o u l d argue t h a t t h e s i l i c o n c o u l d be p r e f e r e n t i a l l y incor-
porated n o t i n t o t h e A F I phase, but i n t o t h e by-product. There-
fore, we have performed a s y n t h e s i s under c o n d i t i o n s t h a t f a v o u r
the formation o f t h e by-product. The s y n t h e s i s p r o d u c t o b t a i n e d
was t h e n separated i n t o t h e A F I phase and t h e by-product by s i m p l e
d e c a n t a t i o n basing on t h e large differences i n the size o f the
p a r t i c l e s . The 2 9 S i MAS NMR and D R I F T s p e c t r a a r e g i v e n i n F i g . 5 .
Only t r a c e s o f s i g n a l s i n d i c a t i n g a s i l i c o n i n c o r p o r a t i o n a r e ob-
served i n t h e s p e c t r a o f t h e by-product. They can be a t t r i b u t e d t o
a non-perfect s e p a r a t i o n o f t h e phases. Hence, we can exclude a
p r e f e r e n t i a l s i l i c o n i n c o r p o r a t i o n i n t o t h e by-products.
546

2 9 ~ i MAS NMR DRIFT

~ ... .----
,-
,I

- 95.4
I

3625 1 13520
I 1 I , L

4000 3800 3600 3LOO 3200

29 .
Fig. 5 . S i MAS NMR and DRIFT s p e c t r a o f t h e by-product ( b r o k e n
l i n e s ) and t h e SAPO-5 phase ( s o l i d l i n e s ) o b t a i n e d f r o m t h e same
synthesis batch a f t e r c a l c i n a t i o n .

100 0 -100

PPm

F i g . 6 . 2 7 A l M A S NMR s p e c t r a o f t h e b y - p r o d u c t :
( a ) as-synthesized and ( b ) c a l c i n e d and d e h y d r a t e d .
 Concerning the chemical nature o f the by-product, we assume
t h a t i t i s an aluminophosphate. T h i s i s n o t o n l y supported by t h e
I R spectrum i n F i g . 5, where bands due t o A l O H and POH a r e p r e -
sent, b u t a l s o by 2 7 A l and 31P MAS NMR. The l i n e p o s i t i o n i n t h e
2 7 A l MAS NMR spectrum o b t a i n e d f o r t h e u n c a l c i n e d by-product (Fig.
6) i s characteristic of aluminium i n o c t a h e d r a l oxygen c o o r d i n a -
t i o n i n an aluminophosphate ( r e f . 1 8 ) . During c a l c i n a t i o n , t h e oxy-
gen c o o r d i n a t i o n i s changed i n t o a t e t r a h e d r a l one r e f l e c t e d by a
characteristic l i n e position a t 37.5 ppm. We f a i l e d t o a s s i g n t h e
by-product t o any known aluminophosphate s t r u c t u r e by XRD.

CONCLUSIONS
Morphology and s i z e of t h e SAPO-5 c r y s t a l s can be c o n t r o l l e d by
t h e composition o f t h e s t a r t i n g g e l .
For t h e c r y s t a l l i z a t i o n procedure used, a predominant monomeric
incorporation o f silicon i s achieved f o r q u i t e d i f f e r e n t c r y s t a l
morphologies. We1 1-shaped SAPO-5 crystals containing up to 4%
s i l i c o n on h y p o t h e t i c a l phosphorus T s i t e s can be synthesized.
An upper l i m i t for monomeric incorporation of silicon into
SAPO-5 can be expected. Above t h i s limit, only the fraction of
s i l i c o n present i n s i l i c a - r i c h islands w i t h i n the structure (and/
o r i n amorphous m a t e r i a l ) i s i n c r e a s i n g .
The s t r u c t u r a l changes caused by t e m p l a t e removal and by rehy-
d r a t i o n are n o t s i g n i f i c a n t l y i n f l u e n c e d by t h e incorporation o f
s i 1 icon.
A sometimes o b t a i n e d by-product o f t h e s y n t h e s i s was shown t o
be an aluminophosphate w i t h o u t s i l i c o n .

REFERENCES
1 E.M. F l a n i g e n , R.L. P a t t o n and S . T . Wilson, i n : P.J. Grobet,
W.J. M o r t i e r , E . F . Vansant and G. S c h u l z - E c k l o f f ( E d s . ) ,
I n n o v a t i o n i n Z e o l i t e M a t e r i a l Science, E l s e v i e r , Amsterdam,
1988, pp. 13-28.
2 G. F i n g e r , J . Kornatowski, J . Richter-Mendau, K . Jancke,
M. Bulow and M. Rozwadowski, t h i s volume.
3 C . Peuker, G. F i n g e r , E. L o f f l e r and W . P i l z , i n p r e p a r a t i o n .
4 W.M. Meier and D.H. Olson, A t l a s o f Z e o l i t e S t r u c t u r e Types,
2nd. edn., B u t t e r w o r t h s , London, 1987.
5 D. M u l l e r , E. Jahn, B. Fahlke, G. Ladwig and U . Haubenreisser,
Z e o l i t e s , 5 (1985) 5 3 - 5 6 .
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6 C . S . B l a c k w e l l and R.L. P a t t o n , J . Phys. Chem., 88 ( 1 9 8 4 )

6135-6139.
7 C . S . B l a c k w e l l and R . L . P a t t o n , J . Phys. Chem., 92 ( 1 9 8 8 )
3965-3970.
8 M. Goepper, F . Guth, L. D e l m o t t e , J . L . Guth and H . K e s s l e r ,
i n : P . A . Jacobs and R . A . van Santen ( E d s . ) , Z e o l i t e s : F a c t s ,
F i g u r e s , F u t u r e , E l s e v i e r , Amsterdam, 1989, pp. 857-866.
9 B . Z i b r o w i u s , U . Lohse, K . Szulzewsky, H. F i c h t n e r - S c h m i t t l e r ,
W . P r i t z k o w and J . Richter-Mendau, t h i s volume.
10 O . V . K i k h t y a n i n , V . M . M a s t i k h i n and K . G . I o n e , A p p l . C a t a l . , 42
( 1 9 8 8 ) 1-13.
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Phys. L e t t . , 143 ( 1 9 8 8 ) 477-480.
1 2 E. Brunner, H . E r n s t , D. Freude, M. Hunger and H . P f e i f e r ,
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Science, E l s e v i e r , Amsterdam, 1988, pp. 1 5 5 - 1 6 6 .
1 3 J . A . Martens, M. Mertens, P.J. Grobet and P.A. Jacobs,
i n : P.J. Grobet e t a l . ( E d s . ) , I n n o v a t i o n i n Z e o l i t e M a t e r i a l s
Science, E l s e v i e r , Amsterdam, 1988, pp. 97-105.
14 G . F i n g e r , E . Jahn, D . Zeigan, B. Z i b r o w i u s , I<. Szulzewsky,
J. Richter-Mendau and M . Biilow, B u l l . S O C . Chim. B e l g . , 98
( 1 9 8 9 ) 291-295.
1 5 I . P . Appleyard, R . K . H a r r i s and F . R . F i t c h , Chem. L e t t . , ( 1 9 8 5 )
1747-1750.
1 6 S.G. Hedge, P. Ratnasamy, L.M. Kustov and V . B . Kazansky,
Z e o l i t e s , 8 (1988) 137-141.
1 7 C . H a l i k . J.A. L e r c h e r , H . Mayer, J . Chem. SOC., Faraday
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G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 549
0 1991 Elsevier Science Publishers B.V., Amsterdam

ON THE SYNTHESIS AND STRUCTURE OF A1P04-14

B. ZIBROWIUS, U. LOHSE, K . SZULZEWSKY, H. FICHTNER-SCHMITTLER,

W. PRITZKOW and J. RICHTER-MENDAU
C e n t r a l I n s t i t u t e o f P h y s i c a l Chemistry, Academy o f Sciences o f
t h e GDR, Rudower Chaussee 5, B e r l i n , DDR - 1199
(German Democratic R e p u b l i c )

SUMMARY
A l P O -14 was prepared u s i n g p i p e r i d i n e as t e m p l a t i n g agent. The
4
XRD and MAS NMR r e s u l t s i n d i c a t e s i g n i f i c a n t s t r u c t u r a l changes o f
t h i s aluminophosphate d u r i n g template removal and r e h y d r a t i o n . The
l a t t i c e parameters o f t h e as-synthesized as w e l l as t h e c a l c i n e d
and dehydrated form o f A l P O -14 were determined f r o m X-ray powder
4
d i f f r a c t i o n d a t a . The l a t t i c e parameters o f t h e c a l c i n e d samples
correspond t o t h e i d e a l i z e d geometry suggested f o r A1P04-14, b u t
which has n o t y e t been a c t u a l l y observed. From 31P MAS NMR t h e
e x i s t e n c e o f a t l e a s t t h r e e non-equivalent phosphorus s i t e s i n t h e
c a l c i n e d form o f A l P O -14 i s d e r i v e d .
4

INTRODUCTION
The s y n t h e s i s and c h a r a c t e r i z a t i o n o f microporous c r y s t a l l i n e
aluminophosphates (A1P04-n (ref. 1) ) has a t t r a c t e d much i n t e r e s t
d u r i n g t h e l a s t few years. Because o f t h e i r s t r u c t u r a l and compo-
sitional diversity, A l P O -based m o l e c u l a r s i e v e s can be t a i l o r e d
4
t o many d i f f e r e n t processes. Only some o f t h e AlPO t y p e m a t e r i a l s
4
have framework t o p o l o g i e s i d e n t i c a l w i t h those o f known z e o l i t e s .
Among t h e huge number o f newly s y n t h e s i z e d A1P04 t y p e s , there are
some m a t e r i a l s which have been p a t e n t e d a c c o r d i n g t o their XRD
patterns, b u t l i t t l e i s known about t h e i r s t r u c t u r e s and proper-
ties.
The goal of the present study was to characterize A1P04-14
(ref. 2) by XRD, solid state NMR as w e l l as thermoanalytical
measurements. The structure type of as-synthesized A1P04-14 is
presumed t o be t h a t o f a g a l l i u m phosphate s y n t h e s i z e d by means o f
iso-propylamine (refs. 3,4). A r e f i n e m e n t o f t h e A1P04-14 struc-
t u r e has n o t y e t been p u b l i s h e d .
550

EXPERIMENTAL
Sample p r e p a r a t i o n
As d i s t i n c t from t h e U.S. patent ( r e f . 2), the synthesis o f
A l P O -14 was performed n e i t h e r w i t h t - b u t y l a m i n e n o r w i t h i s o -
4
propylamine, b u t w i t h p i p e r i d i n e as t h e t e m p l a t i n g agent. The f o l -
l o w i n g procedure was used: 13 g o f water, 6.6 g o f p h o s p h o r i c a c i d
(85 mass%) and 2.8 g o f pseudoboehmite ( 7 4 mass% A 1 2 0 3 , 2 6 mass%
H 0 ) were mixed by v i g o r o u s s t i r r i n g . After addition of 4 g of
2
p i p e r i d i n e t h e f i n a l c o m p o s i t i o n o f t h e r e a c t i o n m i x t u r e was

1 A1203 . 1.4 P 0 . 2.3 (CH ) NH ' 40 H20.

2 5 2 5

The pH v a l u e o f t h e g e l was found t o be 3.6...4.5. The c r y s t a l -

l i z a t i o n was performed i n s t a i n l e s s steel autoclaves lined with
p o l y t e t r a f l u o r e t h y l e n e a t 473 K f o r 90 h. After centrifugation,
washing and d r y i n g t h e sample c o m p o s i t i o n o f the as-synthesized
sample was determined t o be a p p r o x i m a t e l y

1 2 A1P04 ' 3 (CH215NH ' 8 H20.

Concerning t h e chemical c o m p o s i t i o n o f t h e c a l c i n e d A l P O
crys-
4
tals, the A l / P r a t i o was found t o be 1 : 1 b o t h i n t h e b u l k phase
(chemical a n a l y s i s ) and i n t h e s u r f a c e l a y e r s (XPS).

Instrumental
Crystal habit and size were ascertained using a scanning
e l e c t r o n microscope TESLA BS300 w i t h p l a t i n u m coated specimens.
The X-ray powder diffraction p a t t e r n s were recorded using a
G u i n i e r f i l m camera (CuK r a d i a t i o n ) , a high-temperature G u i n i e r
Crl
camera and a diffractometer with Bragg-Brentano geometry (CuK
CI
radiation).
The thermal analyses (DTA and TG) were carried out using a
Derivatograph supplied by MOM, Budapest. Samples (200 mg) s a t u -
r a t e d w i t h water a t room temperature were heated f r o m 293 K to
1073 K a t a r a t e o f 5 K/min. For DTA measurements, 0 - A 1 0 powder
2 3
was used as t h e r e f e r e n c e m a t e r i a l .
The magic angle s p i n n i n g (MAS) NMR s p e c t r a were recorded on a
Bruker MSL 400 spectrometer. The 2 7 A l NMR s p e c t r a were o b t a i n e d a t
a resonance frequency o f 104.2 MHz and a s p i n n i n g r a t e o f 5 . 3 kHz.
S i n g l e p u l s e e x c i t a t i o n (SPE) w i t h n/12 p u l s e s o f 0.6 p s length
was used. The l i n e positions are reported r e l a t i v e t o A l C l in
3
 551

aqueous solution. No corrections for second order quadrupole

e f f e c t s are applied. The 31P NMR s p e c t r a were t a k e n a t 162.0 MHz
w i t h a s p i n n i n g r a t e o f 4.8 kHz. Relaxation d e l a y s o f up t o 90 s
were necessary to avoid s a t u r a t i o n effects i n t h e case o f SPE
spectra. Chemical s h i f t s a r e r e p o r t e d r e l a t i v e t o 85 mass% H PO
3 4'
The 1 3 C NMR s p e c t r a were o b t a i n e d a t 100.6 MHz w i t h a s p i n n i n g
r a t e o f 4.8 kHz. For t h e s i n g l e p u l s e e x c i t a t i o n , n/2 pulses o f
4.4 p s l e n g t h w i t h a r e l a x a t i o n d e l a y o f 5 s were used. 13C chemi-
c a l s h i f t s are r e p o r t e d r e l a t i v e t o TMS. Durene was used as secon-
dary standard (6(CH3) = 19.2 ppm ( r e f . 5 ) ) . I n b o t h t h e 13C and
31 P cross-pol a r i z a t i o n ( C P ) experiments, proton n / 2 pulses o f 5 p s
were a p p l i e d . A l l 13C and 31P NMR s p e c t r a were recorded a p p l y i n g
high-power p r o t o n decoupling.

RESULTS AND DISCUSSION

X-ray powder d i f f r a c t i o n
The scanning e l e c t r o n micrograph i n F i g . 1 shows t h e t y p i c a l
crystal morphology of the aluminophosphate obtained. Usually,
c r y s t a l s o f t a b u l a r h a b i t a r e observed w i t h dimensions up t o ca.
15 pm i n l e n g t h and 3 p m i n w i d t h .

F i g . 1. Scanning e l e c t r o n micrograph o f t h e A1P04-14 c r y s t a l s .

The X-ray powder pattern of the as-synthesized form o f the

alurninophosphate investigated ( c f . Fig. 2) can be indexed on t h e
b a s i s o f a t r i c l i n i c u n i t c e l l w i t h t h e f o l l o w i n g parameters:
552

2Thefa /degre es-

F i g . 2 . X-ray powder d i f f r a c t i o n p a t t e r n o f t h e as-synthesized
form o f A1P04-14.

a = 9.697(2) 6 CI 74.92(2)'
b 9.947(2) p 75.14(2)' V = 953.6 A3
c = 10.612(2) A y 89.40(2)'.

These l a t t i c e parameters a r e c l o s e l y r e l a t e d t o those o f a g a l l i u m

phosphate g i v e n i n r e f . 3. T h i s g a l l i u m phosphate r e f e r r e d t o as
GaPO - 1 4 has been s t a t e d t o correspond t o A l P O - 1 4 because o f t h e
4 4
s i m i l a r i t y o f i t s powder p a t t e r n w i t h t h e d i f f r a c t i o n d a t a l i s t e d
i n t h e U.S. patent ( r e f . 2). The d e v i a t i o n s between t h e powder
p a t t e r n o f o u r as-synthesized sample ( c f . Table 1 ) and X-ray data
g i v e n i n r e f . 2 may be caused by t e m p l a t e i n f l u e n c e . L a t t i c e para-
meters and c r y s t a l symmetry allow a clear identification of the
framework structure type. The aluminophosphate o b t a i n e d can be
unambiguously i d e n t i f i e d as A l P O - 1 4 on t h e b a s i s o f i t s crystal
4
data.
After removal o f t h e template, the calcinated sample o f our
AlPO -14 produced a s i n g l e phase X-ray diagram o n l y i n the f u l l y
4
dehydrated form, i.e. a t room temperature i n dry nitrogen o r at
temperatures above 310 K i n air. N o changes i n t h e XRD p a t t e r n
 553

TABLE 1 . X-ray powder d i f f r a c t i o n d a t a o f as-synthesized AlPO -14.

____ 4
present d a t a d a t a from r e f . 2
2 Theta hkl I/Io 2 Theta I/Io
(degrees ) (%I ( degrees) (%I
_.
8.93 001 100 9.2 100
9.21 010 27 9.4 shou 1 der
11.00 01 1 6 11.2 18
11.17 101 13
12.80 1 io 75 13.1 17
13.29 111 35 13.4 shou 1 der
14.46 oii 16 14.8 3
14.63 1o i 11
15.63 iii ,ii 1 95 15.8 23
17.85 01 2 6 18.0 12
17.92 002,102 6
18.14 112 4
18.27 02 1 2
18.71 20 1 10 18.8 1
18.84 1 ii 15 19.2 1
18.95 200 12
20.01 121 3 - -
20.59 2io 14 20.9 5
21.17 121 10 21.6 10
21.31 120 35
21.45 2i 1 10
21.61 210 10
22.09 172 62 22.2 22
22.43 102,202 37
22.61 122,021 25 22.7 36
22.87 21 2 48
23.04 20i 5 23.4 1
23.50 211 2 23.7 1
25.46 113 20 25.2 2
25.77 220 8 26.1 20
25.92 12i 11
26.12 013 15
26.19 103,217 15
27.04 003 10 27.1 9
27.32 -
221 4
27.40 22 1 2
27.61 30 1 2 27.7 2
27.89 030 9
28.06 123 2
28.25 213 4
28.36 131 23 28.5 5
28.61 300 5
28.82 131 5
28.96 -
032,311 5
29.10 212 5 29.5 12
29.40 3i 1 28
29.56 302,3io 3
30.06 312,130 30 30.2 8
554

were observed up t o a temperature o f 4 7 3 K . I t i s supposed t h a t a t

room temperature t h e c r y s t a l s t r u c t u r e i s always i n f l u e n c e d by t h e
presence o f water o r i g i n a t i n g f r o m atmospheric h u m i d i t y .
The X-ray diagram o f t h e c a l c i n e d and dehydrated sample can be
attributed t o crystals with the following C-centred monoclinic
unit cell :

a = 14.059(6) A
b = 13.480(8) A I; = 107.30(4)' v = 1850.8 a3
c 10.229(4) a.
These l a t t i c e parameters correspond t o t h e i d e a l i z e d geometry o f
t h e A l P O -14 s t r u c t u r e t y p e as d e s c r i b e d i n r e f . 4, b u t which have
4
n o t y e t been a c t u a l l y observed.
The m o n o c l i n i c c e l l o f t h e c a l c i n e d A l P O -14 i s r e l a t e d t o t h e
4
u n i t c e l l o f t h e as-synthesized form. T h i s may be seen a f t e r an
axial transformation o f the l a t t i c e parameters o f t h e C-centred
m o n o c l i n i c c e l l t o t h a t o f a p r i m i t i v e t r i c l i n i c one a c c o r d i n g to
-t
a =
-t
+ %mon ) / 2 , +btr = +
(amon
- +bmon)/2 .)
and ctr = c
+ . The
tr (amon mon
r e s u l t i n g reduced t r i c l i n i c c e l l has t h e f o l l o w i n g parameters:

a = 9.739 A a = 77.60'
b = 9.739 A 0 77.60'
c = 10.229 6 Y 87.59'.

We suppose t h a t s i m i a r t o t h e d i s t o r t on o f t h e i d e a l geometry
o f t h e framework by t h e t e m p l a t e i n t h e as-synthesized form, the
a d s o r p t i o n o f water leads t o one o r even more r e l a t e d s t r u c t u r e s
w i t h reduced symmetry. T h i s assumption would be i n l i n e w i t h t h e
r e s u l t s o f t h e s o l i d s t a t e NMR f o r t h e c a l c i n e d and f u l l y rehydra-
t e d sample.

Thermoanal y s i s and 13C MAS NMR

The removal of the template was studied by thermoanalytical
measurements. I n t h e DTA c u r v e shown i n Fig. 3 , two endothermic
peaks ( a t 4 2 0 K and 648 K i n a i r ) and a s t r o n g e x o t h e r m i c peak
above 800 K w i t h a s h o u l d e r on t h e h i g h temperature s i d e a r e ob-
served. Four w e i g h t l o s s s t e p s may be seen i n t h e TG c u r v e ( c f .
Fig. 3). Two o f these a r e a s s o c i a t e d w i t h t h e endothermic peaks.
I n c o r r e l a t i o n w i t h t h e asymmetric e x o t h e r m i c peak, a fast, fol-
lowed by a slow decrease o f sample w e i g h t occurs.
The endothermic e f f e c t s a r e due t o t h e desorption of water;
 555

t h i s f o l l o w s from t h e comparison o f t h e t h e r m o a n a l y t i c a l d a t a w i t h
those of the elementary analysis. Water can be eliminated in
vacuum, and t h e weight l o s s a t 773 K amounts t o 9 %. A f t e r vacuum
t r e a t m e n t t h e endothermic peaks p r a c t i c a l l y vanish ( c f . F i g . 3).
The minor peak a t 403 K i s due t o t h e r e a d s o r p t i o n o f water d u r i n g
the handling o f t h e sample i n a i r (before the thermoanalytical
measurement).

820

’.....
T/K .---

F i g . 3. DTA and TO curves o f A PO - 1 4 : ( a ) i n a i r , (b) i n a i r

4
a f t e r e v a c u a t i o n a t 773 K and c ) i n argon.

The removal o f p i p e r i d i n e i i p o s s i b l e o n l y by d e g r a d a t i o n - in
a i r by o x i d a t i o n , i n argon by c r a c k i n g . The shape o f t h e DTA/TG
curves c o u l d be e x p l a i n e d assuming e i t h e r two p i p e r i d i n e s p e c i e s
t o be p r e s e n t o r a two-step behaviour f o r t h e d e g r a d a t i o n . From
t h e s y n t h e s i s c o n d i t i o n s (pH o f t h e g e l : ca. 3.6, a f t e r c r y s t a l l i -
+
zation: ca. 6.51, t h e f o r m a t i o n o f p i p e r i d i n i u m i o n s ((CH 2 ) 5 NH 2
i s probable ( r e f . 6 ) . On t h e o t h e r hand, t h e presence o f n e u t r a l
p i p e r i d i n e molecules was d e r i v e d f r o m t h e appearance o f the NH
wagging v i b r a t i o n band (720 ern-') i n t h e I R s p e c t r a ( r e f . 7).
556

'3c 23.0

45.8

F i g . 4. 13C MAS NMR s p e c t r a o f t h e

as-synthesized A1P04-14 obtained
(a) by cross-polarization =
A
-
(T ,
mix
0.25 ms, 2400 scans) and ( b ) by
I I I L I ' I '
single pulse excitation (600
60 40
PPm
20 0 scans ) .
To o b t a i n more i n f o r m a t i o n on t h e n a t u r e o f t h e occluded p i p e -
ridine, we a p p l i e d 13C MAS NMR as another s p e c t r o s c o p i c method.
1 3 C NMR s p e c t r a o f an as-synthesized sample o b t a i n e d by s i n g l e -
pulse excitation (SPE) as well as cross-polarization (CP) are
shown i n Fig. 4. The l i n e shapes o b t a i n e d by t h e two d i f f e r e n t
techniques a r e almost i d e n t i c a l i n d i c a t i n g t h a t t h e CP r e s u l t s a r e
r e l i a b l e w i t h r e s p e c t t o t h e r e l a t i v e i n t e n s i t i e s and t h e number
of lines observed. A prolonged mixing time led to a strong
decrease i n t h e s i g n a l i n t e n s i t y . Above 5 ms no CP s i g n a l was ob-
served i n d i c a t i n g a v e r y s h o r t l o n g i t u d i n a l r e l a x a t i o n t i m e T of
1P
the protons involved in the transfer of magnetization. I n the
l i q u i d phase, the a, and y carbons o f p i p e r i d i n e e x h i b i t reso-
nance l i n e s w i t h t h e i n t e n s i t y r a t i o o f 2 : 2 : 1 a t 47.6, 27.4
and 2 5 . 3 ppm and those o f piperidinium ions a t 45.2, 22.7, and
22.5 ppm ( r e f . 8 ) . Although t h e l a r g e l i n e w i d t h o b t a i n e d f o r t h e
occluded piperidine renders a conclusive interpretation impos-
s i b l e , t h e observed l i n e p o s i t i o n s a t 45.8 and 23.0 ppm s u p p o r t
t h e assumption t h a t p i p e r i d i n i u m i o n s a r e p r e s e n t .
The e n c a p s u l a t i o n o f p i p e r i d i n i u m i o n s i n t h e s t r u c t u r e r a i s e s
t h e q u e s t i o n o f charge compensation. I n t h e case o f A l P O - 1 7 which
4
was a l s o s y n t h e s i z e d by means o f p i p e r i d i n e , i t has been suggested
t h a t t h e p i p e r i d i n e has " r e a c t e d w i t h a water molecule t o y i e l d a
p i p e r i d i n i u m i o n and a h y d r o x y l , which t h e n interacts with the
 557

aluminophosphate framework" (ref. 9). For t h e g a l l i u m phosphate

analogue o f A1P04-14, the formation of iso-propylammonium ions
d u r i n g t h e c r y s t a l l i z a t i o n process was d e r i v e d f r o m XRD d a t a ( r e f .
3 ) . The charge compensation i s accomplished by h y d r o x y l i o n s .

27Al and 31P MAS NMR

F u r t h e r i n f o r m a t i o n on t h e framework s t r u c t u r e and s t r u c t u r a l
changes d u r i n g template removal and r e h y d r a t i o n was o b t a i n e d by
s o l i d s t a t e NMR. 27Al and 31P MAS NMR s p e c t r a o f A1P04-14 are
given i n F i g . 5 . The 2 7 A l MAS NMR spectrum o f t h e as-synthesized
AlPO -14 i s very complex. In this spectrum, there are intense
4
lines i n t h e range o f t e t r a h e d r a l l y (34.0 ppm) and o c t a h e d r a l l y
(-9.0 ppm) coordinated aluminium in aluminophosphates, respec-
tively (ref. 1 0 ) . The l i n e a t ca. 10 ppm c o u l d be caused by o c t a -
h e d r a l l y c o o r d i n a t e d aluminium i n an aluminate, i.e. by a minor
amount o f unreacted pseudoboehmi t e remaining a f t e r s y n t h e s i s , or
more probably by aluminium in fivefold coordination in the
aluminophosphate framework. The l a t t e r e x p l a n a t i o n i s supported by
the fact that a fivefold oxygen coordination of part of the
gallium atoms was found in the above mentioned as-synthesized
GaP04-14 ( r e f . 3 ) . A f i v e f o l d o r t r i g o n a l - b i p y r a m i d a l coordination
o f aluminium was a l s o found i n t h e as-synthesized forms o f some
other aluminophosphate materials (refs. 9,111. Furthermore, the
f o u r non-equivalent g a l l i u m s i t e s w i t h d i f f e r e n t oxygen c o o r d i n a -
t i o n found i n GaPO -14 (Ga(1) i n t r i g o n a l - b i p y r a m i d a l , Ga(2) and
4
Ga(3) i n t e t r a h e d r a l and Ga(4) i n o c t a h e d r a l c o o r d i n a t i o n ( r e f .
3 ) ) would correspond t o t h e v e r y complex 2 7 MAS
~ ~NMR spectrum
o b t a i n e d f o r t h e as-synthesized A l P O -14.
4
C a l c i n a t i o n t r a n s f o r m s t h e oxygen c o o r d i n a t i o n o f a l l aluminium
atoms i n t o a t e t r a h e d r a l one. The non-symmetric l i n e shape i n F i g .
5b i s caused by incomplete removal of second-order quadrupolar
c o u p l i n g as w e l l as t h e presence o f n o n - e q u i v a l e n t crystallogra-
phic sites. T h i s was proven by measurements a t lower f i e l d . The
27Al MAS NMR s p e c t r a taken at 78.2 MHz were t o o complex t o be
attributed t o second-order quadrupolar c o u p l i n g alone (ref. 7).
Measurements at even lower magnetic fields should allow the
e x t r a c t i o n o f quadrupole c o u p l i n g c o n s t a n t s , asymmetry parameters
and i s o t r o p i c chemical s h i f t s as i n t h e case o f A1P04-17 (ref.
12).
558

-30.5
3’ P

-21.9

..*
-17.3

- L - - L - L

100 50 0 -50 0 -20 -40 -GO

PPm PPm

F i g . 5 . 2 7 A l and 31P MAS NMR s p e c t r a o f A l P O -14:

4
( a + d ) as-synthesized sample, (b+e) c a l c i n e d and dehydrated sample
and ( c + f ) c a l c i n e d and f u l l y h y d r a t e d sample. The a s t e r i s k s denote
s p i n n i n g sidebands.

A s i s found f o r many o t h e r s t r u c t u r e s ( c f . r e f . 131, rehydra-

t i o n generates an o c t a h e d r a l c o o r d i n a t i o n o f some o f t h e aluminium
atoms. Furthermore, t h e l i n e a t ca. 10 ppm i s a g a i n p r e s e n t . Be-
cause o f t h e l a c k o f s t r u c t u r a l d a t a f o r t h e r e h y d r a t e d sample, a
d e f i n i t e assignment o f t h i s l i n e t o f i v e f o l d c o o r d i n a t e d aluminium
i s not justified. I n t h e e v e n t t h a t t h i s l i n e i s caused by unreac-
t e d pseudoboehmite, i t s disappearance d u r i n g c a l c i n a t i o n can be
understood as an effect of dehydration. A highly asymmetric
environment produced by d e h y d r a t i o n can render aluminium atoms
i n v i s i b l e t o NMR ( r e f s . 14,151.
The d o w n f i e l d s h i f t o f t h e l i n e assigned t o t e t r a h e d r a l l y co-
o r d i n a t e d aluminium i n t h e rehydrated sample i s striking. A t a
resonance frequency o f 78.2 MHz t h i s l i n e i s o b t a i n e d a t 42.8 ppm.
T h i s f i n d i n g i n d i c a t e s t h a t t h e s h i f t t o lower f i e l d i s o n l y t o a
small degree caused by a reduced quadrupolar coupling. Using a
 559

c o r r e l a t i o n d e r i v e d f o r aluminophosphates by M u l l e r and co-workers

(ref. 1 6 1 , t h i s s h i f t would correspond t o a r e d u c t i o n o f t h e mean
A1-0-P angle under r e h y d r a t i o n o f up t o 10'. T h i s may a t l e a s t be
taken as an e s t i m a t e o f t h e e x t e n t o f t h e s t r u c t u r a l changes.
Large changes i n t h e A l P O -14 framework d u r i n g sample c a l c i n a -
4
t i o n and r e h y d r a t i o n a r e n o t o n l y c o r r o b o r a t e d by t h e above g i v e n
XRD resu t s , b u t a r e a l s o r e f l e c t e d by 31P MAS NMR s p e c t r a . Three
l i n e s i n a chemical s h i f t range ( - 2 2 ...-31 ppm) which i s c h a r a c t e -
ristic o aluminophosphates a r e observed i n t h e case o f t h e as-
synthesized f o r m ( c f . F i g . 5d). The r e l a t i v e i n t e n s i t i e s o f these
l i n e s vary s l i g h t l y from sample t o sample. I n a d d i t i o n , t h e 31P
MAS NMR spectrum o f t h e as-synthesized samples e x h i b i t s a l i n e a t
-7.5 ppm. The highest value of the chemical shift found in a
systematic study o f aluminophosphate m i n e r a l s is 6 -1 1.2 ppm
(ref. 17) f o r w a v e l l i t e which i s an aluminophosphate-hydrate. A
s p e c i f i c i n t e r a c t i o n between t h e t e m p l a t e molecules and t h e phos-
phorus o f t h e framework i s u n l i k e l y t o be t h e reason f o r t h i s un-
usual l i n e position, since t h i s l i n e was n o t observed f o r o t h e r
aluminophosphates synthesized by means of the same templating
agent ( r e f . 18). It i s interesting t o note t h a t there are four
non-equivalent phosphorus s i t e s i n t h e framework o f t h e GaP04 ana-
logue o f as-synthesized A l P O -14 ( r e f . 3 ) .
4
I n o r d e r t o g e t more i n s i g h t i n t o t h e s t r u c t u r a l environment o f
t h e phosphorus n u c l e i g i v i n g r i s e t o t h e d i f f e r e n t l i n e s i n the
31P MAS NMR spectrum o f t h e as-synthesized sample, we a p p l i e d t h e
cross-polarization (CP) technique. I n F i g . 6 , 31P CP/MAS NMR spec-
t r a f o r d i f f e r e n t m i x i n g t i m e s a r e shown i n t h e a b s o l u t e i n t e n s i t y
mode. Using s h o r t m i x i n g t i m e s , one o b t a i n s s p e c t r a t h a t a r e q u i t e
similar to those recorded by single pulse excitation. Conse-
q u e n t l y , a l l phosphorus n u c l e i have p r o t o n s i n t h e i r neighbourhood
from which t h e m a g n e t i z a t i o n can be t r a n s f e r r e d . If the mixing
t i m e exceeds about 1 ms, a l l b u t t h e l i n e a t -30.5 ppm a r e d r a s t i -
cally reduced. The l a t t e r reaches maximum i n t e n s i t y a t a m i x i n g
time o f about 5 ms. Since t h e decay o f CP s i g n a l intensity is
m a i n l y determined by t h e l o n g i t u d i n a l relaxation time T o f the
1P
protons ( r e f s . 17,191, we have t o conclude t h a t t h e p r o t o n r e s e r -
voir for cross-polarization t o phosphorus n u c l e i w i t h resonance
l i n e s a t -7.6, -21.9 and -27.8 ppm i s d i f f e r e n t f r o m t h a t one f o r
t h e remaining n u c l e i .
560

31P CP/MAS 1.5

20 0 -20 -40 - 60
Ppm

Fig. 6. 31P CP/MAS NMR s p e c t r a o f t h e a s - s y n t h e s i z e d A l P O - 1 4

4
u s i n g d i f f e r e n t m i x i n g t i m e s : ( a ) 0 . 5 ms, ( b ) 2 . 0 m s and
( c ) 4 . 0 ms.

The 3 1 P MAS NMR spectrum o f t h e c a l c i n e d sample ( c f . F i g . 5e)

shows t h r e e w e l l resolved l i n e s w i t h the i n t e n s i t y r a t i o o f 1 :
2.0 : 1.1. Hence i t f o l l o w s t h a t t h i s s t r u c t u r e has a t l e a s t t h r e e
c r y s t a l l o g r a p h i c non-equivalent phosphorus s i t e s . I n t h e case o f
four non-equivalent phosphorus sites as in the as-synthesized
GaPO - 1 4 ( r e f . 31, two o f them s h o u l d have a v e r y s i m i l a r geometry
4
l e a d i n g t o a c o i n c i d e n c e o f resonance l i n e s . A s expected f o r t h e
dehydrated sample, the cross-polarization efficiency for all the
t h r e e 31P resonance l i n e s i n F i g . 5e i s v e r y low. A broad l i n e a t
about -18 ppm a d d i t i o n a l l y observed u s i n g CP i s a t t r i b u t e d t o POH
p r e s e n t as d e f e c t s i t e s o f t h e s t r u c t u r e o r i n minor amounts o f
amorphous p r e c u r s o r s .
 561

After rehydration, an ill r e s o l v e d 31P NMR spectrum i s ob-

tained. Since t h e same r e l a t i o n between chemical s h i f t and mean
A1-0-P angle was found f o r both 2 7 A l and 31P NMR ( r e f . 161, the
overall d o w n f i e l d s h i f t o f t h e spectrum would correspond t o t h e
d e r i v e d r e d u c t i o n o f mean A1-0-P angle. By c r o s s - p o l a r i z a t i o n it
was shown t h a t a l l n u c l e i i n t e r a c t strongly w i t h the protons o f
adsorbed water molecules ( r e f . 7). T h i s f a c t must be t a k e n i n t o
account f o r any q u a n t i t a t i v e i n t e r p r e t a t i o n o f t h e d o w n f i e l d s h i f t
o f t h e 31P NMR spectrum d u r i n g r e h y d r a t i o n .
The changes i n t h e 2 7 A l and 3 1 P MAS NMR s p e c t r a caused by rehy-
d r a t i o n a r e completely r e v e r s i b l e . A l s o , t h e a d s o r p t i o n p r o p e r t i e s
( c a p a c i t i e s and k i n e t i c s ) a r e n o t a l t e r e d by dehydration/rehydra-
t i o n cycles ( r e f . 7 ) . Consequently, we have t o conclude t h a t t h e
s t r u c t u r a l changes caused by a d s o r p t i o n o f water a r e indeed r e v e r -
s i b l e processes. The shape o f t h e observed water i s o t h e r m t o g e t h e r
with t h e very small uptake r a t e ( r e f . 20), contradicts a pure
physical a d s o r p t i o n process. The f i r s t water molecules adsorbed
are l i k e l y t o r e a c t w i t h t h e aluminophosphate and cause r e v e r s i b l e
structural changes. The f o r m a t i o n o f an aluminophosphate-hydrate
can be expected. Combined XRD and s p e c t r o s c o p i c investigations a t
d e f i n e d water l o a d i n g l e v e l s would be necessary t o e l u c i d a t e t h e
i n t e r a c t i o n o f water w i t h t h e aluminophosphate framework.

CONCLUSIONS
Using p i p e r i d i n e as t e m p l a t i n g agent, we have s y n t h e s i z e d t h e
small pore molecular s i e v e A l P O -14 as a pure phase w i t h h i g h
4
crystallinity. On t h e b a s i s o f t h e presented XRD d a t a , an unambi-
guous assignment is possible. The topological equivalence of
GaPO -14 and A l P O -14 i s confirmed. Furthermore, t h e l a t t i c e para-
4 4
meters o f t h e c a l c i n e d and dehydrated f o r m correspond t o t h e idea-
lized geometry suggested for A l P O -14, but which has not Yet
4
a c t u a l l y observed.
From 31P MAS NMR spectroscopy it follows that there are at
l e a s t t h r e e non-equivalent phosphorus s i t e s i n t h e framework of
t h e c a l c i n e d f o r m o f A1P04-14.
The f o r m a t i o n o f occluded piperidinium ions during the syn-
t h e s i s i s supposed on t h e b a s i s o f t h e r m o a n a l y t i c a l d a t a and i s
c o r r o b o r a t e d by 1 3 C MAS NMR.
562

The XRD p a t t e r n s as w e l l as t h e s o l i d s t a t e NMR s p e c t r a i n d i -

cate significant structural changes during calcination and re-
hydration. To e l u c i d a t e the interaction of the aluminophosphate
framework with the water molecules and their influence on the
s t r u c t u r e i s a challenge f o r f u r t h e r i n v e s t i g a t i o n s .

ACKNOWLEDGEMENT
We a r e i n d e b t e d t o D r . M. Hunger ( L e i p z i g ) f o r r e c o r d i n g
27Al MAS NMR s p e c t r a a t lower f i e l d .

REFERENCES
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E.M. F l a n i g e n , J. Am. Chem. SOC., 104 (1982) 1146-1147.
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J.V. Smith, Z e o l i t e s , 6 (1986) 349-361.
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I n n o v a t i o n i n Z e o l i t e M a t e r i a l Science, E l s e v i e r , Amsterdam,
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F i g u r e s , F u t u r e , E l s e v i e r , Amsterdam, 1989, pp. 851-866,
14 K.J.D. MacKenzie, I . W . M . Brown, R.H. Meinhold and M.E. Bowden,
J. Am. Chem. SOC., 6 8 (1985) 293-297.
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2 . anorg. a l l g . Chem., 576 (1989) 43-53.
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19-24.
G . Ohlrnann et al. (Editors),Catalysis and Adsorption by Zeolites 563
1991 Elsevier Science Publishers B.V., Amsterdam

Y-ZEOLITE TREATED WITH SiCl, VAPOUR. STRUCTURE AND PROPERTIES

G.M. TELBIZ’, A.I. PRILIPKO’ and I.V. MISHIN‘

’The L.V. Pisarzevski Institute of Physical Chemistry, Ukrainian

Academy of Sciences, Nauki Pr., 31, 252028, Kiev, USSR

‘The N. D. Zelinksi Institute of Organic Chemistry, Academy

of Sciences USSR, Leninski Pr., 47, 117913, MOSCOW, USSR

SUMMARY

A series of dealuminated HY zeolites was prepared by reacting

NaY zeolites with SiC1, at elevated temperatures. High crystalline
products were obtained with unusual distributions of Lewis and
Bronsted acidity and with anticipated catalytic properties.
Infrared and m.a.s.n.m.r. data demonstrated that the chemical
properties of the A1 in the zeolite lattice were not homogenous
and characterized various types of aluminium sites. A Dempsey
model was used to interpret the data obtained.

INTRODUCTION

Aluminium-deficient zeolites are an important class of material

because of their increased chemical and thermal stability, in
comparison to normal HY zeolites. They have an appropriate combi-
nation of pore size and selectivity which is induced by their high
silicon content. The dealumination can be obtained through the use
of steam, by chelating agents (ref. 1) or by the treatment of the
zeolites with silicon tetrachloride (Beyer et al. , 1980).
The relationship between the strength of Bronsted acid sites and
the distribution of the aluminium framework is a basic issue in aci-
dity faujasite-like zeolites. In 1974, Dempsey (ref. 2) , in an at-
564

tempt t o i n t e r p r e t e x p e r i m e n t a l d a t a of Bartomeuf and Beamount,

proposed a model i n which t h e a c i d s t r e n g t h of z e o l i t e s was r e l a t e d
t o t h e environment of t h e A 1 atoms, i . e . , t h e s t r e n g t h o f t h e a c i d
s i t e s was r e l a t e d t o t h e number of aluminium atoms w i t h 0 , 1, o r 2
d i a g o n a l n e i g h b o r a l u m i n i u m a t o m s i n t h e r i n g s o f t h e s o d a l i t e cage.
Beagley ( r e f . 3 ) produced a review and d i s c u s s i o n of t h e r e l a t i o n -
s h i p between z e o l i t e a c i d i t y and aluminium d i s t r i b u t i o n i n f a u j a -
s i t e - l i k e z e o l i t e s . On t h e o t h e r hand, d e a l u m i n a t i o n of t h e z e o l i t e
latticemaybeconnectedtotheappearanceofnon-skeletalaluminium
s p e c i e s . I n d i r e c t d e d u c t i o n s have beenmade u s i n g , b u t many a s p e c t s
remain t o be c l a r i f i e d .
The p r e s e n t work is p a r t of t h e c o n t i n u i n g work i n t o t h e i n f l u e n c e of
surfacestructureontheacidityandcatalyticpropertiesofzeolites.
I n t h i s workwe, p a r t i c u l a r l y , p r e s e n t t h e r e s u l t s o f a d e t a i l e d exami-
nationofdealuminatedHYzeoliteswhichwerepreparedbyreactingNaY
zeoliteswithSiC1,vapor.

METHODS

NaY z e o l i t e s ( S i / A 1 = 2 . 4 5 ) w e r e d e a l u m i n a t e d b y r e a c t i o n w i t h a
flowing S i C 1 , vapour, a c c o r d i n g t o a procedure described elsewhere
( r e f . 4 ) . Samples, having a range of S i / A 1 r a t i o s , were p r e p a r e d by
r e a c t i n g 30 g of t h e p r e t r e a t m e n t z e o l i t e w i t h S i C l , / N , a t t e m p e r a t u r e s
r a n g i n g from430-723 K f o r 4 0 m i n . The z e o l i t e s w e r e t h e n w a s h e d w i t h
d e i o n i z e d w a t e r a n d ionexchanged inlMNH,NO,.
A l l t h e z e o l i t e e x h i b i t e d g o o d c r y s t a l l i n i t y a s w a s p r o v e d b y X-
r a y d i f f r a c t i o n a n d t h e i r d e s o r p t i o n c a p a c i t i e s . The I . R . s p e c t r a of
s k e l e t a l v i b r a t i o n s , OH-groups a n d p y r i d i n e a d s o r p t i o n w e r e r u n o n a
Specord 1 . R . - 7 5 spectrophotometer u s i n g s e l f - s u p p o r t i n g z e o l i t e
p l a t e s . The s p e c t r a d e p i c t e d c o r r e s p o n d e d t o a sample t h i c k n e s s of 3
mg/cm2. The samples were evacuated t o about lo-‘ Pa a t 7 2 3 K , p r i o r t o
measuring t h e s p e c t r a . The “ S i and 27Al s p e c t r a w e r e r e c o r d e d on a
Brucker CXR-200 s p e c t r o m e t e r w i t h t h e magic a n g l e s p i n n i n g . A 1 ( H 2 0 ) 2 *
c o m p l e x w a s u s e d a s a n internalstandardandsamplesweremeasuredin
theirhydratedstate.Atemperature-programmedsurfacemethod (TPSR)
( r e f . 5)wasusedtoinvestigatethebehaviourofmethanolpreadsorbed
onzeolites.
 565

To i d e n t i f y t h e p r o d u c t s formedduringtheexperiment, t h e m a s s
range10-70m/ewasexaminedat15Kintervals. D e s o r p t i o n w a s c a r r i e d
outinvacuosothatthedesorbingspecies c o u l d b e d i r e c t l y o b s e r v e d
u s i n g a m o d i f i e d m a s s spectrometerM1-201. Methanolwas p u r i f i e d by
r e p e a t e d l y f r e e z i n g and pumping. Methanol vapour a d s o r b e d a t room
temperature.

