Unit-I Haber-True and App Density, Mechanical Strength

Pure &App/. Chem., Vol. 63, No. 9, pp, 1227-1246,1991.
ADONIS 206922209100117L
Printed in Great Britain.
@ 1991 IUPAC
INTERNATIONAL UNION OF PURE

AND APPLIED CHEMISTRY
PHYSICAL CHEMISTRY DIVISION
COMMISSION ON COLLOID AND SURFACE CHEMISTRY
INCLUDING CATALYSIS*
SUBCOMMITTEE ON CATALYST CHARACTERIZATION?
MANUAL ON CATALYST
CHARACTERIZATION
(Recommendations 1991)
Prepared for publication by

J. HABER
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,
30239 Krak6w, Poland
Memberships of the Commission and Subcommittee during the period (1983-91) the report was prepared were as
follows:
*Chairman: 1983-91 K. S. W. Sing (UK); Vice Chairman: 1983-87 J. Haber (Poland); 1987-91 J. H. Block (FRG);
Secretary: 1983-85 E. Wolfram (Hungary); 1985-91 B. Vincent (UK); Titular Members: J. Czarnecki (Poland;
1989-91); B. Delmon (Belgium; 1989-91); P. C. Gravelle (France; 1985-89); J. Ralston (Australia; 1987-91); J.
RouquBrol (France; 1987-91); P. J. Stenius (Sweden; 1983-89); L. Ter-Minassian-Saraga (France; 1983-87);
Associate Members: J. B. Butt (USA; 1987-91); N. V. Churaev (USSR; 1983-87); J. Czarnecki (Poland; 1987-
89); B. Delmon (Belgium; 1987-89); D. Fairhurst (USA; 1987-91); P. C. Gravelle (France; 1983-85); J. W.
Hightower (USA; 1983-87); R. J. Hunter (Australia; 1983-87); H. N. W. Lekkerkerker (Netherlands; 1985-89);
A. J. G. Moroto (Argentina; 1983-91); M. Misono (Japan; 1989-91); G. I. Panov (USSR; 1989-91); P. Pendleton
(USA; 1989-91); D. Platikanov (Bulgaria; 1987-91); J. RouquBrol (France; 1983-87); P. B. Wells (UK; 1983-87);
National Representatives: G. F. Froment (Belgium; 1983-91); I. G. Ionescu (Brazil; 1983-85); L. A. Petrov
(Bulgaria; 1987-91): S. G. Mason (Canada; 1983-87); C. W. Fairbridge (Canada; 1987-91); A. Weiss (FRG; 1983-
87); G. Lagaly (FRG; 1987-89); G. H. Findenegg (FRG; 1989-91); K. Meyer (GDR; 1983-87); G. ohlmann
(GDR; 1987-91); L. G. Nagy (Hungary; 1983-91); J. C. Kuriacose (India; 1983-85); S. R. Sivaraja Iyer (India;
1985-89); D. K. Chattoraj (India; 1989-91); A. S. Kertes (Israel; 1983-85); J. Manassen (Israel; 1985-91); S.
Ardizzone (Italy; 1989-91); A. Kitshara (Japan; 1983-85); M. Misono (Japan; 1985-89); T. Kunitake (Japan;
1989-91); M. S. Suwandi (Malaysia; 198491); J. Lyklema (Netherlands; 1983-91); J. Haber (Poland; 1987-91);
M. Brotas (Portugal; 1985-91); H. Chon (Republic of Korea; 1989-91); M. S. Scurrell (RSA; 1989-91); J. A.
Pajares (Spain; 1983-91); H.-F. Eicke (Switzerland; 1985-91); S. Peker (Turkey; 1985-91); K. R. Kutsenogii
(USSR; 1989-91); D. H. Everett (UK; 1983-91); C. J. Powell (USA; 1985-89); S. MilonjiC (Yugoslavia; 1989-91).
tchairman: 1983-91 J. Haber (Poland); Secretary: 1983-91 J. H. Block (FRG); Members: L. Berlnek (Czecho-
slovakia; 1985-91); R. Burch (UK; 1985-91); J. B. Butt (USA; 1987-91); B. Delmon (Belgium; 1985-91); G. F.
Froment (Belgium; 1983-85); P. C. Gravelle (France; 1983-91); R. S. Hansen (USA; 1983-85); R. A. W. Haul
(FRG; 1983-87); J. W. Hightower (USA; 1983-85); C. S. McKee (UK; 1985-91); M. Misono (Japan; 1985-91);
J. A. Pajares (Spain; 1983-91); G. I. Panov (USSR; 1985-91); L. Riekert (FRG; 1983-91); M. W. Roberts (UK;
1983-85): K. S. W. Sing (UK: 1983-91); K. Tamaru (Japan; 1983-91); J. C. Vedrine (France; 1985-91); P. B.
Wells (UK; 1983-87).
~ ~~
Republication of this report is permitted without the need for formal IUPAC permission on condition that an
acknowledgement, with full reference together with IUPAC copyright symbol (0 1991 IUPAC), is printed.
Publication of a translation into another language is subject to the additional condition of prior approval from the
relevant IUPAC National Adhering Organization.
Manual on catalyst characterization
(Recommendations 1991)
CONTENTS
1. INTRODUCTION 1229
2. CATALYST FORMULATION AND METHOOS OF ITS PREPARATION 1229
2.1 Methods of Preparation