RESULTBANDDISCUSSION

Structure
T h e Z e o l i t e p r e p a r e d w i th . S i C l , , h a d a f r a r n e w o r k S i / A l r a n g i n g from
4.3 t 0 4 2 . Itwasarguedthatmid-infrared s p e c t r o s c o p y m i g h t y i e l d

CM"
F i g . 1. Mid. i . r . spectraofnormalHYanddealuminatedsamples:
1. HY-(2.5) ; 2 . DY-(4.3); 3. DY-(4.8); 4 . DY-(7.3) ; 5. D Y - ( 4 2 ) .
informationabouttheframeworkchangesduringthedealuminationpro-
cess. The infraredspectraofdealuminatedYarecompared i n F i g . 1.
F r o m t h e s p e c t r a it i s e v i d e n t t h a t a l l t h e f r a m e w o r k v i b r a t i o n a l
.
modes a r e s h i f t e d upon d e a l u m i n a t i o n (&V= a b o u t 50 cm-‘) when t h e S i / A 1
r a t i o is i n c r e a s e d t h e medium bands a t 682 and 6 7 0 cm-’ a p p e a r . N o v i -
s i b l e d e s t r u c t i o n o f t h e frameworkduetodealumination isobserved.
Dealumination w i t h S i C 1 4 l e a d s t o t h e f o r m a t i o n o f non-framework
aluminium s p e c i e s i n t h e z e o l i t e p o r e s . T h i s is shown by t h e “ S i and
2 7 A l m.a.s.n.m.r. s p e c t r a of t h i s m a t e r i a l (see F i g s . 2 A , B ) . The A 1
m.a.s.n.m.r. spectrashowtwodistinctkindsofsignals- s h a r p p e a k s
( a t 5 6 ppm) d u e t o t e t r a h e d r a l l y c o o r d i n a t e d A 1 i n t h e z e o l i t e frame-

-90 -100 -110

PPM

F i g . 2 . S o l i d s t a t e 2 7 A l ( A ) and 29Si ( B) m.a.s.n.m.r. s p e c t r a of normal

HYanddealuminatedsamples:l.HY-(2.5);2.DY-(4.3);3.~~-(4.8);4.
DY-(7.3); 5. D Y - ( 4 2 ) .
 567

work and r e l a t i v e l y s h a r p s i g n a l s ( o c t a h e d r a l l y A l ) a t 2 . 0 ppm. The

relativeamountsofthesealuminiumspeciesdependuponthecondition
of d e a l u m i n a t i o n . An examination of “Si m.a.s.n.m.r. spectra fauja-
sitesdealuminatedwithSiClcshowsthattheSi(3A1)s i g n a l i s a l r e a d y
a b s e n t i n sample 2 . I n t h i s c a s e t h e S i ( 2 A l ) a n d S i ( l A 1 ) s i g n a l s a l s o
d e c r e a s e a n d S i ( O A 1 ) predominates i n t h e s p e c t r a .

OH-UrOUDS
I . R . spectra intheOH-stretchingregionofy zeolites,dehydrated
a n d d e a m m o n i a t e d a t 7 2 3 K, are r e p r e s e n t e d i n F i g . 3A.

\
3700 3500 CM-~ 1700 1500
A B

F i g . 3. I . R . s p e c t r a i n t h e regionoftheOH-stretchingnumber ( A ) :
t o ( - ) a n d a f t e r (---) p y r i d i n e a d s o r p t i o n (B) O f n o r m a l H Y a n d d e a l u -
minated samples: 1. HY-(2.5) : 2 . DY-(4.3) : 3. DY-(4.8) : 4 . DY-(7.3) :
5. D Y - ( 4 2 ) .
 I n c l o s e a g r e e m e n t w i t h t h e l i t e r a t u r e c o n c e r n i n g H f o r m s o f zeo-
l i t e s o b t a i n e d through NH; exchange, I . R . bands are observed a t 3640
and 3540 cm-‘, a t t r i b u t e d t o t h e hydroxyl i n t h e l a r g e and s m a l l c a g e s ,
c o r r e s p o n d i n g l y . DifferencesintheI.R.spectraofhydroxyldea1umi-
natedwithSiCl4productsprovidedevidenceoftheessentialinfluence
ofthemodificationprocedure onthepropertiesofthesegroups.
The band a t 3 6 4 0 cm-’ s h i f t e d t o c a . 3630 cm-‘ f o r S i / A 1 = 4 . 8 and t o c a .
3 6 2 0 cm-’ f o r S i / A l > 4 . 8 . The i n t e n s i t y of t h e I . R . band changed w i t h
increasingSi/Alratio.Newunspecifiedhydroxylvibrationsappeared
a t 3610 cm-’ and 3510 cm*’. Slow d e c r e a s e of i n t e n s i t y of t h e I . R .
bands accompanied by t h e appearance and r a p i d i n c r e a s e o f a band a t
3 7 2 0 cm-’ w e r e observed.
T h e n a t u r e o f t h e a c i d s i t e s a n d t h e i r r e l a t i v e strengthswere
s t u d i e d by means of i n f r a r e d s p e c t r a f o l l o w i n g p y r i d i n e a d s o r p t i o n .
Pyridinewasadsorbedandthenevacuatedat423 K.Thebandsduetothe
c h e m i s o r b e d p y r i d i n e a r e shown i n F i g . 3 . U n e x p e c t e d r e s u l t s f o r a l l
dealuminated samples were o b t a i n e d . I n c o n t r a s t w i t h t h e l i t e r a t u r e
d a t a f o r H forms of f a u j a s i t e - l i k e z e o l i t e s , a d s o r p t i o n of P y r i d i n e
c a u s e s a s h a r p d e c r e a s e i n t h e i n t e n s i t y of t h e OH-bands a t 3 5 4 0 cm-’.
Simultaneously, a s s e e n i n t h e s p e c t r a , bands a t t r i b u t e d t o t h e C-C
s t r e t c h i n g v i b r a t i o n o f t h e p y r i d i n i u m i o n (1550 cm-’) a n d c o o r d i n a t i v e
bonded p y r i d i n e complex ( 1 4 5 0 cm-’) were observed. Besides, thermal
s t a b i l i t y t h e s e complexes i n c r e a s e w i t h i n c r e a s i n g S i / A 1 r a t i o .
According t o Belanski thermal s t a b i l i t y can be used a s a measure o f t h e
acidstrengthof zeolites.
Moreover,basicstrengthhasbeenstudiedinzeolitesdealuminated
w i t h S i C 1 , by u s i n g p y r r o l e a d s o r p t i o n . A s h i f t i n t h e NH s t r e t c h i n g
bandofadsorbedpyrroleandthepresenceo€comb~nat~onbandsat2940
and 2850 cm-’ were observed ( r e f . 6 ) .

TPSRofmethanol
Inordertomoreclearlyunderstandthepropertiesofthedealu-
minatedYzeolitesweinvestigatedthetemperature-progra~edsurface
r e a c t i o n of methanol preadsorbed a t ambient t e m p e r a t u r e . The TPSR
spectrafortheproductsofthemethanol-zeoliteinteractionareshown
i n Fig. 4A.
 569

The r e s u l t s showthatmethanoldesorbing f r o m t h e samples g i v e s a

peakcenteredatapproximately400K, dimethyletherat500Kandole-
f i n s (especiallyetheneandpropene) a t 6 0 0 K . N o t e t h a t t h e m a x i m a o f
t h e o l e f i n s ' d e s o r p t i o n s h i f t e d i n t h e h i g h e s t t e m p e r a t u r e r e g i o n as
theSi/Alratioincreased.Negligibleamountsofaromaticspeciesare
observedat700K.
I n Fig. 4 B t h e m a x ~ m a o f t h e r e l e a s e d p r o d u c t s a r e p l o t t e d a g a i n s t
t h e molar f r a c t i o n of aluminium. With i n c r e a s i n g d e a l u m i n a t i o n t h e
amounts of methanol and dimethyl e t h e r a r e d e c r e a s e d , w h i l e o l e f i n s
mainlydesorbfromthemoderatelydealum~natedzeol~tes.Sincemetha-

A B C

+
x 5
-7

473 673 T, K 473 673 T, K 0 0.1 0.2

e
AL

F i g . 4 . TPSR s p e c t r a of methanol (A) DY-(4.3) : (B) DY-(7.3) :

(C)depedence ontheheightofthepeakofdesorbedproducts
(&methanol ( m / e = 3 1 ) : (+) dimethyl e t h e r (m/e=45) :
( 0 ) o l e f i n s ( m / e = 4 1 ) on t h e aluminium mole f r a c t i o n normal HY and
dealuminatedy.
570

n o l d o e s n o t evacuate e a s i l y i n a n u l t r a h i g h v a c u u m , w e b e l i e v e t h a t
theseolefinsareformedbythereactionbackgroundgasespassingover
thezeoliteathightemperaturesduringTPSR.~sit~infraredspectra
of t h e methanol dealuminated samples r e i n f o r c e t h i s c o n c l u s i o n
( r e f .7).
Thus, f r o m t h e a b o v e r e s u l t s , itcanbeconcludedthatinthecaseof
S i C l , t r e a t m e n t , h i g h c r y s t a l l i n e p r o d u c t s are o b t a i n e d w i t h u n u s u a l
distributionsofLewisandBronstedacidityandwithanticipatedcata-
l y t i c p r o p e r t i e s . I.R. and m.a.s.n.m.r. d a t a demonstrated t h a t t h e
chemical p r o p e r t i e s of A 1 i n t h e z e o l i t e l a t t i c e are n o t homogenous
and c h a r a c t e r i z e ( v a r i o u s ) t y p e s of aluminium sites. I n agreement w i t h
Kubelkova e t a l . ( r e f . 8 ) , it seems r e a s o n a b l e t o assume t h a t t h e
cationicaluminiumspeciesgenerallyprovidetheAlelectronaccepting
centers.Thequestionremainsoftheoverlookedfactoftheinteraction
of p y r i d i n e w i t h low f r e q u e n c e h y d r o x y l s a t 3 5 4 0 cm-’. I t seems t o be
i m p o s s i b l e , when t a k i n g i n t o account t h e p e c u l i a r s t r u c t u r e o f t h e
f a u ja s i t e .
Ontheotherhand,itisevident,thatextra-framework-typealumina
affectthepropertiesofYzeolites.Thedea1uminationprocessenhan-
cedtheacidityofthe zeolitesbutthismay occureitherviathenon-
frameworkspeciesorbygeneratinga z e o l i t e i n w h i c h m o s t o f t h e a l u -
minahavenonearestneighborsalumina. I t i s a l s o c o n s i s t e n t w i t h t h e
conceptofapreferredaluminiumdistributionsimilartotheDempsey
model.
Thebasicityofoxy-compoundscanalsobediscussed i n t e r m s o f t h e
dataobtained.ComparedwithnormalHY,dealuminatedzeolitesexhibit
anacido-basiccharacterandthusconsitutearelatedsystemwithnew
p r o p e r t i e s . I n summary, w e b e l i e v e t h a t t h e r e s u l t s p r e s e n t e d h e r e g i v e
a b e t t e r u n d e r s t a n d i n g o f t h e d u a l c h a r a c t e r of z e o l i t e s ( r e f . 9).
F u r t h e r s t u d i e s on t h e n a t u r e of a c i d o - b a s i c s i t e s and t h e c a t a l y t i c
propertiesofdealuminatedSiCl4Yzeolitesareinprogress.

AC KNOW LEDOMENT

TheauthorsexpresstheirappreciationtoDr.V.V. B r e i ( I n s t i t u t e
ofSurfaceChemistryUkrainianAcademyofSciences,Kiev)f o r h i s k i n d
presentationofthem.a.s.n.m.r.data.
 571

REFERENCES

1. J. S h e r z e r , Octane-enhancing, z e o l i t e F C C c a t a l y s t s : S c i e n t i f i c a n d
t e c h n i c a l a s p e c t s , Catal.Rev.Sci.Eng., 31(3) (1989) 215-354.
2. E. Dempsey, Acid S t r e n g t h and aluminium s i t e r e a c t i v i t y o f Y zeo-
l i t e s , J . C a t a l . , 33(3) (1974) 497-499.
3. B. Beagly, J. Dwyer, F.R. F i t c h , R. M a n n a n d J . Walters, Aluminium
d i s t r i b u t i o n and p r o p e r t i e s o f f a u j a s i t e s . B a s i s of models and
z e o l i t e a c i d i t y , J . Phys.Chem., 88(4) (1984) 1744-1751.
4. I . V . Mishin, G.K. Beyer, A.L. Klyachko, G.A. Ashavskaja, V.D.
Nissenbaum and G. Borbely, R e c e i p t of h i g h s i l i c a f a u j a s i t e w i t h
S i c l , , Kin. i k a t . , 28(3) (1987) 706-711.
5. A . I . P r i l i p k o . G.M. T e l b i z , V.G. I l i n , V.P. Shabelnikov, E.N. Korol,
Somepeculiaritiesofdesorptionofthe z e o l i t e i n t h e T P S R c o n d i -
t i o n , Dokl. ANUkr. SSR, s e r B , 3 (1989) 55-57.
6. G.M. T e l b i z , A.V. S v e t z , s u b m i t t e d f o r p u b l i c a t i o n .
7. G.M. T e l b i z , V . V . B r e i , i n p r e p a r a t i o n .
8. L. Kubelkova,S. Beran, A . M a l e c k a , . V . M a s t i k h i n , A c i d i t y o f m o d i -
fiedzeolite.EffectofnonskeletalAlformedbyhydrothe~a1treat-
ment, d e a l u m i n a t i o n w i t h SiC1, and c a t i o n exchange w i t h A l l Zeo-
l i t e s , 9(1) (1989) 12-17.
9. D. Bartomeuf, C o n j u g a t e a c i d - b a s e p a i r s i n z e o l i t e s , J. Phys.Chem. ,
88(1) (1984) 42-45.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 573
0 1991 Elsevier Science PublishersB.V., Amsterdam

CHARACTERIZATION AND NUCLEATION OF Na,TPA-ZSM-5 ZEOLITE WITH

DIFFERENT ALUMINIUM CONTENT

G. Golemme', A. Nastro', J. B.Nagy2, B. SubotiA', F. Crea' and

R. Aiello'.
lDipartimento di Chimica, UniversitA della Calabria. 1-87036
Rende (Italy).
2Laboratoire de Catalyse, Facult& Universitaires Notre-Dame de
la Paix. 61, Rue de Bruxelles, 0-5000 Namur (Belgium).
3Ruder BoskoviC Institute. P . O . Box 1016, 41001 Zagreb, Croatia
(Yugoslavia).

ABSTRACT
The formation of zeolite ZSM-5 is studied from five different
gels having various A1 content. The crystallization kinetics, the
nucleation kinetics, the pH of mother 1 iqiiors, the physical state
and the composition of the solid phases are examined by combined
physico-chemical techniques: SEM, X-ray Diffraction, Atomic Absor-
ption, Elemental analysis and Thermal Analysis (TG, DTG, DTA).

INTRODUCTION
Zeolite ZSM-5 (see ref. 1) is widespread in the petrochemical
industry as a catalyst for various processes. Because of its note-
worthy properties this zeolite has been widely investigated, and
the numerous information gathered makes ZSM-5 a good model to
test current theories on zeolite nucleation (see refs. 2,3) and
growth (see refs. 4-12). The object of the present work is to cha-
racterize the products and derive nucleation kinetic curves of
Na,TPA-ZSM-5 zeolite in five systems differing by the aluminium
content in the starting gel. The products are characterized in
different ways: the pH of the mother liquors is measured, and the
sol id phases during the crystal 1 ization are analyzed and examined
by TGA and chemical analysis methods.

EXPERIMENTAL
Zeolites ZSM-5 were synthesized hydrothermally in static condi-
tions at 170f2'C under autogenous pressure from systems having mo-
lar ratios 5Na,0-8.8(TPA),0-xA1,03-100Si02-1250H20, with x=O. 125,
0.177,0.289, 0.626, 0.987,for runs A, B, C , D and E, respective-
ly. Reagents were carefully admixed in the order: Al(OII), gel dry
(Serva 'reinst' grade) with composition AI,OR.4.6iOFI,O (TBA.
574

12OO'C) ; freshly prepared 30% NaOH soln. (Baker Analyzed, NaOH

98.6%, A1 2ppm) ; n-Pr,NBr (Fluka, purum grade); distilled H,O; pre-
cipitated SiO, (BHD) having composition SiO,. 0.2951120. 0.0049NaZ0.
0.00116A1,03 (TGA, 1200'C, AAS).
One part of the gel was saved for further characterization. The
remaining part was divided in different portions, transferred to
50 cm3 PTFE autoclaves and immediately put into the preheated o-
ven. The autoclaves were taken from the oven at various intervals
of time, one by one, and immediately quenched under cold water.
The pll of the mother liquors was measured using Lyphan strips and
the solid phases were filtered and dried at 100°C overnight.
The temperature variation inside the teflon lined steel autocla-
ves was followed, and time zero for the crystallization was assu-
med as the moment when the reacting gel reached a temperature of
160-165'C.
Crystallinity was measured by X-ray diffractometry. The Na and
the A1 content of the solid phases were determined by Atomic
Absorption Spectroscopy (AAS) . Thermogravimetric measurements and
elemental analyses were carried out to determine the TPA' content
of the crystalline phases. Granulometric distributions for each
kinetic series were obtained from micrographs of the final, not
sonicated samples (see ref. 13).

11.5

11.1

10.7 ' I I I 1
1'0
I I I I
210
I I I

t/h

Fig. 1. Variation of the pH of the mother liquors as a function

of time.
RESULTS
The pH values of mother liquors immediately after the cooling
of the autoclaves are shown in Fig. 1 f o r the fastest and the
slowest kinetics, C and E respectively. The pH vs. time curves
show a sharp increase when the amorphous material is completely
consumed.
The pI1 decreases during the nucleation, stabilizes during the
growth of the crystals, and rises again when the crystallization
is over. This behaviour is consistcnt with the presence of
multiple equilibria between the solid phases (amorphous polymer
and crystals) and the (a1umino)silicate species in solution, of
the kind shown below:

I I I I I I
-~i-o-Si- + 0118 2 -Si-OII + 'O-Si- 7 -si-o-si- + OH^
I I I I I I
(amorph .) (aq. 1 (aq. 1 (cryst.)

When the gel i s present, its solubility determines the amount of

soluble species; when, instead, the crystallization process is
over, the concentration of si 1 icate species drops suddenly beca-
use it is determined by the solubility of the zeolite, and the pll
rises accordingly. The pll vs. time curves nicely recall the desu-
persaturation profiles derived by the theory of the solution me-
diated phase transformations (see ref. 1 4 ) .
The ZSM-5 crystals show regular squared shapes f o r a low A1 con-
tent, and get rounded when its amount increases. The length/width
ratio (crystallographic axes c and a) is always equal t o 1 , with
the exception of a small fraction of crystals in the series of
synthesis B (9%) and A (2.5%) (ratio up t o 2.3). The maximum dia-
meters of the crystals at the end of the crystallization proces-
ses range from 19 (C) t o 4 4 pm ( B ) .
In table 1 are listed the compositions of the solid phases from
runs C and D .
The DTA curve of the dried aged starting gel f o r run E is shown
in Fig. 2. The DTA curves f o r the corresponding samples f o r runs
A to D are quite similar, thc only difference being the lowering
of the temperature in correspondence of the second peak, due to a
smaller A1 contcnt. The first pcak around 112'C is not accompanied
by a weight loss, and must therefore be assigned to a phase tran-
sition. T h i s phase transition is reversible, and becomes exother-
mal upon cooling (see ref. 1 5 ) . This peak was assigned to [TPABr],
576

aggregates t r a p p e d i n t h e gel, and a p p e a r s at l o w e r t e m p e r a t u r e s

than for p u r e TPABr. The peak around 240'C was assigned to the
d e c o m p o s i t i o n of b o t h t h e m o n o m e r i c TPA a n d t h e aggregates, w h e r e -
as p u r e TPABr d e c o m p o s e s a t 280-29O'C.

TABLE 1
C o m p o s i t i o n of t h e s o l i d p h a s e s : runs C and D

Run C Run D
amorph. crystals amorph. crystals
t/hNa% 8 Naa Ala
A1
TPAa'b Na% 3 Naa Ala
A1
TPAajb

0 1.5 173 2.9 80

6.5 1.3 138
7.5 1.1 135 2.0 0.42 226 3.36
8.2 1.0 125 2.0 0.46 207
9 2.1 0.51 186
11 2.1 0.58 166
12 2.5 0.52 182 3.54 0.92 72 1.75 0.80 119
13.6 0.80 67 1A8 0.89 107 3.66
16 2.0 1.02 93
19.6 2.3 1.14 83
24.8 2.0 0.52 183 tl$
a)Atoma o r c a t i o n s per u n i t c e l l
b)From e l e m e n t a l a n a l y s i s
c ) F r o m t h e r m o g r a v i m e t r y ( t h e l o s s of w a t e r d u e t o d e h y d r o x y l a t i o n
is a l s o i n c l u d e d )

100 200 300 "C

P i g . 2 . DTA curve of t h e d r i c d s t a r t i n g g c l of r u n E aged 30 d a y s

a t 26'C.
 577

Fig. 3 represents the five kinetic curves of crystallization.

All of them show t h e typical sigmoid shape. T h e crystallization
rates in the five runs are in the o r d e r C>B>A>D>E.

z (t)
1.0

0.5

0
0 5 10 15 20 25
t/h

Fig. 3 . Crystallization curvcs for the ZSM-5 samples.

The hystograms o f the granulornetric distributions in the final

products of each run can be constructed together with the mono-
tonic curvcs approximating them. These monotonic curves and the
curves of the maximum average diametcrs of crystals are used t o
derive thc be1 1 shaped curves representing nucleation kinetics
(sce r c f . 16) (Fig. 4 ) .
The linear growth rates of crystals, and also the times at
which nucleation is maximum in each run, are reported in Table 2.
Thc detailed quantitative analysis will be included in a future
publication (see ref. 1 3 ) .

TABLE 2
Linear growth rate of crystals and maximum nucleation time

A B C D E

(AL/2At)/(pm/h) 1.35 2.25 0.89 0.89 0.63

/h
tmax.""cl. 3.6 3.15 1.9 5.3 8.8
578

40

ik
0
IC
30

20

10

I
0 5 10 15

t/h

F i g . 4 . Nucleation rate as a function of time for the ZSM-5

samplcs.

DISCUSSION
Previous studies (see ref. 8) showed that the conversion rate
and the yield of silicalitc-1 arc favored by the amount of TPA
ions up t,o TPA/Si m o l a r ratio equal to 0.08. Hence, an excess of
‘ W A beyond that, v a l u e i s not influent, any more on these parame-
ters. The amount of organic ion in our samples (TPA/Si=0.088) is
t h e r e f o r e optimal and does not. c n n R t , i t r i t . e PL 1 i m i t . i n r f f n * o * n r
 579

cithcr for the yield or for the crystallization rate.

The crystallization rates in the five runs are in the order
C>B>A>D>E. The relevant data t h a t can be found in literature
(see refs. 13,17-19) for similar studies also confirm that there
is a n optimum amount of aluminium to speed up the crystallization
kinetics of ZSM-5. The linear growth rates of crystals (Table 2 )
are in the ordcr B>A>C,D>E. The granulometric distributions, and
hencc the kinetic nucleation curves, are narrow (Fig. 4 ) and show
a tendency to broaden in the systems with higher A1,0, content.
The results shown in Figs. 3 and 4 demonstrate that the faster
crystallization rate found for ZSM-5 in run C is not a consequen-
ce of a higher crystallite growth rate, but is rather the effect
of a faster nucleation.
I t is clear from Fig. 4 that nucleation of ZSM-5 in o u r systems
starts at time zero, o r even before. It must be pointed out that
maximum crystalline dimensions are an averaEe of the diameters of
the largest crystals found in each sample. S o , e.g., in the sam-
ple of run B at 20.5 h it is possible to find one crystal as long
as 44 pm (lcngth to width 1) whereas the average diameter of the
15 largest crystals is 10 pm less. This fact is a strong evidence
for the autocatalytic theory (see ref. 3) according to which nuc-
lcation starts immediately in the gel already at room temperatu-
re.
The analyses of the solid phases during the syntheses show that
both the gcl and the crystals of zeolite enrich in A1 with time.
This means that the crystallisation of zeolite ZSM-5 proceeds via
the formation of an A1 poor core, and an aluminous outer shell.
An exception to this behaviour seems to be run E .
The number of TPA' ions per unit cell of ZSM-5 is nearly cons-
t a n t in all of the phascs of the crystallyzation process, ranging
from 3 . 1 to 3.8,that is close to the theoretical value of 4 .
Elemental analyses always show a lower content of organic ion
with respect to the thermogravimetric measurements. This effect
may be due to the annealing of lattice defects (groups Si-OR,
with R = 11, Na', TPA') during thermogravimetric measurements,
which produccs water molecules. Nmr studies on *'Si in ZSM-5 (see
ref. 20) showed that calcination at 440'C for 24 hours eliminated
most of the latticc defects.
CONCLUSIONS
It is shown that the nucleation starts when the crystallization
580

temperature is reached or evcn earlier, the gel still being at

room temperature.
The crystal1 ization rates as expressed by crystal1 inity pcr
unit time are essentially linked to the nucleation rates.
The analyses carried out on the solid phases show that the
crystallization of Na,TPA-ZSM-5 in the five series examined
proceeds by the formation of aluminium poor cores. The
concentration of this element is higher on the external parts of
t h e crystallitcs.

ACKNOWLEDGEMENTS
We gratefully acknowledge D r . Nicola La Rosa for kindly supply-
ing calculation facilities. This work h a s been supported by CNR
(Italian National Rcsearch Council), Progetto Finalizzato Chimica
Fine e Sccondaria.

REFERENCES
1 R.J. Argauer and G.R. Landolt, U . S . Pat. 3,702,886.
2 J.C. Jansen, C.W.R. Engelen and 11. van Rekkum, ACS Symp. Ser.,
398 (1989) 257.-68
3 B. Subotib, ACS Symp. Ser., 398 (1989) 110-21.
4 R . A . Van Santen, J. Keijsper, G . Ooms and A.G.T.G. Kortbcek,
Stud. Surf. Sci. Catal., 26 (1986) 169-75.
5 D.C. Hayhusrt, R. Aiello, J. B.Nagy, F. Crea, G . Giordano, A .
Nastro and J .C. Lee, ACS Symp. Ser., 368 (1988) 277-91.
6 G . Boxhoorn, 0. Sudmeijer and P . 1 I . G . van Kasteren, J. Chem.
SOC.,Chem. Commun., (1983) 1416-8.
7 J. B.Nagy, P. Bodart, E.G. Derouane and Z. Gabclica, Stud.
Surf. Sci. Catal., 26 (1986) 231-8.
8 F . Crea, A . Nastro, J. B.Nagy and R . Aiello, Zeolites, 8
(1988) 262-8.
9 R . Aiello, F. Crea, A. Nastro and C. Pellegrino, Zeolites, 7
(1987) 549-53.
10 A. Araya and B.M. Lowe, Zeolites, 6 (1986) 111-8.
11 B.M. Lowc, Stud. Surf. Sci. Catal., 37 (1987) 1-12.
12 G . Bellussi, G . Perego, A. Carati, U . Cornaro and V. Fattore,
Stud. Surf. Sci. Catal., 37 (1987) 37-44.
13 G. Golemmc, A. Nastro, J. B.Nagy, B. Subotik, F. Crca, and R .
Aiello, in preparation.
14 P.T. Cardew and R . J . Davey, Proc. R . SOC. London A, 398
(1985) 415-28.
15 Z. Gabelica, J. B.Nagy, P. Bodart, N. Dewaele and A. Nastro,
Zeolites, 7 (1987) 67-72.
16 S . P . Zhdanov and N.N. Samulcvich, in: L.V.C. Rees (Ed.), Proc.
5th Intl. Conf. on Zeolites, lleyden, London, 1980, p p . 75-84.
17 V.N. Romannikov, V.M. Mastikhin, S . HoEevar and B . Driaj,
Zeolites, 3 (1983) 311-20.
1 8 S . B . Kulkarn i , V.P. Shi ralkar, A.N. Kotasthane, R.B. Borade
and P . Ratnasamy, Zeolites, 2 (1982) 313-8.
19 K.-J. Chao, T.C. Tasi and M.-S. Chen, J. Chem. SOC., Faraday
Trans. I , 77 (1981) 547-55.
20 P. Bodart, J . B.Na y , 2. Gabalica and E;.G. Derouane, J. Chim.
Phys., 83 (11-12) fi986) 777-90.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 581
0 1991 Elsevier Science PublishersB.V., Amsterdam

NEW MOLECULAR SIEVE - VANADIUM SILICALITE KVS - 5

J . Kornatowskil, M. Sychev2. V. GoncharukZ, W.H. Baur3

1Institute of Chemistry, N. Copernicus University, Gagarina 7, 87-100 Toruh,
Poland
2Institute of Colloid and Water Chemistry, Ukrainian Academy of Sciences,
Vernadsky Ave. 42, 252680 Kiev, USSR
31nstitut fur Kristallographie und Mineralogie der J.W. Goethe-Universitat,
Senckenberganlage 30. D-6000 Frankfurt am Main 1, PRG

SUMMARY
Vanadium silicalite KVS-5 has been grown under conditions of hydrothermal
synthesis. Its structure corresponds to the MFI type. The product can be syn-
thesized with a yield of 100% in form of slightly coloured large crystals up to
300 m. The incorporation of V5+ ions on T-sites in the zeolitic framework has
been investigated by a variety of methods: XRD, MAS M,SSIMS, ESR, TGIDTA.
IR. and XRF.

INTRODUCTION
The catalytic properties of vanadium compounds and especially of its oxides
have been investigated and used since the 1960's. These studies of vanadium ca-
talysts were dealing mainly with the changes of oxidation state of vanadium
during the catalytic process as well as with the role of support. Commonly. si-
lica or alumina [l-31 have been used as supports for the vanadium compounds. No
catalysts have been prepared with an exactly defined state of this metal except
for the synthesis of heteropolyacids [4].
An introduction of vanadium into the ZSM-5 zeolite crystals has been already
reported: Kucherov et al. 15-81 and later Sass et al. [9] introduced V4+ ions
into extra-framework cationic positions by a solid state reaction. Inui e l al.
[lo] introduced vanadium compounds instead of the A1 component already into the
reaction gel for synthesis of the zeolitic catalyst. The possibility of isomor-
phous substitution of a large number of elements with vanadium in three diffe-
rent oxidation states 111, IV, and V has been published by Xu Ruren et al.[ll].
Nevertheless, they have given neither synthesis conditions nor any proof or me-
thod for checking the actual incorporation of those elements into the crystal
structure except that they report lattice constants. The differences in these
lattice constants compared to ZSM-5 seem to be much too high considering the
amounts of heteroatoms which could be possibly incorporated into the framework.
582

The aim of this work was to prepare a crystalline porous zeolite with iso-
morphously substituted Vt5 ions in the framework as a precursor of a catalyst
for oxidation reactions and to check the product with a variety of methods
which could show real substitution.

EXPERIMENTAL
The zeolite was synthesized in teflon-lined autoclaves by reacting silica s o l ,
alkali metal vanadate, sodium bicarbonate, tetrapropylammonium hydroxide
(TPAOB) and water at 160-190.C and autogeneous pressure for 5-9 days followiiig
the procedures given in refs. [12.13]. Reference samples were prepared by im-
pregnation of silicalite with VOSO4 and by synthesis of VA1-ZSM-5 using analo-
gous methods to KVS-5. The impregnation procedure was the following: siljcalite
was stirred for 24 hs at RT and pH = 3 in an 0,1 M water solution of VOSO4 ( 2 0
ml/lg of zeolite), then washed with water, dried at 80'C for 3 hs and finally
calcined at 500.C for 1 h in air. Calcination of KVS-5 samples was made at
500'C for 48 hs in a slow air stream and 24 hs i n an 02 stream.
The products were characterized by XRD. SEM. MAS NMR, SSIMS, ESR, TG/DTA,
and IR techniques.
Apparatus used and condi.tionsof measurements:
XRD: DRON 3 with PC, CuKa radiation, 0,5'/min
SEM: NOVOSCAN 30. samples covered with Au
MAS NMR: BRUKER CXP 200 equipped with 4.8 T magnet
ESR: TSN-254 and SE/X 2544 Radiopan
TG/DTA: MOM Q-1500, heating rate 1O0C/min, sample 400 mg
IR: UR 20
SSIMS: LAS-3000 RIBER. range 0-200 amu. time 30 min.

RESULTS AND DISCUSSION

The experiments were successful in obtaining vanadium silicalite with a 100%
yield and in form of slightly violet large crystals up to 300 vm in length.
Fig. 1 shows the material of euhedral habitus of MFI topology from a sample
with -200 long crystals. Crystal sizes distribution was usually within the
range of 210% and their aspect ratio length to width was about 2 - 2 . 5 . F.ig. 2
shows the crystals grown together with Al3' ions. They were obtained only up to
-90 pm in length and with distinctly wider size distribution. The XRD pattern
was typical for an MFI topology for both cases. The KVS-5 crystals had lattice
constants 20.087, 19.943, and 13.420 I for the a, b, and c axes, respectively.
They were changing from one sample to another but it was impossible to get a
relation between the lattice constants and content of vanadium as the diffe-
rences were usually smaller than experimental error. A decrease of lattice
 583

la

lb

Fig. 1. Scanning electron micrographs of molecular sieve KVS-5.

584

2a

2b

Fig. 2. Scanning electron micrographs of vanadoaluminosilicalite molecular

sieve VAL-ZSM-5.
 585

constants larger than the experimental error occurred after calcination which
suggests a relaxation of the framework after removal of the template molecules.
Thermogravimetry analysis (Fig. 3 ) shows that the calcination process pro-
ceeds with three thermal effects: endo- and exo-thermal effects at about 350 -
360'C overlapping one another and coinciding with a weight loss and the third

T
PC

800
DTG
-.----L -'\~
\ -
600

LOO

200

Fig. 3 . Thermogravimetry analysis curves for KVS-5.

strong exothermal effect at -520.C not followed by a weight loss. The endo-ef-
fect. is connected with the template decomposition. Then the decomposition pro-
ducts leave the sample (weight loss) causing a relaxation of the framework
(exo-effect and decrease of lattice constants). The exo-effect at -520.C can be
due to combustion of the organic decomposition products outside the sample. The
last effect is not observed when the calcination proceeds in a stream of gas
(the decomposition products are taken away from the system). The possibility of
a two step mechanism of the template removal was already reported [14]. All
these effects are probably well resolved due to both the large dimensjons of
the crystals and the high amount of sample hindering diffusion processes.
The static SINS data (Fig. 4) show that KVS-5 samples are free from A1 and
F e impurities (confirmed in ESR spectra) and the vanadium content (lines 51 and
67 for V(+) and VO(+), respectively, and no 181 line for V*O5(+) [15]) can
586

72

LL
I
Fig. 4. Static
secondary ions
mass spectroscopy
data for
vanadium s i l i c a l i t e
KVS-5.

Fig. 5. Infrared
spectra of vanadium
s i l i c a l i t e KVS-5
before ( a ) and
a f t e r (b)
calcination.

l l . l l l . l l l l l
1500 1000 500 cm-'
 587

reach about 1%. This is i n agreement with t h e X-ray fluorescence a n a l y s i s re-

s u l t s . For unknown reasons V atom cannot be d e t e c t e d by e l e c t r o n probe micro-
a n a l y s i s of t h e samples.
The I R s p e c t r a of KVS-5 (Fig. 5 ) show t h e weak band at -950 cm-l. I t w a s ob-
served f o r t h e f i r s t time f o r T i s i l i c a l i t e [16] and its i n t e n s i t y was l a t e r
r e l a t e d t o t h e T i content [17]. The band of o u r KVS-5 material i n c r e a s e s its
i n t e n s i t y a f t e r c a l c i n a t i o n (Fig. 5b) which might suggest a n improvement of t h e
ordering of t h e vanadium atoms i n t h e c r y s t a l .

3PPH

I __c
H

200 G
I-----+

DPPt

F i g . 6. ESR s p e c t r a of KVS-5 samples with complete ( a ) and incomplete ( b ) in-

c o r p o r a t i o n of V i n t o t h e t e c t o s i l i c a t e framework. S p e c t r a l parameters:
g~ = 1,961; ggg = 1.939; geff = 1.954; b = 8.78 mT; A,, = 19.25 mT; t h e broad
l i n e i n spectrum ( b ) geff = 1,965, AH e 50 mT.

The ESR spectrum of t h e as-prepared KVS-5 sample (Fig. 6 ) shows t h a t vana-

dium occurs as V4+. The w e l l resolved hyperfine s t r u c t u r e shows a very high
d i s p e r s i o n of t h e V4+ ions. As a pure s i l i c a l i t e s t r u c t u r e would have no pre-
f e r r e d p o s i t i o n s , a reason f o r such d i s p e r s i o n could be i n c o r p o r a t i o n of t h e
588

V atoms i n t o t h e framework. The p a r a m e t e r s of t h e s p e c t r u m are similar t o t h o s e

f o r V s p e c i e s i n n e a r l y s q u a r e p l a n a r environment [ 6 ] though t h e d i f f e r e n c e s
are large enough t o allow a l s o o t h e r d i s t o r t i o n s of t h e f o u r f o l d c o o r d i n a t i o n
[ 9 ] . The v e r y broad l i n e i n F i g . 6b serves as a background f o r t h e h y p e r f i n e
s t r u c t u r e and c a n be a s s i g n e d t o c l u s t e r e d extra-framework V4+, as i t is i n t h e
s i l i c a l i t e impregnated w i t h VOSO4 ( F i g . 7 a ) .

Fig. 7. ESR s p e c t r a of
a ) sample p r e p a r e d by
impregnat ion of sit i c a l i t e
w i t h VOSO4, b ) VAL-ZSM-5
a f t e r calcination.

I I I I I I

3,lO 330 35 0 37 0
H [kGl

F i g . 8. 51V s o l i d s t a t e MAS NMR F i g . 9. 51V s o l i d s t a t e MAS NMR spec-

spectrum of vanadium s i l i c a l i t e trum of s i l i c a l i t e impregnated w i t h
KVS-5 a f t e r c a l c i n a t i o n (6 = 0 f o r VOSO4 ( c o n d i t i o n s s e e Fig. 8 , 100,000
VOC13. f r e q u e n c y 52,6 MHz, s p e c t r a l transients).
w i d t h 720 kHz. r o t a t i o n 3 , l kHz,
D 1 = 0 , 5 vsec, D 0 = 0 , 3 s e c ,
p u l s a n g l e 22,5', 70.000 t r a n s i e n t s )
 589

After calcination, the vanadium ions represented by the hyperfine ESR spec-
trum are completely oxidized to V5+ and the ESR signal vanishes. The broad
lines in Figs. 6b and 7a remain unchanged after calcination showing that the
clustered V4+ is not oxidized. In the ESR spectrum of calcined VAl-ZSM-5. the
hyperfine structure is not vanishing completely (Fig. 7b) which might suggest a
hindering role of A1 in the oxidation of V4+.
The 51V MAS NMR spectrum of calcined KVS-5 shows the band at -557 ppm
(Fig. 8 ) corresponding to vanadium complexes with a tetrahedral oxygen envi-
ronment [ I , 181 which might indicate again the incorporation of vanadium into
the framework. Fig. 9 presents the spectrum for silicalite impregnated with
VOSO4 (measured immediately after calcination). As V4+ should not give any NMR
spectrum, the extremely broad band (Av 0 110 kHz) at about -620 ppm can be
identified as the band due to a small amount of V5+ ions broadened because of
the influence of V4+ present in excess. A similar band at about -530 ppm with a
small shoulder at --I000 ppm is observed for as-prepared KVS-5 except for a
narrower width -17,5 kHz probably due to a much lower content of vanadium.
As it appears from 27Al MAS NMR spectrum of as-prepared VAL-ZSM-5 (Fig.10).
5 - 20% of the Al3+ ions are in octahedral coordination ( s e e the band at -0
pprn). This band vanishes completely after calcination and only the band for
tetrahedral A 1 at +50 ppm remains, thus proving the tendency of A1 for entering
tetrahedral coordination during heat treatment [ 1 9 ] .

Fig. 10. 27Al MAS NMR

spectrum of VA1-ZSM-5 before
calcination ( 6 = 0 for
A ~ ( H * O ) ~ ~in
+ aqueous
solution, frequency 52.2 Mlz,
spectral width 42 kHz,
rotation 3 , 1 kHz,
D 1 = 10 vsec, D 0 = 0,3 sec,
5.000 transients).

80 60 LO 20 0 ' -20 -LO 6 pprn

590

CONCLUSIONS
The results show the possibility of preparation of vanadium silicalite KVS-5
containing approximately 1% vanadium. The vanadium atoms in the as-prepared
material exist mainly as V4+ ions and after calcination they are oxidized to
V5+. In both cases, they are tetrahedrally coordinated and they occur in a
highly dispersed state. Depending on synthesis conditions, a part of the vana-
dium can occur as clustered extra-framework V4' species which are difficult to
oxidize. After calcination, the vanadium atoms in KVS-5 appear to be in a more
uniform state than before.

The work was partially supported by the Polish Ministry of National Education
within the Project CPBP 01.06.

REFERENCES
1 V.M. Mastikhin, K.l. Zamaraev. Z. Phys. Chem. Neue Folge, 152 (1987). 317.
2 B. Taouk, M. Guelton, J . Grimbolt. J.P. Bonnelle, J . Phys. Chem., 92
(1988). 6700.
3 K.J. Zhen, M.M. Khan, C.H. Mak, K.B. Lewis, G.A. Somorjai, J . Catal., 96
(1985). 501.
4 M.A. Fox et al., J . Am. Chem. SOC. 109 (19831, 6347.
5 A.V. Kucherov. A.A. Slinkin, Zeolites, (1986). 175.
6 A.V. Kucherov, A.A. Slinkin, Zeolites, I_ (1987), 38.
7 A.V. Kucherov. A.A. Slinkin, Zeolites, L (1987). 43.
8 A.V. Kucherov. A.A. Slinkin, Zeolites, 7 (1987). 583.
9 C . E . Sass, Xinhua Chen, L. Kevan, J . Chem. SOC., 86 (1990). 189.
10 T. Inui, A. Miyamoto. H. Matsuda, H. Nagata, Y. Makino, K. Fukuda. F.
Okazumi, Proc. 7th Int. Zeolite Corif.. Tokyo, 1986, Y. Murakami et al.
(Eds.). Kodansha, Tokyo, 1986. 859 and refs. 12-14 therein.
1 1 X u Ruren. Pang Wenqin, Proc. Tnt. Symp. Zeolites, Portoroz, 1985, B. Drzaj
et al. (Eds.), Elsevier, Amsterdam, 1985, Stud. Surf. Sci. Catal.. 24
(1985). 27.
1 2 J . Kornatowski, M. Rozwadowski, Pol. Pat. Appl., P 281513, (1989).
13 J . Kornatowski. Zeolites, 8_ (1988), 77.
14 G . Debras, A. Gourgue, J.B. Nagy, G. De Clippeleir, Zeolites. 2 (1985),
377.
15 C. A. Altomare, G.S. Koermer, E. Martins, P.F. Schubert, S.L. Suib, W.S.
Willis, Appl. Catal., 45 (1988). 291.
16 G . Perego, S. Bellussi, C. Corno, M. Taramasso, F. Buonorno, A. Esposito,
Proc. 7th Int. Zeolite Conf., Tokyo, 1986, Y. Murakami et al. (Eds.),
Kodansha, Tokyo, 1986, 859.
17 B. Kraushaar. J.H.C. van HooIf, Catal. Lett., L(1988). 81.
18 L.R. Le Coustumer. B. Taouk, M. Le Meur, E. Payen, M. Guelton. J. Grimblot,
J. Phys. Chem.. 92 (1988), 1230.
19 J. Kornatowski. M. Rozwadowski, W. Schmitz, A. Cichowlas, Proc. 8th Int.
Zeolite Conf., Amsterdam, 1989. Recent Research Reports Val., J.C. Jansen
et al. (Eds.). L.. Moscou, Akzo Chemicals, Amsterdam, 1989, 79.
G. Ohlmann et 01. (Editors),Catalysis and Adsorption by Zeolites 591
01991 Elsevier Science Publishers B.V., Amsterdam

MULTINUCLEAR NMR STUDY OF THE CRYSTALLIZATION OF SAPO-37

N. Dumontl, T. lto2, J. B.Nagy1, Z. Gabelical and E.G. Derouanel

Facultks Universitaires N.-D. de la Paix, Laboratoire de Catalyse, 61, rue de Bruxelles,

B-5000-Namur (Belgium)
Tamai Sangyo CO., LTD, Zenibako 3-chome, 524-11, Otaru 047-02 (Japan)

ABSTRACT
A series of intermediate phases, isolated during the synthesis of
SAPO-37, have been characterized by XRD, SEM, NMR of adsorbed Xe, and
solid state 27Al- and 31P-NMR, in order to evidence the successive steps
occurring during the crystallization process. SAPO-37 stems from a
direct gel restructuration: large cavities form in the amorphous phase
during the aging period at ambient temperature. Upon heating at 200°C,
aluminum and phosphorus respectively incorporate in configurations
Al(4P) and P(4AI) in the framework, at the expense of the amorphous
phase, giving rise to the formation of well-defined SAPO-37 crystals,
showing an octahedral morphology, and growing with time. The
crystallinity reaches a maximum after 32h. For excessive synthesis times
(149h), the appearing of structural defects observed by NMR illustrates
the partial degradation of the SAPO-37 framework, whereas a side-phase,
SAPO-40, possibly involving interconnected channels limited by 12T
puckered rings, co-crystallizes from the mother liquid phase.

INTRODUCTION
The synthesis of SAPO-37, a silicoaluminophosphate involving a
Faujasite topology [ref. 11 was first reported by Lok et al. [ref. 21. Because
of its open pore structure, this material possesses potential interesting
and attractive applications in catalysis or adsorption, this explaining the
increasing attention that is now being devoted to the understanding of its
synthesis and to its better characterization. We have recently examined
the influence of various synthesis variables (aging time and temperature,
agitation and crystallization time) on the nature and final properties of
the various SAPO-type open structured phases obtained by two different
methods currently yielding SAPO-37 [ref. 31. Our study allowed us to
define the optimal conditions under which pure SAPO-37 could be obtained
in high yield by using both the conventional "aqueous" synthesis [ref. 21 or
592

the new biphasic (water-hexanol) route [ref. 41. The short range structural
configuration and coordination of Si, Al and P and their distribution in the
SAPO-37 framework, as well as the mechanisms governing the potential
framework substitution of Al or P by Si in the Faujasite structure, have
been thoroughly investigated by high resolution solid state NMR (29Si,
27AI, and 31P) [refs. 3, 5-71. The same techniques [ref. 81, complemented
by 129Xe-NMR [ref. 91 were used to follow the structural changes occurring
when water and organic template molecules progressively escape from the
SAPO-37 intracrystalline volume upon various thermal treatments.
Finally, we have recently taken advantage of the multiple potentialities of
the 129Xe-NMR method, linked to the great sensitivity of the xenon nucleus
to its close environment [refs. 10, 111 to characterize a series of
intermediate phases isolated during the hydrothermal synthesis of SAPO-
37 [ref. 121.
In the present work, we confirm and complete these preliminary
129Xe-NMR data by investigating more in depth the successive stages of
the crystallization (gel restructuration, crystal growth, formation of a
side-phase) and by characterizing all the solid intermediates using
complementary 27Al- and 31 P-NMR, in combination with XRD and SEM
techniques.

EXPERIMENTAL
The optimized procedure followed to synthesize the intermediate and
final SAPO-37 phases was described in details in our previous papers
[refs. 3, 121. Several aliquots of a hydrogel of molar composition 1.0
A1203 : 0.9 P2O5 : 0.4 Si02 : 0.86 (TPA)20 : 0.023 (TMA)20 : 50 H20,
previously aged at 20°C for 48h, were heated at 200°C under stirring
conditions for various periods of time. For the present study, we have
selected the more representative samples among the intermediates
isolated during the crystallization course. These specimens were obtained
after 0, 5, 10, 32 and 149h of heating, and are referred to as Pn, where n
denotes the crystallization time (Tablel).
The as-synthesized materials were checked for nature and purity by
X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).
The percentage of SAPO-37 in each phase was estimated by comparing the
total surface area of the characteristic XRD peaks measured for this
sample to the area of the same peaks recorded for the most crystalline
SAPO-37 of the series, arbitrarily considered 100% crystalline (P32)
(Tablel). The xenon adsorption isotherms were measured at 34% using a
classical volumetric apparatus, following operating conditions described
 593

TABLE 1
Nature, relative xenon adsorption capacities and relative crystallinities of
the intermediate phases isolated during the crystallization course of
;APO-3;

Sample a Nature Relative Xe % of crystallinity C

Pn m SBA 129Xe-NMR adsorption XRD 129Xe-NMR d
(mean diameter) capacities b

PO amorphous amorphous cavities 18 0 e

p5 amorphous amorphous cavities 18 0 e
p10 SAPO-37 octahedra SAPO-37 81 78 83
(7.7 w )
p25 SAPO-37 octahedra f f 95 f
(14.8 l m )
p32 SAPO-37 octahedra SAPO-37 100 100 100
(15.1 pm)
SAPO-37 octahedra SAPO-37 135 g h 55
p149
+ + +
SAPO-40 platelets SAPO-40
n denotes the crystallization time (h).
Relative xenon adsorption capacities calculated from the isotherms with
respect to the most crystalline SAPO-37 phase (P32) arbitrarily considered to
have a 100% adsorption capacity.
C Weight percentage of SAPO-37 in each intermediate phase determined with
respect to the most crystalline SAPO-37 (P32) considered to be 100%
crystalline.
d Determined from the ratio between the slope of the straight line &=f(nXe/g) for
each crystalline intermediate phase and the slope obtained for P32 [ref. 121
e The crystallinities of Po and P5 could not be determined by 129Xe-NMR because
these two phases do not contain well-defined SAPO-37 crystals.
f not investigated.
9 Xe isotherms only allow to calculate the global Xe adsorption capacity of the
mixture (SAPO-37 + SAPO-40).
h It is not possible to estimate the XRD crystallinity of SAPO-37 in the mixture
Pi49 , as most of the XRD peaks of SAPO-37 and SAPO-40 overlap.

elsewhere [ref. 121. The 129Xe-NMR spectra of xenon adsorbed at different

pressures on all the intermediate phases were recorded at t h e same
temperature, with a Bruker CXP-200 spectrometer operating at 55.3 MHz.
The 27Al- (105.3 MHz) and 31P- (162.0 MHz) high resolution solid state
MAS N M R measurements were performed o n a Bruker MSL-400
spectrometer. The pulse length and recycle time were lps and 200ms for
594

27Al and 3ps ( d 2 ) and 30s for 31P, respectively. Typical measuring
conditions for the 31P- CP-MAS NMR experiments were a 1H pulse length of
2.5ps, a contact time of l m s and a recycle time of 5s.

RESULTS AND DISCUSSION

i ) XRD, SEM and 129Xe-NMR
The structural and morphological characteristics of the SAPO-37
intermediate phases, determined by X-ray diffraction and scanning
electron microscopy, are summarized in Table 1. These data are compared
to those obtained previously by 129Xe-NMR [ref. 121. The relative xenon
adsorption capacities of the calcined samples are compared to their
relative crystallinities estimated by XRD and IzgXe-NMR, respectively.
For Po and P5, we observe a broad 129Xe-NMR line, distinguishable
from the one belonging to the gaseous xenon, and characterized by a quasi
constant chemical shift value ( about 45 ppm), whatever the xenon
pressure. This signal arises from the interactions of the xenon atoms
with the walls of large cavities of about 25 A. We therefore conclude
that, at these early stages of the crystallization, the gel already contains
a preliminary void structure, responsible of the non-negligible adsorption
capacity of these materials (about 20% of the maximum observed in the
case of 100°/~ crystalline SAPO-37, P32). The degree of connection
between these cages is small, but increases as the crystallization
proceeds. These cavities do not show any regular ordering, which explains
why no crystalline phase is detected in PO and P5, by XRD and SEM.
P l o is found to contain already about 80% crystalline SAPO-37. The
crystals show the typical octahedral morphology characterizing Faujasite-
type materials (Fig. 1) [ref. 31. The crystal size increases with the
crystallization time (Table 1). X-ray diffractograms indicate that P32 is a
100% crystalline SAPO-37, whereas, for longer synthesis times, a
crystalline side-phase, SAPO-40, consisting of platelet-like crystallites,
is found admixed with SAPO-37 (P149) (Fig. 1). In contrast to SAPO-37
that stems from a direct gel restructuration, SAPO-40 nucleates in the
liquid-phase , probably because of the marked change in its composition
observed as soon as 100% crystalline SAPO-37 is formed [ref. 121. The
relative xenon adsorption capacities of P10 and P32 are in very good
agreement with their relative crystallinities measured by XRD or
calculated from the slopes of the straight lines 6 1 2 9 ~=f(nXe/g)
~ [ref. 121.
We took advantage of this latter method to determine the weight
percentage of SAPO-37 admixed with SAPO-40 in P14g (Table 1) [ref. 121,
which is rather difficult to estimate by XRD, as most of their
 595

Fig. 1. SEM micrographs of the various intermediate phases. (a) Po, (b) P5, (c) Pio,
(4 P25, (el P32, (f) PIN.

diffractogram peaks overlap [ref. 21. Distinct 129Xe-NMR signals

characterize these two SAP0 materials. The chemical shift of the high
field resonance extrapolates to 53 ppm at zero xenon concentration for
samples Plo, P32 and PI49 and confirms the presence of SAPO-37. For the
low field signal, the corresponding parameter 1 3 ~is larger (95 ppm), which
suggests that SAPO-40 has a pore structure narrower than SAPO-37, the
cavities of which are connected by 12 T windows. n-hexane adsorption
measurements confirm this assumption. Indeed, the porous volume of
SAPO-40 was found to be about 60% of the void volume defined by the
supercages of SAPO-37. We recently proposed a tridimensional structure
for SAPO-40, consisting of interconnected straight channels limited by
puckered 12 T rings [ref. 121. These structural properties, in line with the
typical tetragonal crystal morphology, justify the behavior of this
material upon adsorption. Indeed, whereas SAPO-40 shows a n-hexane
adsorption capacity quasi identical to that of ZSM-5, xenon atoms diffuse
596

much more rapidly in the S A P 0 than through the ZSM-5 structure.

Moreover, marked confinement effects, due to the puckered channels, give
rise to a particularly high xenon sorption capacity explaining why, in
spite of its narrower pore system, SAPO-40 adsorbs more xenon than
SAPO-37 (Table 1) [ref. 121. For too long heating times, the SAPO-37
framework starts collapsing, as indicated by the broadening of the high
field signal for the phase P14g.

ii) 27AI- and 3 1 P - N M R

The progressive structuration of the gel into crystalline SAPO-37 is
illustrated by the 27AI-NMR spectra presented in Fig. 2.
As the octahedral aluminum resonates at higher fields (see below), we
tentatively attribute the single line observed for samples Po and P5 at
about +6 ppm (line P) to penta-coordinated aluminum in the amorphous
phase. No signal is detected at lower fields, which confirms the absence
of any crystalline material at these stages of the crystallization.
The pure and well-crystalline SAPO-37 phases P l o , P25 and P32
exhibit an additional 27AI-NMR line at about +37 ppm (line T) due to
tetrahedral aluminum in the configuration Al(4P) [refs. 5-61. From P i 0 to
P32, the intensity of line P decreases, and that of line T increases, as the
crystallization proceeds, i.8. as the amount of SAPO-37 increases. This
reflects the progressive incorporation of aluminum into the tetrahedral
positions of the SAPO-37 framework, at the expense of the amorphous
phase. However, line P does not disappear completely, even for P32 which
does not contain any amorphous phase detectable by XRD or SEM. We
therefore conclude that an additional contribution to signal P, probably due
to some (otherwise tetrahedral) aluminum atoms distorted by secondary
coordinations with occluded molecules, adds on the contribution of the
penta-coordinated aluminum belonging to the amorphous phase. Indeed, as
shown in Fig. 3, this resonance is sensitive to the effects of dehydration
and calcination. Upon heating to various temperatures (1 20, 230°C), the
intensity ratio I(lineT)/l(line p) for sample P25 progressively increases.
Moreover, line P tends to disappear when the sample is calcined under dry
air up to 550°C. Saldarriaga et al. [ref. 51 and Blackwell et al. [ref. 61 have
also suggested that such interactions with intracrystalline water
molecules, OH- groups or organic templates could modify the geometry
around some framework aluminum atoms and give rise to this additional
signal appearing at a chemical shift value that characterizes aluminum in
a coordination larger than 4. However, we observe that this "penta"-
coordination is not restored upon rehydration, which supports the
 597

100 0 -100
PPM

Fig. 3. 27AI-NMR spectra of phase

p25.
(a) as-synthesized, (b) heated in a
100 0 -100 N p flow to 230°C, (c) heated in a N2
PPM flow to 550°C then calcined in air
at 550°C, ( d ) sample c left
Fig. 2. 27AI-NMR spectra of the as- overnight in moist atmosphere,(e)
synthesized intermediate phases. sample c dispersed in water for 15
(a) Po, (b) P5, (c) Pie, ( 4 P25, (el min then dried at 100°C, (f) sample
p32, (f) p149. e recalcined to 550°C.
598

hypothesis of a distortion of the Al tetrahedra by organic compounds, such

as TMA+ or TPA+. Indeed, when calcined SAPO-37 is exposed overnight to
atmospheric moisture or dispersed in water for 15 minutes and then dried
at 100°C, another signal appears at about -11 ppm. It is attributed to
octahedral aluminum stemming from a reversible coordination of some
framework aluminum atoms with water molecules (Fig. 3). The hydration
state of SAPO-37 also affects the chemical shift of line T: the higher the
degree of hydration, the larger the chemical shift (calcined P25: +29 ppm,
as-synthesized P25: +37 ppm, hydrated P25: +42 ppm). According to an NMR
study reported by Muller et al. on a series of AIP04 phases [ref. 131, the
27AI chemical shift depends linearly on the AI-0-P bond angle. In the case
of SAPO-37, such angular changes are probably induced by the presence of
water molecules.
The instability of SAPO-37, in its H-form, in the presence of water
was well-recognized [ref. 81. We have also previously evidenced by 129Xe-
NMR the formation of larger cavities and a partial pore blockage in SAPO-
37 leading to a dramatic decrease of the adsorption capacity [ref. 91. This
loss of crystallinity, due to the partial structure collapse, is confirmed by
XRD: the samples hydrated by contact with atmospheric moisture or by
dispersion in water, become totally amorphous to X-rays. By contrast, the
SEM micrographs reveal that the octahedral crystals still keep intact their
outer shell, which suggests that moisture induces a true perimorphic
transformation. However, as indicated by the persistency of line T, the
tetrahedral geometry of some framework aluminum atoms is retained.
The two main signals characterizing the crystalline SAPO-37
intermediate phases are also found in P14g (mixture of SAPO-37 and
SAPO-40) (Fig. 2) but the ratio of their respective intensities is
completely reversed: line P appears only as a shoulder. This inversion
could be interpreted in terms of a decrease of the relative number of
penta-coordinated aluminum atoms in the SAPO-37 framework but, if we
balance the absolute intensity of this resonance by the percentage of
SAPO-37 in the mixture, we find that this decrease is only apparent. The
main cause of this ratio inversion is the large increase of the intensity of
signal T. It is explained by the marked incorporation of aluminum into the
tetrahedral positions of the SAPO-40 network, from the mother liquid
phase.
The 27AI-NMR spectrum of sample PI49 shows a broad shoulder at
around -15 ppm, a ppm range that usually characterizes octahedrally
coordinated aluminum. This shoulder noteworthly decreases when sample
PI49 is calcined at 550°C, and nearly completely disappears after another
 599

100 0 -100
PPM

Fig. 4. 27AI-NMR spectra of phase

p i 49.
(a) as-synthesized, (b) heated in a
N p flow to 550°C then calcined in
air at 550°C, (c) sample b left
overnight in moist atmosphere then
recalcined to 550°C.

I . . . . I . . . . I . . . . I ..
0 -50
PPM
I
-25
I
' I
-35
PPM Fig. 5. 31P-NMR spectra of the as-
Fig. 6. Simulation of the 31P-NMR synthesized intermediate phases.
spectrum of as-synthesized phase (a) Po, (b) P5, ( 4 Pie, (4 P25, ( 4
p25. p32, ( f ) p149.
600

rehydration-calcination cycle (Fig. 4). We therefore assign this line to

structural defects (terminal AI(0H)” groups, ...) created during a long
hydrothermal crystallization (149h) at a rather high temperature (200°C).
Such defects easily recombine upon successive calcinations at 550°C.
These findings go in line with the information obtained from 129Xe-NMR
investigations of phase Pi49 in which SAPO-37 was found to have
undergone a partial structural degradation.
Finally, a weak line located at +19 ppm (P’) can be tentatively
assigned to aluminum atoms in the SAPO-40 framework involving a
secondary coordination with occluded organic molecules. As for SAPO-37,
this line logically disappears upon calcination of PI49 at 550°C, a
temperature at which all the organic molecules are released.
Decoupled 31P-NMR spectra of non crystalline samples Po and P5 show
a single but broad line located at about -20 ppm (Fig. 5). It obviously
characterizes phosphorus atoms belonging to the amorphous phase. Its
important width (about 2900 Hz) accounts for different types of
phosphorus atoms located in various environments. They possibly could be
terminal P(OH), groups. For sample P10, in which about 20% of amorphous
phase is still present, this line still remains visible next to the resonance
due to framework tetra-coordinated phosphorus (Fig. 5 ) . It becomes hardly
detectable (and only by using cross polarization) for P25 and completely
disappears in the case of the 100% crystalline P32. This progressive
decrease in intensity confirms the attribution of this resonance to the
presence of amorphous phase and quite well illustrates the progressive
disappearing of this latter, as the crystallization proceeds.
The main resonance at -31 ppm, due to SAPO-37 framework P(4AI)
configurations [refs. 5-61 shows an asymmetrical character. An accurate
decomposition of the spectrum (Fig. 6) suggests the presence of an
additional small line at about -33 ppm. Its presence is not a simulation
artifact, as evidenced by a series of calcination or ethanol washing
experiments. Indeed, after such treatments, this shoulder completely
disappears and the main line becomes symmetrical and narrow. We
therefore assign the small shoulder at -33 ppm to slight deformations of
P-O-AI angles produced by weak interactions of the framework atoms with
the neighbouring organic molecules. The main line is broader by 100 Hz for
PI49 with respect to that present in P32 (pure SAPO-37). Obviously such a
broadening can be explained by the superposition of two very similar
resonances of P(4AI) configurations belonging to both SAPO-37 and SAPO-
40 ordered structures. Blackwell et al. [ref. 61 have indeed observed small
differences in position of the 3 1 P-NMR lines characterizing identical
 601

P(4AI) configurations in various SAP0 frameworks.

Finally, 31P-NMR confirms a partial collapse of the SAPO-37 lattice
upon long heating times (149 h). Indeed, the presence of P-OH defects that
appear upon partial degradation of the framework can be evidenced by a
weak NMR line at -20 ppm, markedly enhanced under cross polarization.
Internal P-OH terminal groups are indeed characterized by a small
resonance in the -20 ppm range for a series of AIP04-n and SAPO-n
partially degradated structures [ref. 141.

CONCLUSION
129Xe-, 27Al- and 31 P-NMR techniques, combined with XRD and SEM,
have been proved a useful tool to investigate the successive steps
occurring during the crystallization process of SAPO-37. 129Xe-NM R was
of particular interest to detect the presence, at the early stages of the
crystallization, of preliminary void structures in the gel, which are not
observable by XRD or SEM. It allowed to follow to progressive increase of
the crystallinity of SAPO-37 and to evidence the partial degradation of its
framework, as well as the formation of the side-phase SAPO-40, upon too
long hydrothermal crystallization. The progressive incorporation of
phosphorus and aluminum into tetrahedral positions in the SAPO-37
network, at the expense of the phosphorus and penta-coordinated aluminum
belonging to the amorphous phase, was well illustrated by the 31P- and
27AI-NMR spectra of the successive intermediate phases. 27AI- and 31 P -
NMR also allowed to evidence the formation of structural P(OH), and
AI(0H)n defects in SAPO-37, and the appearing of SAPO-40 after a long
period of heating at 200°C, as well as the interactions of some framework
Al and P atoms with occluded organic molecules.

REFERENCES
B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan and E.M.
Flanigen, J. Am. Chem. SOC., 106 (1984) 6092-6093.
B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan and E.M.
Flanigen, U.S. Patent 4, 440, 871 (1984).
L. Maistriau, N. Dumont, J. B.Nagy, 2. Gabelica and E.G. Derouane,
Zeolites, 10 (1990) 243-250.
E.G. Derouane and R. von Ballmoos, Eur. Patent 185, 525 (1986).
L.S. Saldarriaga, C. Saldarriaga and M.E. Davis, J. Am. Cham. SOC, 109
(1987) 2686-2691.
C.S. Blackwell and R.L. Patton, J. Phys. Chem., 92 (1988) 3965-3970.
J.A. Martens, C. Janssens, P.J. Grobet, H.K. Beyer and P.A. Jacobs, Stud.
Surf. Sci. Catal., 49A (1989) 215-225.
M. Goepper, F. Guth, L. Delmotte, J.L. Guth and H. Kessler, Stud. Surf.
602

Sci. Catal., 498 (1989) 857-866.

9 N. Dumont, T. Ito and E.G. Derouane, Appl. Catal., 54 (1989) Ll-L6.
1 0 J. Fraissard and T. Ito, Zeolites, 8 (1988) 350-361, and references
therein.
1 1 T. Ito, J. Fraissard, J. B.Nagy, N. Dewaele, Z. Gabelica, A. Nastro and E.G.
Derouane, Stud. Surf. Sci. Catal., 49A (1989) 579-588.
1 2 T. Ito, N. Dumont, J. B.Nagy, Z. Gabelica and E.G. Derouane, in: Proc.
Intern. Symp. on Chemistry of Microporous Crystals, Tokyo, Japan, July
27-29, 1990, Kodansha/Elsevier, in press.
1 3 D. Muller, E. Jahn and G. Ladwig, Chem. Phys. Lett., 109 (1984) 332-
336.
1 4 L. Maistriau, Z. Gabelica, E.G. Derouane, E.T.C. Vogt and J. van Oene,
Zeolites, in press.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 603
0 1991 Elsevier Science Publishers B.V., Amsterdam

METASTABILITY OF ZEOLITES I N TETRAETHYLAMMONIUM MEDIA

F r a n c e s c o D I R E N Z O I , A b d e r r a h m a n ALBIZANE1, Ma rie -A gn8s NICOLLE1,

F r a n q o i s FAJULAI, F r a n c o i s FIGUERASl a n d T h i e r r y DES COURIERES2
1 L a b o r a t o i r e d e Chimie Organique Physique e t CinCtique Chimique
A p p l i q u e e s , URA 418 d u CNRS, E c o l e N a t i o n a l e S u p e r i e u r e d e C h i m i e ,
8 r u e d e 1 ’ E c o l e N o r m a l e , 34053 M o n t p e l l i e r C e d e x 1 ( F r a n c e )
* C e n t r e d e Recherche ELF-France, Solaize

SUMMARY
T h e i n f l u e n c e of o r g a n i c c o n c e n t r a t i o n , S i / A 1 r a t i o , s t i r r i n g
and n a t u r e o f t h e s i l i c a s o u r c e on z e o l i t e s y n t h e s i s i n t h e
p r e s e n c e o f t e t r a e t h y l a m m o n i u m h a v e b e e n s t u d i e d . Examples o f
m e t a s t a b i l i t y o f z e o l i t e b e t a a n d ZSM-5 t o w a r d s ZSM-12 p r o p o s e t h e
l a s t a s t h e more s t a b l e z e o l i t i c p h a s e i n t e t r a e t h y l a m m o n i u m m e d i a
f e a t u r i n g h i g h e s t Si/A1 r a t i o . E v i d e n c e s of h e t e r o g e n e o u s
n u c l e a t i o n o f z e o l i t e s o v e r amo r p h o u s o r c r y s t a l l i n e p h a s e s a r e
discussed.

1NT RODUCT I ON
Many s t u d i e s h a v e d e a l t w i t h z e o l i t e s y n t h e s i s i n t h e p r e s e n c e
o f t e t r a e t h y l a m m o n i u m , s i n c e t h e f i r s t r e p o r t of t h e s y n t h e s i s o f
z e o l i t e b e t a ( r e f . 1 ) . Recent p a p e r s have been e s p e c i a l l y d e v o t e d
t o t h e s y n t h e s i s o f z e o l i t e b e t a ( r e f s . 2 , 3 ) and t o t h e
c o m p e t i t i v e f o r m a t i o n o f z e o l i t e b e t a a nd ZSM-PO ( r e f s . 4 , 5). T h e
open l i t e r a t u r e p r e p a r a t i o n s o f t h e s e z e o l i t e s a r e a l w a y s b a s e d on
te t r a a l k y l o r t h o s i l i c a t e s , w h i l e p a t e n t s y n t h e s e s p r o p o s e i n o r g a n i c
s o u r c e s o f s i l i c a b o t h i n t h e case o f z e o l i t e b e t a ( r e f s . 1, 6 )
and i n t h e case of ZSM-12 ( r e f . 7 ) . The c r y s t a l l i z a t i o n
s e l e c t i v i t y i n t e t r a e t h y l a m m o n i u m m e d i a when c o m m e r c i a l i n o r g a n i c
s o u r c e s of s i l i c a a r e u s e d appears h en c e a s a p r o m i s i n g f i e l d of
investigation.
T h e n a t u r e of t h e s o u r c e of s i l i c a i n f l u e n c e s t h e
c r y s t a l l i z a t i o n i n a m u l t i p l e way. Beyond t h e d i f f e r e n t d e g r e e o f
polymerization of t h e s i l i c i c species i n s o l u t i o n , t h e s u r f a c e
p r o p e r t i e s o f t h e a m o r p h o u s s o l i d p r e s e n t i n t h e s y n t h e s i s medium
are deeply a f f e c t e d . A s a consequence, heterogeneous n u c l e a t i o n of
d i f f e r e n t p h a s e s can o c c u r and modify t h e s e l e c t i v i t y of t h e
p r e p a r a t i o n . E v i d e n c e s of p r e f e r e n t i a l n u c l e a t i o n of z e o l i t e s o v e r
604

non-crystalline s o l i d s i n o t h e r s y n t h e s i s media have been r e c e n t l y

p r o p o s e d ( r e f s . 8 - 1 1 ) . M o r e o v e r , t h e o r i e n t e d n u c l e a t i o n of a
z e o l i t e framework o v e r a d i f f e r e n t z e o l i t i c s t r u c t u r e is a well
known phenomenon ( r e f s . 1 2 - 1 4 ) . I t seems t h e n e s p e c i a l l y
i n t e r e s t i n g t o pay a t t e n t i o n t o t h e i n t e r f a c e phenomena r e l a t e d t o
t h e h e t e r o g e n e i t y o f t h e s y n t h e s i s medium.

METHODS
C r y s t a l l i z a t i o n e x p e r i m e n t s h a v e b e e n c a r r i e d o u t u s i n g two
t y p e s o f e x p e r i m e n t a l d e v i c e s : 120 a1 s t a i n l e s s s t e e l a u t o c l a v e s
f o r e x p e r i m e n t s i n s t a t i c c o n d i t i o n s and a 0.5 l i t r e s s t a i n l e s s
s t e e l r e a c t o r f o r experiments under s t i r r i n g . T h i s l a s t autoclave
wad e q u i p p e d w i t h a n a n c h o r - s h a p e d s t i r r e r and a sampling o u t l e t
a l l o w i n g specimens t o be withdrawn w i t h o u t a l t e r i n g t h e s y n t h e s i s
c o n d i t i o n s . The s y s t e m w a s d e s i g n e d s o a s t o a v o i d a c c u m u l a t i o n of
material i n s i d e s a m p l i n g p i p e and v a l v e s i n t h e c o u r s e of t h e
r e a c t i o n ( r e f . 1 5 ) . The r e a c t o r was h e a t e d b y a n e l e c t r i c a l
f u r n a c e r e g u l a t e d t h r o u g h a t h e r m o c o u p l e immersed i n t h e r e a c t i o n
m e d i u m . T h e h e a t i n g r a t e was 3 "C/min a n d t h e s t i r r i n g r a t e 150
rpm. S a m p l e s o f 1 U m l w e r e p e r i o d i c a l l y w i t h d r a w n f r o m t h e
a u t o c l a v e . T h e s o l i d f r a c t i o n was r e c o v e r e d b y f i l t r a t i o n . The
::lcar s o l u t i o n , c o n t a i n i n g t h e d i l u t e d m o t h e r l i q u o r , was
p r e s e r v e d f o r e l e m e n t a l a n a l y s i s . The s o l i d w a s washed w i t h
d e i o n i z e d w a t e r up t o p H Y a n d d r i e d a t 70 "C i n a i r . The
temperature of a l l syntheses, both s t i r r e d and i n s t a t i c
c o n d i t i o n s , was 1 5 0 ° C .
T h e r e a g e n t s w e r e s i l i c a s o l ( C e c a s o l 3 0 , S i O z 2 5 % , Na 0 . 2 % , A 1
6 0 ppm, pH 8 . 8 , g r a i n s i z e 1 2 - 1 8 n m ) , p r e c i p i t a t e d s i l i c a ( Z e o s i l
175MP f r o m Rhane P o u l e n c , Na U . Y % , A 1 0.4%, Hz0 6 . 5 % , grain s i z e
2-2U u , p o r e volume 0 . 0 8 m l / g ) . s o d i u m a l u m i n a t e ( C a r l o E r b a R L E ) ,
t e t r a e t h y l a m m o n i u m (TEA! h y d r o x i d e s o l u t i o n ( A l d r i c h ) , sodium
h y d r o x i d e ( P r o l a b o KP N o r m a p u r ) , d e i o n i z e d w a t e r . T h e r e a g e n t s
were m i x e d u n d e r s t i r r i n g i n t h e o r d e r : a l k a l i n e s o l u t i o n , o r g a n i c
a g e n t , a l u m i n a t e , s i l i c a . T h e m i x t u r e was s t i r r e d f o r 4 h r s a t
roam t empe r a t u r e b e f o r e t he b e g i n n i n g o f t h e s y n t lies i s .
X - r a y p o w d e r d i f f r a c t i o n ( C t i R T h e t a 60 d i f f r a c t o m e t e r , C u K a
r a d i a t i o n ) was u s e d t o i d e n t i f y t h e p h a s e s p r e s e n t i n t h e s o l i d
f r a c t i . o n . C r y s t a l s i z e and h a b i t were d e t e r m i n e d b y s c a n n i n g
e l e c t r o n m i c r o s c o p y ( C a m b r i d g e S l 0 0 i n s t r u m e n t , r e s o l v i n g power 7
nm).
 605

RESULTS A N D DISCUSSION
C.om0p e t i Lian...be-ttwaen. an al.c.ine_,_. mx.deni..f_e.and..ze~l,i.t a .bet a
S y n t h e s i s b a t c h e s o f s t o i c h i o m e t r y 8.10[xNa-(l-x)TEA]~Alz03~
l Y . O S i 0 2 . 6 3 0 H z O (OH-/SiOz 0.72), w h e r e x s p a n n e d f r o m 0 t o 1, h a v e
b e e n h e a t e d a t 150°C f o r 72 h o u r s i n s t a t i c c o n d i t i o n s .
P r e c i p i t a t e d s i l i c a was u s e d a s s i l i c a s o u r c e . T h e p h a s e s f o r m e d ,
t h e e l e m e n t a l composition o f t h e p r o d u c t and t h e y i e l d s of s i l i c o n
and aluminum t h r o u g h o u t t h e p r e p a r a t i o n a r e r e p o r t e d i n t a b l e 1.
As t e t r a e t h y l a m m o n i u m c o n c e n t r a t i o n i n c r e a s e s t h e main p h a s e
formed p a s s e s from a n a l c i m e t o z e o l i t e b e t a t h r o u g h m o r d e n i t e . The
r o l e of t h e tetraethylammonium c a t i o n i n t h e formation of s i l i c a -
r i c h l o w - d e n s i t y c r y s t a l l i n e p h a s e s is e v i d e n t . From t a b l e 1 i t
emerges t h a t t h e aluminum i n c o r p o r a t i o n p r e s e n t s a minimum f o r
i n t e r m e d i a t e v a l u e s o f t h e t e t r a e t h y l a m m o n i u m c o n c e n t r a t i o n . The
phenomenon seems t o b e c o n s i s t e n t w i t h t h e f o r m a t i o n of m o r d e n i t e
more s i l i c i c t h a n t h e c o r r e s p o n d i n g z e o l i t e b e t a .
T h e m o r p h o l o g y o f some p r o d u c t s a r e d e p i c t e d i n f i g u r e 1. A t a
TEA/SiOz r a t i o o f 0 . 5 0 ( f i g u r e l a ) r o u g h i r r e g u l a r g r a i n s o f
z e o l i t e b e t a u p t o 1 . 5 cc l a r g e a r e f o r m e d , t o g e t h e r w i t h t a b u l a r
c r y s t a l s of mordenite 12 CI l o n g . Some o f t h e g r a i n s o f z e o l i t e
b e t a a p p e a r t o h a v e grown a r o u n d t h e e d g e s o f t h e m o r d e n i t e
c r y s t a l s . Rare s p h e r e s o f a n a l c i m e ( n o t d e p i c t e d ) p r e s e n t a
d i a m e t e r up t o 7 u . A t a TEA/SiOz r a t i o o f 0 . 1 6 ( f i g u r e lb)
co-crystallization of m o r d e n i t e and a n a l c i m e can be o b s e r v e d .
A n a l c i m e c r y s t a l s a r e l a r g e r ( u p t o 16 u) a n d p r e s e n t t h e {211}
t r a p s z o h e d r o n h a b i t . When n o t e t r a e t h y l a m m o n i u m was p r e s e n t i n t h e
s y n t h e s i s m i x t u r e ( f i g u r e l c ) t h e p r o d u c t i s composed by 2 5 u
l a r g e a n a l c i m e t r a p e z o h e d r a . The c r y s t a l e d g e s a r e e t c h e d by
c o r r o s i o n l i n e s , s u g g e s t i n g t h a t t h e s y s t e m h a s grown
u n d e r s a t u r a t e d f o r a n a l c i m e . Analcime is s p r e a d of 2 CI large

TABLE 1
Phase composition, e l e m e n t a l composition and material b a l a n c e a s a
f u n c t i o n a f t h e tetraethvlaamonium c o n t e n t af-the s y n t h e s i s b a t c h .

T E AL cristallinity % mole f r a c t i o n Yield

S i02 (ele.ment/Si+Al>-
beta MUR ANA - Al N Na. Si A I-
u 74 80 - - 0.087 0.083 0.027 0.94 0.85
0.5U 62 28 10 0.061 0.069 0.160 0 61 0.37
0.16 - 52 48 0.185 0.022 0.179 0.35 U 75
0.00 - - 1UO 0 252 0.000 0.305 0 25 0.78
606

F i g . 1. S y n t h e s e s a t d i . f f e r e n t t e t r a e t h y l a m m o n i u m c o n c e n t r a t i o n .
F r o m t o p t o b o t t o m : TEA/Si02 0 . 5 0 ( a ) , 0 . 1 6 ( b ) a n d 0 . 0 0 ( c ) .
 607

-\
\
0.038

Q, 0.020

-a 0.002

100
t (h) 200

F i g . 2 . N u c l e a t i o n l a g s o f z e o l i t e b e t a ( 0 ) a n d ZSH-12 ( 0 ) a s
f u n c t i o n s o f t h e m o l e f r a c t i o n of a l u m i n u m .

f l a k e s o f g i s m o n d i n e , d e t e c t a b l e i n t r a c e amount f r o m t h e p o w d e r
X-ray d i f f r a c t i o n s p e c t r a .

F ~ o u .~ e ~ l i tb.afa.t~-..Z.~n--_l.Z
e
Mixtures of s t o i c h i o m e t r y 0.08Na~0.30TEA-(x/2)Al~O~~(l-x)SiO~~
16Hz0 (OH-/SiOz 0.35) w i t h x r a n g i n g f r o m 0.038 t o 0 . 0 0 2 h a v e b e e n
h e a t e d a t 150°C i n a s t i r r e d r e a c t o r . S i l i c a s o l w a s t h e s o u r c e of
s i l i c a . T h e i n d u c t i o n lags p r e c e d i n g t h e d e t e c t i o n of t h e
c r y s t a l l i n e phases are r e p o r t e d i n f i g u r e 2. I n moderately s i l i c i c
s y s t e m s ( S i / A l 2 5 - 5 0 ) z e o l i t e b e t a f o r m s b e f o r e ZSM-1%. T h e
n u c l e a t i o n l a g o f ZSH-12 d e c r e a s e s when S i / A 1 i n c r e a s e s a n d a t
h i g h e r S i / A 1 r a t i o ( 5 0 0 ) ZSM-12 i s t h e f i r s t and u n i q u e
c r y s t a l l i n e p h a s e f o r m e d . Aluminum seems n e e d e d t o f o r m t h e
l a d d e r s o f 4-membered r i n g s t y p i c a l o f z e o l i t e b e t a ( r e f s . 16,
17), a l r e a d y p r o p o s e d a s a l u m i n u m l o c a t i o n ( r e f . 18). On t h e o t h e r
hand, t h e p r e s e n c e of s i l i c o a l u m i n a t e s p e c i e s a p p e a r s t o i n h i b i t
tlie f o r m a t i o n of t h e c r i s t o b a l i t e - l i k e w a l l s of i n t e r c o n n e c t e d
6-membered r i n g s t y p i c a l o f ZSM-12 ( r e f . 19).
O n t h e o t h e r hand a l u m i n u m a l s o m o d i f i e s t h e p h y s i c s o f t h e
s y s t e m . I f t h e amount o f s o l i d f r a c t i o n r e c o v e r e d f r o m
i n t e r m e d i a t e s a m p l i n g is c o n s i d e r e d , m a i n d i f f e r e n c e s a r e f o u n d a s
a f u n c t i o n of composition. I n t h e more a l u m i n i c s y s t e m a n
amorphous s o l i d is p r e s e n t t h r o u g h o u t t h e h y d r o t h e r m a l t r e a t m e n t .
I n t h e c a s e o f t h e more s i l i c i c s t o i c h i o m e t r y t h e s y s t e m i n i t i a l l y
c o n s i s t s o f a c l e a r s o l u t i o n . G e l l i n g , and r e c o v e r y of a n y s o l i d
f r a c t i o n from s a m p l i n g , b e g i n o n l y a f t e r one d a y a t t h e s y n t h e s i s
t e m p e r a t u r e . Anyway a n a m o r p h o u s s o l i d i s a l w a y s p r e s e n t when
zeolite nucleates.
608

C ~ m p e tf;iQo...he.tween
i z.e.Q.l.i.t.e..hzta...an.d._ZS.M.-...5
T h e n a t u r e o f t h e s o u r c e o f s i l i c a may i n f l u e n c e t h e p h a s e
s e l e c t i v i t y o f t h e s y n t h e s i s . Two g e l s o f s t o i c h i o m e t r y
(O
1.2Na20.9.2TEA~0~A120~~78SiOz~128O HH
zO-/Si02 0.24) h a v e b e e n
p r e p a r e d f r o m p r e c i p i t a t e d s i l i c a o r s i l i c a s o l . Under
hydrothermal treatment i n a non-stirred a u t o c l a v e t h e experiment
with p r e c i p i t a t e d silica has given o r i g i n t o z e o l i t e b e t a . In t h e
e x p e r i m e n t w i t h s i l i c a s o l u n d e r t h e same h y d r o t h e r m a l c o n d i t i o n s
ZSH-5 h a s b e e n f o r m e d .
T h i s s e l e c t i v i t y e f f e c t h a s n o t b e e n o b s e r v e d when t h e
s y n t h e s i s h a s b e e n c a r r i e d o u t u n d e r s t i r r i n g . Two g e l s o f
stoichiometry 2.2Na~0-8.8TEA~0~A1~0~~51Si0~~
(OH-/Si02
1040Hz0
0.36) have been p r e p a r e d from p r e c i p i t a t e d s i l i c a or s i l i c a s o l .
Under h y d r o t h e r m a l t r e a t m e n t b o t h g e l s g a v e o r i g i n t o z e o l i t e
b e t a . The c r y s t a l l i z a t i o n from s i l i c a s o l f e a t u r e d a l o n g e r
i n d u c t i o n t i m e (22 h o u r s v e r s u s 15) a n d b i g g e r c r y s t a l s o f z e o l i t e
( 1 . 5 v e r s u s 0.8 p ) .
T h e n u c l e a t i o n o f z e o l i t e b e t a is h e n c e e a s i e r when t h e
s y n t h e s i s g e l is p r e p a r e d f r o m p r e c i p i t a t e d s i l i c a , b o t h i n
s t i r r e d a n d s t a t i c c o n d i t i o n s . On t h e c o n t r a r y , s t i r r i n g seems t o
h i n d e r t h e f o r m a t i o n o f ZSH-5. T h i s e f f e c t a p p e a r s i n agreement
w i t h t h e l o c a t i o n o f ZSH-5 e m b r y o s a t t h e e x t e r n a l s u r f a c e o f t h e
a m o r p h o u s g r a i n s ( r e f . 8), w h e r e s t i r r i n g may a f f e c t t h e e p i t a x i a l
cond i t i o n s .

F r ~ mZ.SMk5 t Q ZSM-12
I n t h e p r e v i o u s l y c i t e d e x p e r i m e n t o f s t o i c h i o m e t r y 1.2Na2O.
u r i n g s i l i c a s o l , ZSH-5 p r o v e d
Y . Z T E A 2 0 ~ A 1 ~ 0 s ~ 7 8 S i 0 2 ~ 1 2 8f0eHa~t O
u n s t a b l e on l o n g e r s y n t h e s i s t i m e . The p h a s e c o m p o s i t i o n o f t h e
s y s t e m is r e p r e s e n t e d i n t a b l e 2 a s a f u n c t i o n o f t h e s y n t h e s i s
t i m e . A f t e r t e n d a y s i n h y d r o t h e r m a l c o n d i t i o n s ZSH-12 n u c l e a t e s
a n d ZSM-5 b e g i n s t o d i s s o l v e . A f t e r t w e n t y d a y s ZSM-12 is t h e main
c r y s t a l l i n e p h a s e p r e s e n t . The e v o l u t i o n o f t h e s o l i d c o m p o s i t i o n
i s a l s o r e p o r t e d i n t a b l e 2 . The o r g a n i c c o n t e n t f e a t u r e s a
minimum i n c o r r e s p o n d e n c e w i t h t h e h i g h e r y i e l d o f ZSH-5.
The e l e c t r o n m i c r o g r a p h s o f t h e s o l i d a t d i f f e r e n t s y n t h e s i s t i m e s
a r e r e p o r t e d i n f i g u r e 3 . F i g u r e 3a r e p r e s e n t s t h e z e o l i t e f o r m e d
a f t e r 10 d a y s i n h y d r o t h e r m a l c o n d i t i o n s . T h e X-ray d i f f r a c t i o n
p a t t e r n o f t h i s s a m p l e i n d i c a t e s t h e p r e s e n c e o f t r a c e s of ZSM-12
besides well-crystallized ZSM-5. The s a m p l e c o n s i s t s o f 35 p long
c h a r a c t e r i s t i c e u h e d r a l c r y s t a l s o f ZSM-5.
 609

Fig. 3. Synthesis of ZSM-5 and ZSM-12. Crystallization time, from

top to bottom: ( a ) 10, (b) 15, ( c ) 2 0 d a y s .
610

TABLE 2
P h a s e c o m p o s i t i o n , e l e m e n t a l c o m p o s i t i o n and material b a l a n c e
d u r i n g the 4-~xma!i.ii~n.nf
_zSK:3xd-_zSHzL2,
time crisfa.lLi~fy--% m o l e f r a c t i o n Y-isI d
(days) L e l e m e n t / S i + A l L

._ ZSMz5 __ - ZSK=l2.. -Al-..-.-.--N--_ ---N& -Al-

_Si-
3 amorphous 0.026 0.053 0.027 0.57 0.59
10 70 3 0.022 0.041 0.007 0.83 0.73
15 64 14 0.024 0.045 0.007 0.94 0.89
20 39 40 0.025 0.053 0.006 0.91 0.89

E x t e n d e d t w i n n i n g i m p l i e s t h a t t h e l a t e r a l f a c e s of t h e p r i s m s
a r e e s s e n t i a l l y ( 1 0 0 ) f a c e s . T h e c r y s t a l s p r e s e n t a l s o some l e s s
common f e a t u r e s . T h e i r l a t e r a l f a c e s a r e s p r e a d o f r e c t a n g u l a r
e t c h i n g f i g u r e s , c l e a r l y showing t h a t t h e s y n t h e s i s system h a s
grown u n d e r s a t u r a t e d f o r ZSM-5. This e f f e c t should be accounted
f o r by t h e p r e s e n c e o f a l e s s s o l u b l e c r y s t a l l i n e p h a s e . I n d e e d a
d e n s e p o p u l a t i o n o f s u b m i c r o n p r i s m a t i c c r y s t a l s are embedded i n
t h e ( 1 0 0 ) f a c e s of ZSM-5. T h e smaller p r i s m s a p p e a r t o h a v e g r o w n
up f r o m t h e s u r f a c e p r e c i s e l y o r i e n t e d w i t h r e g a r d s t o t h e ZSM-5
l a t t i c e . T h e i r main a x i s l a y s i n t h e (010) p l a n e a n d f o r m s a 53”
angle w i t h the <loo>direction o f ZSM-5. Also t h e n o r m a l t o o n e
f a c e o f t h e smaller p r i s m s l a y s i n t h e ( 0 1 0 ) p l a n e o f ZSH-5.
I t c a n b e o b s e r v e d t h a t t h e o r i e n t a t i o n of t h e smaller c r y s t a l s
c o u l d c o r r e s p o n d t o 234-12 c r y s t a l s g r o w i n g i n t h e <loo> d i r e c t i o n
f r o m a ( 2 0 1 ) f a c e l a y i n g o n t h e ZSM-5 ( 1 0 0 ) f a c e . T h i s o r i e n t a t i o n
a c c e p t e d , t h e ZSM-12 < 0 1 0 > d i r e c t i o n s h o u l d c o r r e s p o n d t o t h e ZSM-
5 < 0 1 U > d i r e c t i o n . An e p i t a x i a l r e l a t i o n c a n b e f o u n d b e t w e e n t h e
b parameters: 5 . 0 and 1 9 . 9 A , r e s p e c t i v e l y . O r i e n t e d n u c l e a t i o n of
a z e o l i t e over a n o t h e r z e o l i t e f e a t u r i n g e p i t a x y i n only one
d i r e c t i o n h a s a l r e a d y b e e n o b s e r v e d , f o r i n s t a n c e i n t h e case o f
o f f r e t i t e a n d m a z z i t e ( r e f . 14).
F i g u r e 3b d e p i c t s t h e s o l i d f o r m e d a f t e r 1 5 d a y s o f s y n t h e s i s .
The s u r f a c e o f t h e ZSM-5 c r y s t a l s is d e e p l y e t c h e d a n d a h o p p e r
p i t i s open i n t h e ( 0 1 0 ) f a c e s . The s u r f a c e o f t h e l e s s - e r o d e d
c r y s t a l s is s p r e a d o f s l i g h t l y f l a t t e n e d s p h e r e s 3 LI large, with a
r o u g h s u r f a c e . X-ray d i f f r a c t i o n a l l o w s t o i d e n t i f y t h e s p h e r i c a l
c r y s t a l s a s ZSM-12. Some c h a r a c t e r i s t i c p i t s i n t h e ZSM-5 s u r f a c e
seem t o c o r r e s p o n d t o t h e o r i g i n a l l o c a t i o n o f d e t a c h e d s p h e r o i d a l
c r y s t a l s . The i n war d g r o w t h o f a c r y s t a l a f t e r i t s n u c l e a t i o n on
 611

a n h e t e r o g e n e o u s s u r f a c e is a we1 -known p h e n o m e n o n . I t h a s b e e n
carefully described, for instance i n t h e case o f ZSM-5 n u c l e a t i o n
o v e r amorphous s i l i c a ( r e f . 8 ) .
A c h a n g e o f m o r p h o l o g y o f ZSM- 2 f r o m e u h e d r a l p r i s m s t o h i g h -
i n d e x s u r f a c e s p h e r e s i s s u c h a n u n u s u a l phenomenon t h a t i t
d e s e r v e s a comment. I t c o u l d b e e x p l a i n e d o n l y b y a s h a r p r i s e o f
s u p e r s a t u r a t i o n , as i f a p r e v i o u s l y confined source of s o l u b l e
s p e c i e s had b e e n made a c c e s s i b l e t o t h e s o l u t i o n . T h e h o p p e r p i t s
i n t h e (010) f a c e s o f t h e ZSM-5 c r y s t a l s p r o p o s e t h e c o r e o f t h e
ZSM-5 c r y s t a l s a s a p o s s i b l e s o u r c e o f more s o l u b l e s p e c i e s . U n d e r
t h i s h y p o t h e s i s , once t h e o u t e r l a y e r of (100) t w i n n i n g d i s s o l v e d ,
t h e r a p i d d i s s o l u t i o n o f t h e ( 0 1 0 ) f a c e s would i n c r e a s e t h e r a t e
o f g r o w t h o f ZSM-12 b e y o n d t h e t h r e s h o l d o f d e v e l o p m e n t o f h i g h -
index f a c e s from t h e e d g e s of t h e f l a t f a c e s .
The f i g u r e 3 c , r e p r e s e n t i n g t h e s o l i d a f t e r 20 d a y s o f
s y n t h e s i s , c l e a r l y shows t h e growth of t h e f l a t t e n e d s p h e r e s of
ZSM-12, t h e s h r i n k i n g o f t h e ZSM-5 c r y s t a l s a n d t h e d e e p e n i n g of
t h e hopper p i t s i n t h e (010) f a c e s of t h e l a t t e r .