2.1.1 Precipitation
2.1.2 Deposition
2.1.3 Encapsulation
2.1.4 Selective removal
2.1.5 Treatment of intermediate solids o r precursors
2.1.6 Activation of the precursor
2.2 Chemical Composition
2.3 Aggregate Morphology
2.4 Forming Operations
2.5 Stability of Catalyst Systems
2.5.1 Physical stability
2.5.2 Chemical stability
3. PHYSICAL PROPERTIES 1233
3.1 Total Surface Area

3.2 Pore Structure
3.3 Density
3.4 Mechanical Strength
4. FINE STRUCTURE 1236
4.1 Surface Structure and Topography

4.2 Surface Area of Different Phases
4 . 3 Surface Elemental Composition of Different Phases
4.4 Surface Chemical Characterization
4.4.1 Acid-base sites
4.4.2 Redox sites
5. CATALYTIC PROPERTIES 1239
5.1 General Considerations

5.2 Catalytic Activity
5.2.1 Reaction rate
5.2.2 Measurements of activity parameters
5.3 Selectivity
5.4 Relative Activities
5.5 Inhibition of the Catalytic Action
5.5.1 Types of inhibitory substances
5.5.2 Characterization of catalyst response to
inhibitory substances
5.6 Time-Dependent Characteristics
5.7 Regeneration
1228
Manual on catalyst characterization (Recommendations 1991) 1229
1. INTRODUCTION
This manual h a s been prepared by t h e Commission o n Colloid and S u r f a c e
Chemistry including C a t a l y s i s o f t h e I U P A C . I t results, from t h e g e n e r a l
feeling among surface and c a t a l y s i s c h e m i s t s both f r o m academia and industry
that t h e rapid increase o f k n o w l e d g e in s c i e n c e of c a t a l y s i s a n d t h e better
understanding of t h e mechanism o f c a t a l y t i c processes i s n o t accompanied by
the development of the appropriate scientific language. Many t e r m s , widely
used i n t h e literature, r e m a i n vague and undefined. T h u s , t h e S u b c o m m i t t e e o n
Catalysis w a s created with t h e task o f preparing a c a t a l y s t c h a r a c t e r i z a t i o n
c h a r t , listing all parameters which should be specified i n o r d e r to obtain
a f u l l description of a c a t a l y s t , and o f formulating t h e d e f i n i t i o n s o f t h e s e
parameters a s well a s recommendations concerning t h e terminology.
The p,resent manual i s based o n t h e s a m e g e n e r a l principles a s t h o s e used i n
the Manual o f S y m b o l s and Terminology f o r Physicochemical Q u a n t i t i e s and
Units' o f the Commission o n S y m b o l s , Terminology and U n i t s of t h e Division o f
P h y s i c a l C h e m i s t r y , D e f i n i t i o n s , Terminology ayd S y m b o l s in Colloid and
S u r f a c e Chemistry o f . t h e Commission o n Colloid and S u r f a c e C h e m i s t r y ,
Appendix I 1 P a r t I D e f i n i t i o n s , Terminology and S y m b o l s in Colloid and Surface
Chemistry , P a r t I 1 Heterogeneous Catalysis , and Recommendations i n Reporting
Physisorption Data for Gas/Solid S y s t e m s . (ref. 1-3)
S i n c e t h e present proposals should b e considered a s o n e o f t h e s u b - s e t s o f
the t e r m s and s y m b o l s o f physical c h e m i s t r y , t h e general p r i n c i p l e s a r e not
repeated h e r e . (see Note a )
This manual provides d e f i n i t i o n s and r e c o m m e n d a t i o n s concerning t h e terminology
o f c a t a l y s i s . It should b e read in conjunctio? with t h e Manual o f M e t h o d s
and Procedures f o r Catalyst Characterization which p r o v i d e s d e t a i l s and
recommendations concerning t h e experimental methods used i n c a t a l y s i s .
2. CATALYST FORMULATION AND METHODS OF ITS PREPARATION
2.1 Methods of preparation
Many catalysts consist o f a n active component o r components ( s e e 2.2)