CONCLUSIONS

C h e m i c a l and p h y s i c a l f a c t o r s a f f e c t t h e s e l e c t i v i t y o f
formation of t h e c r y s t a l l i n e p h a s e s t y p i c a l of t h e
tetraethylammonium m e d i a . The i s s u e of b o r d e r l i n e s i t u a t i o n s i n
w h i c h s e v e r a l p h a s e s c a n b e f o r m e d may b e d i r e c t e d b y t h e n a t u r e
of s o l i d s u r f a c e s p r e s e n t i n t h e s y n t h e s i s s y s t e m .

ACKNOWLEDGMENTS

Many t h a n k s a r e d u e t o t h e S e r v i c e C e n t r a l d ' A n a l y s e o f CNRS i n

S o l a i z e f o r e l e m e n t a l a n a l y s i s and t o George Nabias f o r e l e c t r o n
microscopy e x p e r i m e n t s .

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c o m p o s i t i o n o f a c r y s t a l l i n e z e o l i t e , US P a t . 3 , 3 0 8 , 0 6 9 ( 1 9 6 7 ) .
2 J . P e r e z - P a r i e n t e , J . A . M a r t e n s and P.A. J a c o b s ,
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and K2O c o n t a i n i n g a l u m i n o s i l i c a t e g e l s , A p p l i e d C a t a l . , 31
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i o n s , Z e o l i t e s , 8 (1988) 46-53.
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Derouane, D i r e c t i n g p a r a m e t e r s i n t h e s y n t h e s i s of z e o l i t e s
ZSM-20 and b e t a , ACS Symp. S e r i e s , 3 9 8 ( 1 9 8 9 ) 5 1 8 - 5 4 3 .
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ibidem 544-559.
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(1989).
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P a t . 3,832,449 (1974).
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t y p e , ACS Symp. S e r . , 398 ( 1 9 8 9 ) 2 5 7 - 2 7 3 .
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A . N a s t r o and R . A i e l l o , C h a r a c t e r i z a t i o n of c r y s t a l l i n e a n d
a m o r p h o u s p h a s e s d u r i n g t h e s y n t h e s i s o f (TPA,M)-ZSM-5 Z e o l i t e s
( M = L i , Na, K ) . J . Chem. S O C . F a r a d a y T r a n s . 1 , 85 ( 1 9 8 9 )
2749-2765.
10 F . D i R e n z o , F . Remoue, P . M a s s i a n i , F . F a j u l a , F . F i g u e r a s a n d
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( 1 9 8 9 ) 3-11.
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( 1 9 8 9 ) 432-435.
14 F . F a j u l a , F . F i g u e r a s , C . Gueguen a n d R . D u t a r t r e , B i n a r y
z e o l i t i c s y s t e m s , t h e i r s y n t h e s i s a n d t h e i r u t i l i z a t i o n , US
P a t . 4,847,224 (1989).
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K i n e t i c s and m e c h a n i s m o f c r y s t a l g r o w t h o f z e o l i t e o m e g a , ACS
Symp. S e r . , 398 ( 1 9 8 9 ) 4 9 3 - 5 0 5 .
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M . K . Kubin and W . J . R o h r b a u g h , T h e f r a m e w o r k t o p o l o g y o f
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17 J . M . Newsam, M.M.J. T r e a c y , W . T . K o e t s i e r a n d C . H . d e G r u y t e r ,
S t r u c t u r a l c h a r a c t e r i z a t i o n of z e o l i t e b e t a , Proc. ti. S O C .
( L o n d o n ) A, 42il ( 1 9 8 8 ) 375-4135.
18 N.A. B r i s c o e , J . L . C a s c i , J . A . D a n i e l s , D.W. J o h n s o n , M.D.
S h a n n o n a n d A. S t e w a r t , Some a s p e c t s o f t h e s y n t h e s i s ,
c h a r a c t e r i z a t i o n a n d p r o p e r t i e s o f z e o l i t e Nu-2, S t u d . S u r f a c e
S c i . C a t a l y s i s 45A, E l s e v i e r , A m s t e r d a m 1 9 8 9 , 1 5 1 .
19 J . B . H i g g i n s , K.B. L a P i e r r e , J . L . S c h l e n k e r , A . C . Rohrman J r . ,
J . D . Wood, G . T . Kerr a n d W . J . R o h r b a u g h , T h e f r a m e w o r k topology
of z e o l i t e b e t a , Z e o l i t e s , (1988) 446.
G. Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 613
0 1991 Elsevier Science Publishers B.V., Amsterdam

SYNTHESIS OF FERRIERITES WITH HIGH GALLIUM CONTENT

M.A. Camblor*, J.A. Martens, P.J. Grobet and P.A. Jacobs

Laboratorium voor Oppervlaktechemie, Kathol ieke Universitei t Leuven,

Kardinaal Mercierlaan 92, 8-3030 Leuven, Belgium
* on leave from Instituto de Catalisis y Petroleoquimica, C.S.I.S, Madrid,
Spain.

SUMMARY
Ferrierite samples with Ga/GatAl compositions ranging from 0 t o 90% are
synthesized hydrothermally in the presence o f piperidine. The incorporation of
aluminium and gallium in the zeolite is monitored with 27Al, 29Si and 71Ga
MAS - NMR .

INTRODUCTION
The isomorphic substitution of A1 and Si by other elements in the framework
of zeolites is of considerable interest. For example, gallium zeolites possess
surface chemical properties which are different from those o f aluminosil icate
zeolites and have special catalytic properties, e.g. in LPG aromatization
(refs. 1 and 2). A number of (Si, Ga)-analogs o f (Si,Al)-zeolites have been
made by direct synthesis (see e.g. the references cited in ref. 3).
In this paper we report on the synthesis of aluminosilicate ferrierite
samples with extensive isomorphous substitution by Ga. We developed a new
synthesis method according to which alumino-galloferrierites can be obtained
with Si/(GatAl) ratio’s ranging from 7.1 t o 3.4. The gallium content of
alumino-galloferrierites can be considerably higher than the aluminium content
of aluminosilicate ferrierites, for which the lower limit of Si/A1 is ca. 6
(ref. 3).

EXPERIMENTAL
Synthesis mixtures with the following molar compositions are used:
23.3 Na20 : T2O3 : 46.5 Si02 : 18.6 CSHIONH : 976 H20
where T stands for Ga and Al. The Ga/(GatAl) fractions used were 0.0, 0.5,
0.75 and 0.9. The gels were prepared as follows. In a first solution NaOH
(Merck) was added t o waterglass (Merck) with stirring and then piperidine
(Aldrich) was added. The second solution, consisting o f A12(S04)3.18H20
614

(U.C.6) and Ga(N03).xH20 (Janssen) solved i n water, was added t o t h e f i r s t

solution with agitation. The synthesis mixtures were transferred into
s t a i n l e s s steel autoclaves o f 120 m l ; a g i t a t i o n was performed by r o t a t i n g t h e
autoclaves a t 50 rpm. C r y s t a l l i n e phases were obtained a f t e r ca. 22 h o f
crystallization a t 473 K.
The phase p u r i t y o f t h e f e r r i e r i t e products was v e r i f i e d using XRD patterns,
recorded w i t h a Siemens instrument, which was equipped w i t h a Mc Brawn
p o s i t i o n s e n s i t i v e detector. The chemical compositions were determined by I C P .
The MAS NMR spectra were obtained w i t h a Bruker 400 MSL spectrometer. The
experimental conditions used were as f o l l o w s :

Parameter I 29Si I 27Al 1 71Ga

NMR frequency (MHz) 79.5 104.2 122.0

Pulse angle ( * ) 45 20 20
Pulse l e n g t h ( p s ) 4 0.6 0.6
R e p e t i t i o n time ( s ) 3 0.1 0.1
Spinning r a t e (kHz) 3 5 15
Number o f scans 18,000 3000 150,000
Reference f o r chemical s h i f t TMS AlC13 Ga(N03) 2

The 29Si spectra were deconvoluted according to a procedure described

previously (ref. 4).

RESULTS AND DISCIUSSION

The XRD p a t t e r n s o f t h e c r y s t a l l i z a t i o n products are shown i n Fig.1. The
XRD l i n e s which are c h a r a c t e r i s t i c f o r t h e f e r r i e r i t e f a m i l y o f m a t e r i a l s are
present. Traces o f quartz may be present i n samples S3 and S4. The T-atom
composition o f synthesis g e l s and c r y s t a l l i z a t i o n products are given i n Table
1. I t can be seen t h a t the Ga/GatAl r a t i o o f the f e r r i e r i t e product r e f l e c t s
t h a t o f the synthesis mixture.
Scanning e l e c t r o n micrographs o f t h e samples are shown i n Fig.2. Sample S 1
c o n s i s t s o f elongated c r y s t a l s w i t h a l e n g t h o f up t o 20 pm. Some c r y s t a l s
have t h e shape o f hexagonal prisms. I n sample S2 p l a t e l e t and r o d - t y p e
morphologies are observed. The rods reach a l e n g t h o f up t o 40 Fm. Samples S3
and S4 e x h i b i t the p l a t e l e t - t y p e morphology. I t seems t h a t t h e morphology
changes from r o d - l i k e t o p l a t e l e t - l i k e when t h e g a l l i u m content i s increased.
 615

s1

5 10 15 20 25 30 35 40 45 50 55
2e

5 10 15 20 25 30 35 40 45 50 55
2 e

5 10 15 20 25 30 35 40 45 50 55
2e

5 10 15 20 25 30 35 40 45 50 55
2e
Fig. 1. The XRD patterns o f samples S1-S4.
616

Fig. 2 . The scanning electron micrographs o f the samples Sl-S4.

 617

TABLE 1
T-atom c o mp os it i o n o f s y n t h e s i s m i x t u r e and f e r r i e r i t e p r o d u c t s

Sample S y nt h es i s q e l C r y s t a l 1 i z a t i o n Droduct
Ga/(GatAl ) Ga/(GatAl ) S i / ( G a t A l ) Si/(GatAl ) Ga/U.C. Al/U.C.
ICP ICP MAS NMR

s1 0 0 7.6 7.1 0 4.4

s2 0.5 0.4 6.4 5.9 2.1 3.2

s3 0.75 0.7 4.1 4.4 4.7 2.0

s4 0.9 0.9 4.1 3.4 7.4 0.8

D i r e c t evidence f o r t h e A1 and Ga i n c o r p o r a t i o n i n t h e f e r r i e r i t e s t r u c t u r e
i s f o und i n t h e 27Al and 71Ga MAS-NMR s p e c t r a , shown i n F igs. 3 and 4,
r e s p e c t i v e l y . The 2 7 A l resonance a t 54 ppm ( F ig. 3) and t h e 71Ga MAS-NMR s i g n a l
a t 152 ppm (F ig. 4 ) a r e c h a r a c t e r i s t i c o f a t e t r a h e d r a l environment.
The "Si MAS-NMR s p e c t r a o f t h e samples a r e shown i n Fig.5. and t h e
chemical s h i f t v a l u e s o f t h e "Si l i n e s summarized i n T able 2. The "Si
spectrum o f S4, which c o n t a i n s t h e l a r g e s t amount o f g a l l i u m (T able l),
c l e a r l y d i s p l a y s f i v e l i n e s c o r r e s p o n d i n g t o t h e f i v e p o s s i b l e Si(n(A1,Ga))
s t r u c t u r a l s urro u n d i n g s , w i t h 0 < n < 4. I n t h e 29Si s p e c t r a o f t h e S2 and S3
samples, which c o n t a i n i m p o r t a n t amounts o f b o t h aluminium and g a l l i u m , no
d i r e c t d i s c r i m i n a t i o n between Si(nA1) and S i (nGa) s i g n a l s c o u l d be made, s i n c e
no extra splittings in the Si(n(A1,Ga)) lines are observed (Fig.5).
Nev ert heles s , t h e n = 0 l i n e s have a tendency t o s h i f t t o l o w e r ppm values
when h i g h e r Ga l o a d i n g s a r e achieved ( Ta b l e 2); t h e chemical s h i f t v a l u e s o f
t h e Sil(Ga,Al) and SiZ(Ga,Al) l i n e s , f o r example, move u p f i e l d w i t h i n c r e a s i n g
g a l l i u m content .
T h i s i n f l u e n c e o f t h e presence o f Ga on t h e 2 9 S i chemical
s h i f t was a l s o observed i n o t h e r g a l l i u m s i l i c a t e s ( r e f s . 5 and 6 ) . Probably,
a homogeneous d i s t r i b u t i o n o f A1 and Ga i n t h e f e r r i e r i t e framework can be
assumed.
The Si/GatAl r a t i o s o f t h e samples were c a l c u l a t e d f r o m t h e i n t e n s i t i e s o f
t h e i n d i v i d u a l S i (n(A1 ,Ga)) 1 i n e s o f t h e d e convolut ed 29Si s p e c t r a (T able 1).
The r e s u l t s a r e i n agreement w i t h t h e r e s u l t s f rom ICP.
618

Fig. 3. The 2 7 A l MAS NMR spectra o f samples Sl-S4. The *’s indicate the
position o f the spinning side bands.

52

51

Fig. 4 . The 71Ga MAS NMR spectra o f samples Sl-S4.

 619

SiO(AI,Ga)
I
Sil(A1,Ga)
I

Fig. 5. The "Si MAS NMR spectra o f samples Sl-S4.

620

TABLE 2
2 9 S i chemical s h i f t s of S i (n(A1 ,Ga)) 1 i n e s i n f e r r i e r i t e .

Sample 29Si chemical s h i f t s ( m m l

Si4(A1 ,Ga) Si3(A1 ,Ga) Si2(A1 ,Ga) S i l ( A 1 ,Ga) SiO(A1 ,Ga)

s1 / / -99.1 -105.8 -112.4

s2 / / -97.4 -105.1 -112.3

s3 / -90.6 -96.5 -105.2 -112.9

s4 -85.0 -90.5 -96.5 -104.6 -112.6

I f one assumes t h e complete i n c o r p o r a t i o n o f b o t h Ga and A1 i n t h e z e o l i t e

framework, as suggested by t h e absence o f s i g n a l s due t o o c t a h e d r a l
c o o r d i n a t i o n i n t h e 71Ga and 27Al s p e c t r a ( F i g s . 3 and 4 ) , one can c a l c u l a t e
t h e amount o f Ga and A1 atoms p e r u n i t c e l l f r o m a c o m b i n a t i o n o f t h e
Ga/(GatAl) and S i / ( G a t A l ) r a t i o s , measured b y I C P and MAS NMR, r e s p e c t i v e l y
and c o n s i d e r i n g a u n i t c e l l o f 36 T-atoms ( T a b l e 1). S4 c o n t a i n s 7.4 g a l l i u m
atoms p e r u n i t c e l l . T h i s i s a h i g h e r g a l l i u m c o n t e n t compared t o t h e 4.7
g a l l i u m atoms p e r u n i t c e l l i n an a l u m i n i u m - f r e e g a l l o f e r r i e r i t e , r e p o r t e d by
Sulikowski e t a l . ( r e f . 3). A l u m i n o s i l i c a t e f e r r i e r i t e s c o n t a i n t y p i c a l l y 6 o r
l e s s aluminium atoms p e r u n i t c e l l ( r e f . 7 ) . It seems t h a t i n t h e presence o f
g a l l i u m , t h e u n i t c e l l can c o n t a i n up t o 8 t r i v a l e n t atoms (T able 1 ) . The
y i e l d o f z e o l i t e , c a l c u l a t e d as t h e w e i g h t o f t h e p r o d u c t over t h e w e i g h t o f
Si02, Ga2O3 and A1203 i n t h e s y n t h e s i s mixture, i s p l o t t e d against the
Ga/GatAl f r a c t i o n i n Fi g . 6 . I t shows t h a t t h e replacement o f aluminium w i t h
g a l l i u m reduces t h e p r o d u c t y i e l d c o n s i d e r a b l y . When no aluminium was p r e s e n t
i n t h e s y n t h e s i s m i x t u r e (Ga/(GatAl) = l . O ) , t h e c r y s t a l l i z a t i o n o f f e r r i e r i t e
f a i l e d . T h i s r e s u l t suggests t h a t t r a c e s o f A1 a r e necessary, p r o b a b l y a t t h e
n u c l e a t i o n s t a ge o f t h e s y n t h e s i s , and t h a t A1 can be r e p l a c e d by Ga i n t h e
c r y s t a l gro w t h process.
The A1 c o n t e n t p e r u n i t c e l l i s p r o p o r t i o n a l t o t h e a b s o l u t e i n t e n s i t y o f t h e
2 7 A l resonance, as shown i n F i g u r e 7 . The 71Ga a b s o l u t e l i n e i n t e n s i t i e s do
n o t show p r o p o r t i o n a l i t y w i t h t h e Ga c o n t e n t o f t h e u n i t c e l l (Fig.7).
Q u a n t i f i c a t i o n o f t h e g a l l i u m c o n t e n t w i t h 71Ga MAS-NMR i s n o t p o s s i b l e
d e s p i t e t h e use o f a resonance magnetic f i e l d o f 9.4 T, a s t r o n g R F - f i e l d o f
10 mT, a s h o r t RF-pulse o f 0.6 ps and a h i g h s p i n n i n g f requency o f 15 kHz. The
71Ga MAS NMR l i n e s a r e s t i l l b r o a d ( F i g . 4 ) and, p r o b a b l y , s t r o n g l y a f f e c t e d by
 621

a
M
0
'2 3 0
d
.-
0 20
c1
6
N
Irl
m
10
cd
c1
m
h o
6 0.00 0.25 0.50 0.75 1 .oo
Ga/(Ga+Al) in initial mixture
Fig. 6. The yield o f alumino-galloferrierite zeolite as function of the
Ga/(GatAl) fraction in the synthesis mixtures o f samples S1-S4.

120
100

9 80
v
cd 60
n
40
20
0
0 1 2 3 4 5 6 7 8
Al or Ga / (u.c.)
Fig. 7. The 27Al and 71Ga NMR line intensities versus their content per unit
cell in the samples Sl-S4.
622

s p i n n i n g s i d e bands due t o t h e i n c o m p l e t e r e d u c t i o n o f t h e second o r d e r

qu adru polar e f f e c t s .

CONCLUSIONS
The f e r r i e r i t e structure seems to be p a r t i c u l a r l y susceptible t o Ga
i n c o r p o r a t i o n . The l o w e s t Si/Ga r a t i o o f alumino g a l l o f e r r i e r i t e s o b t a i n e d i n
t h i s work i s ca. 4, whereas t h e S i / A l r a t i o s f ound w i t h a l u m i n o s i l i c a t e
f e r r i e r i t e s a r e equal t o o r l a r g e r t h a n 6. Traces o f aluminium seem t o be
necessary i n o r d e r t o c r y s t a l l i z e f e r r i e r i t e s w i t h h i g h g a l l i u m c o n t e n t s . The
g a l l i u m c o n t e n t o f alumino g a l l o f e r r e i r i t e s c o u l d n o t be q u a n t i f i e d w i t h 'lGa
MAS-NMR, even when u s i n g a s p i n n i n g f r e q u e n cy o f 15 kHz.

ACKNOWLEDGMENTS
The a u t h o r s acknowledge t h e Fl e m i s h NFWO and t h e B e l g i a n M i n i s t e r y f o r
Science P o l i c y f o r a r e s e a r c h g r a n t . J.A.M. and P.J.G acknowledge t h e F lemish
NFWO f o r a re s e a r c h p o s i t i o n as Research A s s o c i a t e and S e n i o r Research
A s s oc iat e , r e s p e c t i v e l y .

REFERENCES

1 J.R. Mowry, R.F. Anderson and J.A. Johnson, O i l Gas J., 83 (1985) 128.
2 H. Kitagawa, H. Sendoda and Y. Ono, J. C a t a l . , 101 (1986) 12.
3 B. S u l i k o w s k i and J. K l i n o w s k i , J. Chem. SOC., Chem. Commun., 1289 (1989).
4 P.J. Grobet, H. Geerts, M. T i e l e n , J.A. Martens and P.A. Jacobs, Stud.
S u r f . S c i . C a t a l . , 46 (1989) 721.
5 D.E. Vaughan, M.T. M e l c h i o r and A.J. Jacobson, i n : G.D. St uck and F.G.
Dwyer (Eds.), I n t r a z e o l i t e Chemistry, ACS Symp. Ser. 218 (1983) 231.
6 S. Hayashi, K. Suzuki, S. Shin, K. Hayamizu and 0. Yamamoto, B u l l . Chem.
SOC. Jpn., 58 (1985) 52.
7 P.A. Jacobs and J.A. Martens, Stud. S u r f . S c i . C a t a l . 33 (1987) 217.
 G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 623
01991 Elsevier Science Publishers B.V., Amsterdam

S Y N T H E 5 I S O F ARTIFICIAL %EC>LIYE-LIKF N1O~If:'lAIPJITE

M.Ii.EPBA?iX\', C.B.TP.GIYEV
L!.n4.C-AP.'l~f~h.(-:V,
Irlstitute of Inorganic a n d Fhysica.1 Ckemistry Gf t h e A zerbaijan S S R
Academy of S c i e n c e s , 370143 Baku., Narimanov p r o s p e c t 29, USSF

suR.I MAR 1-
T h e p e p e r clenlsi wit11 kiyclrotl-:errv. e.1 t l cLricfi.>r mation of artificial g k s s e s
into zeolite-.like silica.t€?s,systr?r~leticallS. studied.Syr.thetic mowntainite,teing
a n a n a l o g u e of prirrary n r i r e r a l , w a s p r o d u c e d for t l i e first tir!ic.Ffft:(.t:- (.I
vc:riijt .c I . ~c t c r s , i . e . t e r ~perclture,coricentration,g r a s s grading,nature o f s c l -
ver,t, solid plie.se/liquid p h a s e ratic, on p h a s e forniaticiri w a s c o x s i d e r e d .
Zeolite-.like n a t u r e of sodiuri hydros.ilica.te w e s p r o v e d by radiography.,
t h e r m o g r a ~ i m e t r i c u l , chenlical &nd electrorir;,icro..copic methc.-ds of irivesti -
g,i+tiCIr..

I i i T K ODUCTIOP I
Due to uriique s t r u c t u r a l p r o p e r t i e s a n d wide r a n g e of c h a - a c t e r i u t i c s
ze o lites a r e u s e d iri cateil)rtic, a d s o r p t i o r p r o c e s s e s a n d in vm-ious bran-
c h e s of ratiorial econoniy. To meet gron-irig dec;ands of nioderri t e c h r o l o -
gi cal p r o c e s s e s it i s n e c e s s a r y tG s t u d y a n d select n o v e l nELtLral Emcl
syrithetic alunmiriosilicate s,yster,is which c a n b e u s e d for production of
z eo lites witk? predeterniinec! crysteillirte s t r u c t u r e , compositior. e n d proper-
ties.
In t h e F r o c e s s of z e ol i t e s s y n t h e s i s natural a n d s y n t h e t i c alur.?iriosilica-
tt?s with c r) stallirie arid a ni orphous s t r u c t u r e ( t h e latter being p r e s e n t e d
by gels arid g$rsses) were used 2.5 an iritial s t c c k . High reactivity of
g l a s s e s b ein g ar. a m orphous material arid r i e c e s c i w of reproductiorl o f rla-
tural p r o c e s s . e s with a c t i ve Farticipatiori of n i i r . e r d s formation in labora-
tory, w ad e r e s e e . r c k e s to s t u d y thorotighly ra.w n.aterial.However,ccmplexi-
t-, a n d uristability of chemical c o n i p o s i t i o ~ ,i t s urivaria.Dilit4.,cryste.llic in-
clu.sioris, admixtLires iri natureil g l a s s e s turr-ed r e s e a r c h e s attention to
sy n th etic glasses.
A nuntber of w o r k s has b e e n d e v o t e d to crystellizatiori of zeolites
from v a r i o u s syr~tl-ieticg l a s s e s . O n e of t h e s e i s s y n t h e s i s of zeolite-like
si l icate, e.g. r h ode si t e - hydrosi l i c a t e of alkali a n d alkali-earth metetle.WE
h a v e p r c d L . c e c i two syr:thetic forms-K- a n d Na-rhodesits.It must Ire r.otec!
that z.ccordir.g to its, s t r u c t u r e mountainite a s well a s r h o d e s i t e could b e
r e g a r d e d as n:irierel of c.elhq:elite grc'up.
624

TABLE 1.

Ccmparison of minerals charecteristics

- ~ -
N a m e of Chemical composition Lattice p r r a m e t e r s , A Space
mirt e r a1 group
a b C
-_____ ------- -- I - - - - - ---
&odesite KNa[ Ca2Si8019 ( H 2 0 ) 2] 4 H 2 0 23,8 6,54 7,05 Pnin2

Delheyelite K,Na F a 2 ( E i A1)801g] F, C1 6,56 24,6 7,lO Pmn2

- 2

Hydrcdel-
hayelite KF (H 2 0 ) 44H20
C2 ( S I N ) 7039 6,65 23,84 7,07 Pmri2
4 2
Mountainte K 2 N a 2 k a 2 S i g ) 03 9 ( O H ) 2] 4 H 2 0 3 3,51 13,51 13,51 Pniri2

W..ecdonaldite BaH2 F a 2 S i e O l 9 ( H 2 0 ) 8H20 14,OE

;I 13,08 23,52 CniCnc

Moriteregia.nite K N a 2 [ Y S i80 1 9 ] 10K20 14,OI 23,91 13,09 B m a t

0 r . e c a n s e e analogy- between peranletere a n d chenlice.1 p r o p e r t i e s

of r e L - e r a l minerals and mountairiite. T h i s a n d o g y i s d u e to t h e s t r u c t u -
ral l i k e n e s s of t h e s a i d mir.ernls. Mirierals of t h i s g r o u p h a v e wide
eigkt- nierrber c a v i t i e s * 4A0 , filled with l a r g e ce8tior.s a n d w&er molecu-
les: K + cations a n d water rr.olecules in delhayelite, hydrodelha.yelite,m~un-
tairiite a.rid r h o d e s i t e ; R a 2 + a n d water n i o l e c d e s in macdor:aldite. I t was
found t h a t b a s i c s t r u t u r o l L.r,its of rhodesite / r e f . l / , a n d also h y d r o -
delhayelite / ref.21 and rrountairiite a r e C.ct-octnhedron c o h m r - e.nd two-
dimensiocal r a d i c a l ( two- l e v e l 1cttice) .Colurr.ns a l o n g tk.e r x i s fornlod
by C a - octe.hedr0r.s a r e c o n n e c t e d by wollastonitr c h a i n whick i s arrar.-
g e d aroL1r.d t h e columns s o that two silica- o x y g e n t e t r a h e d r o n s in t h e
s a i d chair1 a r e corijugated witti r i k of Cz- o c t a . h e l r c n s andtk.e third is
c o n n e c t e d with tkle adjacer?t columns. Wollastonite c h a i n s a r e tied by
additional diorthogbGps fornmir g two- le\ el lattice cef t h e chemical com-
positiort [sic;olg]
N.
. Togetk.er t h e y form tt-ireedinier,sic,r.e~lstrL:cture with
zeolite-like cavities. Cations of Ir.etals a n d water n.olecules a r e p l ~ c e c ?in
the c h a n n e l s . Water rrolecules a r e conrNected Icy t-,ydroSerr h0r.d witti
frame tetre.hedrons. Water p&rtially t & k e s p e r t in Ca- atoms coordinaticr.
(fis. 3.).
ME: T H 0 D S
Res,u.lts of s y s t e m a t i c kvestigatiori of crystallization p r o c e s s of syrlthe-
tic gle,ss with chemical composition, m a s s %: S i 0 2 71,6 ; A1203 3,2 ;
 625

Fig.1. Stt cictcire of R h o d e f i t e .

Fe203 0,3 ; CaO 6,4 ; MgO 3,6 ; N a 2 0 14,4 a r e s i v e n in t h e

pres er . t p a p e r . Wk.en treetiris g l a s s powder by NaOW solution s ynthetic
mourtainitc v * a s pt.ciduced for t h e first time. OptirrJuni conditions of syri-
tl:esis were: g l a s s fraction 1 , O O nies,h. ccncentratior,- 1 n solutior. of
NaOE ; g l a s s / solutior. ratior. = 1:Fs ; t e mperature cf s y r , t h e s i s 170 C ;
0

crysta.llizatior time is, 2 0 dr?ys.

E x p e r i a e r t s w e r e c a r r i e d out a t 60- 25OCC with t h e terxperature
0 0
dr o p of f 2 C. In l ow- t e m pe ra t ure experinierlto ( p 90 C ) ql;artz
~ to
g k s s h b e s witk. i nne r volume of 3 0 c m 3 w e r e u s e d . At higker tempere-
h i r e s "Mori" a u t o c l a v e s rr,ade of 45 M h - F T s t a i n l e s s steel of differert of
3
volumes ('7.5, 1 9 . 6 , 13.0, 9 G cm ) w e r e used.Hydrotk~erma1crystalliza-
tior, ar.d r ecr y s t a l l i z a t i on experimerlts w e r e c a r r i e d out in a u t o c l a v e s ,
without building t h e t e m pe ra t ure gra di e nt (&?'=O) and without s tirring
the r eactio n mixture.
After finishing t he experinNer,t e u t o c l a b e was t a k e n out of t h e fur-
n a c e a n d water quer.ched. P r o d u c t s w e r e filtered, w a s h e d u p to pEI=e,
dried a.t 80 c C , horrogenized a n d further StLdied.
Qualitative a n d quantitative ar.alysis of s a m p l e s w a s c a r r i e d out by
powder r~ etl.od orr DEC)b.j-3,0 diffractor. e t e r ( C.LLK d - radia.tion, Ni-filter).
Irrier a n d o u ter s t a n d a r d s K a C I , S i 0 2 ( q u a r t s , ) as well a s p u r e zeoli-
tes w e r e applied. Diffractrometry w a s c a r r i e d out a t a n o d e b-oltage 3 2
kV, c u r r e n t 1 4 mA, velocities 4 ar.d 2 grad/rr.ir. Survey w a s d o n e in t L J e
626

r a c g e of reflection a n g l e s 8 = 2 - 70
0
. Angles m e a s u r e m e n t accuracy
w a s of -
+ o
0.1 .
Thermogravimetrical a n a l y s i s of t h e s a m p l e s was c a r r i e d out in dyna-
mic mode with t h e u s e of “(3- Derivatograph 1500-D” of Eiurigariari firm
MOM. T e m p e r a t u r e r a n g e w a s within 20
0
- 1000°C.
0
S u r v e y conditi0ns:heating r a t e i s 10 /min ; pa.per t r a v e l s p e e d is 2,s nim/

miri ; sensitivity of DTA, D T G a n d TG i s 500 rniV; ceramic cubicles were

u s e d ; standa.rd i s A1203.
Chemical s i l i c a t e a n a l y s i s of th.e nitial material a n d of prrJducts Of

transformation WBS c a r r i e d out with t h e u s e of niultichannel X-ray CPW

- 18 s r e c t r o m e t e r ( W e s t G e r m a n y ) .
M e e s u r e m e n t mode: P d - ar.ode ; v o l t a g e i s 2 5 kV; c u r r e n t i s 7 0 niA; ex-
- -- -- ~-- -
p o s u r e period i s 1 0 0 s ; sensitivity’ limit
-2
i s 1 0 . S a m p l e s for ariG1~~sis
w e r e p r e p a r e d a s ftrllbws: t h e s u b s t a n c e beir.5 a n a l y s e d w a s fLsed with
0
f1v.x Li B 0 ( r a t i o 3. : 1 0 ) a t 1 2 5 0 C. Ohttiiried g l e i s s WES powdered
2 4 7 2
up to 300 m e s h a n d p r e s s u r i z e d at 2 0 ton / c m with time l a g of 1. minu-
te.
Electronmiroscopic investigation w a s c a r r i e d ol;t with t h e u s e of e l e c -
tron s c a r i n i r g m i c r o s c o p e B S - 3 0 1 ‘TESLA. T h i s vetkiod a l l c ~ w sto irives-
t i s a t e s p z c e a n d time relatioriship of microtlrysteils. It hits been shown
that t h e s e relationships a r e more complicated thar. t h o s e obteiir e d by ro-
entyenonl etry.

RE; SUL’I’S
Diffredonietry d a t a for synthetic rrokntainite (Table 2 )
d a t a for i t s n a t u r a l a n a l o g u e /ref. .?I.
TARLE: 2.
Ciffrectometr)- d a t a f a r s y n t h e t i c moLnteir.ite ar.d i t s thermally t r e s t e d
C
( a t 370 C ) fvrr.;.

---
Mourlttrinite --
0
d A0 J P. J
exp I dexp 9

13,18 90 11, 24 46
6,58 90 6,38 6
6,OO 16 5, 7 8 52
5, 59 14 4, 3 6 8
4,72 62 4, 06 1c
4,18 44 3,9 2 5
3,76 16 3, 06 21
3,62 11 2, e9 26
3,41 25 2, 7 7 16
3,22 13
3,04 21
2,92 100
 627

2, 84 36
2, 70 18
2, 34 23
1, 96 32
1, 74 22

Mounta.inite i s crystallized iri mor1ocliriic systec. with t h e fcillovuing

p a r a m e t e r s of w.it cell: a= 13,53 A
0
, b = 13,O.S A@, c = 13,53 A
0
.
3
VolLme of the unit cell i s 2 4 2 8 A .
To determine relative s t a t i l i t y of newly fcjrnied p h a s e s orid tc: estotr-
lish their ste.bili@ limits influence of v a r i o u s p m a n l e t e r s of syntkiesis ori
p r o d u c t s crystetllizi’.tiori in this s y s t e m w a s studied.
Influence cf temperature. To c r e a t e fo\-orc?..ble conditions for t h e transfor-
miition of t h e ir.itial raw material into rriouritainite a n d a t t h e sane time
to s u p p r e s s q u a r t z formation optinla1 temperature region w a s s e a r c k e d . I n
spite of coniplexity of tt:e prot,len: c a u s e d by pi.opensib of c . q s t a l l i z a t i c n
of both niir e r a l s to high-teniper&tLire conditions, coritrolliriy hydrothernial
crystallizatior; we singled out wide t e m p e r a t ~ i r eregiorr of riiaxirnurri yield
of nicmntairiite c r y s t a l s 150 - 195
0
C . Syr:tk.esis of nlol;r.t&inite from
higher temperatures g a v e r.0 r e s d t . TemperatLre r i s e r e s u l t e d in c h a n g e
of reaction direction, witti fornation of pec tolite. Higher teniperatu-es
bL.t low cor.centrations of solutions a r e more prefers.ble fcr ec‘ucing
quarts rather than pectolite. Attempts to s y n t h e s i z e mouritiiinite s t teni-
0
peratures lower than 150 C were unsuccessful.
Influence of concentration. A s a therrnd solution sodium bydroxide w a s
-- - __- - - -__ - - -- -
c k o s e n . It w a s found t k t c h i w g e CJf ccirocc~ntrfiticn had greatly inf1uer.c-
ed pl-lase formatior.. I n c r e s s e o f tkie solution pH prcrniotes solubility Gf

gle.ss.es, h r e a k i n g down their silica- o x y g e r lattice. In 0,3 N NaOH SO-

I~itiori as.r.ccintiorl of p11i:c-ez. Q z + F c i s crystiilliaed arid in t h e c o u r s e

of r i s i n g solu.tior, cor!cer.tra.tior. from 0 , 3 N to l,ON abovesaicl essocieticin
i s su.bstituted by n,ountainite ( T a b l e 3 ) . I n c r e a s e in coficer.trettion of
NaGHcclutior, u p to 1 K l e a d s to destruction of rhodesite. F u r t h e r r i s i n g of
cor.certratiori of N a O E solution fron lr’! to 2N a n d more w l f a v o u r a t l y in-
f l u e n c e s the p r o c e s s of nlourrta.inite cry-stalliz.eticr. Mear:wkiIf? syt>thc?tic
mounteinite i s b e i n s reple.ced by- pectolite.
1nfluer.ce of s o l v e n t riatL re. In our e x p e r i n er.ts direction of t h e crystalli-
- - - -- -- -- - - - - - - - -
za,tior p r o c e s s w a s determiried f:y ttie s.ol\.ent nature. At t h e i d e c t i c a l
concentratior.s of h’a- c a t i o n s but with ce.rlr*onate solL.tion acting, c r y s t a l -
lization of mountainite d e c e l e r a t e s ar.d forniaticln of k,oth n.,c)uritairiite
and quertz i s o b s e r v e d , t h e latter o n e predomina.tiny. At low cor,centra-
628

tiori of P\’a2C03 solution q u a r t s i s formed, a t ccncentraticir: of 1 N asso-

ciation of cluartz a n d r h o d e c i t e apFeara.. Mour.ta.inite i s not crq’stdlized
urider the action of soliunl c a r b o n a t e solution.
I r f l u e n c e of solid p h a s e /liquid p h a s e ratio. Glass/solu.tior; ratio g o v e r n s
pot only cor.ipositior of mother liquor, but e k o conipcjsitic,r: a.nd structL r e
of t h e products. In t h e c o u r s e cf interaction of alkali s o l u t i o n s with s i l i c a
rich g l a s s ratio glass/ solution g r e a t h , i n f l u e n c e s t h e p r o c e s s of p r o d c c -
ts crysterllizatior ( T a b l e 3 ). Obtained exprriniental dwta confirm obser-
vation of the p r o c e s s of silica- r i c h z e o l i t e s formation. Thus., a t l o w so-
lution / gJnss ratio boundery k y e r i s s a t i a t e d witL S i 0 2 a n d alkali catinrls
n e c e s s a r y for silica-rick z e o l i t e s formatior.. At high solution / g l a s s ratio,
i. e. a t soluticri excess, s i o ,
L.
diffuses from t h e t o u n d a r y l a y e r of s o h . -
tion to more f r e e s p c c e , a n d pec.tolite c r rkJodesite r a t h e r tk.an mountaini-
te i s formed.

TABLE 3.
Ccnditions a n d crq.stallizetiori p r o d u c t s of silica- r i c h g l a s s i r NaOH ar.d
N a 2 C 0 3 so1utior.s

_ _ - --_ ---- ---

___----------c___----
___ _I- --
i
m Ccr.centration Concentration Solid F h h s e TeniFerature, F r o d L c t s
of NaOH,N of N a 2 C 0 ,hT liquid p h a s e o
C
ratio
--- -- I--_
~ --- -- - - - ~
1 0,3 25 170 Mn
2 0,3 1:10 170 Rd
3. 0,3 1:15 200 45: + Rd
4. 03 1:5 170 Rd + Mn
5. 085 1:1 5 170 Rd
6. 0,5 1:15 PO0 Rd
7. 0,5 1:5 200 92
8. 1 1:5 170 Mn
9. 1 1:3 170 amorphous
10. 1 1:5 150 a n 1 CI r p k 10LI s
11. 3 1:5 1eo hlrr + P c
3 2. 1 1:1 5 200 Pc
13. 1 1:5 200 Pc
14. 1 1:10 170 Pc
1 5 2 - 6 1:5 170 Pc
16. O,-? 1:5 170 Qz
17. 0: 5 1:5 170 Qz -t Rd
18. 1 1:5 170 amorphous
19 1 1:5 200 on.orplious,
Note: hln - mountainitc
Rd - rk.odecite
Qz - quartz
Pc - pectolite
 629

It could b e s e e n from T a b l e 3 that solid p h a s e / liquid p h a s e ratio cor-

respor.ding to 1:10 l e a d s to d i s a p p e a r a n c e of n ountainite a n d i-..olation
of pectolite. At 1 N concentration of NaOH solution cryste.llization of so-
diun. r h o d e s i t e i s o b s e r v e d . A s to lower r a t i o n s solid pklase/ liquid p h a s e
- e.g. 1:3 - s u c h proportions a r e unefficient for p h e s e formation in tk-.is
system.
Thermogravimetrical investigations s h o w that dehydration of synthetic
mountainite i s continuous , whick c o r r e s p o n d s to t h e 3--5t type of d e -
hydratior c h a r a c t e r i s t i c of zeolites. DI'A c u r v e of nlom-lta.inite den;onst -
0
eristic t h r e e endo- a n d tvro exo-effects. Ecclotkrermal p e a k s a t 1 7 0 and.
320° C w e r e indticed Icy dehydration of water which got lost r e v e r s i b l y
0
at 340 C. Water losses constitute 3.2,A %. Week exotk.ermal band a t 3 7 0 ° ~
could b e a s c r i k e d to destruction. Diffraction d a t a of t h e n e w p r o d u c t
0
a p p e a r i n g a t 370 C a r e given iri T a b l e 2. Smee.rir.g of endo-therrral peak
0
a t 7 2 0 OC could b e ascrik,ed to fLsior, exo- effect a t 8 3 5 C- to produc-
tion of pseudowollastonite.
Chemical conipositiori of synthetic mour.ta.ir.ite i s ( m a s s %): Si02- 55,
43; CaO - 1 4 , l l ; hIg0 - 2,61; K 2 0 - 3,79; N a 2 0 -
11,38; H 2 0- 12,8.
It i s known that c r y s t a l s of nature.1 niounteinite a r e fibrous formaticrs
/ref. 31. Electron microccoFic investigction h a s shown that crystetls of
synthetic mountainite c o u l c b e not only fibrous, but also needle-like
ar.d in the form of thin pellets.
When studying ior.- e x c h a n g e ability of synthetic mountainite in rela-
2+
tior, with N H K a n d C.a c a t i o n s singnifica.ct c h a n g e s in i n t e n s i t i e s of
4.
+

' 0
reflections d = 13,18; 6,58; 3,22 A were observed.
R e v e r s i b l e chare.cter of dehydration, ion-exchange ability, p r e s e n c e
of specific cavities, c h a r a c t e r r i s t i c for z e o l i t e s , in tkje s t r u c t u r e cor.firr.
that rr.otir.tainite b e l o c g s to s i l i c e t e s having z e o l i t e s piroperti es.

R E F E R E N CE S

1. H.P... H e s s e " Verfeinerung d e r s t r u c u r d e s R h o d e s i t s H K 2 C a 4 S i 1 6

O Z 8 . 1 0 H 2 0 . " Zeifur Kristallograpl-y 1 9 8 7 , V 178, N 1-2, p.99-98.

2. Rd. D. P o r f n a n , M. I. Chiragov, Noviye darmiye c mineralack S S S R ,

1 9 7 9 , NO. 28, p. 172-175

r h o d e s i t e a n d mountainite" .
3. J. P. C-ard, H. F. W. Taq-lor, "An irivcstigation of tvro r e w minerals:
Mireral. Was., 1957, V. 31, p. 611-623

4. R. H. Mariner, R C S u r d a n o , "Alkaliri a n d forrt1e.tic.r c.f zeolites in

s a l i n e alkaline lakes". S c i e n c e , 1 9 7 0 , V . 70, p. 977-582
This Page Intentionally Left Blank
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 63 1
0 1991 Elsevier Science PublishersB.V., Amsterdam

THE D I S T K I B U ' r ~ O N OF IRON I N Z S M - 5 TYPE IRON CONTAINING ZEOLITES

AND FERRI SI L I CATES: ACIDIC AND CATALYTIC PROPERTIES

G . VOREECK, M. RICHTER, R. FRICKE, B. PARLITZ, E. SCHREIER,

K . SZULZEWSKY and E . ZIBROWIUS
lnstitute of Physical Chemistry, Academy o f Sciences, 1199 Berlin,

SUMMAKY
The state of iron in microporous ferrisilicates with MFI -
structure as well as in template free synthesized FeZSM-5 zeolites
has been examined by XRD, IR, ESR, Si MAS NMR, ammonia TPD, and
catalysis. The percentage of iron in the ferrisilicate framework
could reliably be determined by two independent methods, ammonia
TPD and Si MAS N M R . Catalytically, the Fe related acid sites are
weaker than those of the parent ZSM-5 but. nevertheless, they
isomerize m-xylene and convert ethylbenzene. Nonframework iron
dehydrogenates ethylbenzene to styrene, where the selectivity
correlates with the amount of nonframework iron.

INTRODUCTION
One possibility to modify the acidic and catalytic properties of
zeolites and zeolite-like metallosilicates (1) consists in varying
their chemical composition at the stage of synthesis.
Advantageously, this a1 lows the tailored design of active
molecular sieve components via substitution of A1 or Si by several
elements (e. 8 . E, Ga, Cr, V, Co, and others) ( 1 - 15). Iron
containing zeolites or pure ferrisilicates with MFI structure are
of special interest as catalysts for the conversion of several
aromatic compounds, above a l l C 8 nlkylaromatics. Numerous
investigations have been performed in order t o confirm the
incorporation of iron into the molecular sieve framework and to
reveal the nature of iron in both framework and nonframework
positions (1,16 - 2 6 ) . Incontestably, the location and the state of
iron are essentially for their acidic, catalytic and
shape-selective properties. But the knowledge about the exact
distribution of iron between the lattice and channels is still
incomplete. Therefore, this contribution emphasizes the
quantitative determination of iron throughout the matrix of
aluminum free ZSM-5 type ferrisilicates. The consequences for the
aciditiy and catalytic activity of the samples are discussed and
the results are related to reference samples such as iron
632

containing ZSM-5 zeolites, where aluminum is only partially

r e p l a c e d by i r o n , a n d a p u r e ZSM-5 z e o l i t e .

EXPERI MENTAL
Samale w&am.Lu?n
. . .
- . .
( i ) Perrlslllcates ( F e S i 1 ) . T h e A 1 f r e e f e r r i s i l i c a t e s with
Z S M - 5 s t r u c t u r e were s y n t h e s i z e d b y m X i n g a n a c j.d s o l u t i o n of
i r o n s u l f a t e w i t h h a l f t h e v o l u m e of a s o d i u m s i l i c a t e s o l u t i o n a t
room t e m p e r a t u r e . An a q u e o u s s o l u t on o f tetrapropylammonium
bromi de and t h e r e m a i n d e r o f t h e d i l u t e d so d iu m s i l i c a t e s o l u t i o n
were a d d e d t o t h e r e s u l t i n g g e l ( a f t e r a n a g i n g p e r i o d o f 1 h ) . T h e
mixture w 3 s s t i r r e d f o r 1 h, then placed i n a t e f l o n coated
s t a i n l e s s s t e e l a u t o c l a v e an d k e p t u n d e r a u t o g e n o u s p r e s s u r e a t 4 4 3
K f o r 48 h . The r e s u l t i n g w h i t e o r p a l e y e l l o w s o l i d was filtered,
washed a n d d r i e d a t 383 K . T h e t e m p l a t e was removed b y calcination
a t 773 K f o r 7 h i n a i r f o l l o w e d b y a t h r e e f o l d e x c h a n g e o f Na'. by
NH4+ i . o n s a t 353 K for 2 h . AAS was u s e d f o r a n a l y s i s ( T a b l e l a ) .
. .
( i i j E.e contalnlna Z S M - 5 0 . Ferric nitrate, sodium
a l u m i n a t e , s i l i c a s o l a n d s o d i u m h y d r o x i d e were used as starting
materials f o r t h e s y n t h e s i s . S i l i c a s o l was added to a diluted
solution containing the aluminate, t h e sodium hydroxide a nd the
f e r r i c n i t r a t e . T h e m o l a r r a t i o s o f t h e c o m p o n e n t s were: 2-8 N a g O *
(Al2O3+FezO3j * 3 0 - 9 0 S i Oz *
6 0 0 - 2 , 5 0 0 HzO. The r a t i o Fe 203 : A 1 2 0 3
was v a r i e d b e t w e e n 0 . 1 a n d 0 . 8 . Th e c r y s t a l l i z a t i o n o f t h e z e o l i t e s
was p e r f o r m e d h y d r o t h e r m a l l y u n d e r a u t o g e n e o u s p r e s s u r e w i t h i n 8 -
24 h a t 4 5 3 - 4 8 3 K . T h e a d d i t i o n of s e e d c r y s t a l s ( a b o u t 3 w t . % of
ferrisilicate) was f o u n d t o b e n e c e s s a r y f o r p r o m o t i n g the
c r y s t a l l i z a t i o n p r o c e s s . Ho wev er , n o o r g a n i c t e m p l a t e was n e e d e d .
The r e m o v a l o f Na+ cations in the as-synthesized products was
a c c o m p l i s h e d b y i o n - e x c h a n g e ( T a b l e l b ) . T h e f i n a l ammonium f o r m o f
t h e z e o l i t e s c o n t a i n e d less t h a n 0 . 1 w t . % N a p O . T h e d e s i g n a t i o n of
t h e samples is t o be read as HFeSil for the H form of the
f e r r i s i l i c a t e s r e s p . HFeZSM-5 f o r t h e i r o n c o n t a i n i n g z e o l i t e s . The
a n a l y t i c a l (Si0z/Fez03)z r a t i o s are g i v e n i n p a r e n t h e s e s .
( i i i ) Reference samples.A c o m m e r c i a l ZSM - 5 p r o d u c t (HS 3 0 ,
C h e m i e - AG Bitterfeld) i n t h e H form a s well a silicalite
as
i m p r e g n a t e d w i t h a F e( N0 3 ) 3 s o l u t i o n t o r e a c h a n i r o n c o n t e n t o f 1
w t . % a f t e r c a l c i n a t i o n ( 7 7 5 K , 2 h ) were u s e d a s reference (Table
lb).
 633

TABLE 1
List of samples and characterization data
a) ferrisilicates

a
NH3 desorbed T~(KP
Overall Htpd

HPeSil (58) 91 0.44 0.25 657 130 45

HFeSil (74) 97 0.45 0.25 653 129 58
HFeSil (76) 97 0.47 0.26 648 126 61
HFeSil (78) 84 0.45 0.31 655 104 75
HFeSil (94) 98 0.40 0.25 653 132 72
HFeSil (155) 91 0.29 0.19 64 5 172 89
HFeSil (180) 95 - - - -
HFeSil (259) 86 0.14 0,12 274 93
HFeSil (508) 68 0.10 0.06 520 97

b ) iron containing zeolites

Sample ( sio2)
Fe203 E
( sio2
Me203
fe203
Z A1203
1 cXRDe
Z
NH3 desorbedb
Overall Htp
d Tm(K)'

HFeZSM-5 ( 1 5 2 ) 36 0.31 90 1.07 0.57 705

HFeZSM-5 ( 1 1 8 ) 40 0.52 87 1.04 0.54 695
HFeZSM-5 (100) 41 0.70 80 0.99 0.53 680

HFeZSM-5 ( 0 ) 40 0.00 100 1.30 0.84 720

a: Crystallinity parameter, estimated from n-hexane adsorption,

b: Desorbed ammonia in inmol/g,
c: Temperature of the peak maximum (high temperature peak),
d : High temperature peak,
e: Crystallinity parameter derived from XRD,
Subscripts X. and f: Analytical r e s p . framework values,
Me: sum o f Fe and Al,
%Fef: percentage of framework iron.

SamDle characterization
The XRD data were obtained with a HZG 4 diffractoineter by using
qi-filtered Cu K, radiation. IR spectra were recorded with a
Specord M 85 (Zeiss Jena) using the KBr pellet technique. ESH
measurements were performed with a ZWG ERS - 220 X - band
634

s p e c t r o m e t e r a t 7 7 an d 2 9 5 K. T h e 2 9 S i HAS N M K s p e c t r a were
measured with a B r u k e r MSL 400 s p e c t r o m e t e r a t a r e s o n a n c e
f r e q u e n c y o f 7 9 MHz u s i n g s i n g e - p u l s e e x c i t a t i o n w i t h high-power
p r o t o n d e c o u p l i n g . NH3-TPD m e a s u r e m e n t s were c a r r i e d o u t a t n o r m a l
3
p r e s s u r e i n a f l o w r e a c t o r w i t h He a s c a r r i e r g a s ( f l o w r a t e 1 cm
s - l j c o n t a i n i n g 3 Vo1.X o f NH3. T h e h e a t i n g r a t e a m o u n t e d t o 12 K
min-l. Sample w e i g h t s of 200 mg were used (mesh size 25-60).
Details are g i v e n e l s e w h e r e ( 2 9 ) .

B d s o r D t i q n and catalvsis
A f t e r a c t i v a t i o n in VUCUO ( p < = Pa, T = 570 K , t > = 5 h)
t h e f e r r i s i l i c a t e s were c h a r a c t e r i z e d b y i s o t h e r m a l a d s o r p t i o n a nd
d e s o r p t i o n of n-hexane (T = 293 K , 0.02 <= p/p
S
<= 0.9, ps
saturation pressure) using a McBain balance. The crystallinity
parameter CAds was e s t i m a t e d b y r e f e r r i n g the experimental
s a t u r a t i o n v a l u e a t p/p, = 0 . 5 t o t h e c a l c u l a t e d m i c r o p o r e v o l u m e
3
o f a n i d e a l MFI s t r u c t u r e ( 0 . 1 9 cm / g > . A d s o r p t i o n d a t a f o r b e n z e n e
a n d water o f t h e template f r e e synthesized Fe-ZSM-5 samples are
reported i n Ref. ( 2 9 ) .
Both t h e conversion of ethylbenzene and the isomerization of
m - x y l e n e were c a r r i e d o u t i n a fixed-bed, continuous glass
flow
r e a c t o r ( 2 cm i n t e r n a l d i a m e t e r ) a t a t m o s p h e r i c p r e s s u r e a n d a
s t a n d a r d f l o w r a t e o f 1 0 1 h-' h y d r o g e n , l o a d e d w i t h 1 V o 1 . X of t h e
o r g a n i c s u b s t r a t e . I n e i t h e r case 1 8 : of t h e b i n d e r - f r e e zeolite
p o w d e r i n i t s H f o r m was u s e d ( m e s h s i z e 2 5 t o 6 0 ) . D e t a i l s c a n b e
f o u n d i n Ref. ( 2 9 ) .

RESULTS AND DISCUSSION

. .
C r v s t a l l l n l t v andclualltativecDnfirmatlon
. Q€ Lhe i n c o r t o r a t i Q n Q €
irpn
A c c o r d i n g t o t h e XRD p a t t e r n a l l s a m p l e s a r e well crystallized
a n d show t h e t y p i c a l r e f l e c t i o n s of t h e MFI s t r u c t u r e . I n t h e case
o f t h e FeZSM-5 zeolites some ZSM-11 admixtures were d e t e c t e d .
N e v e r t h e l e s s , t h e c r y s t a l l i n i t y C X R D o f t h e samples i s h i g h , b u t i t
obviously d e t e r i o r a t e s with increasing iron content ( c f . Table l b ) .
In c a s e of t h e f e r r i s i l i c a t e s w h i t e and p u r e c r y s t a l l i z a t i o n
p r o d u c t s were o b t a i n e d f o r a ( S i 0 2 / F e 2 0 3 ) x r a n g e o f a b o u t 50- 150
i n t h e s y n t h e s i s g e l . H i g h e r r a t i o s l e a d t o t h e a p p e a r a n c e o f an
a l i e n p h a s e ( q u a r t z ) . Lower r a t i o s r e s u l t i n p r o d u c t s o f a s l i g h t l y
y e l l o w c o l o u r i n d i c a t i n g t h a t a p a r t of t h e f e r r i c i o n s r e m a i n e d
o u t s i d e t h e f r a m e w o r k . T h e l a r g e l y p u r e f o r m a t i o n o f t h e ZSM-5
 635

s t r u c t u r e i s c o n f i r m e d by t h e r e s u l t s o f n - h e x a n e adsorption (cf.
T a b l e 1 ) . T h e v a l u e s o f t h e r e a l m i c r o p o r e volum e f o r m o s t of the
samples were f o u n d t.0 be near the theoretically calculated pore
v o l u m e o f a n i d e a l MFI s t r u c t u r e ( 0 . 1 9 cm 3/ g ) . T h e h i g h v a l u e s o f
t h e c r y s t a l l i n i t y parameter C A c o n f i r m the successful synthesis.
The low Cads v a l u e o f H F e S i l ( 5 0 8 ) o b v i o u s l y comes a b o u t b y t h e low
a d s o r p t i o n c a p a c i t y of t h e a l i e n quartz phase. Figure 1
d e m o n s t r a t e s t h e m o d i f i c a t i o n of t h e u n i t c e l l volume w i t h t h e i r o n
c o n t e n t . A t i n c r e a s i n g i r o n c o n c e n t r a t i o n ( d e c r e a s i n g (Si02/Fe203)=
r a t i o s ) t h e u n i t c e l l is expanded d u e t o t h e different length of
t h e S i - 0 and F e - 0 b o n d s . This r e s u l t p r o v e s t h e i n c o r p o r a t i o n o f a t
l e a s t a c e r t a i n p a r t o f i r o n atoms i n t o t h e l a t t i c e . S z o s t a k e t al.
(21) found similar r e s u l t s f o r a n a l o g o u s f e r r i s i l i c a t e s .

0 100 200 Si02/Fe203

F i g . 1. Expansion of t h e u n i t c e l l volume V u . c of ferrisilicates

w i t h i n c r e a s i n g i r o n c o n t e n t ( d e c r e a s i n g (Si0,/Fe2O3>, ratio).

1 2
I

3 Fe/UC
-
F i g . 2 . D e p e n d e n c e o f t h e wavenumber v f o r t h e T-0-T vibration on
t h e i r o n c o n t e n t per u n i t c e l l F e / u . c .

IR spectroscopy provides further evidence for the iron

636

i n c o r p o r a t i o n . A s shown i n F i g u r e 2 t h e a b s o r p t i o n band at about

llUll cm-l w h i c h is u s u a l l y a s s i g n e d t o t h e a s y m m e t r i c T - 0 - T lattice
v i b r a t i o n s h i f t s t o l o w e r wav en u mb er s w i t h i n c r e a s i n g i r o n c o n t e n t .
'This s h i f t o r i g i n a t e s f r o m t h e d i f f e r e n t a t o m i c w e i g h t s a nd radii
of s i l i c o n a n d i r o n . The e x t e n t o f t h e shift corresponds to the
number of iron atoms isomorphously substituted for silicon.
4 : o t a s t h a n e eL el. (2'1) found an analogous diminution of the
u a v e n u m b e r c o m p a r i n g a HZSM-5 a n d a FeZSM-5 z e o l i t e .
Finally, the incorporation of iron i n t o t h e framework is also
c o n f i r m e d by ESR s p e c t r o s c o p y . A l t h o u g h t h e d e t a i l e d i n t e r p r e t a t i o n
a f t h e ESR s p e c t r a i s s t i l l a m a t t e r o f d e b a t e ( 2 3 , 2 5 , 2 6 , 2 8 ) there
is a f a r - r e a c h i n g a g r e e m e n t t h a t t h e b r o a d s i g n a l a t g = 2.0 a nd
the signal a t g = 4.3 indicate octahedrally a nd tetrahedrally
c o o r d i n a t e d i r o n s p e c i e s i n n o n f r a m e w o r k and franiework positions,
r e s p . . b o t h t h e FeZSM-5 z e o l i t e s an d t h e F e S i l s a m p l e s show these
two s i g n a l s d e m o n s t r a t i n g t h e s u b s t i t u t i o n o f i r o n f o r silicon in
t h e frameworks a s well as t h e l o c a t i o n of i r o n i n t h e c h a n n e l s .

d e t e r l n i n a t i o n p f u i r n n distrlb .vtion between

franlework and nonframmd !GLQSiLiQns
Mi3 T L F i g u r e 3b s h o w s t h e N H 3 TPD s p e c t r a o b t a i n e d f o r H P e S i l
- ' i v r ~ l e sw i t h different overall iron contents. The amounts of
ammonia
~ i e ~ ~ . ~ ~ l : ~ ~a d
r e s u mn i ar i zed i n T a b l e l a . The e s t i m a t i o n o f the
'<i(J ;,/Ft+. O j rramework r a t i o is based on the a m ount of ammonia
& L
r e p r e s e n t e d by t h e a r e a of t h e h i g h t e m p e r a t u r e peak ( c f . T a b l e
la). R e a s o n a b l y , it. is as s u med t h a t o n e ammonia is a d s o r b e d a t o n e
ijr-iisted s i t e c r e a t e d b y t h e i n c o r p o r a t i o n of iron into the
f e r r i s i l i c a t e f r a m e w o r k . 'The r e s u l t i n g d a t a a r e c o n t a i n e d i n Table
l a . As expec-:t.ed t h e p a r t o f i r o n s u b s t i t u t e d f o r s i l i c o n atoms is
high a t low u v e r a l l iron contents and decreases markedly with
h i g h e r i r o n c o n c e n t r a t i o n s . Ho wev er , a s m a l l a m ount of iron can
a l w a y s tgc f o u n d i n n o n f r a m e w o r k p o s i t i o n s , e v e n a t v e r y low o v e r a l l
iron contents. Figure 4 illustrates the distribution for the
t e r r i s i l i c a t e samples.
S o l i d P t a t a WE -&OSCODY, Th e "Si MAS NMR s p e c t r o s c o p y has
become a routine met h o d for the determination of Si02/AlZ03
f r a m e w o r k r a t i o s i n a l u m o s i l i c a t e s (31). T h e d e t e r m i n a t i o n of the

-
Sic)?/Pe 0
2'3
f r a m e w o r k r a t i o i n f e r r i s i l i c a t e s is e x p l a i n e d by help
of F i g u r e 5 which shows a typical "Si MAS NMR spectrum of a
f e r r i s i l i c a t e s a m p l e . Two s i g n a l s c a n b e d i s t i n g u i s h e d : a n i n t e n s e
a s y m m e t r i c l i n e a t a h o u t -113 ppm w h i c h i s c a u s e d b y s i l i c o n a t o m s
 637

655

Fig. 3. NH3 TPD profiles of zeolites and ferrisilicates

a) comparison of (1) HZSM-5(0), (2) HFeZSM-5(100), (4) HFeSil(94)
b ) Influence o f the iron content on the NH3 TPD profiles o f the
ferrisilicates HFeSil(78) (3), 94 (4), 155 ( 5 ) , 259 ( 6 ) . 508 (7).
Note that a) and b) were recorded at different magnification (cf.
curve 4 )

0 2 4 6 8 10 12 11 16 18
Overall iron content
(Fe203/Si02) x lo3

Fig. 4. Distribution of iron versus the overall iron content of the

ferrisilicate series according to ammonia TPD.

4
bonded via oxygen to four other silicon atoms (Q ( O F e ) ) ( 3 1 ) and a
shoulder at about -104 ppm which is assigned to silicon atoms
4
surrounded by three other silicon atoms and one iron atom (Q (1Fe))
(20). An evaluation of the Si02/Fe203 framework ratio is based on
the relative intensities of these two signals but has to account
3
for the fact that silanol groups in silicalite (Q (OFe)) exhibit a
resonance line at the same position o f -104 ppm as the
638

I I . l , l l l l , l, , I , I , , , , I , , , I, , , , , I , , , , , , , , I , , ,

-90 -1 00 -110 -1 20 -130

q -
Fig. 5. &'Si MAS N M K spectrum of sample HFeSil(76).

configuration Q4 (1Fe) (31,32). Therefore, the amount of silanol

groups was determined by 'H MAS NMR (33). A value of ( 8 ~ 2 ) 1019
SiOH g-l was found for all samples. After substraction of the "Si
MAS N M K line intensity at -104 ppm the Si/Fe resp. Si02/Fe203
framework ratio could be calculated by applying the equation
proposed in Kef. (32) for the determination of Si/A1 ratios in
alumosilicates. The results for some ferrisilicates are given in
Table 2.

TABLE 2
Quantitative "Si MAS NMR data f o r some ferrisilicates

Sample Chemical analysis "si MAS NMH

(Si02/Fe203)T Fe/u.c. (Si02/Fe203)f Fe/u.c. %Fef
~

HFeSil (79) 79 2.57 140 1.35 57

HFeSil (108) 108 1.74 150 1.26 72
HFeSil (146) 146 1.30 182 1.04 80
 639

The f r a m e w o r k r a t i o s o b t a i n e d b y N H 3 TPD a n d NMR are compared in

F i g u r e 6 . The a g r e e m e n t of t h e r e s u l t s a l l o w s t h e conclusion that
both methods can alternatively be used for the quantitative
d e t e r m i n a t i o n of Si02/Fe203 r a t i o s i n f e r r i s i l i c a t e frameworks.

Id0 200 300

( Si 02 I Fe 203 1

F i g . 6 . C o m p a r i s o n b e t w e e n t h e d a t a f o r t h e SiO / F e 0 f r a m e w o r k
2 2 3
r a t i o o b t a i n e d f r o m N H 3 TPD ( X ) an d "Si MAS NMR ( 0 )

UCiiLx
F i g u r e 3a s h o w s t y p i c a l TPD s p e c t r a of a n HZSM-5 z e o l i t e (curve
l ) , a n HFeZSM-5 z e o l i t e ( c u r v e 2 ) an d a ferrisilicate (curve 4).
TPD s p e c t r a o f f e r r i s i l i c a t e s with different iron contents are
p r e s e n t e d i n F i g . 3b ( c u r v e s 3-7). Characteristically, both the
o v e r a l l c o n c e n t r a t i o n o f a c i d s i t e s an d t h e a m ount o f B r a n s t e d a c i d
s i t e s d e c r e a s e d i s t i n c t l y f o r samples with comparable Si02/Fe203
r a t i o s when t u r n i n g f r o m HZSM-5 t o t h e H F e S i l samples (Table 1).
S i m u l t a n e o u s l y , t h e maximum p o s i t i o n f o r t h e h i g h t e m p e r a t u r e peak
s h i f t s t o i o w e r v a l u e s ( F i g . 3 a ) . W i t h i n t h e HFeZSM-5 series Ccf.
T a b l e l b ) t h e d i m i n u t i o n of t h e o v e r a l l a c i d i t y a n d o f the a m ount
of Brprnsted centres with increasing iron content is small.
N e v e r t h e l e s s , t h e maximum p o s i t i o n o f the high temperature €leak
c h a n g e s t o l o w e r v a l u e s . F o r t h e H F e S i l samples t h e o v e r a l l a c i d i t y
as w e l l a s t h e amount o f Brprnsted a c i d s i t e s d e p e n d on t h e
(Si02/FeL03)t r a t i o , although the a c i d i t y does not change
r e m a r k a b l y w i t h i n t h e r a n g e f r o m 5 8 t o 9 4 . ( c f . F i g . 3 b a nd T a h l r
1 ) . A small s h i f t i n t h e maximum p o s i t i o n o f t h e high temperature
p e a k i s a ss u m e d t o l i e i n t h e m a r g i n of e r r o r . Thus, if iron is
s u b s t i t u t e d f o r aluminium b o t h t h e number a nd strength of acid
s i t e s , e s p e c i a l l y t h a t of Brmnsted a c i d c e n t r e s are i n f l u e n c e d .
640

b t a l v t i c erooerties
The activity of the samples shown in Figure 7 follows the same
sequence as the concentration of strong acid centres revealed by
NH3 TPD, U L Z . HZSM-5 > HFeZSM-5 > HFeSil. The iron-impregnated
silicalite does not possess isomerization activity, but converts
ethylbenzene at T > 675 K, yet to a minor extent (5 X at 775 K).
Within the ferrisilicates series the sample HFeSil(58) with the
highest Fe content shows t,he highest activity. It is, however, low
in comparison to the parent ZSM-5 (especially for the ethylbenzene
conversion). The lower activity may primarily be attributed to the
lower concentration of framework acid sites (theoretically 3 . 2 Fe 3+
per unit cell in case of the ferrisilicates compared to
approximately 4.6 A13+ per unit cell in case of ZSM-5).

-s 60
- 50
5 40
._
Ln
& 30
5 20
10

600 700 800 600 700 800

T(KI T(K)

Fig. 7. Catalytic properties of the catalysts. (a) conversion of

ethylbenzene (b) m-xylene isomerization ( A , HZSM-5 (Si02/A1203 =
4 U ) , ( 0 ) HFeZSM-5(152), ( 0 ) HFeZSM-5(100), ( ) HFeSil(58), (x)
HFeSil(SU8), ( V ) iron impregnated silicalite (1 wt.X Fe).
The dashed line indicates equilibrium conditions.

As regards the m-xylene isomerizatinn sample HFeSil(58) compares

better to the HFeZSM-5(100) resp. to the parent HZSM-5 zeolite.
However, it has t o be taken into account that the m-xylene
isomerization is a reversible reaction with an equilibrium
conversion of about 50 X . That is, higher conversions are only
possible due to side reactions ( e .6. disproportionation,
 64 1

I
10 20 30 40 50
m- Xylene Conversion (YO1

Fig. 8. Shape selectivity (ratio of p-/o-xylene) for the

isomerization of m-xylene. (m) HZSM-5 (Si02/A 1203 = 401, (0)

HFeZSM-5(100), (A) H F e S i 1 ( 5 0 8 ) , ( X ) H F e S i 1 ( 2 5 9 ) , (+) H F e S i l ( S 8 ) .

The d a s h e d l i n e i n d i c a t e s e q u i l i b r i u m c o n d i t i o n s a t 5 7 3 K.

d e a l k y l a t i o n ) . Moreover, the isomerization of m-xylene on the

f e r r i s i l i c a t e s b e n e f i t s f r o m t h e low mass t r a n s f e r resistances in
comparison to the ZSM-5 as is reflected by the low shape
s e l e c t i v i t y (see b e l o w ) .

. .
shaee s e l e c t i v i t s
During the isomerization of m-xylene catalysts with shape
selective properties maintain p/o-isomer ratios higher than
p r e d i c t e d by thermodynamics. Th e isomer ratio depends on the
m-xylene c o n v e r s i o n ( 3 0 ) . I t is e v i d e n t ( F i g . 8 ) that the HZSM-5
sample sh o w s t h e s t r o n g e s t s h a p e s e l e c t i v i t y f o l l o w e d b y HFeZSM-5.
The p u r e f e r r i s i l i c a t e s e x e r t o n l y weak selective e f f e c t s .
shape
The d a t a seem t o i n d i c a t e a s l i g h t i n c r e a s e with
decreasing iron
c o n t e n t s . This c o n t r a d i c t s c u r r e n t i d e a s t h a t f e r r i s i l i c a t e s should
r e v e a l h i g h e r s h a p e s e l e c t i v i t y d u e t o t h e nonframework i r o n which
i n e v i t a b l y is p r e s e n t a f t e r s y n t h e s i s a nd w h i c h r e n d e r s mure
d i f f i c u l t t h e mass t r a n s p o r t i n s i d e t h e p o r e s y s t e m . I n t h e p r e s e n t
c a s e a l l i n v e s t i g a t e d s a m p l e s h a v e ZSM-5 s t r u c t u r e w h e r e t h e p o r e
d i a m e t e r s h o u l d b e t h e same. Th e e n l a r g e m e n t o f t h e u n i t c e l l
dimensions as observed f o r t h e f e r r i s i l i c a t e s should b e n o t great
e n o u g h a s t o e x p l a i n t h e d i f f e r e n t s h a p e s e l e c t i v i t i e s . The c o k e
d e p o s i t i o n c a n n o t b e t h e r e a s o n s i n c e more c o k e i s f o r m e d on t h e
f e r r i s i l i c a t e s a s a l r e a d y i n f e r r e d f r o m v i s u a l i n s p e c t i o n . REM
p h o t o g r a p h s s h o w , h o w e v e r , t h a t t h e ZSM-5 h a s t h e l a r g e s t c r y s t a l
s i z e f o l l o w e d by t h e F e a n a l o g u e s . Large c r y s t a l s d o n o t o n l y
642

prolong t h e d i f f u s i o n pathways but they also exhibit a lower

p e r c e n t a g e of o u t e r s u r f a c e area. Both f a c t o r s s h o u l d enhance t h e
s h a p e s e l c t i v i . t y . Form and s i z e of t h e f e r r i s i l i c a t e c r y s t a l s
d e p e n d on t h e F e c o n t e n t (35). Sample HFeSi1(508), f o r example,
r e s e m b l e s i n i t s s h a p e t h e p a r e n t ZSM-5 but, nevertheless, the
shape s e l e c t i v i t y i s s t i l l low. T h i s p o i n t s t o a f u r t h e r e f f e c t
superimposing t h e i n f l u e n c e of t h e c r y s t a l s i z e . Presumably, the
f r a m e w o r k i r o n a t l o w c o n c e n t r a t i o n i s o v e r w h e l m i n g l y b e l o c a t e d on
t h e o u t e r s u r f a c e what a l l o w s t h e approximative establishment of
equilibrium regarding the isomers.

DehvdruaenationQ€ethvlben,ene
7 indeDendenceQnucontentnf
nonframeworkksDecies
Since t h e iron impregnated s i l i c a l i t e has no Fe in framework
p o s i t i o n s t h e a c t i v i t y observed f o r t h e c o n v e r s i o n of ethylbenzene
originates from nonframework Fe species. These species
dehydrogenate ethylbenzene t o s t y r e n e ( F i g . 9). The relationship
b e t w e e n t h e s t y r e n e s e l e c t i v i t y an d t h e n o n f r a m e w o r k iron content
is n o n l i n e a r . O b v i o u s l y , n o t o n l y t h e c o n c e n t r a t i o n o f n o n f r a m e w o r k
Fe b u t also its dispersity determines the extent of styrene
f o r m a t i o n . A similar r e l a t i o n s h i p between styrene formation from
-:bvlbenzene an d t . h e o v e r a l l iron content is reported for the

P i g . 9 . S t y r e n e s e l e c t i v i t y enhancement w i t h i n c r e a s i n g c o n t e n t of
nonframework i r o n i n t h e ferrisilicate series for two reaction
temperatures. (0) 673 K , ( 0 ) 773 K.
 643

HFeZSM-5 s e r i e s (29). But contrary to the ferrisilicates the

s t y r e n e s e l e c t i v i t y was f o u n d t o b e c o n s i d e r a b l y lower. This, of
course, occurs due t o t h e A 1 r e l a t e d a c i d sites p r e v a i l i n g in the
HFeZSM-5 s a m p l e s w h i c h , above all, lead to a dealkylation of
ethylbenzene.
B u t as a whole t h i s c a t a l y t i c e f f e c t of nonframework Fe species
opens t h e p o s s s i b i l i t y t o prove the existence of such species,
a d d i t i o n a l l y t o o t h e r c h a r a c t e r i z a t i o n t e c h n i q u e s , b y m e a ns o f the
c a t a l y t i c dehydrogenation of ethylbenzene.

CONCLUSIONS
Microporous f e r r i s i l i c a t e s , synthesized with Si02/Fe203 ratios
o f 58 - 5 0 8 , i n c o r p o r a t e i r o n t o a p e r c e n t a g e > 80 % only at low
i r o n c o n c e n t r a t i o n s an d w i t h i n c r e a s i n g a m o u n t s o f q u a r t z ( u p t o 30
X). At higher iron content the part of nonframework species
i n c r e a s e s u p t o 50 % . I r o n i n framework p o s i t i o n s e n l a r g e s t h e u n i t
c e l l v o l u m e and s h i f t s the T-0-T vibration frequency to lower
v a l u e s . Si0H:Pe B r e n s t e d s i t e s are weaker t h a n Si0H:Al sites. The
c a t a l y t i c a c t i v i t y f o r t h e t e s t r e a c t i o n s is directly related to
t h e c o n c e n t r a t i o n of Brensted sites. N onfra m e w ork iron species
dehydrogenate ethylbenzene t o s t y r e n e t h e formation of which can
t h u s be t a k e n a s evidence for the presence of these species.
Template-free synthesized FeZSM-5 zeolites show intermediate
p r o p e r t i e s c o m p ar ed t o t h e p a r e n t ZSM-5 a nd t h e f e r r i s i l i c a t e s . T h e
A 1 r e l a t e d a c i d s i t e s of FeZSM-5 zeolites decide the catalytic
p r o p e r t i e s predominantly.

ACKNOW LEDGEMENT
The a u t h o r s g r a t e f u l l y ack n o wl ed g e t h e supply of FeZSM-5 and
s i l i c a l i t e samples b y Dr. U . H P d i c k e ( C h e m i e AG B i t t e r f e l d ) a n d by
Dr. B . F a h l k e ( I n s t . I n o r g . C h e m . ) , resp., a nd s u p p o r t by Dr. M.
H u n g e r ( U n i v e r s i t y of L e i p z i g , 'H MAS N H R ) , Mr. J. Richter-Mendau
(REM), D r s . H . K o s s l i c k ( S y n t h e s i s ) and J . Janchen ( A d s o r p t i o n ) .

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13 A . B . H a l g a r i , R . B . E o r a d e , T . S . R . P r a s a d a Ra o, P r o c . 2nd
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14 L . M a r o s i , J . S t a b e n o w , M . S ch war z m a nn, DE 2 8 3 1 6 3 1 ( 1 9 8 0 ) .
15 A . J . D a b r o w s k i , K. M o s t o w i c z , 9 . C z e r w i n s k a , M . S o l i k -
D a b r o w s k a , B u l l . P o l i s h Acad . S c i . , Chem. 36 ( 1 9 8 8 ) 2 4 3 .
lb: P . R a t n a s a m y , R. B . B o r a d e , 5 . S i v a s a n k e r , V . P . S h i r a l k a r , S.
G . H e g d e , P r o c . I n t e r n . Symp. Z e o l . C a t a l . , S i o f o k 1 9 8 5 , 137.
17 H . B. E o r a d e , Z e o l i t e s 7 ( 1 9 8 7 ) 3 9 8 .
18 G. C a l i s , P. F r e n k e n , E . d e B o e r , A . S w o l f s , M . A. H e f n i ,
Zeolites 7 (1987) 319.
19 T . I n u i , H . N a g a t a , 0 . Yamase, H . M a t s u d a , T . K u r o d a , M .
Y o s h i k o w a , T . T a k e g u c h i , A . Mi y amoto, A p p l . C a t a l . 2 4 ( 1 9 8 6 )
257.
20 W . J . B a l l , J . Dwy er , A . A . G a r f o r t h , W . J . Smith, Proc. 7th
I n t e r n . C o n f . Z e o l . , To k y o 1 8 8 6 , 1 3 7 .
21 K . S z o s t a k , V . N a i r , T . L . T h o mas , J . Chem. S O C . F a r a d a y T r a n s .
1, 8 3 ( 1 9 8 7 ) 4 8 7 .
22 A . Meagher, V. N a i r , R . S z o s t a k , Z e o l i t e s 8 ( 1 9 8 8 ) 3.
23 L . M . Kustov, V . B . Kazansky, P . Ratnasamy, Z e o l i t e s 7 (1987)
79.
24 G. P . H a n d r e c k , T . D . S m i t h , J . Chem. S O C . F a r a d a y T r a n s 1. 85
(1989) 3195.
25 G . V . Kharlamov, V . N. Romanikov. V. J . Kuznetzov, V . F.
A n u f r i e n k o , K i n . i R a t . 30 ( 1 9 8 9 ) 1 1 8 2 .
26 D . H . Lin, G . Coudurier, J . C . Vedrine, Proc. 8 t h I n t e r n . Conf.
Z e o l . , Amsterdam 1 9 8 9 , 1 4 3 1 .
27 A . N . K o t a s t h a n e , V . P . S h i r a l k a r , S . G . H e gde , 5 . B . K u l k a r n i ,
Z e o l i t e s 6 ( 1 9 8 6 ) 253.
28 L . M. K u s t o v , V . B . Kazansky, Proc. 3rd Indo-Soviet
C o n f . C a t a l . , Baku 1 9 8 8 , 1 2 8 , 2 8 .
29 M . R i c h t e r , R. F r i c k e , B . P a r l i t z , U . H a d i c k e , G . O hlm a nn, Z .
Phys. Chemie, ( L e i p z i g ) , i n press.
30 M . R i c h t e r , W . F i e b i g , H.-G. J e r s c h k e a i t z , G . L i s c h k e , G .
ohlmann, Z e o l i t e s , 9 (1989) 238.
31 G . E n g e l h a r d t , D . Michel, High R e s o l u t i o n Solid-state NMR of
S i l i c a t e s an d Z e o l i t e s , ( W i l e y , C h i c h e s t e r . 1 9 8 7 ) .
32 G . E n g e l h a r d t , B . F a h l k e , M . M a e g i , E . L i p p m a a . Z . P h y s . Ch m.
( L e i p z i g ) , 266 ( 1 9 8 5 ) 239.
33 D. F r e u d e , M . H u n g e r , H . P f e i f e r , Z . P h y s . Chem. (NF) 1 5 2
( 1 9 8 7 ) 171.
34 A. R. Halgeri, T. S. R. P r a s a d a Ra o, P r o c . I n t e r n . Symp.
Acid-Base C a t a l . , Sapporo 1988, 319
35 J . Richter-Mendau, M. R i c h t e r , G. V o r b e c k e t a l . , t o be
published.
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 645
0 1991 Elsevier Science Publishers B.V., Amsterdam

ZEOLITE ZSM-57: SYNTHESIS, CHARACTERIZATION AND SHAPE SELECTIVE

PROPERTIES

S.ERNST and J. WEITKAMP

Institute of Chemical Technology I, University of Stuttgart, Pfaffenwaldring 55,
D-7000 Stuttgart 80 (Federal Republic of Germany)

SUMMARY
Zeolite ZSM-57 can be synthesized from sodium-containing alumosilicate els using
%
hexaethyl-C5-diquatas organic template and silica sol as silica source. ZSM-57 can e readily
distinguished from the structurally closely related zeolites with the FER framework topology
by its X-ray powder attern and mid-infrared spectrum. From thermogravimetric analysis of
as-synthesized ZSM-!7 it follows that a plying an air calcination at 550 "C for several hours is
P
sufficient to remove the organic temp ate from the pores of the zeolite. The results of two
selected test reactions for probing the effective pore width of zeolites, viz. ethylbenzene
dis ro ortionation and n-decane isomerization su est that the pore width is lar er for
ZSb-f7 as compared to ZSM-35 (ferrierite) and 8 M - 5 . This is in agreement wit8; their
crystallographic structures and offers new opportunities in shape selective catalysis and
molecular sieve separation.

INTRODUCTION
ZSM-57 is a medium pore, high silica zeolite with a structure very similar to ferrierite
(refs. 1,2). Both zeolites possess channel systems consisting of intersecting linear eight-
membered and ten-membered ring pores. However, the ZSM-57 framework contains four-
membered rings which are not present in ferrierite (refs. 1,2). Interestingly, the structure of
ZSM-57 appeared in a systematic derivation of hypothetical structures based on the
ferrierite net (ref. 3).
Although the apertures of the eight-ring channels in ZSM-57 and ferrierite are of a
comparable size (0.33 x 0.48 nm versus 0.35 x 0.48 nm), the ten-ring channels are significantly
larger in the former zeolite (0.51 x 0.58 nm versus 0.42 x 0.54 nm) (refs. 1,2), and they are
even slightly larger than the sinusoidal (0.51 x 0.54 nm) and the linear (0.54 x 0.56 nm)
channels in zeolite Z S M J (ref. 4). Hence, from their crystallographic structures differences in
the shape selective properties of these zeolites can be expected.
The hydrothermal synthesis of zeolite ZSM-57 was first described by Valyocsik et al.
(ref. 5 ) from sodium containing alumosilicate gels using N,N,N,N,N,N - hexaethylpenta-
methylenediammoniumdibromide (hexaethyl-C5-diquat) as organic template. Here we report
on our attempts to synthesize zeolite ZSM-57, and on its characterization by X-ray powder
diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TGA), mid-
infrared- (IR-) spectroscopy and selected catalytic test reactions. For comparison, data
-
obtained with a material of the FER structure type, viz. ZSM-35, are also included.
646

EXPERIMENTAL
The template required for the synthesis of zeolite ZSM-57 was prepared by refluxing
1J-dibromopentane and a surplus of triethylamine in ethanol as solvent for several hours
(ref. 5). After cooling the mixture with an ice bath, a white solid precipitated which was
recovered by filtration, washed with diethylether und then used for the synthesis experiments
without further purification. As silica sources, either sodium waterglass (Merck; 28.5 wt.-%
Si02, 8.8 wt.-% Na20, ca. 62.7 wt.-% H20) or colloidal silica sol (Ludox HS-40, DuPont;
40 wt.-% Si02 in water) were used. All synthesis experiments were conducted at 160 "C and
the crystallization time was restricted to 6 days. After this time the autoclaves were quenched
in cold water and the solid products recovered by filtration, washed with distilled water and
dried at 120 "C. Characterization of the as-synthesized materials occurred by X-ray powder
diffraction (Cub-radiation; 40 kV, 30 mA) and IR-spectroscopy in the region of the lattice
vibrations using the KBr pellet technique. The product of an optimized synthesis was further
subjected to scanning electron microscopy and thermogravimetric analysis.
HZSM-57 was obtained by calcining the as-synthesized material for 16 hours at 540 "C in
air, followed by an ion exchange with a 1 n aqueous solution of NH&l and a second air
calcination for 16 hours at 350 "C. The bifunctional form (HZSM-57 loaded with 0.27 wt.-%
of palladium) was prepared via an optimized procedure which has been described previously
(ref. 6). For a characterization of the shape selective properties of ZSM-57, two established
test reactions, viz. the disproportionation of ethylbenzene (ref. 7) and the bifunctional
conversion of n-decane (ref. 8) were selected. Both reactions were performed in a flow-type
apparatus with fixed bed reactor under atmospheric pressure. The partial pressures of the
feed hydrocarbons ethylbenzene (E-Bz) or n-decane (n-De) amounted to pHC= 1.3 kPa.
Nitrogen or hydrogen was used as the carrier gas with ethylbenzene or n-decane as feed,
respectively. Product analysis was achieved by automatic sampling and on-line analysis via
temperature programmed capillary glc.
For a comparison of zeolite ZSM-57 with materials of the ferrierite structure, zeolite
ZSM-35 was synthesized according to a published method using 1,Zdiaminoethane as
template (ref. 9).

RESULTS AND DISCUSSION

In the first synthesis experiments, sodium waterglass was used as the silica source. The
synthesis gel was prepared by subsequently adding to the sodium waterglass, aqueous
solutions of the alumina source (usually Al(NO3)3 * 9H20, in some cases Al2(SO& * 18 H20)
and the template, and concentrated (98 wt.-%) sulfuric acid. The gel composition was
systematically varied within the following molar ratios (calculated as described in ref. 10):
Si02/Al,03 = 30 to 120, H20/Si02 = 20 to 60, Na+/Si02 = 0.6 to 0.8, OH-/Si02 = 0.1 to
0.3 and R/Si02 = 0.05 to 0.2. No ZSM-57 at all crystallized from these gel compositions
under our synthesis conditions. Instead, in some cases a not yet identified crystalline
component, which reversibly adsorbs/desorbs ca. 7 wt.-% of water, was obtained. Even if
seeds of uncalcined ZSM-35 were added to the gel, the system could not be forced to produce
 647

a ferrierite material or the structurally related zeolite ZSM-57. However, if sodium waterglass
is replaced by colloidal silica sol as the silica source, pure ZSM-57 was obtained after 6 days
at 160 "Cfrom a gel with the composition: Si02/A1203 = 60, H20/Si02 = 40, Na+/Si02 =
0.6,OH-/Si02 = 0.1 and R/Si02= 0.1. Note that in this case no sulfuric acid was required to
adjust the pH, instead a concentrated aqueous solution of NaOH was added. This example
demonstrates that, like in numerous other zeolite syntheses, the nature (reactivity) of the
silica source plays an important role in directing the structure of the crystallizing material.
The X-ray powder pattern of as-synthesized zeolite ZSM-57 is shown in Figure 1 (upper
part). The agreement of line positions and relative intensities with literature data (ref. 5) is
very good. However, ZSM-57 and ZSM-35 can be readily distinguished on the basis of their
X-ray powder patterns: The most significant differences are the presence of an additional
reflexion of zeolite ZSM-57 around 7.5 degrees 2 8 and the absence of a peak of medium

I I I I I I I I

ZSM-57

>
k
v) 5 10 15 20 25 30 35 40 45 50
Z
w
I- I I I I I I I I

-
Z

5 10 15 20 25 30 35 40 45 50

ANGLE 28 , d e g

Fig. 1. X-ray powder patterns of as-synthesized zeolites ZSM-57 and ZSM-35 (Cub-
radiation; 40 kV, 30 mA).
648

intensity at ca. 14 degrees 2 8 . Indeed, it was stated in the original patent (ref. 5) that due to
the latter difference, ZSM-57 can be "readily distinguished from ferrierite-type zeolites, such
as ZSM-35".
Mid-infrared spectra of ZSM-57 and ZSM-35 are depicted in Figure 2. The pattern for
ZSM-35 essentially agrees with those published in the literature (refs. 11,12). The pattern for
ZSM-57 is reported here for the first time. Both zeolites have two characteristic absorption
bands around 1230 cm-1. These two bands can be assigned to the vibrations of five-membered
oxygen rings (refs. 12,13), which is in agreement with the crystallographic structures of both
materials. Slight shifts in the frequency of each IR-band may be explained by the unique
framework structure of every zeolite (ref. 14). One significant difference between both
zeolites appears in the region around 600 cm-1, which is known to be sensitive to structural
changes (ref. 15). Whereas ZSM-35 shows a single band in this range, ZSM-57 possesses a
doublet. This additional band may be tentatively assigned to the presence of four-membered
rings in the structure of the latter zeolite (ref. 1,2) which are absent in the ferrierite
framework. Hence, in addition to X-ray powder diffraction, IR-spectroscopy also offers a
means to distinguish between both zeolites.

60
55
50
45
40
35
30
25
20
15
10
5
1400 1200 1000 800 600 40 0

60
55
50
45
40
35
30
25

1400 1200 1000 800 600 400

-1
WAVE NUMBER , c m

Fig. 2. Mid-infrared spectra of ZSM-57 and ZSM-35.

 649

Fig. 3. shows a scanning electron micrograph of a typical preparation of zeolite ZSM-57.

The sample consists of small platelet-like crystallites with a diameter of ca. 0.5 to 1 p m and a
thickness of ca. 0.1 to 0.2pm. Frequently, these platelets are intergrown.

Fig. 3. Scanning electron micrograph of zeolite ZSM-57. The white scale bar corresponds to
10pm.

100

M 95
I--
I
c,
LLJ 90
B

85

80 '
0 70 140 210 280 350 420 490 5 6 0 630 7 0 0 770

Temperature, O C

Fig. 4. Weight-loss of as-synthesized ZSM-57 upon heating from room temperature to 770 "C
(rate: 5 K/min) in an air flow ($air = 50 cm3/min). Full line: Sample weight in dependence of
temperature, dotted line: first derivate of that curve.
650

As-synthesized ZSM-57 was further characterized by thermogravimetric analysis in order

to obtain guidelines for the removal of the organic template occluded in the pores during
synthesis. For this purpose, the sample was heated in a flow of dry air (Vab = 50 cm3/min)
from room temperature to ca. 770 "C with a heating rate of 5 K/min. The weight-loss curve
and its first derivative are plotted in Fig. 4. The main weight-loss occurs between
temperatures of 350 "C and 550 "C and amounts to ca. 11 wt.-%. It can be attributed to the
desorption of water and the combustion of the organic template occluded inside the pores.
There is a further weight-loss corresponding to ca. 3 wt.-% at temperatures above 550 "C
which can be tentatively assigned to dehydroxylation of Bronsted-acid sites at these high
temperatures. However, combustion of an additional, more strongly bound template species
may also be envisaged. As a whole, it follows from the TGA-experiments that an air
calcination at ca. 550 "C for several hours should be sufficient to remove the organic material
from the pores.
The catalytic and shape selective properties of HZSM-57 were characterized by the
disproportionation of ethylbenzene to benzene and diethylbenzenes. This test reaction was
initially proposed by Karge et al. (refs. 16,17) to characterize the Bronsted-acidity (number
and/or strength of acid sites) in zeolites. Later the method was shown to be also useful for
probing the shape selective properties of zeolites (ref. 7). From the time on stream behaviour
of the catalyst four criteria can be derived which enable to characterize the effective pore
width of the investigated material: (i) the presence or absence of an induction period, (ii) the
ratio of yields of diethylbenzenes and benzene, (iii) the selectivities for ortho-, meta- and
para-diethylbenzene and, (iv) the rate of catalyst deactivation. The results with HZSM-57 are
plotted in Figure 5. There is no induction period, viz. conversion of ethylbenzene ( X E - ~ ~ )
decreases continuously with time on stream, and the ratio of yields of diethylbenzenes
(YDE-BJ and benzene (YBz)amounts to ca. 0.77. Both features are typical for medium pore
(ten-membered ring) zeolites (ref. 7). By contrast, the selectivities for the three
diethylbenzene isomers resemble more closely to what could be expected with a large pore
zeolite. However, there may be a marked contribution of the non-shape selective outer
surface of the small zeolite crystallites of the sample used in this case. Again typical for
medium pore zeolites is the increase of the selectivity for the slim p-diethylbenzene at the
expense of the bulkier m- and o-diethylbenzenes with time on stream and hence coke content.
This effect has been referred to as "coke selectivation" in the patent literature (ref. 18). As a
whole HZSM-57 behaves in the disproportionation of ethylbenzene like a medium pore
zeolite. This is in agreement with its proposed framework structure. For a more accurate
ranking of ZSM-57 among other members of the group of ten-membered ring zeolites, the
Modified Constraint Index (CI*) of 0.27 Pd/HZSM-57 was determined. It is defined as the
ratio of selectivities for the formation of 2-methylnonane and 5-methylnonane in the
isomerization of n-decane at an isomer yield of 5 Yo (ref. 8). A Modified Constraint Index
of 4.3 was determined for ZSM-57. This is a typical value for a medium pore zeolite. As
compared to the corresponding CI*-values for ZSM-5 and ZSM-35 (6.8 and 8.1, respectively,
 651

M 12 75
L
i T = 250 "C
n 10 = 200 gh/mol-
-1
- W/FE-,z
= 0.2 g
W
-
>. 8 50
IY
0
t
X
6
Z
0
- 4 25
cn
of
W
> 2

0 2 4 6 8 1 0 0 2 4 6 8 1 0
TIME ON STREAM, h
~ 1.3 kPa, PN2 = 100 @a.
Fig. 5. Disproportionation of ethylbenzene in HZSM-57; P E - B=

ref. 19), this indicates a larger effective pore width of ZSM-57 compared to ZSM-5 or
ZSM-35, which is in good agreement with the structures of these zeolites.