deposited on a support (such a s s i l i c a , alumina,, carbon). T h e r o l e o f t h e
s u p p o r t may be to i m p r o v e t h e properties (e:g. stability) o f t h e active
component(s), or t o participate directly in t h e c a t a l y t i c r e a c t i o n (e.g. by
providing acidic sites). T h e following t e r m s d e f i n e general preparation
methods.
2.1.1 Precipitation
Precipitation is a method often used for producing both s u p p o r t precursors
and catalyst precursors (including precursory f o r m s o f zeolites) and o c c u r s
when two o r moro s o l u t i o n s are mixed in a s u i t a b l e w a y . I n addition t o
providing general d e t a i l s o f the method (e.g., c o n c e n t r a t i o n , t e m p e r a t u r e ,
p H , etc.) it i s necessary t o indicate specifically t h e order and r a t e of.
addition o f o n e solution i n t o t h e o t h e r , a description o f t h e mixing procedure
and t h e details o f the a q e i n q p r o c e d u r e , if a n y . T h e a s s o c i a t i o n o f t w o or
more active e l e m e n t s in t h e p r e c i p i t a t e , in a s i n g l e o r s e v e r a l p h a s e s , may
be achieved by co-precipitation.
2.1.2 Deposition
Deposition describes t h e application o f the catalytic c o m p o n e n t (e.9. n i c k e l ,
a s . n i c k e l nitrate) o n t o a separately produced s u p p o r t (e.9. silica). Any
treatmen-t of the s u p p o r t before t h e deposition s t e p must be described
precisely.
Deposition may b e achieved by i m p r e g n a t i o n , i . e . , contacting t h e s u p p o r t f o r
a specified time with a solution containing t h e active elements. When t h e
active elements a r e contained i n a volume o f s o l u t i o n c o r r e s p o n d i n g t o t h e
pore v o l u m e , the procedure i s called or o r e volume i m r e n a t i o n . T h e
term incipient idetness method i s used t o d L c r i b e impregn:tiEn when t h e
volume of the solution i s empirically determined a s corresponding t o that
beyond which t h e . c a t a l y s t begins to look w e t . One o r s e v e r a l parallel
processes such a s a d s o r p t i o n , ion e x c h a n g e , s e l e c t i v e reaction o n o r with t h e
surface of .the support may t a k e place during impregnation. S o m e t i m e s the
Note a: Revised and extended edition of the aforementioned 'Manual' has been published as a book
under the title Quantities, Units and Symbols in Physical Chemistry (Blackwell Scientific Publications,
Oxford, 1988).
1230 COMMISSION ON COLLOID AND SURFACE CHEMISTRY INCLUDING CATALYSIS
process o f impregnation i s carried o u t by percolation o f t h e impregnating