CONCLUSIONS
Provided that the right silica source is used, ZSM-57 can be readily synthesized with the
hexaethyl-C5-diquat cation as organic template. It can be readily distinguished from the
structurally very closely related zeolites with the FER structure-type, e. g. ZSM-35, on the
basis of their X-ray powder patterns and mid-infrared spectra. Thermogravimetric analysis
revealed that, like with many ofther high-silica zeolites, the template occluded inside the
pores during synthesis can be readily burned off by air calcination for several hours at 550 "C.
According to the results of selected catalytic test reactions the effective pore width of zeolite
ZSM-57 is larger than that of ZSM-35 and ZSM-5. Hence, this new high-silica zeolite offers
the opportunity to close the gap in the effective pore widths between ZSMJ and the twelve-
membered ring zeolite with the most restricted pore system, ZSM-12. This probably offers
new possibilities for shape selective catalysis in zeolites and molecular sieve separations.

ACKNOWLEDGEMENTS
The authors gratefully acknowledge financial support by Deutsche Forschungsgemein-
schaft, Fonds der Chemischen Industrie and Max Buchner-Forschungsstiftung.
652

REFERENCES
1 J.L. Schlenker, J.B. Higgins and E.W. Valyocsik, in: J.C. Jansen, L. Moscou and M.F.M.
Post (Eds.), Zeolites for the Nineties; Recent Research Reports, 8th Intern. Zeolite
Conference, Amsterdam, July 10-14, 1989, pp. 287-288.
2 J.L. Schlenker, J.B. Hi ins and E.W. Valyocsik, Zeolites 10 (1990) 293-296.
3 R. Gramlich-Meier, Z%istallographie 177 (1986) 237-245
4 D.H. Olson, G.T. Kokotailo, S.L. Lawton and W.M. Meier,J. Phys. Chem. 85 (1981)
2238-2243.
5 E.W. Val ocsik and N.M. Page, Europ. Patent Appl. 174 121, Mar. 12, 1986, assigned to
Mobil OirCom.
6 J. Weitkamp, %’.Gerhardt and P.A. Jacobs, in: Proc. Intern. Symp. on Zeolite Catalysis,
Si6fok, Hungary, May 13-16, 1985, pp. 261-270.
7 J. Weitkamp, S. Ernst, P.A. Jacobs and H.G. Karge, Erdol, Kohle-Erdgas-Petrochem. 39
(1986) 13-18.
8 J.A. Martens, M. Tielen, P.A. Jacobs and J. Weitkamp; Zeolites 4 (1984) 98-107.
9 P.A. Jacobs and J.A. Martens, Synthesis of Hi h-Silica Aluminosilicate Zeolites, Elsevier
Science Publishers, Amsterdam, Oxford, New$ork, Tokyo, 1987, p. 8.
10 L.D. Rollmann and E.W. Valvocsik. Inoreanic Svnthesis 22 f 1982) 61-68.
11 Reference 9
12 K. Suzuki, $ . k ~ ~ ~ m mS. iShin,
, K. Fujisawa, H. Watanabe, K. Saito and K. Noguchi,
Zeolites 6 (19861 290-298.
13 G. Coudurier, C. Nacchache and J.C. Vedrine, J. Chem. SOC.,Chem. Commun. (1982)
1413-1415.
14 J.C. Jansen, F.J. van der Gaag and H. van Bekkum, Zeolites 4 (1984) 369-372.
15 E.M. Flanigen, in: J.A. Rabo (Ed.), Zeolite Chemistry and Catalysis; ACS Monograph
171, American Chemical Society, Washington, D.C., 1976, pp. 80-1 17.
16 H.G. Karge, J. Ladebeck, Z. Sarbak and K. Hatada, Zeolites 2 (1982) 94-102.
17 H.G. Karge, K. Hatada, Y. Zhang and R. Fiedorow, Zeolites 3 (1983) 13-21.
18 R.M. Dessau, US Patent 4 444 986, Apr. 24, 1984, assigned to Mobil Oil Corp.
19 P.A. Jacobs and J.A. Martens, in: Y. Murakami, A. Iijima and J.W. Ward (Eds.), New
Developments in Zeolite Science and Technology; Proc. 7th Intern. Zeolite Conference,
Kodansha/ Elsevier, Tokyo/Amsterdam, 1986, pp. 23-32.
G . Ohlmann et al. (Editors),Catalysis and Adsorption by Zeolites 653
0 1991 Elsevier Science PublishersB.V., Amsterdam

NEW DATA ON THE STRUCTURE AND PROPERTIES OF ACIDIC SITES IN HZSM-5 ZEOLITES:
IR-SPECTROSCOPIC STUDIES AND NONEMPIRICAL QUANTUM CHEMICAL CALCULATIONS

1.N.SENCHENYA and V.Yu.BOROVKOV

N.D.Zelinsky Institute of Organic Chemistry, Academy of Sciences of the USSR,
Leninsky prospect,47. Moscow B-334 117913 (USSR)

SUMMARY
The quantum chemical analysis of the influence of geometry on properties of zeo-
lite acidic OH-groups and on the strength of the A1-0 bond in SiOAl bridges is
given. It is shown that bridge hydroxyls possessing high values of SiOAl angle
(-180O) are able to form a strained hydrogen bond with the neighboring lattice
oxygen atom attached to aluminum resulting in the appearance of HZSM-5 zeolites
.
of the broad absorption band at 3250-3300 cm-l in IR spectra The increase of
SiOAl angle in bridged hydroxyl and alkoxide leads to continuous weakening of
A1-0 bond. Therefore in the presence of basic molecules the A1-0 bond in the
straitened SiOAl bridges of alkoxides could be broken with the formation of tri-
gonal A1 cation coordinated with the base being a strong Lewis acid. Such unusu-
al manifestation of Lewis acidity of alkoxylated HZSM-5 zeolite is proved spect-
roscopically. The new hypothetical mechanism of the methanol conversion with the
participation of such Lewis acidic sites is proposed.

INTRODUCTION
Decationated ZSM-5 zeolites are active in the production of high quality ga-
soline from non-oil row materials (methanol, light olefins, paraffins etc). From
the scientific point of view they are convenient model objects for the study of
the influence of different structural factors on properties of their acidic si-
tes. Indeed the structure of the lattice and pores for these catalyst are well
established by X-ray analysis (ref.1). The high Si/Al ratio in HZSM-5 zeolites
provides rather homogeneous chemical surrounding of their active sites (ref.2).
Moreover among other zeolites they have a higher thermal stability and practi-
cally do not undergo dealumination during thermovacuum treatment.
The present report deals with the theoretical analysis of two novel phenomena
detected recently by ourselves using IR spectroscopy:
1. The existence in HZSM-5 zeolites of the considerable amount of acidic OH-
groups hydrogen bonded with the basic oxygen atom of the lattice (ref.3).
2. An unusual manifestation of Lewis acidity in the presence of adsorbed ba-
sic molecules for zeolites in which a fraction of OH-groups is substituted by
alkoxide fragments (ref.4).
In addition, on the basis of considered theoretical and experimental data the
new mechanisms of acid catalyzed reactions over HZSM-5 zeolites are discussed.
654

METHODS
IR spectra of powdered samples were measured in diffuse reflected light as
described in ref.5. Before study HZSM-5 zeolites (Si/Al = 17 and 351 were pre-
treated in vacuum for 2-3 h at 50OoC. The partial substitution of acidic OH-
groups of zeolites for alkoxide fragments was performed by chemisorption of
small quantities of propene on the zeolites at 300'K. MAS 13C NMR spectra were
measured using CXP-300 "Brucker" spectrometer.
Quantum chemical calculations were carried out using nonempirical SCF method
with a "Gaussian-80''program (ref.6). Five different basis sets ranged from mi-
**
nimal STO-3G to 6-31G were used (ref.71. Zeolite lattice was simulated by clu-
sters of following composition: H3A10HSiH3 (I), (OH)3A10HSi(OH)3 (11) and
OH(H)A1(OH)20Si(OH)ZOHAl~OH)3 (1111, (OH)3SiOSi(OH)20HA1(OH)3 (IY). Calculations
for cluster 11-IY were made only with STO-3G basis set. All calculations were
carried out with complete geometry optimization using gradient technique.

RESULTS AND DISCUSSION

The literature data suggest that acidic OH-groups of HZSM-5 zeolites are non-
homogeneous (ref.8-9). Thus the substitution of only 20 % of acidic hydroxyls
for methoxide fragments by zeolite treatment with methanol vapor is accompanied
by the complete suppression of zeolite activity in ethylene oligomerisation
(ref.8). At the same time the remained 80 % of OH-groups are "free" as they are
still able to adsorbe benzene molecules with the larger kinetic diameter than
that of ethylene. The detailed analysis of the band shape in IR spectra of aci-
dic OH-groups perturbed by hydrogen bonding with adsorbed cyclohexane and benze-
ne molecules showed the existence at least of 5 types of hydroxyls with diffe-
rent acidic strength in HZSM-5 zeolites. It was also found (ref. 9 ) that poiso-
ning no more than 10 % of the sites (counted as lattice aluminum ions) was suf-
ficient to eliminate the activity of zeolites.
Quantum chemical interpretation of the broad IR band at 3250-3300 cm-' The typi-
cal spectrum of OH-groups measured at room temperature in diffuse reflected
light is shown in Fig.1. It consists of two narrow lines at 3740 and 3610 cm-l
corresponding to terminal silanols and isolated acidic hydroxyls respectively.
Additionally the broad absorption band with the maximum at 3250-3300 cm-l is
present. This band is always detected in the spectra of HZSM-5 zeolites but the
position of its maximum could be changed a little for the samples of different
origin.
The broad absorption band displays an unusual behavior. Under cooling of the
sample its maximum is shifted to higher wave numbers as in complexes with hydro-
gen bond. Adsorption of weakly basic molecules (C -C paraffins, CC1 , cyclohe-
 655

xane, C02, etc) on zeolite leads to vanishing of both 3610 and 3250-3300 cm-l
bands and to the development of a single band at 3480-3530 cm-' characteristic
of acidic OH-groups forming H-complexes with these adsorbed molecules. The inte-
nsity of the broad 3250-3300 cm-l band in the IR spectrum measured at 500'C is
greatly reduced but can be completely restored after sample cooled to room tem-
perature. On the basis of these observations this band was assigned in ref.3 to
two different states of the same bridged hydroxyls such as isolated OH-groups
and those forming the strained hydrogen bond with the nearest basic oxygen atom
attached to aluminum.
, 3610

Fig.1.
IR diffuse reflectance
spectrum of HZSM-5 zeo-
lite (Si/A1=35) pretrea-
ted in vacuum at 70 K
for 4 h.

I I 1 I

2400 2800 3200 3600 v, cm-1

We tried to elucidate theoretically what type of hydroxyls is able to form

such hydrogen bond. It is known that zeolites of higher protic acidity have a
range of T-0-T bond angles higher than those of lower protic acidity. For insta-
nce, in ZSM-5 these values are changed from 133 to 177' (ref.1). and those in
mordenites are varied in the range of 143-180' (ref.10). At the same time in Y
zeolites the T-0-T angle variation is much smaller, from 137 to 143'.
It is reasonable to propose that the increase of SiOAl angle in the bridged
hydroxyl will promote the formation of strained hydrogen bonding of OH-group
with the nearest basic lattice oxygen atom due to the decrease of the distance
between H and 0 atoms. To verify this assumption we performed corresponding cal-
culations for clusters simulating the lattice fragments with different SiOAl an-
gle values in the bridged hydroxyl. The obtained results demonstrate that the
straighten SiOAl angle leads to the significant elongation of the T-0 and 0-H
bonds as well as to the increase of the OH-group acidity (ref.11). Fig.2 shown
the geometry of cluster I 1 with the SiOAl bond angle close to 180'. There is al-
so the noticeable flattening of the A103 fragment. As a result the distance bet-
ween the proton of the bridged OH-group and the basic oxygen atom in such clus-
656

ter becomes equal to 1.56 1 which is characteristic of a strong hydrogen bond.

The incline of the OH-group towards basic site equals to 12'.
Thus the broad 3250-3300 cm-' band in I R spectra of HZSM-5 zeolites indeed
could be assigned to the bridged hydroxyls with the large SiOAl angle which
forms rather strong and strained hydrogen bond with the oxygen atom attached to
aluminurn.

Fig.2
Completely optimized
geometry of cluster I1
(LSiOA1 = 178O).

The main difference in the catalytic action of HZSM-5 and other zeolites is
usually explained by the higher protic acidity of the pentasil. Taking into
account that the acidic strength of the bridged hydroxyls should rise with the
increase of SiOAl angle we can assume that the hydroxyls characterized by the
broad 3250-3300 cm-l I R band would have the highest acidity. It is therefore
worthwhile to pay special attention to the analysis of broad I R bands of OH-
groups of high silica zeolites.
Lewis acidity of HZSM-5 zeolites The nature of Lewis acidic sites (L-sites) and
their role in catalysis by zeolites is widely discussed in the literature
(ref.12). Now the existence of several types of Lewis sites well established.
Among them there are the extralattice aluminum containing species and the latti-
ce trigonal aluminum or silicon cations appeared as a result of zeolite dehydro-
xylation at high pretreatment temperatures. In our opinion these sites, however,
could be considered as the active sites in the catalysis by zeolites with
caution. The reasons for this are as follows:
1. HZSM-5 zeolites hardly undergo dealumination during their activation under
conventional conditions and therefore the concentration of extralattice aluminum
is usually small. Moreover these sites are believed to participate in the coke
formation which is not characteristic of HZSM-5 zeolites.
2. The formation of lattice L-sites are known to proceed at temperatures abo-
ve 5OO0C (ref.12). So their appearance under usual activation conditions also
has a low probability. Moreover during catalytic reactions these L-sites could
be easily poisoned by moisture traces of the feedstock.
 657

In this connection we would discuss the idea about two different ways of the
interaction between basic molecules and the acidic OH-groups in zeolites propo-
sed by Uytterhoeven et a1 in 1965 (ref.13). The first one is the usual reaction
of the base protonation:
H HB+

The second route is associated with the break of the Al”’0 bond in the Si-0-A1
bridge accompanied by the formation of complex between basic molecule and the
trigonal A1 cation being the strong Lewis acid:
H H

To estimate the probabilities of these two reaction paths we performed the

quantum chemical calculations of the A1-0 bond energies in model clusters I-IY.
These values were estimated as the energy of the reaction
H

which is equal to the difference between total energy of the initial cluster and
/
the sum of total energies of 3i-OH and A ~ Kseparated fragments having equilib-
rium geometries.
The energies of complete A1-0 bond break for cluster I calculated with diffe-
rent basis sets are listed in Table 1.

TABLE 1
Basis set dependence of A1-0 bond energy (AE, kJ/mole) for cluster I

9
Basis set STO-3G 3-21G 6-31G MF’2/6-31G

AE 176.5 156.5 79.5 91.0

9
According to the estimation at the MF’2/6-31G level the energy of Si-0 and 0-
H bonds breaking in the molecule H3SiOH which respectively correspond to enthal-
pies of reactions H3SiOH - H3SiO’ + H’ and H3SiOH - H3Si‘ + HO’ is approximately
the same and equal to 500-550 kJ/mole. Therefore the strength of the A1-0 bond
in the SiOAl bridge is much smaller than that of the Si-0 and 0-H bonds.
It is clear that minimal cluster model I is only a very primitive model of
the zeolite lattice. Therefore we also calculated the BE values of the A1-0 bond
in more extended clusters 11-IY. The transition from cluster I to I 1 is accompa-
nied by the decrease of the A1-0 bond energy from 176.5 to 136.5 kJ/mole. The
658

substitution of one H atom in cluster I1 for real silicon-oxygen tetrahedron

does not lead to significant changes in cluster geometry whereas similar substi-
tution of the same H atom for aluminum-oxygen tetrahedron is accompanied by no-
ticeable shortening of the A1-0 bond. This evidences the increase of the A1-0
bond strength with the decrease of the Si/Al ratio in the zeolite lattice. The
direct calculation indicates that the A1-0 bond strength in cluster I 1 1 is the
same as in cluster 11. The existence of aluminum-oxygen tetrahedron in the
neighborhood of bridged hydroxyl (cluster I Y ) increases the A1-0 bond strength
by the factor of 1 . 5 (197 kJ/mole).
Quantum chemical analysis (clusters I and 1 1 ) of the influence of zeolite
lattice geometry and substitution of the acidic proton for sodium cation or
methoxy fragment on the A1-0 bond strength led us to the following conclusions:
1. The change of the SiOAl angle from its equilibrium value to -180’ leads to
a significant decrease of the A1-0 bond strength and to the flattening of Al-
atom surrounding.
2. The substitution of the bridged proton for Na’ is accompanied by shorte-
ning of the Si-0 and A1-0 bonds along with sharp strengthening of the A1-0 bond
as compared to that in the cluster containing bridged hydroxyl.
3. The energies of the A1-0 bond in the methoxylated cluster I calculated
with STO-3C and 3-21G basis sets are noticeable lower than those in the cluster
containing OH-group, by 20 and 50 kJ/mole, respectively. On the contrary the de-
crease of the A1-0 bond energy in the methoxylated cluster I 1 is much smaller (*

5 kJ/mole) due to formation of the intermolecular hydrogen bond between the hyd-
rogen atom of the methoxy group and the oxygen atom attached to aluminum.
The weakness of the Al-0 bond strength in high-silica zeolites could be mani-
fested in the course of chemical reactions as well as during interaction of the
acidic hydroxyls with adsorbed basic molecules. Let us demonstrate this using
the interaction of the bridged OH-group with the ammonia molecule as an example.
The nonempirical STO-3G calculations indicate that the interaction of ammonia
with the SiOAl bridge, which leads to the breaking of the A1-0 bond (scheme 2 )
proposed by Uytterhoeven is allowed energetically. Nevertheless the ammonia pro-
tonation (scheme 1) which in practice usually takes place is energetically more
favorable. There is, however, an opportunity to switch off the protonation chan-
nel by substitution of the acidic proton for an alkoxy fragment. As was mentio-
ned above such a substitution also results in weakening of the Al-0 bond. There-
fore the interaction of the NH3 molecule with the alkoxy group by the route
R R
0 0
>Si’ \AIL
\ + B -+ >Si’ B’.’Alf (4)
is even more probable.
 659

IR spectroscopic studies of the basic molecule adsorption (NH3. CD3CN) on

HZSM-5 zeolites support this assumption (ref.4).
Fig. 3 displays the IR spectra of NH3 and CD CN molecules adsorbed both on
3
fresh HZSM-5 zeolite and on the sample with propene preliminary chemisorbed at
300 K. There are only two bands at 1460 and 2295 cm-l in IR spectra of the ini-
tial H-form which correspond respectively to bending 6N-H and stretching v
CeN
vibrations of ammonium ions and CD3CN molecules coordinated with the acidic OH-
groups. Additional bands at 1610 and 2370 cm-' appear in the zeolites containing
chemisorbed C3H6. They are characteristic of ammonia (aNH = 1610 cm-'1 and deu-
teroacetonitrile ( uC=N = 2370 cm-'1 molecules adsorbed on L-sites.

I I I I I I I ,
-1 -1
2400 2300 u.cm 1700 1600 1500 v,cm

Fig.3. IR spectra of NH3 (A)and CD3CN (B) adsorbed on fresh HZSM-5 zeolite (1)
and on the sample with propene preliminary chemisorbed at 300 K (21. Line ( - -1
corresponds to the background.
The process of such an L-sites formation is a reversible one. They disappear
after removal of chemisorbed hydrocarbons by evacuation of the sample at higher
temperatures but are restored again after repeated chemisorption of the olefin.
It is worthwhile to emphasize that in this case no additional coordinatively un-
saturated L-sites was found from IR spectra of adsorbed weak basic molecules (H2
and CO). The conclusion was made that the formation of L-sites in the presence
of strongly basic molecules in zeolites Containing chemisorbed olefins proceeds
according scheme (4).where the oligomer hydrocarbon chains play a role of the
alkoxide R. The formation of alkoxy structures is evidenced by the appearance of
the intense line at 70 ppm corresponding t o resonance of C-atom in the fragment
'0-bH in MAS 13C NMR spectrum of chemisorbed 13C-enriched ethylene (Fig.4 ) .
/ I
The energy calculated for reaction (4) (B = NH3) indicates that this process
is energetically favorable: AE = 33.5 kJ/mole for cluster I (3-21C1 and AE = 13
660

kJ/mole for cluster I1 (STO-3G). For the acetonitrile molecule the energetics of
such reaction is less advantageous. It, however, became much more favorable f o r
bridged alkoxy groups with the larger SiOAl bond angle. Indeed, the increase of
this angle by 50' from its equilibrium meaning leads to essential enhancement of
system total energy and, as consequence, to sharp lowering the energy of A1-0
bond breaking in the presence of strong bases. At the same time for zeolites
with the low Si/A1 ratio the energy of the A1-0 bond is higher, than the energy
of the interaction between the basic molecule and the L-site. This explains why
L-sites are not formed in methoxylated zeolites of such type with strong basic
molecules adsorbed. 29

Fig.4.
MAS 13c NMR spectrum of
chemisorbed I3C en-
riched ethylene on
HZSM-5 at 370 K.

75 50 25 0

The theoretical results considered above demonstrated that the formation of

L-sites in the presence of strong bases occurs only in the moieties of the zeo-
lite framework having large values of angles in SiOAl bridges. As only protons
localized on such SiOAl bridges are able to form a strained hydrogen bond with
neighbor lattice oxygen atom, the substitution of OH-groups characterized by the
broad IR band at 3250-3300 cm-l f o r alkoxides results in the manifestation of
the unusual L-sites in the presence of adsorbed basic molecules.
It is reasonable to suppose that such L-sites could also appear during chemi-
cal reactions with the participation of basic molecules, for instance, methanol.
In this case they can play a role of active sites for methanol conversion.
L-sites and chemical reactions. Let us analyze this assumption in more detail.
Indeed, the first step of the CH OH molecule interaction with acidic OH-groups
3
is the formation of bridge methoxy fragments.
.H

The next methanol molecule is able to break A1-0 bond and consequently to
 661

transfer the bridge methoxide into the terminal one, as well as to dissociate on
the pair consisting of the formed trigonal A1 cation and the basic oxygen atom
attached to aluminum. This process could proceed via two energetically favorable
ways with the formation of either terminal A1-0 group and bridged methoxide or
A1-OCH3 fragment and bridged hydroxyl. The second structure is more preferable
in the presence of the methanol excess due to the formation o f the additional
strong hydrogen bond between the acidic OH-group and CH OH molecule.
3
In the first case the production of methane and formaldehyde could be accomp-
lished from the formed structure by the following synchronous mechanism (scheme
6 ) . It includes the attachment of the basic OH-group to bridge methoxide accom-
panied by hydride ion abstraction. The interaction of hydride ion with the nelg-
hboring terminal methoxide results in the break of the 0-C bond and formation of
the methane molecule. Simultaneously the restoration of initial SiOAl bridge and
the formation of an unstable bridged hydroxymethoxide group take place.

Abstraction of the proton from the latter complex being accompanied by the 0-C
bond breaking produces the formaldehyde molecule and regenerates the initial
acidic OH-group.
When second type structure is formed via CH30H dissociation on the A1-0 pair
the next adsorbed methanol molecule is activated by the acidic OH-group. Its
.further conversion could be presented by the scheme:

H
I

H3C'
662

The proton transfer from bridged hydroxyl to the adsorbed CH30H molecule is
accompanied by the nucleophylic attack of terminal methoxide by the protonated
methanol molecule. As a result the abstraction of hydrogen atom from terminal
methoxlde to neighboring oxygen and the formation of the acidic OH-group and
terminal ethoxide occur. In this case the regeneration of the initial SiOAl
bridge unit and acidic hydroxyl proceeds throughout the desorption of methanol
and ethylene molecules. The schemes similar to (6) and (7) could be also suggest
for dimethylether conversion.
The realization of scheme (7) would be accomplished only in the excess of
methanol. In the lack of the CH OH molecule the structure containing the A1-OCH
3 3
group and acidic OH-group would be isomerized into a more energetically prefe-
rable one, which leads to methane and formaldehyde formation. It is worthwhile
to mention that the schemes presented here allow to explain the difference
observed in the products of methanol conversion at low (methane and formaldehy-
de) and high (hydrocarbons) pressures of alcohol (ref.161.

REFERENCES
K.J.Chao, J.C.Lin, Y.Wang, G.H.Lee, Single crystal structure refinement of
TPA ZSM-5 zeolites, Zeolites 6(1) (1986)pp. 35-38.
V.B.Kazansky, Theory of Broensted acidity of crystalline and amorphous
aluminosllicates: quantum chemical cluster model and IR spectra Kinet.
Catal. 23(6) (1982) pp.1334-1348.
V.L.Zholobenko, L.M.Kustov, V.Yu.Borovkov, V.B.Kazansky. A new type of
acidic hydroxyl groups in ZSM-5 zeolite and in mordenite according to
diffuse reflectance i.r. spectroscopy, Zeolites 8 ( 5 ) (1988)175-178.
A.S.Medin, V.Yu.Borovkov. V.B.Kazansky, A.G.Pelmenshchikov,G.M.Zhidomirov,
On the unusual mechanism of Lewis acidity manifestation in HZSM-5 zeolites,
Zeolites 1990 (in press)
V.B.Kazansky, Diffuse reflectance IR spectroscopy and its new potentialities
in studying chemisorbed species and the structure of surface oxide
catalysts, Izv. AN SSSR 1 (1984) pp.40-51.
J.S.Binkley, R.A.Whiteside,R.Krishnan, R.Seeger, D.J.DeFrees. H.B.Schlege1,
S.Topio1, L.R.Kahn, J.A.Pople, QCPE, 13 (1981) 507.
W.J.Hehre, L.Radom. P.v.R.Schleyer, J.A.Pople, Ab initio molecular orbital
theory, Willey Intersci., New York etc., 1986.
A.S.Medin, Ph.Diss., Moscow, 1990.
E.A.Lombardo. G.A.Si11.W.K.Hal1. The assav of acid site on zeolites as
measured by ammonia poisoning, J. Catal., 119(2) 1989 pp.426-40.
10 J.L.Schlenker, J.J.Pluth, J.V.Smith,Position of cations and molecules in
zeolites with the mordenite framework. IX. Dehydrated H-mordenite via acid
exchange, Mat. Res. Bull., 14(7) (1979)pp.849-56.
11 I.N.Senchenya, V.B.Kazansky, S.Beran, Quantum chemical study of the effect
of the structural characteristics of zeolites on the properties of their
bridging OH groups, J. Phys. Chem., 90(20) (19861 4857-4859.
12 V.B.Kazansky, On the nature of Lewis acidic sites in high silica zeolites
and the mechanism of their dehydroxylation, Catalysis Today,3 (1988) 367-72.
13 L.B.Uytterhoeven, L.G.Crystner,W.K.Hal1, Studies of the hydrogen held by
solids, J. Phys. Chem., 69(6) (1965) pp.2117-2126.
14 L.Kubelkowa, J.Novakova, P.Jiru, Reaction of small amounts of methanol on
HEM-5, HY and modified Y zeolites, In: Structure and Reactivity of
Modified Zeolites, Stud. Surf. Sci. Catal. 18 (1984) pp.217-224.
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 663
01991 Elsevier Science Publishers B.V., Amsterdam

FTIR IN-SITU INVESTIGATION OF ZEOLITE ACTIVATION

R. SALZER', B. EHRHARDT', J. DRESSLER', K.-H. STEINBERG' and

P. KLAEBOE~
'Department of Chemistry, University of Leipzig, Talstr. 35,
Leipzig 7010, GDR
*Department of Chemistry, University of Oslo, N-0315 Oslo, Norway

ABSTRACT
Activation of powdered, undiluted zeolites was studied in-situ
by FTIR diffuse reflectance (DRIFT) spectroscopy. From the DRIFT
spectra we constructed contour plots, which display the process
quasi continuously.
At temperatures below 2OO0C, the diffusion of water and
ammonia towards the cation coordination sphere is seen.
The maximum loss of a particular NH species was observed at
500°C. The concentration of OH species increases most strongly at
430"C, after the on-set of an almost uniform decomposition of all
NH species. The activation of 0.93 NH,' erionite was completed at
around 600°C.

INTRODUCTION
Diffuse Reflectance Infrared Fourier-Transform (DRIFT-)
spectroscopy has a high potential for in-situ studies of
heterogeneous catalytic systems. Even very slow processes can be
monitored over long periods (ref. 1). Most samples may be
investigated without further pretreatment in a wide range of
temperatures and pressures (ref. 2). Lateral resolution in the
millimeter range can be achieved.
We used DRIFT spectroscopy to investigate the activation
process of zeolites i n - s i t u under atmospheric pressure between room
temperature and 640°C. NH,' exchanged erionites were selected as
test compounds. The DRIFT results were compared to the results of
a thorough study of erionites by conventional infrared transmission
technique (ref. 3).
Here we describe the experimental technique and present the
first results.
664

SAMPLING SYSTEM
DRIFT spectra are given in Kubelka-Munk units f (R) (ref. 4 ) ,
which are directly related to the absorbance coefficient k of the
sample and its scattering coefficient s via
f(R) = (1 - R/R')' / 2R/R' = k / S . ( 1 )
R is the single-beam reflectance spectrum of the sample, R' the
single-beam reflectance spectrum of a non-absorbing standard.
The Kubelka-Munk equation (1) was derived for the ideal case
of purely diffuse reflectance. For real samples, diffuse
reflectance is always accompanied by specular reflectance, which
upsets the ordinate scale and deteriorates the detection limits.
The only way to prevent contributions of specular reflectance from
reaching the detector is to select a DRIFT attachment of a
particular optical design, the so-called off-axis geometry
(ref. 5), where the incoming beam and the normal to the sample
surface do not share a common plane (or axis) with the reflected
beam (Fig. 1).
A heatable sample stage for DRIFT spectroscopy, which is
commercially available (HVC-DRP chamber of Harrick Scientific
Corp., Ossining/NY), was tested over a wide temperature range. The
vacuum chamber body, which encloses the sample stage, was omitted
because the investigation was carried out at ambient pressure. Any
change in the sample position during the measurement series,
including realignment, was avoided.

reflected beam
incoming beam

sample
to power supply
heater
thermal insulator
adjustment screw
base

Fig. 1. Scheme of the sample heater for the DRIFT

investigations.
 665

S i n g l e beam s p e c t r a of t h e t e s t sample ( c o r r e s p o n d i n g t o R i n
e q n . 1) a r e summarized i n F i g . 2 . The a r e a below a p a r t i c u l a r c u r v e
r e f e r s t o t h e t o t a l amount of modulated r a d i a t i o n r e a c h i n g t h e
d e t e c t o r . Upon h e a t i n g t h e HVC-DFW sample s t a g e , t h e s i n g l e beam
s p e c t r a become i n c r e a s i n g l y f l a t ( F i g . 2 a ) . The observed r e d u c t i o n
i n e n e r g y t h r o u g h p u t i s more s e v e r e a t s h o r t e r w a v e l e n g t h s (compare
the lowering of t h e c u r v e maxima at 4 0 0 0 a n d 2200 cm-I). This
s u g g e s t s a g e o m e t r i c a l e f f e c t dominating t h e energy d r o p d u r i n g
h e a t i n g , p r o b a b l y b e due t o t h e r e l a t i v e l y l o n g h e a t i n g zone of t h e
HVC-DRP sample s t a g e , c h a n g i n g t h e sample p o s i t i o n r e l a t i v e t o t h e
reflectance mirrors.

1 1

/p
25 *C a)

i 0,5 I
~
i 0.

,
0 0
6000 4000 2000 0 6000 4000 2000
+- cm-' +- cm-'

F i g . 2 . S i n g l e beam s p e c t r a of 0 . 9 3 NH,' e r i o n i t e a t d i f f e r e n t
t e m p e r a t u r e s . a ) Sample s t a g e of HVC-DRP chamber. b ) Oven a s i n
F i g . 1.

The o b s e r v e d e n e r g y l o s s d u r i n g h e a t i n g r e d u c e s t h e S / N r a t i o ,
causes background fluctuations in the spectra and introduces
ordinate non linearities. These effects can be reduced
c o n s i d e r a b l y , when t h e r e f e r e n c e s p e c t r u m i s measured a t t h e same
t e m p e r a t u r e a s t h e sample spectrum.
The b e s t results c o u l d be observed using a sample stage
according t o Fig. 1, whose t h e r m a l e x p a n s i o n was minimized by
i n t r o d u c i n g t h e h e a t e r d i r e c t l y i n t o t h e sample b u l k ( F i g . 2 b ) .
666

EXPERIMENTAL
A Bruker FTIR spectrometer IFS 88 was used for all tests of
the heatable sample stage of the HVC-DRP reaction chamber. The
sample stage was inserted into a diffuse reflectance attachment
D R A 3 (Harrick Scientific Corp. , Ossining/NY, USA) .
All the other FTIR spectra were scanned on an IRF 180 (ZWG,
Akademie der Wissenschaften der DDR, Berlin), equipped with a the
off-axis diffuse reflectance attachment of the same manufacturer.
128 interferograms were co-added before Fourier transformation.
The thermal insulator of the heatable sample stage was made of
glass ceramics (Fig. 1). A micro thermocouple was used for
temperature measurement. The alignment of the thermocouple to the
uppermost layer of the powder is important for exact measurement.
Samples were heated by 2 K min-', and during the spectral
measurements the temperature was kept constant.
The synthesis and ion exchange of the erionites used in this
study have already been described (ref. 3). The samples were
investigated as received. Finely ground KBr was used as reference.
No features, e.g. peaks due to atmospheric C02, have been omitted
from the spectra.

RESULTS AND DISCUSSION

The OH and NH stretching bands are selected in order to
monitor the activation of undiluted 0.93 NH,' erionite in the open
atmosphere (Fig. 3). All the band locations and intensity ratios
correspond completely to the transmission spectra (ref. 3).
The graduate loss of physisorbed species is indicated by the
overall reduction in the size of the band complex. The almost
complete desorption of NH species up to 550°C is seen by the
disappearance of the corresponding NH stretching bands below
3 3 0 0 cm-'. Simultaneously, the band appearing above 3600 cm-!
indicates the formation of OH groups.
A detailed investigation of the whole activation process
(Fig. 3) is difficult because of the complicated shape of the
bands. For this purpose we applied a complex evaluation procedure
to the spectra. It is important to note, that no individual
assumptions are necessary in course of the following computations.
 667

A s a first step,
all the constant
(background) features
apparent during
heating are removed by
s u b t r a c t i n g
consecutive spectra.
It depends upon the
available software,
w h e t h e r t h e
temperature intervals
have to be constant or
not. A high S/N ratio
and a constant
ordinate accuracy in
the single beam
s p e c t r a a r e
prerequisites.
The ordinate
accuracy of DRIFT
spectra is mainly
determined by the
scattering coefficient
s in eqn. 1. It varies
remarkably for
Fig. 3. DRIFT spectra of 0.93 NH,' different sample
erionite during activation at the open preparations, even for
atmosphere.
samples from the same
batch. One must only
evaluate spectra, which belong to one consecutive series of
measurements.
The D R I F T difference spectra in Fig. 4 enhance all the changes
taking place during activation, which have been discussed regarding
Fig. 3. The removal of all the constant features did not simplify
the shapes significantly.
In the following, we shall regard the complete set of curves
in Fig. 4 as a landscape. The height of the hills corresponds to
the increase of a particular XH species per temperature step, the
668

Fig. 4 . DRIFT d i f f e r e n c e spectra for the activation of

0 . 9 3 NH4’ e r i o n i t e

d e e p n e s s of t h e v a l l e y s t o t h e d e c r e a s e i n c o n c e n t r a t i o n . A t e v e r y
v i e w i n g a n g l e mountains i n t h e f o r e g r o u n d h i d e f e a t u r e s b e h i n d ,
whereas a map, t h e s o - c a l l e d c o n t o u r d i a g r a m , p r o v i d e s immediate
a c c e s s t o a l l t h e d e t a i l s of t h e measured s e r i e s .
Contour d i a g r a m s f o r t h e DRIFT d i f f e r e n c e s p e c t r a i n F i g . 4
a r e g i v e n i n F i g s . 5 and 6 . To e n s u r e c l e a r n e s s of t h e monochrome
d i s p l a y , t h e r e g i o n s of n e g a t i v e r e f l e c t a n c e c h a n g e s ( d e c r e a s i n g
c o n c e n t r a t i o n s ) d u r i n g h e a t i n g a r e h i g h l i g h t e d i n F i g . 5, r e g i o n s
of p o s i t i v e r e f l e c t a n c e c h a n g e s ( c o r r e s p o n d i n g t o i n c r e a s i n g
concentrations) i n Fig. 6 .
A t t e m p e r a t u r e s below 200°C t h e I R r e f l e c t a n c e d e c r e a s e s i n
t h e r e g i o n 3700 - 2800 cm-’ due t o d e s o r p t i o n o f w a t e r and ammonia
( F i g . 5 ) . The r e f l e c t a n c e l o s s e s s t a r t most pronounced around
3450 cm-’ (OH s p e c i e s ) and 3 1 0 0 cm-’ ( N H s p e c i e s ) . Above 150°C t h r e e
bands f o r d e s o r b i n g NH c a n be s e e n ( 3 3 0 0 , below 3100, below
2900 cm-I).
Up t o 200°C a s i m u l t a n e o u s i n c r e a s e i n r e f l e c t a n c e i s o b s e r v e d
between 2800 and 2200 cm-’. The i n c r e a s e d r e f l e c t a n c e i s e a s i l y s e e n
 669

640

O C

530

420

310

200

130

Fig. 5. Contour plot of DRIFT difference spectra in Fig. 4. The

bright area indicates decreasing concentrations.

640

O C

530

420

310

200

130
Cm-'

Fig. 6. Contour plot of DRIFT difference spectra in Fig. 4. The

bright area indicates increasing concentrations.
670

in Fig. 6, whereas it could only be guessed in Figs. 3 and 4. The

increased reflectance amounts to ca. 10% compared to the decrease
mentioned above. It points to diffusion towards the cation
coordination sphere. The assignment of the bands to water and
ammonia is under study.
At 26OoC, a minimum of reflectance changes across the
investigated spectral region is indicated in Figs. 5 and 6 . Above
this temperature the decomposition of the NH,+ cations starts. Three
bands are observed (ca. 3 2 5 0 , 3 0 3 0 and 2 7 8 0 cm-') . The decomposition
is first indicated for the band having the highest frequency. This
band a l s o shows the maximum loss of NH,' ions at 500°C. The on-set
of an almost uniform decomposition of all the NH,' species is
indicated by the spread of the contour line at 400°C (Fig. 5).
The formation of new OH groups is first observed for species
absorbing above 3 6 0 0 cm-' (Fig. 6 ) . This band has been assigned to
strong Brernsted acid sites (ref. 3 ) . An OH species, absorbing at
3 5 6 0 cm-' and located in the six-membered ring units (ref. 3 ) , is
formed at somewhat higher temperatures. The stretching frequencies
of both OH species are red shifted with increasing temperature.
The concentration of OH groups increases most strongly around
430"C, after the beginning of the uniform decomposition of all NH,'
species.
At ambient pressure the activation of 0 . 9 3 NH,' erionite is
completed at around 650°C.

ACKNOWLEDGEMENT
This research was supported by The Norwegian Research Council
for Science and the Humanities (NAVF).

REFERENCES
1 R. Salzer, K.-H. Ste nberg, P. Klaeboe, B. Schrader, Zeolites
submitted.
2 S. A. Johnson, R.-M Rimkus, T. C. Diebold and V. A. Maroni
Appl. Spectr. 42 1 9 8 8 ) 1 3 6 9
3 A. Kogelbauer, J. A . Lercher, K.-H. Steinberg, F. Roessner,
A. Soellner and R V. Dmitriev: Zeolites 9 ( 1 9 8 9 ) 2 2 4 .
4 P. Kubelka and F. Munk: 2. Techn. Phys. 1 2 ( 1 9 3 1 ) 5 9 3 .
5 D. M. Hembree and H. R. Smyrl: Appl. Spectr. 4 3 ( 1 9 8 9 ) 2 6 7
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 671
0 1991 Elsevier Science Publishers B.V., Amsterdam

IR SPECTRA OF CO ADSORBED AT LOW TEMPERATURE (77 K) ON TITANIUM-

SILICALITE, €I-ZBMS AND SILICALITE

A. ZECCHINA~,G. SPOTO~,s. BORDIGA~,M. PA DO VAN^, G. LEO FAN TI^

and G. PETRINI~
'Dipartimento di Chimica Inorganica, Chimica Fisica e Chimica dei
Materiali, Via P. Giuria 7, 10125 Torino (Italy)
'Montedipe, Unit& di Ricerca, Via San Pietro 50, 28100 Bollate
(MI) (Italy)

ABSTRACT
The IR band at 960 cm'l observed on TS is due to a local
stretching mode of a [Ti04] unit in the silicalite framework.
Framework Ti does not show Lewis acidity as probed by CO adsorp-
tion at 77 K. TiOH and SiOH have undistinguishable IR properties.
At 77 K they form with CO very weak 1:l OH...CO adducts. Small
amount of extralattice Ti in form of Ti02 can be probed by CO
adsorption at 77 K.

INTRODUCTION
The substitution of Ti and A1 for Si in zeolites of the penta-
sil family (Silicalite) leads to Ti-Silicalite and ZSMS which are
two important catalysts for oxidation with HZOZ (refs. 1-3) and
acid catalyzed reactions (ref. 4 ) .
The characterization of Titanium-Silicalite (TS) by means of
physical methods has been recently published (ref. 5). However, a
few problems are still open concerning: i) the presence of extra-
lattice Ti (as Ti02 microparticles); ii) the interpretation of
the vibrational spectrum of the solid; iii) the crystallinity of
TS with respect to pure S and ZSMS; iv) the presence of titanols
in the channel8 and cavities.
The CO molecule is an efficient probe of Lewis and Broensted
acidity and can be used to explore the acidity of OH groups in
the channels (TiOH and SiOH in TS, (Si,Al)OH, SiOH and AlOH in
H-ZSM5). On dehydroxylated samples coordinatively unsaturated
Ti4+ and A13+ ions in lattice and extralattice positions can be
revealed as well, because they can form Lewis adducts with CO.
In this contribution we report on the IR spectra of CO ad-
sorbed at 77 K on TS, s and ZSMS. The vibrational spectra of s,
TS and Na-ZSM5 are also compared and discussed.

EXPERIMENTAL
Silicalite and Titanium-Silicalite have been synthesized in
Montedipe laboratories following the method described in ref. 2;
Na-ZSM5 and H-ZSM5 (external surface area 60 m’9-l) have been
provided by the same laboratory. The ER spectra have been ob-
tained on a Bruker IFS 113V FTIR spectrometer using a specially
designed silica cell permanently attached to a vacuum manifold
and allowing in situ outgassing procedures at temperatures in the
273-1073 K interval and gas dosing at 7 7 K. The samples were
either in form of thin pellets or of films deposited on KBr or Si
plates.

RESULTS AND DISCUSSION

IR modes associated with framework Ti
The spectra recorded at 7 7 K of S, TS and ZSM5 (sodium form;
Si/A1=35) films outgassed at 573 K are compared in Fig.1.
The major difference between S and ZSM5 on one side and TS on
the other side is represented by the presence in the spectrum of
TS of a (finger print) peak at 960 cm-l. In order to give a
correct assignment of this band the following considerations have
to be made: a) it cannot be assigned to an optical mode of TiOZ
microparticles entrapped into the channels or at their intersec-
tion because neither rutile nor anatase show strong IR bands at
this frequency; b) despite the similarity with the IR manifesta-
tions of homogeneous titanyl containing analogs , the 960 cm-’
peak cannot be attributed to the stretching mode of internal
(Ti=O)’+ because: i) it is not perturbed by filling the pores and
channels with CO (results not reported), which, being a weak
Lewis base, is expected to interact with the positive centres and
to perturb them; ii) it does not have the expected counterpart in
the UV-Vis diffuse reflectance spectrum (absorption in the
25000-35000 cm’l range) (ref. 6); iii) it cannot be removed by
reductive treatments in H2 and CO even at very high temperature
or under plasma discharge conditions (Ha).
On the basis of the previous **negativet*
evidences, the hypoth-
esis has been made that the 960 cm-l band is due to a local mode
of the Titanium-doped pentasilic structure (essentially a
stretching mode of a [Si04] unit perturbed by an adjacent Ti)
(ref. 5 ) .
 673

0.5 F'LI
A / I

1
I0
YRVENUHBER C H - I

Fig.1. IR absorbance spectra (recorded at 77 K) of: a) Silica-

lite, b) Na-ZSM5 (Si/A1=35) and c) Ti-Silicalite. In the inset:
W-Vis reflectance spectra of a) Silicalite and c) Ti-Silicalite.

A full assignment of the IR spectra of s, TS and ZSM5 requires

a detailed unit cell vibrational analysis and is outside the
scope of this contribution. However, an explanation of the
presence of the extra-absorption in the TS spectrum can be equal-
ly given on the basis of the following qualitative considera-
tions.
The vibrational representation of the stretching modes of an
tetrahedral [ S i O , ] unit is:
llisolatedll
rstret.= T2 *I +

(TZ: IR active; A1: IR inactive). Packing of the [Sio,] (by shar-

ing the corners) to form the zeolitic structure has two conse-
quences: i) the local *'site1@symmetry of each [SiO,] primary
674

building unit is lowered to C2 (ref. 7) so that the triply degen-

erated T2 mode is splitted into three, one weak (A) and two
strong (B), components and ii) due to the high number of [SiO,]
units forming the unit cell (where 9 6 tetrahedral units are
present) broad bands are expected because of the further split-
ting of each component into a maximum of 96 sub-components. On
these basis, the spectrum of S in the stretching region can be
interpreted as follows: i) the two clear absorption at 1235 (m-
w) and 1200-1050 (vs) cm-l, are essentially associated with the A
and B modes of the primary unit broadened by unit cell splitting
effects; ii) the complex (vw) band centered at =770 cm-l derives
from the A1 (IR inactive) mode (the fine structure observed at 77
K being associated with the unit cell sub-components). The bands
at lower frequency belong to skeletal modes having bending char-
acter and will not be considered here for sake of brevity. We
only mention that the peak at ~ 5 5 0cm-l is absent on amorphous
silica and is considered as a gfcrystallinityfg (structure sensi-
tive) band (ref. 5).
As far as TS is concerned, some 1-2% of the [SiO,] building
blocks of pure silicalite framework are substituted for Igheavierff
[TiO,] units. The substitution does not dramatically change the
overall IR spectrum other than for the appearence of localized
fgimpurityggmodes associated with the [TiO,] dopant units. In the
stretching region four additional local modes are, in principle,
expected, three (A+2B) deriving from the T2 degenerate vibrations
of the free [TiO,] unit and one (A) from the A1. These modes
should be shifted to lower frequencies with respect to those of
Silicalite, because of the mass effect. Actually only the band
deriving from the strongest absorption at 1120 cm-l (presumably
of B simmetry) has enough intensity and is enough shifted to show
up clearly in the gap between the 1250-1050 and 820-750 cm-l
absorptions.
The previous analysis predicts that, due to the small differ-
ence in the mass of A1 and Sir the impurity modes associated with
[AlO,] should be not osservable at all. This explains the great
similarity between the Silicalite and Na-ZSM5 spectra.
The assignment of the 9 6 0 cm" peak to local modes of [TiO,]
units is in agreement with: i) the characteristic reflectance
spectrum of TS (inset of Fig.1) where an high intensity band at
48000 cm-', with charge transfer character, is indicative of the
presence of [TiO,] units (ref. 5 and references therein) ; ii)
 675

the IR spectrum of Si02/Ti02 glasses where a similar, although

broader, band is observed (refs. 8,9).
Of course these considerations, based only on the mass effect,
are an heavy approximation. In fact, due to the higher ionicity
of the Ti-0 bond, the Ti-0 and the Si-0 stretching constants are
not the same. This assignment is slightly different with respect
to that given in ref. 5, where a larger ionicity of the Ti-0 bond
was assumed. It can be easily demonstrated that they transform
the one into the other when the ionicity of the Ti-0 bond is
gradually changed from pure covalent to ionic.

Ir spectra of CO adsorbed on Silicalite, Ti-Silicalite and H-

ZSM5: assianment and comarison
The spectra of CO adsorbed at 77 K on S and TS samples out-
gassed at 573 K under vacuo are reported in Fig.2a (3800-3000
cm-l region) , and Fig.2b (2250-2050 cm-l) and Fig.3a and 3b re-
spectively. Similar spectra have been obtained for samples out-
gassed at lower and higher temperature. They are not described in
detail for sake of brevity.
The following can be commented.

Silicalite
The IR spectrum in the OH stretching region (Fig.2a) is char-
acterized by two main absorptions at 3750-3700 cm-' (composit

3710 cm-l) and at 3460 cm

'
l
-
with narrow components at 3750 and 3730 cm-l and a broader one at
(0))112=130 cm") .
These two bands
essentially correspond to free (isolated and terminal, external
and internal) and hydrogen bonded silanols respectively. Upon CO
dosage the bands due to free silanols (both isolated and termi-
nal) are eroded, while two new peaks are formed at 3640 and 3585
.''nrc The presence of a clear isosbestic point indicates that the
free OH (isolated and terminal) are transformed into hydrogen
bonded species (because of formation of 1:l OH...CO adducts) as
illustrated in the following scheme:

OH.. .CO OH...OH...OH...CO

I (isolated)
Si
Upon CO adsorption the peak at
ic changes, in agreement with
small but clear shift at lower
reinforcement of the hydrogen
I l l (terminal)
si Si si
3460 cm" does not undergo dramat-
the given assignment. However, a
frequency is indicative of a small
bond between adjacent OH groups.
676

a
t

a 2

Fig.2. IR spectra of CO adsorbed at 77 K (increasing doses) on

Silicalite outgassed at 573 K. a) OH stretching region: the
evolution of'the bands is indicated by the arrows; Aindicate the
isosbestic points. b) CO region. The spectrum of CO adsorbed on
H-ZSM5 (at 77 K and maximum coverage) outgassed at the same
temperature is reported for comparison.

This can be easily explained on the basis of the previous scheme:

in fact the formation of the 1:l adducts involving terminal OH
groups and CO induces the polarization in the terminal 0-H bond
and this in turn reinforces the hydrogen bonding between the
vicinal groups of the chain. Similar effects have been observed
also in homogeneous conditions (ref. 10). The previous assignment
is confirmed by the following other experiments: i) by outgas-
sing Silicalite at 973 K the peaks at 3460 and 3710 cm-' simul-
taneously disappear; ii) the adsorption of CO on samples con-
taining only isolated OH both on silica and silicalite gives the
3750 cm-' peak only.
In the part b of the figure the parallel spectra in the CO
stretching region is illustrated. Two main absorptions are clear-
ly observed at 2159 and 2137 cm-'. The first peak, with frequency
slightly higher than that of the CO gas (a7=16cm-l) , is due to
 677

the CO stretch of the OH...CO (1:l) adducts (both isolated and

terminal). The second peak (with frequency nearly coincident with
that of (CO)liq) is due to CO molecules physically adsorbed (or
in a liquid-like state) in the channels and pores.
In the same figure (2b) the spectrum of CO on H-ZSM5
(Si02/A1203=28) outgassed at the same temperature is reported for
sake of comparison. We can immediately notice that the two type
of spectra are very similar but for the peak at 2170 cm-' present
only on H-ZSM5: this peak, characterized by a blue shift of 27
cm" with respect to CO gas, is associated with Broensted acid-CO
complexes. This comparison shows that CO is a good probe of the
strong Broensted acidity of H-ZSM5 and that SiOH groups are much
less acidic in agreement with ref. 11.

Titanium-Silicalite
An identical experiment carried out on TS outgassed at 573 K
gives the spectra reported in Fig.3a and 3b (OH and CO stretching
region respectively). The great similarity with the spectra of
Fig.2 is immediately evident. This observation has two main
consequences: i) titanols (either on framework or extra-framework
Ti) cannot be easily distinguished from silanols by IR spectros-
copy (especially when the Titanium content is small) and ii)
titanols (either framework or extraframework) have Broensted
acidity not substantially different from silanols. In conclusion,
the presence of Ti does not substantially modify the OH distribu-
tion and their acidity. In these conditions we can ask wether
TiOH groups are really present (specially if we consider that if
Ti is totally framework and if the Ti-0-Si bridges are not at
least partially hydrolyzed TiOH should be absent). For the time
being we cannot answer this question. However, we shall come back
again on this problem later on, on the basis of further data.
As known from indipendent experiments on the Ti02/C0 system
(ref. 12) , the adsorption of CO on microparticles of Ti02 out-
gassed at temperature t 873 K, gives surface Ti4+cus-C0 (cus:
coordinatively unsaturated) species characterized by a well
defined high intensity peak at 2179 cm-'. The presence, or the
absence, of this peak on properly outgassed TS samples can be so
used as a text of the presence or the absence of extraframework
Ti in form of Ti02 microparticles. The results of this experi-
ments on a TS sample outgassed in vacuo at 873 K are reported in
Fig.4a and 4b. In the same figure the spectrum of CO (CO-stretch-
678

1 n b
t
a TO' Ii1 0.5

-z
r
0

Y
u
z
U
m
w
0
VI
m
U

3888 3688 3400 3288 380022 8

YRVCNUHBtR CM-I YRVt"ljHBtR CH-I

Fig. 3. IR spectra of CO adsorbed at 77 K (increasing doses) on

Ti-Sil icalite outgassed at 573 K. a) OH stretching region. The
arrows and A have the same meaning as in Fig.2. b) CO region.

ing region) adsorbed at 77 K on TiOZ (anatase) outgassed at the

same temperature is reported for sake of comparison. From these
figures we can conclude that: i) the bands at 3450 and 3700 cm"
disappear simultaneously upon outgassing, in agreement with the
given assignment ; ii) isolated silanols (either external or
internal) are the main species present on the sample and give the
expected OH...CO 1:l complexes characterized by peaks at 3650
cm" (OH) and 2155 cm'l (CO); iii) very low intensity band at
~ 2 1 8 0cm-l reveals that Ti4+cus-C0 adducts are indeed present on
the sample outgassed at high temperature. However, comparison
with the spectrum of CO adsorbed on Ti02 clearly indicates that
the amount of extralattice Ti under form of Ti02 microparticles
is negligible. The last observation confirm that the major part
of Ti is in framework position and does not have relevant Lewis
acidity.
We can now go back to the question concerning the presence or
 679

a
I!

h
'

I 3600 3400 3200 31 12250 2200 2150 2100 2 0

YRVENUHBER CM-I YRVENUMBER C H - I

Fig.4. IR spectra of CO adsorbed at 77 K (increasing doses) on

Ti-Silicalite outgassed at 873 K. a) OH stretching region. The
arrows and A h a v e the same meaning as in the previous figures.
b) CO region. The spectrum of CO adsorbed at 77 K (maximum cover-
age) on pure Ti02 outgassed at the same temperature is reported
for comparison.

absence of TiOH groups. First of all we can now say with confi-
dence that TioH or Ti02 microparticles do not play any relevant
role in the spectrum of TS (OH stretching region), and secondly
that TioH (if present) must comes only from partial hydrolysis of
polar Si-0-Ti bridges, as already hypothesized in ref. 5. In
order to prove or reject the hypothesis that Si-0-Ti bridges
exposed in the channels and cavities are preferential sites for
H20 adsorption, the following comparative experiment has been
designed. Silicalite and Ti-Silicalite samples were outgassed at
973 K in high vacuum for 4 hrs to eliminate all the hydrogen
bonded hydroxyl groups. After this treatment the IR spectra in
the OH stretching region were substantially undistinguishable
(with only one peak left at 3720 cm-' similar to that shown in
Fig.4a). H20 vapuor was then dosed (10 torr) on the sample and
680

left to stand for 15 minuts. After this dehydration step the

unreacted H20 was pumped off at 573 K and the hydration state of
the surface monitored by recording the IR spectrum in the OH
stretching region. The result was as follows: after the thermal
treatment Silicalite shows hydrofobic character, as H20 dosage
does not restore the original hydroxyl concentration; on the
contrary, Ti-Silicalite is slightly more hydrophylic and can be
partially rehydrated. We think that this behaviour could be a
consequence of the presence of Si-0-Ti bridges which, being more
polar, can easily undergo H20 attack giving silanols and titanols
in vicinal position.

CONCLUSIONS
The IR band observed in the spectrum of TS at 960 cm-', asso-
ciated with framework Ti, is due to a local impurity stretching
mode of the [Ti04] unit in the Silicalite lattice. The small
fraction of extralattice Ti in form of Tio2 microparticles does
not contribute to the IR spectrum of TS. TiOH and SiOH cannot be
distinguished by IR spectroscopy and have very similar acidity
(as tested by CO adsorption at 77 K). Moreover, comparison with
the spectra of OH...CO adducts on H-ZSM5 shows that their acidity
is much lower. Lewis acidity associated with Ti4+ ions is also
pratically absent even on samples outgassed at 973 K.

REFERENCE8
W. Holderich, M. Messe and F. Naumann, Angew. Chem. Int. Ed.
Engl., 27 (1988) 26.
C. Neri, A. Esposito, B. Anfossi and F. Buonomo, Eur. Pat.
100 119.
C. Neri, M. Taramasso and F. Buonomo, U.K. Pat. 102 665.
J.A. Rabo, Catal. Rev. Sci. Technol., 24 (1982) 202.
M.R. Boccuti, K.M. Rao, A. Zecchina, G. Leofanti and G. Petri-
nil Spectroscopic characterization of Silicalite and
Titanium-Silicalite, in: C. Morterra, A. Zecchina and G.
Costa (Eds.), Structure and Reactivity of Surfaces, Elsevier,
Amsterdam, 1989, pp. 133-144.
P. Comba and A . Merbach, Inorg. Chem., 26 (1987) 1325.
A. Miecznikowski and J. Hamuza, Zeolites, 7 (1987) 249.
M.F. Best and R.A. Condrate, J. Mat. Sci. Letters, 4 (1985)
994.
B.G. Varshal, V.N. Denisov, B.N. Maurin, G . A . Paulova, V.B.
Podobedov and K.E. Stebin, Opt. Spectrosc. (USSR), 47 (1979)
344.
10 G.C. Pimentel and A.L. McClellan, The hydrogen bond, W.H.
Freeman and Co., San Francisco and London, 1960.
11 V.B. Kazanskii, Kinet. Catal., 28 (1987) 482.
12 G. Spoto, C. Morterra, L. Marchese, L. Orio and A. Zecchina,
Vacuum, in press.
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 681
0 1991 Elsevier Science Publishers B.V., Amsterdam

THE PROPERTIES OF BORALITES OF V A R I O U S BORON CONTENTS

J . DATKA. A. CICHCCKI and Z. PIWOWARSKA

F a c u l t y of C h e m i s t r y . J a g i e l l o n i a n U n i v e r s i t y . Karasia 3,
30-060 Krakdw C Poland>

SUMMARY
The p r o p e r t i e s of Bog u n i t s and a c i d p r o p e r t i e s of boralites
w i t h v a r i o u s boron c o n t e n t s w e r e s t u d i e d b y I R s p e c t r o s c o p y . The
band of a n t i s y m m e t r i c s t r e t c h i n g v i b r a t i o n s of 9-0 i s s p l i t i n t o
t w o m a x i m a . I t s e e m s t o b e d u e t o t h e removal of d e g e n e r a t i o n of
t h i s vibration. The i n t e n s i t y of t h e B03 doublet increases
l i n e a r l y w i t h t h e b o r o n c o n t e n t b o t h i n N a - and H - b o r a l i t e s . The
e x t i n c t i o n c o e f f i c i e n t of 9-0 v i b r a t i o n i s d i s t i n c t l y l h i g h e r i n
t h e . . c a s e of H-boralites. The c o n c e n t r a t i o n of 3720 c m hydroxyls
CBronsted a c i d s i t e s 3 i n c r e a s e s l i n e a r l y w i t h b o r o n c o n t e n t i n
H - b o r a l i t e s and i s close t o t h e t h e o r e t i c a l v a l u e s . S m a l l amounts
of L e w i s a c i d sites a r e p r e s e n t i n H-boralites. their acid
s t r e n g t h b e i n g h i g h e r t h a n i n HZSM-5.

I NTRODUCTI ON
Isomorphically substituted zeolites have recently been
studied extensively because of their interesting chenucal
p r o p e r t i e s and p o t e n t i a l i n d u s t r i a l a p p l i c a t i o n [ f o r a r e v i e w see
ref. C1>1. Boron s u b s t i t u t e d z e o l i t e s . boralites, which owing t o
the small s i z e of boron atom show properties not observed in
zeolites. draw the greatest attention. The boron atom is
t r i -coordinated i n d e h y d r a t e d b o r a l i tes , t h e B03 band a p p e a r s i n
t h e spectrum Cref. 2.31. The p r o p e r t i e s of B03 units i n boralites
of v a r i o u s b o r o n c o n t e n t s w e r e s t u d i e d b y I R s p e c t r o s c o p y a n d t h e
r e s u l t s a r e described i n t h e present paper.
Our p r e v i o u s I R s t u d y C r e f . 3,4> h a s shown t h a t f o u r k i n d s of
-1
OH g r o u p s exist i n H - b o r a l i t e s . Only 3720 cm h y d r o x y l s were
f o u n d t o b e B r z n s t e d a c i d sites. Their acid strength is much
lower than in zeolites Cref. 2-51. The concentration of the
B r z n s t e d a c i d s i t e s i n H-boralites of v a r i o u s boron c o n t e n t s w a s
s t u d i e d by I R s p e c t r o s c o p y and t h e r e s u l t s a r e a l s o presented i n
t h i s paper.
682

EXPERIMENTAL
Five samples of MFI boralites were synthesized in the
N a 0-TPABr-B 0 -SiO -H 0 s y s t e m as d e s c r i b e d i n d e t a i l i n r e f . 7 .
2 2 3 2 2
C o n c e n t r a t e d s i l i c a sol, s o l i d o r t h o b o r i c a c i d H3B03. sodium
hydroxide, and distilled water were used as substrates and
tetrepropylammonium bromide TPBABr as a template substance.
Individual synthesis differed only in the molar ratio n
RM
C=Si02/B203 in the reaction mixture). which was varied in the
r a n g e 5-100. C r y s t a l l i z a t i o n w a s c a r r i e d o u t i n steel autoclaves
lined with PTFE. at 438 K. for 7 days, without stirring. The
p r e c i p i t a t e w a s washed w i t h d i s t i l l e d w a t e r a n d d r i e d i n air. In
o r d e r t o decompose o r g a n i c species boralites were c a l c i n a t e d i n
a i r a t 773 K i n a t h i n l a y e r C l - 2 mml. for 4 h. Boralites thus
p r e p a r e d are d e n o t e d as Na-boralites. They w e r e n e x t t r a n s f o r m e d
into the NH4-form by triple ion exchange in ammonium chloride
solution at room temperature. The compositions of Na- and
NH - b o r a l i t e s ( o b t a i n e d from chemical analysis) are presented in
4
T a b l e 1.
XRD studies have shown that all the samples were highly
crystalline without crystalline admixtures. They had the
or thor hombi c MFI s t r u c t u r 8 .
The N a / N H 4 ion exchange resulted in some boron loss from
boralites. This problem is d i s c u s s e d i n detail i n our previous
paper Cref. 81. The c a l c i n a t i o n of NH - b o r a l i t e s r e s u l t s i n a
4
further boron loss Cref. 8). The b o r o n c o n t e n t s i n H-BOR-8.
H-BOR-5. H-BOR-4. H-BOR-3. H-BOR-2 w e r e f o u n d t o be 0.88, 0.59,
0.69. 0.85 a n d 1 . 0 5 B/u. c. r e s p . upon c a l c i n a t i o n i n a i r a t 773 K .
for 4 h C s a m p l e numbers a r e t h e s a m e as i n o u r p r e v i o u s p a p e r ,
ref. 71.
For I R s t u d i e s NH - b o r a l i t e s were p r e s s e d into thin wafers
4
C4-7 m g cm-'). The w a f e r s w e r e activated in situ i n I R c e l l in
vacuum at. 773 K , for 1 h. It was assumed that the boron loss
during this activation was the same as during the calcination
u n d e r c o n d i t i o n s described i n r e f . 8.
T h e s p e c t r a w e r e r e c o r d e d u s i n g a SPECORD 75 I R s p e c t r o m e t e r
CCarl Zeiss J e n a l working on l i n e w i t h a K S R 4100 minicomputer.
Pyr i d i ne C PCCh-G1 i w i c e l u s e d w a s o f a n a l y t i c a l g r a d e .
 683

TABLE 1
Compositions of N a - and NH -boralites
4

Sample
* composition
~~ ~~

Na-BOR-8
30H0.10CCB02’0.
3OcAlo2’0. 1OcSi02’Q5. 6’
NH4 -BOR-8
03CNH4’0.37ccB02’0.2QcA102’0. 1lcsi02’S5. 6’

Na-BOR-5 80CCB02’0.
8OcSi02’Q5. 2’
NH 4 -BOR-5
04CNH4’0.69[cB02’0. 63CA102’0.10csi02395.2’

N a -BOR -4
N a lOO[CBo2’l.
. 0OcSi02’Q5. 0’
NH4-BOR-4
Na0..02CNH4’0. 84CCB02’0. 78cA10220.0ScSi02’Q5. 0’

N a -BOR -3 N a l30H0.
. 4OCSio2’Q4.
10CcB0231. 6’
NH4-BOR-3
01CNH4’0.98[cB02’0. 99csi022Q4. 63

Na-BOR-2 N a l60H1.
, 0OCCB02’2. 6OcSi02’Q3. 4’
NH4-BOR-2 OlCNH4’1. 36[cB02’1. 37csi022Q3.4’

* s a m p l e numbers a r e t h e same a s i n p r e v i o u s p a p e r C r e f . 73

RESULTS AND DISCUSSION

BO vi b r a t i ons
-3
I R spectra of dehydrated b o r a l i t e s show a band about 1400
-1
cm , c h a r a c t e r i s t i c of v3 a n t i s y m m e t r i c s t r e t c h i n g v i b r a t i o n s of
B-0 i n B03 u n i t s . T h i s band i s p r e s e n t b o t h i n t h e s p e c t r a of N a -
and H - b o r a l i t e s Cref. 2.32. The MAS NMR s t u d i e s h a v e also p r o v e d
Cref. 53 that boron is tri-coordinated in dehydrated boralites.
Because of i t s s m a l l s i z e , boron i s n o t s i t u a t e d i n t h e c e n t r e of
TO, t e t r a h e d r o n b u t on ‘ o n e of its f a c e s . Our previous s t u d y has
shown t h a t t h e B03 band i s s p l i t i n t o t w o maxima: 1380 a n d 1 4 0 5
-1
cm .
The o r i g i n of t h i s s p l i t w i l l be now d i s c u s s e d . Two p o s s i b l e
interpretations will be considered. One of them assumes the
existence of two kinds of boron sites in boralite lattice
c h a r a c t e r i z e d by d i f f e r e n t B-0 f o r c e c o n s t a n t . I t c o u l d be d u e t o
d i f f e r e n t f o r c e s of i n t e r a c t i o n between t h e b o r o n a n d t h e f o u r t h
684

o x y g e n i n 0 B---.O u n i t s . A n o t h e r i n t e r p r e t a t i o n a s s u m e s t h e removal
3
o f d e g e n e r a t i o n o f t h e v3 €3-0 v i b r a t i o n i n B03 u n i t s . This c o u l d
be d u e t o t h e f a c t t h a t B03 u n i t s a r e n o t i s o l a t e d b u t e a c h o x y g e n
i s bonded t o a s i l i c o n a t o m of t h e lattice. I t s h o u l d be n o t e d
that the v3 vibration band in the spectra of many crystalline
i n o r g a n i c b o r a t e s i s a l s o s p l i t C r e f . 91.
In order to get more information on the origin of the
s p l i t t i n g , t h e s p e c t r a of Na- a n d H-boralites w i t h v a r i o u s boron
c o n t e n t s C a c t i v a t e d a t 773 KI w e r e r e c o r d e d . I t w a s supposed t h a t
if t w o k i n d s o f b o r o n sites d i f f e r i n g i n B-0 force c o n s t a t e x i s t
in the boralite lattice. one of them should be occupied
p r e f e r e n t i a l l y a t l o w boron c o n t e n t s . I n t h i s case, the intensity
r a t i o of b o t h m a x i m a 1380 a n d 1 4 0 5 c m - l should change w i t h boron
content. On t h e o t h e r h a n d i f t h e s p l i t t i n g t h e v 3 b a n d w a s d u e t o
t h e d e g e n e r a t i o n removal, t h e i n t e n s i t y r a t i o is expected n o t to
depend on boron c o n t e n t . The s p e c t r a of H-boral i tes c o n t a i n i n g :
0.28, 0.59, 0 . 6 9 and 1 . 0 5 B/u. c . are presented i n Fig. 1. The
i n t e n s i t y r a t i o of 1380 a n d 1 4 0 5 c m - l bands p r a c t i c a l l y does n o t
depend on b o r o n c o n t e n t . T h e s a m e w a s a l s o o b s e r v e d i n t h e case of
Na-boralites. It suggests that the degeneration removal is the
reason f o r t h e s p l i t t i n g of t h e v3 b a n d o f €3-0 s t r e t c h i n g i n B03
units. Of course t h e possibility that t w o kinds of boron sites
d i f f e r i n g i n B-0 f o r c e c o n s t a n t but without preference i n their
o c c u p a t i o n c a n n o t b e t o t a l 1y e x c l u d e d .
Fig. 2 shows the plots of intensities of 1380, 1405 cm-l
d o u b l e t as a f u n c t i o n of boron c o n t e n t i n N a - a n d H-boralites. In
t h e case o f H-boralites. t h e loss of boron d u r i n g t h e a c t i v a t i o n
o f NH -form w a s t a k e n i n t o a c c o u n t . B o t h p l o t s a r e l i n e a r . I n t h e
4
case of H - b o r a l i t e s t h e s l o p e i s much h i g h e r t h a n i n N a - b o r a l i t e s .
M o s t probably t h i s is due t o t h e higher e x t i n c t i o n c o e f f i c i e n t of
t h e v3 B - 0 s t r e t c h i n g Cand h e n c e t o h i g h e r 8-0 bond p o l a r i z a t i o n > .
We can however not exclude a possibility that some B atoms i n
Na-boralites are n o t i n B03 units and i t could r e s u l t in a low
i n t e n s i t y o f t h e B 0 3 band.
Our p r e v i o u s s t u d y C r e f . 101 h a s shown t h a t t h e i n c r e a s e i n
boron content results in the contraction of the unit cell of
b o r a l i t e s ( b o r o n i s s m a l l e r t h a n s i l i c o n > . T h e force c o n s t a n t s o f
Si-0 s t r e t c h i n g i n boralites w e r e f o u n d t o be i n d e p e n d e n t of B
content. T h i s l a s t e f f e c t i s d i s c u s s e d i n t e r m s of t h e c o l l e c t i v e
 685

Fig. 1. The B-0 band in t h e spectra of *H-boralites of various

B contents: a - 0.28, b - 0.59, c - 0.69, d - 1 . 0 B1u.c.
686

7 -

c
I
er, 5 -
\

E
\
In
0 3 -
2
0
(0
. -
$ 1
a

1 2 3
D I U.C.

F i g . 2. - The i n t e n s i t i e s of B - 0 bands i n t h e s p e c t r a of:

N a - b o r a l i t e s Col and H - b o r a l i t e s Col as a f u n c t i o n of B c o n t e n t .

-P/ theoret.

.-
0
U
Cl
0
a
c
v)
C
:0
115; -,, Lewis-
L

1.o
(B+Al-Na)/u.C.
F i g . 3. - The c o n c e n t r a t i o n s of Brgnsted a c i d sites COD,
t h e o r e t i c a l values of c o n c e n t r a t i o n of Brgnsted sites Co> and t h e
i n t e n s i t y of PyL band i n H - B o r a l i t e s a s a f u n c t i o n of boron
c o n t e n t Co3
model of zeolites Cthe electronegativities of Si and B are
practically the same>.

Aci d proper ti es of H-bor a1 i tes

-1
N a - b o r a l i t e c o n t a i n s o n l y 3740 c m CtermFnal Si-OH> groups,
analogous to those in zeolites. The NafiH4 ion exchange and
d e c o m p o s i t i o n of NH - f o r m r e s u l t s i n t h e a p p e a r a n c e of t h r e e new
4
k i n d s of OH g r o u p s Cref. 3.4): 3720 cm-' CSi-OH---B>. 3680 cm-'
-1
CB-OH>. 3460 cm-' CSi-OH.--03. Only 3720 cm hydroxyls w e r e found
t o be B r o n s t e d a c i d sites. T h e i r a c i d s t r e n g t h i s much l o w e r t h a n
i n z e o l i t e s C r e f . 2-5) e v e n though t h e e l e c t r o n e g a t i v i t y of boron
is higher t h a n t h a t of aluminum C 2 . 9 3 a n d 2,22 r e s p . > . I t c a n be
e x p l a i n e d by w e a k i n t e r a c t i o n between t h e OH g r o u p a n d s m a l l b o r o n
a t o m i n t h e Si-OH-.--B u n i t s .
The c o n c e n t r a t i o n of B r o n s t e d a c i d sites C3720 cm-' Si -OH-.-B>
in H-boralites of various boron contents was determined by
pyridine sorption. P y r i d i n e molecules react with BrGnsted acid
+
sites f o r m i n g p y r i d i n i u m i o n s CPyH 3 f o r which 1 5 4 5 cm-' I R band
is characteristic. Small portion of pyridine was sorbed in
H-boralites a t 430 K up t o t h e c o n s t a n t i n t e n s i t y of t h e 1 5 4 5 cm-'
band. The c o n c e n t r a t i o n of B r z n s t e d a c i d sites w a s c a l c u l a t e d f r o m
t h e m a x i m a l i n t e n s i t y of t h e 1 5 4 5 cm-' band a n d i t s e x t i n c t i o n
coefficient determined in a previous study Cref. 11>. The
c o n c e n t r a t i o n of B r z n s t e d a c i d sites i n H-boralites is p r e s e n t e d
i n Fig. 3 a s a f u n c t i o n of boron c o n t e n t C t h e loss of boron is
t a k e n i n t o a c c o u n t > . The t h e o r e t i c a l v a l u e s : t h e c o n c e n t r a t i o n s of
B + A1 - N a ( o u r b o r a l i t e s c o n t a i n e d small amounts of Al> are also
p r e s e n t e d i n t h e same f i g u r e . The c o n c e n t r a t i o n of BrGnsted sites
in H-boralite increases linearly with the boron content. The
e x p e r i m e n t a l v a l u e s are close t o t h e o r e t i c a l ones. Small d e f i c i t
of B r z n s t e d sites may be d u e t o s o m e d e h y d r o x y l a t i o n p a r t i c u l a r l y
-1
s i n c e a w e a k 1460 c m band of p y r i d i n e bonded t o Lewis a c i d sites
CPyL3 i s p r e s e n t i n t h e s p e c t r u m of p y r i d i n e s o r b e d i n b o r a l i t e s .
The i n t e n s i t y of t h e 1 4 6 0 cm-' PyL band ( F i g . 2) i s l o w a n d
p r a c t i c a l l y t h e same i n a l l t h e b o r a l i t e s s t u d i e d i n d i c a t i n g t h a t
t h e d e g r e e of d e h y d r o x y l a t i o n i s small a n d i n d e p e n d e n t of boron
content. The f r e q u e n c y of PyL band i n b o r a l i t e s C1460 cm-'> is
h i g h e r t h a n i n t h e case of 234-5 z e o l i t e s C1450 ern-', ref. 11).
T h i s means t h a t t h e e l e c t r o a c c e p t o r p r o p e r t i e s of Lewis a c i d sites
688

i n H - b o r a l i t e s are s t r o n g e r t h a n i n H-ZSM-5. Cref 3. 12.131. I t i s

p r o b a b l y d u e t o s m a l l s i z e and h i g h e l e c t r o n e g a t i v i t y of b o r o n .

The authors thank Professor Jerzy Haber of Institute of

C a t a l y s i s a n d S u r f a c e C h e m i s t r y of t h e P o l i s h Academy of Sciences
i n Krakdw f o r a g r a n t t h a t made t h e p r e s e n t w o r k p o s s i b l e .

REFERENCES
1 M. T i e l e n . M. G a l l e n a n d P. A. J a c o b s , P r o c . I n t . Symp. Z e o l i t e
C a t a l y s i s , , S i o f o k , Hungary, May 1985. p. 1.
2 G. C o u d u r i e r , J . C. V e d r i n e . P u r e Apl. Chem. , 58. C1986>, 1389.
3 J. D a t k a and Z . Piwowarska. J . Chem. Soc. , F a r a d a y T r a n s . I ,
85, C1989>, 47.
4 J . D a t k a and Z. Piwowarska. J . Chem. Soc., F a r a d a y T r a n s . I .
85, C19893, 837.
5 K. F.M.G. J . S c h o l l e . A.P.M. Kentgens. W . S . Veeman, P. F r e n k e n
a n d G. P. M. van d e r Velden. J . Phys. Chem. , 88. C19843, 5.
6 P. Ratnasamy, S.G. Hegde a n d A. J . Chandwalkar, J . C a t a l . , 102,
1986. 467.
7 A. C i c h o c k i , M. M i c h a l i k , M. Buf a n d J . P a r a s i e w i c z -
Kaczmarska, Zeolites. 10. (19893. i n p r i n t .
8 A. C i c h o c k i . M. M i c h a l i k . M. BUS. W. Lasocha a n d Z. Saw&owicz,
Zeolites. 10. Cl989>, i n p r i n t .
9 C.W. Weir and R . A . S c h r o e d e r . J o u r n a l of R e s e a r c h of t h e
N a t i o n a l Bureau of S t a n d a r d s A. 6 8 A C 5 > , 465. 1964.
10 A. Cichocki. J. Datka, M. M i c h a l i k . A. O l e c h , a n d
Z . Piwowarska. J . Chem. Soc., F a r a d a y T r a n s a c t i o n s 1 . 86C4).
c19903. 753.
I1 J . Datka and E. TuPnik, J . C a t a l . , 102. C19863. 43.
12 J . W . Ward, J. C a t a l . , 10. C19681, 34.
13 J . W. Ward, J . C o l l . I n t e r f a c e Ski. , 28, ClQ683. 269.
G . Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 689
0 1991 Elsevier Science Publishers B.V., Amsterdam

AN ELECTROSTATIC MODEL TO PREDICT THE INFRA RED CHARACTERISTICS OF ZEOLITE

HYDROXYL GROUPS AFTER ADSORPTION OF AROMATICS

P a t r i c k J . O'Malley, Department o f Chemistry, UMIST,

Manchester M60 l Q D U.K

SUMMARY

The p e r t u r b a t i o n o f t h e h i g h frequency (h.f.1, h y d r o x y l s t r e t c h i n g

i n f r a r e d band o f a HY z e o l i t e i s i n v e s t i g a t e d a f t e r a d s o r p t i o n o f
benzene, t o l u e n e , o-xylene, p-xylene, m-xylene and cumene. A s h i f t o f t h e
band t o a lower frequency accompanied by an i n c r e a s e i n i n t e n s i t y i s
noted. The f r e q u e n c y s h i f t v a r i e s i n t h e o r d e r , o-xylene > m-xylene =
t o l u e n e = cumene > benzene = p-xylene. U t i l i s i n g a t h e o r e t i c a l model f o r
t h e i n t e r a c t i o n which t a k e s account o f o n l y t h e d i e l e c t r i c p r o p e r t i e s o f
t h e h y d r o x y l group environment i t i s demonstrated t h a t t h e v i b r a t i o n a l
p r o p e r t i e s p r e d i c t e d by such a model i . e . f r e q u e n c y s h i f t and i n t e n s i t y
change a r e i n c l o s e agreement w i t h e x p e r i m e n t a l l y determined q u a n t i t i e s .

INTRODUCTION
The i n t e r a c t i o n o f aromatic molecules w i t h t h e h y d r o x y l groups o f
z e o l i t e s r e s u l t s i n a decreased frequency and an i n c r e a s e d i n t e n s i t y f o r
t h e h y d r o x y l i n f r a r e d band. The e x t e n t o f p e r t u r b a t i o n o f t h e h y d r o x y l
band i s o f t e n r e l a t e d t o t h e a c i d s t r e n g t h (1,21.
I n t h i s s t u d y a s e r i e s o f aromatic molecules i . e . benzene, t o l u e n e ,
o-xylene, p-xylene, m-xylene and cumene a r e absorbed on a 100% exchanged
HY sample and t h e i r e f f e c t on t h e h i g h f r e q u e n c y ( h . f . ) h y d r o x y l group i s
monitored. Both t h e decrease i n frequency and i n c r e a s e d i n t e n s i t y o f t h e
h.f. band a r e m o n i t o r e d and an e l e c t r o s t a t i c model, due o r i g i n a l l y t o
Coggeshall ( 3 1 , i s u t i l i s e d t o p r e d i c t t h e e x p e r i m e n t a l l y observed i n f r a
red properties.

EX PER I MENTAL
D e t a i l s o f t h e sample p r e p a r a t i o n and i n f r a r e d s t u d i e s a r e as
described previously (4). 100% exchange o f Na by NH4 (NH4Y-100) was
achieved by t r e a t i n g t h e sample w i t h c o n c e n t r a t e d NH&l under r e f l u x
c o n d i t i o n s f o r s e v e r a l weeks. Subsequent c a l c i n a t i o n g i v e s r i s e t o
HY-100. For benzene, t o l u e n e and o-xylene s a t u r a t i o n o f t h e a d s o r p t i o n
s i t e s was achieved r a p i d l y , however f o r p-xylene, m-xylene and cumene t h e
o r g a n i c vapour had t o be l e f t i n c o n t a c t w i t h t h e z e o l i t e d i s c f o r 1 hour
f o r reasonable coverages t o be a t t a i n e d .
690

:I
::
z
s
p
v1

B
bp

\J
3600 3400 3200 3600 3400 3200
~/c,'~ p/c In-i
F i g 1 . E f f e c t o f a d s o r D t i o n on F i g . 2. E f f e c t of a d s o r p t i o n on
t h e hydroxyl s t r e t c h i n g ' region of t h e hydroxyl s t r e t c h i n g x g i o n o f
HY-100. ( a ) HY-100, ( b ) HY-1001 HY-100. ( a ) HY-100, ( b ) rlY-lOO/
benzene, ( c ) HY-lOO/toluene, p-xylene, ( c ) HY-lOO/m-xylene,
( d ) HY-lOO/o-xylene. ( d ) HY-lOO/cumene.
 691

RESULTS AND DISCUSSION

The e f f e c t o f a d s o r p t i o n o f benzene, t o l u e n e and o-xylene on t h e

h y d r o x y l s t r e t c h i n g bands o f HY-100 i s i l l u s t r a t e d i n f i g . 1 w h i l e f i g . 2
shows t h e e f f e c t o f a d s o r p t i o n o f p-xylene, m-xylene and cumene. In all
cases, a d s o r p t i o n leads t o a s h i f t t o lower f r e q u e n c i e s o f t h e h . f . band
and a l s o causes a c o n s i d e r a b l e broadening and i n c r e a s e i n i n t e n s i t y of
t h i s band. I n a l l cases, a d s o r p t i o n does n o t l e a d t o p e r t u r b a t i o n o f t h e
1 . f . band which i s s i m i l a r t o t h a t found by p r e v i o u s workers f o r
a d s o r p t i o n o f r a r e gases and alkane molecules (5). T h i s can be e x p l a i n e d
by t h e i n a c c e s s i b l e p o s i t i o n s o f t h e h y d r o x y l groups g i v i n g r i s e t o t h i s
band. The magnitude o f t h e s h i f t o f t h e h . f . band t o lower f r e q u e n c i e s
decreases i n t h e o r d e r o-xylene > m-xylene = t o l u e n e = cumene > benzene =
p-xylene (see Table 1 ) .
The i n c r e a s e i n i n t e n s i t y and s h i f t t o l o w e r f r e q u e n c i e s on a d s o r p t i o n
can be a t t r i b u t e d as r e s u l t i n g f r o m e l e c t r o s t a t i c i n t e r a c t i o n s o f t h e OH
d i p o l e w i t h t h e adsorbed molecules. T h i s r e s u l t s i n a displacement o f t h e
e l e c t r i c a l charge i n t h e s e molecules, and as a r e s u l t , t o an i n c r e a s e i n
t h e d i p o l e moment as w e l l as a decrease i n t h e f o r c e c o n s t a n t o f t h e OH
bond. Coggeshall (3) has g i v e n a t h e o r e t i c a l s o l u t i o n t o t h e problem of
an o s c i l l a t i n g d i p o l e p e r t u r b e d by an e l e c t r o s t a t i c f i e l d . This theory
was subsequently extended by White e t a l . (5) and used q u i t e s u c c e s s f u l l y
i n p r e d i c t i n g t h e s h i f t s and changes i n i n t e n s i t y undergone b y t h e h i g h
frequency OH s t r e t c h i n g band when t h e OH o s c i l l a t o r i n t h e supercage was
surrounded by p o l a r i s a b l e adsorbed molecules. I n order t o deal w i t h t h e
problem o f an OH group p e r t u r b e d by an e l e c t r o s t a t i c f i e l d Coggeshall has
adopted a s i m p l i f i e d f o r c e f i e l d s i t u a t i o n and assumed t h a t t h e h y d r o x y l
group can be c o n s i d e r e d as a d i a t o m i c group possessing a d i p o l e moment
immersed i n a c o n s t a n t e l e c t r o s t a t i c f i e l d . T h i s w i l l r e s u l t i n an
i n t e r a c t i o n energy between t h e d i p o l e and t h e e l e c t r i c f i e l d which w i l l
depend on t h e d i p o l e moment, t h e angle o f o r i e n t a t i o n and t h e e l e c t r i c
f i e l d strength. Since a l l t h e v i b r a t i o n a l energy terms w i l l be s h i f t e d b y
t h e same amount, t h e r e w i l l be no change i n t h e t r a n s i t i o n e n e r g i e s
between t h e v i b r a t i o n a l s t a t e s as a r e s u l t o f t h i s i n t e r a c t i o n energy
term. There w i l l , however, be a change i n t h e p o t e n t i a l energy o f t h e
d i a t o m i c group due t o p o l a r i s a t i o n o f t h e OH bond by t h e e l e c t r i c f i e l d .
T h i s w i l l be g i v e n by -qE z where q i s t h e charge unbalance f o r t h e group,
P
E i s t h e e l e c t r i c f i e l d component p a r a l l e l t o t h e d i r e c t i o n o f t h e
P
valence bond and z i s t h e i n t e r n u c l e a r displacement f r o m e q u i l i b r i u m .
F o l l o w i n g r e f . (3) t h i s leads t o an e x p r e s s i o n f o r t h e p o l a r i s a t i o n f o r c e
 Q,
W
N

TABLE 1
Observed and t h e o r e t i c a l p e r t u r b a t i o n s o f h . f . z e o l i t e hydroxyi band

2
Adsorb a t e t
'obs.
Ap2 6
- -
42 M't
E
-
P
( ", ''talc.
pl Elql P1 41 E

Benzene 2.274 310 5.33 3.729 1.093 2.31 1.61 5.33 2.37 1.49 5.61 300
To1 uene 2.379 350 6.88 4.070 1 .lo6 2.57 1.58 6.64 2.54 1.51 6.45 330
0- Xy 1e ne 2.568 380 8.82 4.330 1.128 2.95 1.47 8.73 2.91 1.55 8.47 410
m-Xy 1e ne 2.374 350 - - - - - - 2.53 1.51 - 330
p-Xylene 2.270 300 - - - - - - 2.35 1.48 - 295
Cumene 2.380 340 - - - - - - 2.54 1.51 - 330
 693

qE as
qE P = [I - $(v/uo) - v / u o ~ + l / 1 6 ( u / v o ~ ) D
(1)
P
where
a = wD
)
i
I f t h e wave number o f t h e f r e e OH v i b r a t i o n i s 3750 cm-’ and t h e
d i s s o c i a t i o n energy ( D ) o f t h e OH bond i s 461.077 kJmol-’, then t h e
p o l a r i s a t i o n f o r c e (qE ) can be deduced f r o m t h e r a t i o v/uo. Equation 1
P
a l s o enables us t o c a l c u l a t e t h e v a r i a t i o n i n t h e p o l a r i s a t i o n f o r c e (Eq)
on t h e hydrogen atom o f t h e OH o s c i l l a t o r b r o u g h t about by t h e p h y s i c a l
a d s o r p t i o n of gases and vapours and i t can be expressed as

where E2 and E l a r e t h e f i e l d s a t t h e d i p o l e , i n t h e presence and t h e

absence of adsorbed molecules r e s p e c t i v e l y and u2 and v1 a r e t h e
c o r r e s p o n d i n g wave numbers.
F o l l o w i n g t h e methods adopted by White e t a l . (5) a model f o r t h e
i n t e r a c t i o n o f t h e OH group w i t h adsorbed a r o m a t i c s can be proposed which
t r e a t s t h e h y d r o x y l group as a p o l a r i s a b l e d i p o l e which i s p l a c e d a t t h e
c e n t e r o f an e l l i p s o i d a l c a v i t y . T h i s i n t u r n i s immersed i n a c o n t i n o u s
d i e l e c t r i c of d i e l e c t r i c c o n s t a n t which i s a c t e d on by a homogeneous
electrostatic f i e l d E parallel t o the a axis of the e l l i p s o i d . Because of
t h e p a r t i c u l a r geometry o f t h e OH group, t h e e l l i p s o i d adopted was
c o n s i d e r a b l y f l a t t e n e d i n t h e d i r e c t i o n o f t h e f i e l d and had dimensions o f
0.994 i n t h e d i r e c t i o n o f t h e f i e l d and a l e n g t h of 2.486 a
perpendicular t o t h e f i e l d . The former v a l u e i s a p p r o x i m a t e l y t h e l e n g t h
o f t h e O H bond w h i l e t h e l a t t e r i s r o u g h l y t h e d i a m e t e r o f t h e oxygen atom
i n silicates. The i n c r e a s e b o t h i n t h e d i p o l e and i n t h e e l e c t r i c f i e l d
a t t h e d i p o l e i n t h e presence o f t h e d i e l e c t r i c a r e subsequently g i v e n ( 5 )
by
MS/M = (1.397+<)/(3.057-0.66&) (3)

Eh/E = /(0.583+0.4176) (4)

where M and E a r e t h e d i p o l e moment and t h e e l e c t r i c f i e l d r e s p e c t i v e l y i n

t h e absence o f t h e d i e l e c t r i c and MX and Eh a r e t h e d i p o l e moment and t h e
e l e c t r i c f i e l d i n t h e presence o f t h e d i e l e c t r i c . T h i s model f i t s t h e
r e p r e s e n t a t i o n o f t h e phenomena o r i g i n a t i n g f r o m t h e a d s o r p t i o n o f
 694

molecules h a v i n g d i e l e c t r i c c o n s t a n t 12 i n t h e v i c i n i t y o f t h e OH d i p o l e .
B e f o r e a d s o r p t i o n , t h i s d i p o l e i s surrounded by a vacuum w i t h t = 1.0 and
M*/M and Eh/E a l s o equal t o 1.0.
The i n c r e a s e d i n t e n s i t y o f t h e p e r t u r b e d band can a l s o be s i m u l a t e d .
The r a t i o o f t h e absorbance o f t h e p e r t u r b e d ( A ) and u n p e r t u r b e d (Au) OH
P
bands can be shown ( 3 , 5 ) t o be

A /A = v / v (q /qUl2r
P U O P
where
2
( ‘ = [C(v/v,) - 31 ( C - 2 )
-
c [v/vo) - 2 I L (C - 3)

S i n c e f does n o t change v e r y much i n t h e u s u a l u/uo range, t h e

i n c r e a s e i n i n t e n s i t y observed f o r t h e d h i f t e d h i g h f r e q u e n c y OH band i s
t h u s almost s o l e l y due t o an i n c r e a s e of t h e e f f e c t i v e charge gained by
t h e hydrogen atom. E q u a t i o n 5 enables us t o c a l c u l a t e t h e r a t i o s o f t h e
e f f e c t i v e charges o f t h e OH o s c i l l a t o r p e r t u r b e d by t h e e l e c t r o s t a t i c
f i e l d e i t h e r i n t h e absence o r t h e presence o f adsorbed molecules.
I f Ap2
and A a r e t h e absorbance o f t h e h i g h f r e q u e n c y OH band i n t h e presence
Pl
o r absence o f adsorbed molecules r e s p e c t i v e l y , t h e n

From e q u a t i o n s 2 and 6, t h e r a t i o s qp2/qp, and E2/E1 can be c a l c u l a t e d

f r o m t h e r e l a t i v e i n t e n s i t i e s and t h e observed f r e q u e n c y s h i f t s and t h e s e
can be compared w i t h t h e t h e o r e t i c a l M”/M and Eh/E v a l u e s . Also, f r o m t h e
t h e o r e t i c a l M*/M and Eh/E values, t h e r a t i o

may be c a l c u l a t e d f o r any g i v e n adsorbate m o l e c u l e . S i n c e qplEl f o r the

3640 cm-l band f r o m e q u a t i o n ( 1 ) i s 0.66 x lO-’N, t h e q u a n t i t y qp2E2 can
be c a l c u l a t e d and t h u s t h e f r e q u e n c y s h i f t f o r a g i v e n adsorbate can be
predicted. The i n c r e a s e i n i n t e n s i t y o f t h e s h i f t e d band may a l s o b e
p r e d i c t e d as b e i n g r o u g h l y

Table 1 g i v e s t h e observed f r e q u e n c y s h i f t s a f t e r a d s o r p t i o n o f
benzene, t o l u e n e , o-xylene, m-xylene, p-xylene and cumene. As was
 695

mentioned i n t h e e x p e r i m e n t a l s e c t i o n , i t was found necessary t o l e a v e

p-xylene, m-xylene and cumene i n c o n t a c t w i t h t h e z e o l i t e f o r 1 hour i n
o r d e r t o e f f e c t an a p p r e c i a b l e p e r t u r b a t i o n o f t h e h . f . band. Thus, as
comparison o f i n t e n s i t i e s depends on s a t u r a t i o n o f t h e z e o l i t e supercage
w i t h t h e adsorbate molecules, and a l s o because t h e t y p e o f s p e c t r a
o b t a i n e d d i d n o t l e n d t o a c c u r a t e i n t e n s i t y measurements, i t was decided
t o c a l c u l a t e t h e change i n i n t e n s i t y undergone by t h e h . f . band f o r
benzene, t o l u e n e and o-xylene a d s o r p t i o n o n l y . Also i n c l u d e d i n t h i s
t a b l e , where a p p r o p r i a t e , a r e t h e q2/q1, E2/E1, (q2/ql) and t h e
2 values f o r t h e v a r i o u s adsorbates
t h e o r e t i c a l Eh/E,M”/M and (M“/M)
c a l c u l a t e d u s i n g e q u a t i o n s 1, 2, 3, 4 and6. It i s c l e a r f r o m
t h e t a b l e t h a t t h e c a l c u l a t e d and t h e o r e t i c a l frequency and r e l a t i v e
i n t e n s i t y changes agree q u i t e w e l l , t h u s g i v i n g s u p p o r t t o t h e c o n c l u s i o n
t h a t i t i s t h e d i e l e c t r i c p r o p e r t i e s i n t h e v i c i n i t y o f t h e OH group t h a t
a r e r e s p o n s i b l e f o r t h e p e r t u r b a t i o n of t h e h . f . band.

REFERENCES

1 P.A. Jacobs, C a t a l . Rev. S c i . Eng., 24, 1982, 215-225.

2 J. Dwyer and P.J. O’Malley i n S . K a l i g u i n e (Ed.), ’Keynotes i n Energy
R e l a t e d C a t a l y s i s , E l s e v i e r , Amsterdam, 1988, pp. 5-55.
3 N.D. Coggeshall, J. Chem. Phys., 18, (1950) 978-985.
4 P.J. D’Malley, Ph.D. Thesis, N a t i o n a l U n i v e r s i t y o f I r e l a n d , 1981.
5 J.L. White, A.N. J e l l i , J.M. Andre and J.J. F r i p i a t , Trans. Faraday
SOC., 63, 1967, 461.
This Page Intentionally Left Blank
G. Ohlmann et al. (Editors), Catalysis and Adsorption by Zeolites 697
0 1991 Elsevier Science Publishers B.V., Amsterdam

THE INFLUENCE OF THE A C I D I T Y OF ZEOLITES ON THE FORMATION OF UNSATURATED

CARBENIUM I O N S

'I.K i r i c s i , 'H. F o r s t e r , 'G. Tasi and ' P . F e j e s

' A p p l i e d Chemistry Department, J o z s e f A t t i l a U n i v e r s i t y , H-6723 Szeged

R e r r i c h Bela t e r l . , Hungary,
' I n s t i t u t e o f P h y s i c a l Chemistry, U n i v e r s i t y o f Hamburg, Bundesstrasse 45,
D-2000 Hamburg 13, Federal R e p u b l i c o f Germany.

SUMMARY
The i n f l u e n c e o f t h e a c i d i t y o f z e o l i t e s on t h e f o r m a t i o n o f u n s a t u r a t e d
carbenium i o n s from propene and a l l e n e was i n v e s t i g a t e d by combined U V - V I S - I R
spectroscopy. The h i g h e r t h e B/L a c i d i t y r a t i o t h e l o w e r t h e frequency o f t h e
a l k e n y l carbenium i o n s and t h e l e s s i n t e n s e t h e g e n e r a t i o n o f monoenyl i o n s
from b o t h a l l e n e and propene o v e r z e o l i t e s HNaY-FAU and HNa-ZSM-5.

INTRODUCTION
The a d s o r p t i o n o f o l e f i n s on z e o l i t e s r e s u l t s i n t h e f o r m a t i o n o f various
s u r f a c e species. G e n e r a l l y t h e s t r e n g t h o f t h e i n t e r a c t i o n between t h e a c t i v e
s i t e s and t h e o l e f i n molecules can be c h a r a c t e r i z e d by t h e frequency s h i f t of
t h e C=C double bond fundamental.
On e s s e n t i a l l y n o n a c i d i c z e o l i t e s , e.g. z e o l i t e A exchanged w i t h a l k a l i n e ,
a l k a l i n e e a r t h o r t r a n s i t i o n metal i o n s , t h e s h i f t o f t h e C=C s t r e t c h proved
t o be p r o p o r t i o n a l t o t h e " p o l a r i z i n g power", i . e . the charge/radius r a t i o o f
t h e c a t i o n s f o r butenes ( r e f . l ) , propene ( r e f . 2) and a l l e n e ( r e f . 3 ) .
On acidic z e o l i t e s the adsorption o f o l e f i n s leads t o t h e generation of
s a t u r a t e d as w e l l as u n s a t u r a t e d carbenium i o n s , b e i n g proven w i t h different
e x p e r i m e n t a l techniques ( r e f . 4 ) .
A c i d i c z e o l i t e s g e n e r a l l y c o n t a i n Bronsted and Lewis a c i d s i t e s , which b o t h
a r e i n v o l v e d i n t h e f o r m a t i o n o f c a r b o c a t i o n s f r o m hydrocarbons. B r o n s t e d a c i d
c e n t e r s may be r e s p o n s i b l e f o r t h e g e n e r a t i o n o f carbonium i o n s f r o m p a r a f f i n s
(ref. 5), a l k y l carbenium i o n s f r o m o l e f i n s ( r e f . 6 ) and a l k e n y l carbenium
ions from d i e n s ( r e f . 7), w h i l e on Lewis a c i d s i t e s t h e f o r m a t i o n o f alkyl
carbenium i o n s from p a r a f f i n s ( r e f . 8 ) and a l k e n y l i o n s f r o m o l e f i n s ( r e f . 9 )
may o c c u r .
Although t h i s generalization o f the formation o f carbocations i n zeolites
is w i d e l y accepted, some i m p o r t a n t d e t a i l s c o n c e r n i n g t h e i n f l u e n c e of the
r a t i o o f t h e Bronsted t o Lewis a c i d i t y (B/L) and/or t h e c o n c e n t r a t i o n o f acid
698

sites on t h e g e n e r a t i o n o f carbenium i o n s have n o t been r e v e a l e d y e t . For a

b e t t e r u n d e r s t a n d i n g o f t h e r o l e o f B r o n s t e d and Lewis a c i d i t y i n t h e case of
t r a n s f o r m a t i o n o f u n s a t u r a t e d hydrocarbons o v e r z e o l i t e s a combined I R and UV-
V I S s p e c t r o s c o p i c s t u d y was c a r r i e d o u t , t h e r e s u l t s o f w h i c h a r e p r e s e n t e d i n
this paper. Attention w i l l be focussed on t h e generation of alkenyl-type
carbenium i o n s o r i g i n a t e d f r o m propene and a l l e n e .

EXPERIMENTAL
HNaY-FAU and HNaZSM-5 z e o l i t e s were used i n t h e e x p e r i m e n t s . Their parent
m a t e r i a l s , NH4NaY-FAU and NHqNaZSM-5, were p r e p a r e d by i o n exchange f r o m t h e i r
sodium forms, c h a r a c t e r i z e d by XRD, K B r - m a t r i x I R and TG, and f o u n d t o be
well-crystalline. The u n i t c e l l c o m p o s i t i o n s determined by AAS a r e l i s t e d in
Table 1.
F o r t h e s p e c t r o s c o p i c measurements s e l f - s u p p o r t i n g w a f e r s were p r e s s e d f r o m
the ammonium forms of t h e samples, deammonated and outgassed at three
different temperatures (673, 773, 873 K ) i n t h e respective optical cell
equipped w i t h e i t h e r q u a r t z o r NaCl windows i n o r d e r t o obtain samples of
d i f f e r e n t amounts o f B r o n s t e d and Lewis a c i d s i t e s . The a c i d i t y o f t h e samples
was determined by I R spectroscopy u s i n g p y r i d i n e as probe molecule (for
d e t a i l s see r e f . l o ) , and l i s t e d i n Table 1.
The I R s p e c t r a were r e c o r d e d on a P e r k i n - E l m e r 225 s p e c t r o m e t e r , w h i l e the
UV-VIS experiments were performed on a Cary 17 s p e c t r o m e t e r operating under
computer c o n t r o l .
Quantum chemical c a l c u l a t i o n s were c a r r i e d o u t u s i n g the PcMol program
system developed f o r microcomputers ( r e f . 11). The MNDO-HE (ref. 12) and
CNDO/S (ref. 13) methods were a p p l i e d f o r t h e c a l c u l a t i o n of the lowest
v e r t i c a l s i n g l e t e x c i t a t i o n e n e r g i e s (LVSEE). The g e o m e t r i e s o f carbocations
were o p t i m i z e d w i t h i n t h e MNDO a p p r o x i m a t i o n . For calculation o f the UV-VIS
s p e c t r a i n t h e case o f a l l y 1 c a t i o n 30 and i n t h e case o f a l l o t h e r carbenium
ions 90 monoexcited c o n f i g u r a t i o n s were taken i n t o account in the con-
figuration interaction.

RESULTS
Fig. 1 shows t h e U V - V I S s p e c t r a o f propene adsorbed on sample No. 6. A f t e r
i n t r o d u c t i o n o f 1.33 kPa propene i n t o t h e c e l l a band was observed a t 318 nm.
At room temperature t h e p o s i t i o n o f t h i s band was s h i f t e d to higher wave-
l e n g t h s w i t h i n c r e a s i n g c o n t a c t t i m e . Heat t r e a t m e n t a t 323 K f o r 1 h r e s u l t e d
in the development o f a new band a t 370 nm and simultaneously the high-
frequency (HF) band s h i f t e d t o 323 nm (see spectrum 4 ) . Upon evacuation at
298, 373 and 473 K t h e i n t e n s i t i e s o f t h e HF bands decreased and their
 699

frequencies were b l u e - s h i f t e d t o 321, 314 and 298 nm, respectively. After

e v a c u a t i o n a t 573 K o n l y t h e background remained.

Table 1. S p e c i f i c a t i o n s o f t h e z e o l i t e samples used

Concentrations o f
Sample Zeolite U n i t c e l l compositions acid s i t e s i n B/L
mol /kg
No. Bronsted Lewis
1 HNaY/673 (NH4)42 Na16 0.441 0.082 5.4
2 HNaY/773 (NH4)42 Na16 0.058 0.305 0.2
3 HNaY/873 (NH4)42 Na16 0.007 0.156 0.04
4 HNaZSM-5/673 (NH4)1.2 Na0.06 ZSM-5 0.033 0.008 4.0
5 HNaZSM-5/773 ( N H 4 ) i a 2 Na0.06 ZSM-5 0.028 0.013 2.2
6 HNaZSM-5/873 (NH4)1.2 Na0.06 ZSM-5 0.018 0.015 1.2

The s p e c t r a a t d i f f e r e n t stages o f a l l e n e a d s o r p t i o n on sample No. 6 are

depicted i n Fig. 2. S h o r t l y a f t e r l o a d i n g t h e sample w i t h 6.65 Pa o f allene
t h r e e bands appeared a t 295, 347 and 450 nm. The i n t e n s i t i e s o f these bands
increased w i t h t i m e and t h e i r p o s i t i o n s r e d - s h i f t e d , although n o t as pro-
nounced as i n t h e case o f propene. The e f f e c t o f e v a c u a t i o n was similar to
t h a t observed w i t h propene.
Spectra recorded e i t h e r immediately o r 1 h a f t e r propene exposure to the
wafers, having been p r e t r e a t e d a t d i f f e r e n t temperatures, and consequently
c o n t a i n i n g d i f f e r e n t B/L r a t i o s , were s e l e c t e d and drawn i n F i g . 3. O b v i o u s l y
the shift of t h e bands o f adsorbed propene i n c r e a s e s with increasing B/L
ratio. From the spectra of a l l e n e adsorbed on the same samples under
investigation similar c o n c l u s i o n s can be drawn (see Fig. 4). It is also
evident from t h e s p e c t r a t h a t t h e l o w e r t h e B r o n s t e d a c i d i t y o f the zeolite
t h e more i n t e n s e t h e HF band, c h a r a c t e r i s t i c f o r t h e monoenyl carbenium i o n s .
Upon a d s o r p t i o n o f propene on HNaY as w e l l as on HNaZSM-5 a f a s t decrease
o f b o t h t h e band a s s i g n a b l e t o t h e C=C s t r e t c h i n g fundamental ( u s u a l l y l o c a t e d
at 1612 cm-’) and t h e OH s t r e t c h i n g band o f t h e B r o n s t e d s i t e s were observed
even a t beam temperature, i n d i r e c t l y p r o v i n g t h e enhanced f o r m a t i o n o f alkyl
carbenium i o n s . R a i s i n g t h e temperature d u r i n g i n t e r a c t i o n a band developed a t
1505-1510 cm-’, being characteristic f o r the CIc-_Cs t r e t c h i n g mode of the
a l k e n y l carbenium i o n s ( r e f . 14). Upon e v a c u a t i o n a t i n c r e a s i n g temperatures
the intensity o f t h e bands o r i g i n a t i n g f r o m propene oligomers and alkenyl
carbenium i o n s a t 1505-1510 cm-’ decreased, w h i l e t h e o r i g i n a l spectrum o f t h e
700
300 400 500 x/nm
F i g . 1. U V - V I S s p e c t r a o f propene
adsorbed on HNaZSM-5 (sample 6 ) .
A f t e r admission o f 1.33 kPa o f
propene a t room temperature (RT)
( a ) , a f t e r 1 h ( b ) and 2 h ( c ) a t
RT, 1 h a t 323 K ( d ) , a f t e r
e v a c u a t i o n a t RT ( e ) , 373 K ( f ) ,
473 K ( 9 ) and 573 K ( h ) .
300 400 500 X/nm
F i g . 3. U V - V I S s p e c t r a o f
propene adsorbed on samples
1-6 (subsequent t o adsorp-
t i o n (a), a f t e r 1 h ( b ) ) .
300 400 500 Nnm
F i g . 2 . U V - V I S spectra o f
a l l e n e adsorbed on HNaZSM-5
(sample 6 ) . I m m e d i a t e l y a f t e r
l o a d i n g t h e sample t o 6.65 kPa
o f a l l e n e a t RT ( a ) , 0.5, 1,
1 . 5 , 2, 2.5, 3, 4 . 5 and 5 h a t
RT ( b - h ) , e v a c u a t i o n a t 373 K
( i ) , 473 K ( j ) and 573 K ( k ) .
300 400 500 A/nm
F i g . 4. U V - V I S s p e c t r a o f
a l l e n e adsorbed on samples
1 - 6 (subsequent t o adsorp-
t i o n (a), a f t e r 1 h ( b ) ) .
 701

z e o l i t e was o n l y p a r t l y r e s t o r e d i n t h e OH s t r e t c h i n g range.
A l l e n e t r a n s f o r m s e a s i l y t o propyne o v e r z e o l i t e c a t a l y s t s ( r e f . 15). This
c o n v e r s i o n c o u l d be d e t e c t e d a l s o on a c i d i c z e o l i t e s by t h e appearence o f the
bands due t o t h e CIC and C-H s t r e t c h i n g v i b r a t i o n s o f adsorbed propyne a t 2116
and 3275 cm-I, r e s p e c t i v e l y . P a r a l l e l t o t h i s i s o m e r i z a t i o n a f a s t o l i g o m e r i z a -
t i o n v i a a l k e n y l carbenium i o n s takes place, i n d i c a t e d by t h e development of
the band c h a r a c t e r i s t i c f o r these t y p e s o f i o n s a t 1505 cm’ and the typical
o l i g o m e r bands a t 1480 and 1380 c d . I t i s w o r t h w i l e t o m e n t i o n t h a t t h e band
o f t h e a l k e n y l carbenium i o n s a t 1505 c f l ’ c o u l d be d e t e c t e d more e a s i l y on t h e
zeolites of l e s s Bronsted a c i d i t y . Upon h e a t t r e a t m e n t t h e colour of the
sample changed f r o m w h i t e t o y e l l o w and a t 473 K t o brown. I n t h i s case the
o r i g i n a l spectrum i n t h e OH r e g i o n c o u l d n o t be r e s t o r e d .

DISCUSSION
The bands observed i n t h e ranges 280-330, 360-380 and 430-470 nm are
a t t r i b u t e d t o t h e n-T: t r a n s i t i o n s o f mono-, d i - and t r i e n y l i c carbenium i o n s .
It has a l r e a d y been s t a t e d t h a t these wavelengths c h a r a c t e r i s t i c f o r alkenyl
carbenium ions formed i n z e o l i t e s agree w e l l w i t h those calculated by the
Sorensen e q u a t i o n d e s c r i b i n g t h e frequency dependence o f p o l y e n y l i c carbenium
i o n s as a f u n c t i o n o f t h e number o f c o n j u g a t e d double bonds i n t h e respective
ion (ref. 4c). Furthermore, the c a p a b i l i t y f o r a1 k e n y l i o n formation of
different hydrocarbons and t h e i r d e r i v a t i v e s f o l l o w s t h e same sequence as
observed i n s u p e r a c i d s o l u t i o n s ( r e f . 7 ) .
As far as t h e i n f l u e n c e o f t h e a c i d i t y o f z e o l i t e s i s concerned i t was
found e a r l i e r t h a t t h e f o r m a t i o n o f mono-, d i - and t r i e n y l i c carbenium ions
slows down w i t h decreasing o v e r a l l a c i d i t y ( r e f s . 4c,17). The results of
quantum chemical c a l c u l a t i o n s u s i n g t h e MNDO e f f e c t i v e charge model rendered
good qualitative c o r r e l a t i o n t o the spectroscopic observations, i .e. the
higher t h e r e l a t i v e p e r m i t t i v i t y o f t h e s o l v e n t (comparable w i t h t h e acidity
of z e o l i t e s i n a coarse f i r s t a p p r o x i m a t i o n ) t h e more s t a b l e i s the alkenyl
carbenium i o n ( r e f . 1 6 ) .
The common f e a t u r e o f t h e s p e c t r a o f adsorbed propene and a l l e n e (see F i g s .
1-2) i s t h e s h i f t o f t h e U V - V I S band t o h i g h e r wavelengths w i t h c o n t a c t time
and i t s r e v e r s i o n upon e v a c u a t i o n . T h i s can be e x p l a i n e d by: t h e band p o s i t i o n
of monoenylic carbenium i o n s (observed g e n e r a l l y i n t h e 275-320 nm range in
s u p e r a c i d s o l u t i o n ) b e i n g s e n s i t i v e t o t h e s u b s t i t u e n t groups (refs. 18-20).
While the i n s e r t i o n o f an a d d i t i o n a l double bond g i v e s r i s e t o a frequency
jump by about 60 nm, the e x t e n s i o n o f t h e carbon chain or formation of
branched o l i g o m e r s r e s u l t s o n l y i n a smooth downscale f r e q u e n c y shift, being
accomplished by c o n s e c u t i v e r e a c t i o n s , as b o t h propene and a l l e n e o l i g o m e r i z e
702

very fast at room temperature o v e r acidic zeolites. Preliminary quantum

chemical c a l c u l a t i o n s showed t h e l o w e s t v e r t i c a l s i n g l e t e x c i t a t i o n energies
(LVSEE) for methyl substituted ally1 carbenium ions to be decrea-
s i n g w i t h growing methyl s u b s t i t u t i o n ( r e f . 16). Assuming t h a t t h e f o l l o w i n g
r e a c t i o n s may occur on z e o l i t e s : t
-----
CH3-CH-CH-CH-CH2-CH3
-H- CH3-CHzCH2
CH3-CHzCHZ --5.
+
CH CH-CH2
- 2:- _ _ -
.>
t ,“I
CHZ-CH-CH-CH2-CH2-CH3
- - -. - - - -

y 3 t y3+
CH3-CH-CH-CH-CH2 CH3-C-CH-CH-CH3 CH2- C- CH- CH2- CH3
-_____ -_-- __---
t h e r e should be an e q u i l i b r i u m m i x t u r e o f v a r i o u s monoenyl carbenium i o n s the
commonness o f which c o n s i s t s i n a c 6 backbone a b s o r b i n g a t d i f f e r e n t frequen-
c i e s . The s p e c t r o s c o p i c measurements were performed on z e o l i t e s w i t h d i f f e r e n t
B/L r a t i o s . I t i s accepted t h a t t h e B r o n s t e d a c i d s i t e s p l a y t h e dominant r o l e
i n oligomerization o f olefins, b u t t h e p a r t i c i p a t i o n o f Lewis c e n t e r s i n t h i s
reaction cannot be n e g l e c t e d ( r e f s . 21,22). It f o l l o w s t h a t the higher the
amount of Bronsted a c i d s i t e s , t h e more pronounced t h e oligomerization of
olefins and consequently the a l k e n y l carbenium ions formed during this
reaction absorb a t h i g h e r wavelengths. This i s the experimental observation
w i t h b o t h propene and a l l e n e on b o t h t y p e s o f z e o l i t e s (see F i g s . 3 , 4 ) .
In the s p e c t r a o f adsorbed a l l e n e t h e p r e v a i l i n g band was found in the
range 359-380 nm characteristic f o r dienyl carbenium ions. Assuming the
f o l 1 owing t r a n s f o r m a t i on : t

CH2-C-CH-CH-CH2
-_------
t h e g e n e r a t i o n o f i n c r e a s i n g l y u n s a t u r a t e d carbenium i o n s s h o u l d be expected.
The i d e a was t h a t i f t h e number o f B r o n s t e d a c i d s i t e s o f t h e z e o l i t e sample
was decraesed by d e h y d r o x y l a t i o n , i n s t e a d o f l o w e r i n g t h e degree o f ammonium
ion exchange (ref. 4c), the e x i s t e n c e o f more and more simple monoenyl
carbenium ions s h o u l d be observed by U V - V I S spectroscopy, since with in-
creasing dehydroxylation the strength o f Bronsted acid s i t e s probably also
increases, t h e r e b y p r o m o t i n g t h e s t a b i l i t y o f a g i v e n carbenium i o n . As shown
in Fig, 4 our e x p e c t a t i o n came t r u e : t h e lower the B/L ratio the more
 703

pronounced band was observed a t ca. 290 nm on b o t h z e o l i t e s . Accepting the

explanation detailed above f o r the s h i f t s o f U V - V I S bands to the higher
wavelengths, t h e i n t e r p r e t a t i o n o f t h e r e v e r s e s h i f t o c c u r r i n g upon e v a c u a t i o n
o f t h e sample a t i n c r e a s i n g temperatures i s t h e f o l l o w i n g : A t about 400 K or
higher the formed o l i g o m e r s undergo c r a c k i n g and/or desorb, thereby the
remaining carbenium i o n s ( i n c l u d i n g t h e a l k e n y l t y p e s ) a r e o f s h o r t e r carbon
c h a i n type, thus a b s o r b i n g a t h i g h e r f r e q u e n c i e s .
The maximum a b s o r p t i o n o f t h e a l l y 1 c a t i o n b e i n g the simplest monoenyl
carbenium i o n was predicted to be a t 293 nm as a result of LCAO-MO
calculations 18). The LVSE e n e r g i e s c a l c u l a t e d by CNDO/S and MNDO-HE
(ref.
methods a r e l i s t e d i n Table 2.

Table 2. Lowest v e r t i c a l s i n g l e t e x c i t a t i o n e n e r g i e s and s t a n d a r d

heats o f f o r m a t i o n o b t a i n e d by s e m i e m p i r i c a l quantum
chemical methods
Carbocation LVSE energies/nm Standard h e a t o f
CNOO/S//MNDO MNDO-HE//MNDO f o r m a t i o n bv MNDO
k c a l /&l
abs re1 . abs. rel. abs. rel.
a1 l y l 220 0 281 0 221.4 0
is o p r o p y l -
a1 l y l 237 17 289 8 200.0 -21.4
n-propyl-
a1 l y l 237 17 289 8 195.8 -25.6
l-ethyl-2-
methyl-ally1 253 33 314 33 195.2 -26.2
l-ethyl-3-
methyl-ally1 234 14 300 19 187.0 -34.4
1,1,3-tri -
methyl -a1 l y l 241 21 313 32 185.4 -36.0
pentadienyl 286 0 299 0 219.8 0
1 -methyl -
pentadienyl 290 4 306 7 207.3 -12.5
2-methyl -
pentadienyl 297 11 311 12 214.7 -5.1
1,1,3,5-
tetramethyl- 305 17 328 29 188.7 -31.1
pentadienyl
1,1,5,5-
tetramethyl - 325 37 330 31 182.8 -37.0
pentadienyl

It can be seen t h a t t h e more s u b s t i t u t e d monoenyl and d i e n y l carbeniurn ions

should absorb a t h i g h e r wavelengts. Futhermore, the s t a b i l i t y o f carbenium
ions under study a l s o i n c r e a s e d w i t h i n c r e a s i n g methyl substitution. These
results a r e i n good accordance w i t h t h e e x p e r i m e n t a l observations discussed
704

above. According t o t h e r e s u l t s o f quantum chemical c a l c u l a t i o n s , t h e a s s i g n -

ment o f a g i v e n U V - V I S band measured t o a w e l l - d e f i n e d a l k e n y l i o n seems t o be
rather d i f f i c u l t . By t h e e x p e r i m e n t a l l y observed band o n l y a group o f a l k e n y l
i o n s can be c h a r a c t e r i z e d .
The generation of unsaturated carbenium i o n s was proven also by IR
spectroscopy. The band g e n e r a l l y observed a t 1505-1510 c d was regarded as t h e
t y p i c a l band o f these types o f carbenium i o n s .

CONCLUSIONS
The lower the B/L a c i d i t y r a t i o o f t h e z e o l i t e , the higher w i l l be the
frequency o f t h e a l k e n y l carbenium i o n s formed f r o m propene and a l l e n e on b o t h
types of zeolites. T h i s c h a r a c t e r i s t i c can be a t t r i b u t e d to the enhanced
f o r m a t i o n o f o l i g o m e r s on t h e z e o l i t e s o f h i g h e r B r o n s t e d a c i d i t y .
The h i g h e r t h e B/L r a t i o o f t h e sample, the l e s s intenses the formation o f
monoenyl carbenium i o n s a b s o r b i n g a t 280-310 nm. T h i s f a c t m i g h t be e x p l a i n e d
by assuming an increase o f the strength o f the Bronsted acid sites with
decreasing c o n c e n t r a t i o n s (as a r e s u l t o f dehydroxyl a t i o n ) , thereby promoting
t h e s t a b i l i t y o f t h e monoenyl carbenium i o n s formed f r o m a l l e n e .

ACKNOWLEDGEMENT
One o f t h e a u t h o r s ( I . K.) thanks t h e Alexander von Humboldt F o u n d a t i o n f o r
a r e s e a r c h f e l l o w s h i p . The f i n a n c i a l s u p p o r t o f t h e Hungarian Academy o f
Sciences (No. OTKA 217/88) and t h e Deutsche Forschungsgemeinschaft i s g r a t e -
f u l l y acknowledged

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 70 7

AUTHOR INDEX

Aiello. R ................. 573

Albizane. A ...............603
Babayev. M.K ..............623
Barrer. R.M ...............257
Barthomeuf. D .............157
Bauer. F .................. 305
Bauermeister. R ...........
367
Baur. W.H ................. 581
Bee, M.................... 445
Bergk. K.-H ............... 185
Bordiga. S ................ 671
Bohlig. H ................. 511
Borovkov. V.Yu ............653
BosaEek. V ................ 337
Bragin. O.V. ..............357
Brunner. E ................ 529
Biilow. M.................. 445.479. 501
Buskens. Ph ................ 47
Buysch. H.-J ..............297
Camblor. M.A ..............613
Caro. J................... 445
Eejka. J .................. 387
Chen. Q................... 219
Cichocki. A ............... 681
Crea. F................... 573
Datka. J .................. 681
Dermietzel. J .............305
Derouane. E.G .............591
Des Courieres. Th .........
603
Di Renzo, F ............... 603
Dressler. J ............... 663
Dumont. N ................. 591
Eckelt. R ................... 1.415
Ehrhardt. B ............... 663
Eic. M.................... 233
Einicke. W.-D .............. 75. 529
Emig. G ................... 479
Ernst. H.................. 397. 529
Ernst. S.................. 297. 645
Fahlke. B................. 315
Fajula. F................. 603
Fejes. P.................. 697
Feoktistova. N.N.......... 287
Fichtner-Schmittler. H.... 549
Figueras. F............... 603
Finger. G................. 501. 537
Forster. H ................ 697
Fraissard. J .............. 219
Freude. D.................. 89. 397
Fricke. R................. 631
Fujimoto. K............... 203
.................
Fiirtig. H 185
Gabelica. 2 ...............591
Ganbarov. D.M............. 623
Geidel, E................. 511
.................
Geus. E . R 457
Golemme. G................ 573
Goncharuk. V.............. 581
708

Grobet. P.J............... 613

Gross. T..................
Hadicke. U
415
................185
Hantel, K.................367
Hayward. C.-M.T...........171
Hilgert. W................ 479
Hoffmann, J ............... 367
Hunger. B ................. 367
Hunger, M ................. 397,537
Huybrechts. D.R.C ..........47
Ito, T.................... 591
Jacobs. P.A ................ 47. 613
Jaeger. N.1 ............... 327
Jancke, K ................. 501
Jansen, A.E ...............457
Jansen. J.C ............... 457
Jerschkewitz.H G.- ........... 1. 415
Jobic, H .................. 445
Jockisch. W ............... 305
Joyner. R.W ...............357
Karge. H.G ................133
Karger. J .................. 89. 445
Kazansky, V.B .............117.425
Kiricsi. I ................ 697
Klaeboe. P ................ 663
Kojima. M.................491
Kornatowski. J............501.537, 581
Kubelkova. L..............337. 405
Kustov, L.M...............425
aaniecki. M............... 377
Leofanti. G...............671
Lindner. D................297
Lischke. G..................1. 415
Loffler. E.................. 1.425. 537
Lohse. U.................. 425. 549
Lucke. B..................315
Martens. J.A..............613
Martin. A.................315
Meier, B..................529
Meier, W.M................247
Minachev. Kh.M............357
Mishin, 1.V............... 563
Muller, B................. 521
Nagy. J.B.................573. 591
Nastro. A................. 573
Nicolle, M.-A............. 603
Novakova. J...............337. 405
Nowak, 5.................. 315
O'connor. C.T.............491
ohlmann. G.................. 1.415. 425
O'Malley, P.J.............689
Padovan. M................ 671
Parlitz, B..................1,415.631
Parton. R.F................ 47
Petrini. G................671
Peuker, Ch................425. 511
Pfeifer, H.................89,397. 445
Pilz, W...................511
Piwowarska. 2.............681
Pradhan. A.R.............. 347
 709

Preobrazhensky. A.V
Prilipko. A.1
.......357
.............563
Pritzkow, W............... 549
Rao. B.S..................347
Raurell. G.L.............. 387
Rees. L.V.C................61
Reschetilowski. W.........529
Richter, M................631
Richter-Mendau. J.........501. 549
............501
Rozwadowski, M
.............. 233
Ruthven. D.M
.................663
Salzer. R
...............75
Schollner. R
..............457
Schoonman, J
Schreier. E................. 1. 631
Schroder. K.-P............ 435
Schulz. I.................415
Schulz-Ekloff. G..........327
Schwartz. S............... 491
Schwieger. W.............. 185
Senchenya. 1.N............653
............347
Shiralkar. V . P
Shpiro, E.S............... 357
Siegel. H................. 367
Sonntag. E................ 537
Spoto, G.................. 671
Springuel-Huet, M.A.......219
Steinberg, K.-H...........367. 663
Suboti6. B................ 573
Svensson. A............... 327
Sychev. M.................581
Szulzewsky. K............. 549. 631
Tagiyev. D.B.............. 623
Tasi, G...................697
Tatsumi. T................203
Telbiz. G.M...............563
Timm, D...................415
Tkachenko. 0.P............357
Tominaga. H............... 203
Tuleuova. G.J.............357
Ullmann. G................367
Van Bekkum, H............. 457,467
Vasina. T.V...............357
Vaughan, D.E.W............275
Von Ballmoos. R........... 171
Voogd. P.................. 467
Vorbeck. G................ 631
Vtjurina. L.M.............287
Wehner. K ................. 415
Weitkamp. J ................21.297. 645
Wichterlova. B ............387
Wieker. W .................315
xu. z..................... 233
Zecchina. A ...............671
Zhdanov. S.P .............. 287
Zholobenko. V.L ...........425
Zibrowius, B
Zmierczak. W
................1,537,549, 631
..............377
This Page Intentionally Left Blank
 711

SUBJECT INDEX
Acetone adsorption ...............
Acetone. conversion from
337
.........405
Acid-base pair
Acidity
...................1171.89.563.631.681. 697
............................
Acid site characterization
Activation
.......133
....................... 663
Active sites ..................... 425
Adsorption .......................
Adsorption of CO .................133.157.435.479.
671
689

Alcohol-water mixtures ............75

Al in zeolites ...................
Alkali metal exchanged ZSM-5 .....387
297
Alkene oxidation ..................
Alkylation of toluene ............387
47

Allene...........................
Alloying particles ...............357
697

Al-0 bond strength ...............653

AlPO-14 .......................... 549
Alumination...................... 467
Alumino-galloferrierite..........613
Approximate assignment...........511
Aromatic hydrocarbons............233
Aromatics ........................ 203. 689
Atlas............................ 247
Base catalysis .................... 21
Basicity ......................... 1571563
Bimetallic cluster ...............203
B03 units ........................ 681
Boralites MFI
Carbenium ions
....................
...................697
681

Carbocations on zeolites .........337

Carbon deposits ..................327
Carbon filaments .................367
Catalysis ........................ 157
Catalyst characterization ........315
Catalytic activity ...............397
Catalytic test reaction ..........645
Cellular configuration ...........521
Characterization ................. 5731645
Coke deposition .................. 415
Coke deposits on zeolites
Coke in H-ZSM-5
........
.................. 337
405
Controlled crystal growth
Cracking
........501
......................... 117. 467
Cracking selectivity .............171
Crystal growth ................... 2871603
Crystallinity .................... 529
Crystallization ..................2871591
Crystallization kinetics .........573
..................... ..247
Crystallographic pore diameters
Crystal size
Curvature of configuration ....... 491
521
DABCO (triethylenediamine)
Deactivation
.......
..................... 297
347. 397
Dealumination ...................... 1.185.415. 425
Density of acid sites ............133
para-Diethylbenzene ..............479
Diffuse of reflectance ...........663
712

Diffusion
Diffusivity
........................
...................... 257
2331305145714671479

Dispersion .......................
Electronegativity ................
327
157
Electronic structure .............653
Erionite ......................... 663
Ethane hydrogenolysis ............ 357
Ethylbenzene conversion ..........6 3 1
EXAFS ............................ 357
Extraction of aluminium..........415
Extrudates....................... 491
Faujasite........................ 27Sl 327
FCC catalysts.................... 171
Ferrisilicates...................6 3 1
Fe-ZSM-5......................... 631
Framework density distribution...247
Heteroatom incorporation.........5 8 1
Heterogeneous nucleation.........603
n-Hexane cracking................425
High pressure chromatography.....479
H-mordenite...................... 347
Host/guest chemistry ..............2 1
Hybrid catalyst..................203
Hydrocarbon pyrolysis ............315
Hydrothermal crystallization.....623
Hydroxyls......................... ag1563168i
H-ZSM-5 zeolite.................. 3 3 7 14 2 5
H-ZSM-12 ....................... ..347
Influence of geometry ............653
In-situ study .................... 663
Interface........................ 257
Intergrowth of structure.........219
IR diffuse reflectance spectr ....1 1 7
IR spectroscopy ..................4 2 5 1 5 3 7 1 6 6 3 1 6 8 1
Isomerization .................... 3 0 5
Isomorphous substituted ZSM-5 ....5 8 1
Isomorphous substitution .........537
Iso-paraffins .................... 203
Isopropylation of benzene ........347
Isotherms ......................... 4 4
Kinetics ......................... 2a 7 1 3 0 5
Kinetics of cumene sorption ......347
KVS-5 molecular sieve ............5 8 1
La-H-Y ...........................
Large crystals ...................35 40 7l I 5 a i
Large pore zeolites
Lewis acidity
..............347
.................... i1 7 1 6 5 3
Linde L .......................... 275
Liquid phase adsorption ........... 7 5
MAS NMR .......................... 397
MAS N M R ( 2 7 Al) .................. 529
Matrix activity..................1 7 1
Matrix vs zeolite................1 7 1
Mechanism .......................... il i a 5
Membranes ........................ 2 5 7 1457
Methane aromatization............357
Methane splitting................367
Methanol ......................... 563
Methanol conversion ..............3 1Sl653
Methanol conversion to olefins...4 1 5
 713

Methanol-to-olefins ................1
Methylation ...................... 305
Microdynamics .................... 445
Modelling ........................ 257,689
Modelling by computer ............ 435
Modification ....................... 1. 1171327
Molecular sieve ..................501
Mountainite ...................... 623
MO-Y ............................. 377
Multinuclear N M R .................591
Nay ............................... 4 7 1 61
Ni-Mo-Y .......................... 377
Nitrogen bases ...................297
Ni-ZSM-5 catalyst................367
N M R in alumino-galloferrierite...613
NMR spectroscopy ............337
(13c)
NMR spectroscopy. multinuclear
Normal coordinate analysis
...
537. 549
.......
511
Nucleation .......................
287. 591
Nucleation kinetics ..............
573
Oligomerization ..................
491
Organic intermediates ............
297
Para selectivity
Path of oxidation
.................
387
................
405
Pelletization .....................
75
Pentasil-type ....................
185
Pentasil zeolites .................
75
Permeation .......................
457
Phase transitions in AlPOs .......
549
Piperazine .......................
297
Porosity .........................
247
Propene ..........................
Properties
697
.......................
623
Proton-MAS-NMR
Pt-Cr pentasils
....................
89
..................
357
Pulsed field gradient N M R .........
89. 445
Quasi-elastic neutron scattering.445
Realumination ....................
529
Regeneration .....................
Restoration of active sites
315
......
405
Restoration of void volumes ......
405
SAPO-5 ........................... 5011537
SAPO-37 .......................... 591
SAPO-40 ........................ ..591
Secondary synthesis..............529
Self-diffusion .................... a gI445
Separation........................ 61
Shape selective catalysis .........21
Shape selective photochemistry ....21
Shape-selectivity ................387
Ship-in-the-bottle catalysts......21
Silicalite .......................233.457. 4 6 7 1 6 7 1
Silicalite-1 ......................
61.435
Silicon incorporation ............
537
Single crystal ...................
457
Sorption ..........................611257
Spectroscopy .....................
Strength of acid sites
697
...........
133
Structure defect .................219
Structure effect .................
157
714

Structure types ..................

Sub-unit cluster models
247
..........511
Sulfidation ...................... 377
Syngas conversion ................327
Synthesis ........................ 1851275157312 1
Synthesis gas
Tailoring
.................... 203
........................
Template-free .................... 501 185
Template removal
Templates
.................
........................ 549
491
Tetraethylammonium
Thermal desorption
...............
................ 603
75
Thermal reduction
Thiele theory
................
.................... 367
467
Ti-silicalite .....................
Topological constraints .......... 471671
521
Topological parameters ...........
Topological structure functions ..521 .

TPD of ammonia ...................521 415

Transition state theory
USY as support
..........
................... 233
377
Vanadium silicalite KVS-5
Vibrational frequencies
........ 581
..........511
Vibration reactor
Void space
................
....................... 367
219
VPI-5.............................
Water-gas shift .................. 377 47

Xenon-=
XRD
........................ 219
.............................. 549
XRD in alumino-galloferrierite
para-Xylene
...613
...................... 435
meta-Xylene isomerization
Zeolite 13 x
........631
..................... 479
Zeolite A ........................ 233
Zeolite activity
Zeolite 8
................. 603
........................ 171

Zeolite genesis
Zeolite H-ZSM-5
..................
.................. 275
Zeolite-like silicates ...........397623
Zeolite NaX
Zeolites
...................... 511
......................... 20714451689
Zeolite sub-units
Zeolite synthesis
................
................275 645
Zeolite X
Zeolite Y
........................
........................ 233
563
Zeolite ZSM-57
ZSM-~
...................
............................ 645
3 0 ~ 1 3 ~ ~ 1 3 a 7 1 4 3 5 1 ~ ~ ~ l ~ ~ ~ 1
ZSM-12 ........................... 603
ZSM-35 ........................... 645
ZSM-57 ........................... 645
 715

STUDIES IN SURFACE SCIENCE AND CATALYSIS

Advisory Editors: 6. Delmon, Universite Catholique de Louvain, Louvain-la-Neuve,Belgium

J.T. Yates, University of Pittsburgh, Pittsburgh, PA, U S A .

Volume 1 Preparation of Catalysts 1. Scientific Bases for the Preparation of Heterogeneous

Catalysts. Proceedings of the First International Symposium, Brussels, October 14-
17,1975
edited by B. Delrnon, P.A. Jacobs and 0. Poncelet
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Volume 3 Preparation of Catalysts It. Scientific Bases for the Preparation of Heterogeneous
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Volume 4 Growth and Properties of Metal Clusters. Applications to Catalysis and the
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Volume 5 Catalysis by Zeolites. Proceedings of an InternationalSymposium, Ecully (Lyon),
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Volume 6 Catalyst Deactivation. Proceedings of an InternationalSymposium, Antwerp,
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Volume 12 Metal Microstructures in Zeolites. Preparation - Properties - Applications.
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Volume 13 Adsorption on Metal Surfaces. An Integrated Approach
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Volume 14 Vibrations at Surfaces. Proceedings of the Third InternationalConference,
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7 16

Volume 15 Heterogeneous Catalytic Reactions Involving Molecular Oxygen

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Volume 16 Preparation of Catalysts Ill. Scientific Bases for the Preparationof Heterogeneous
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Volume 18 Structure and Reactivity of Modified Zeolites. Proceedings of an International
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Volume 19 Catalysis on the Energy Scene. Proceedings of the 9th Canadian Symposium on
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Volume 23 Physics of Solid Surfaces 1984
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Volume 24 Zeolites: Synthesis, Structure, Technology and Application. Proceedings of an
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Volume 25 Catalytic Polymerization of Olefins. Proceedings of the International Symposium
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Volume 26 Vibrations at Surfaces 1985. Proceedings of the Fourth International Conference,
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Volume 28 New Developments in Zeolite Science and Technology. Proceedings of the 7th
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Volume 29 Metal Clusters in Catalysis
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 717

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Volume 37 Innovation in Zeolite Materials Science. Proceedings of an International
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Volume 39 Characterization of Porous Solids. Proceedings of the IUPAC Symposium (COPS
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1989
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Volume 63 Preparation of Catalysts V. Proceedings of the Fifth International Symposium on
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Volume 66 Dioxygen Activation and Homogeneous Catalytic Oxidation. Proceedingsof the
fourth International Symposium on Dioxygen Activation and Homogeneous
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Volume 67 Structure-Activity and Selectivity Relationships in Heterogeneous Catalysis.
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Volume 68 Catalyst Deactivation 1991. Proceedings of the fifth International Symposium,
Evanston, IL, June 24-26, 1991
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