solution through a bed o f s u p p o r t , o r by d i p p i n g t h e s u p p o r t in the
impregnation solution.
Two o r more active elements may b e introduced either i n a s i n g l e s t e p by
co-impregnation o r subsequently o n e after the other in successive impregnations.
Drying and often calcination ( s e e 2.1.5) take place between impregnations.
Deposition involving t h e formation o f a strong (e.g. a covalent) bond between
the support and t h e active element i s usually described a s g r a f t i n g o r
anchorin . This i s achieved through a chemical reaction between functional
-8.g . hydroxyl groups) o n the s u r f a c e of the support and a n
appropriately selected inorganic, or organometallic compound o f t h e active
element. When deposition t a k e s place by adsorption o r reaction from the g a s
p h a s e , t h e term chemical vapour deposition i s used.
Sometimes a special technique o f precipitation-deposition i s u s e d , in which
a n active element (e.9. nickel) i s deposited onto a carrier (e.g. silica) in
suspension in t h e precipitating solution (_e.g. nickel nitrate) by s l o w
a d d i t i o n , or in s i t u formation (e.g. of OH by hydrolysis o f urea) of a
precipitating agent.
Ion exchange, which a s already mentioned may occur during impregnation, i s
an important process i n the synthesis o f z e o l i t e s and also in t h e preparation
o f s o m e supported metal catalysts.
2.1.3 Encapsulation
Enzymes o r c e l l s , which a r e o f relatively l a r g e s i z e may be entrapped in a
maze of polymeric molecules ( a gel). This procedure i s called immobilization
by inclusion. When t h e biocatalyst i s enclosed inside a semipermeable
m e m b r a n e , usually approximately spherical, the method is known as
enca sulation. I n t h e process o f reticulation t h e primary biocatalyst
----e--T-
particles individual enzyme molecules, cofactors o r individual cells) a r e
covalently attached t o each other by organic c h a i n s , into a three-dimensional
network. T h e term g r a f t i n g i s also used i n this context. Attachment t o t h e
support by adsorption f o r c e s i s called immobilization by adsorption.
2 . 1 . 4 Selective removal
Preparation o f the catalyst by t h e reaction of a precursor (e.g. NiAl alloy)
with a reactant (e.g. a n aqueous NaOH solution) which selectively dissolves
part o f the precursor (Al) leaving t h e active agent (Nil i s described a s
selective removal method.
2.1.5 Treatment of intermediate s o l i d s or precursors
Very often t h e intermediate solid i s l e f t f o r s o m e time under specified
conditions in t h e presence o f t h e impregnating o r precipitating mixture.
This i s called ageing. Washing o f t h e intermediate solids formed by
prgcipitation i s generally required t o r e m o v e adsorbed ions such as
Na which were introduced during t h e precipitation.
The solvent may be eliminated without chemical transformation by drying. Many
different processes may be applied t o t h i s end such a s drying in a n o v e n ,
fluidized bed d r y i n g , spray d r y i n g , freeze drying.
The intermediate s o l i d s a r e usually subjected to heat t r e a t m e n t , s o m e t i m e s
called calcination. The term calcination should only be used when heating i s
carried o u t in air or oxygen. I t i s essential to describe t h e exact
conditions o f heat treatment, in particular t h e condition of t h e introduction
of t h e s a m p l e , temperature and t h e r a t e o f i t s c h a n g e , pressure, g a s f l o w
c o n d i t i o n s , e t c . Chemical transformation of t h e solid may t a k e place in t h e
course of t h e heat treatment. When t h i s transformation proceeds without
interaction with t h e atmosphere t h e term thermal decomposition may be used.
2.1.6 Activation of t h e precursor
The final step in t h e preparation o f a catalyst i s the transformation o f t h e
precursor t o t h e active phase (e.g. metal, sulfide) which i s s o m e t i m e s
called activation. T h e activation may be a reduction (e.9. by H ) , reduction-
sulfidation e.g. by H + H s), deh drox lation (e.g. by r z m o v a l o f H20
from zeolite; or oxidaZion 2(e.g. b; 0,); The details of the activation
Manual on catalyst characterization (Recommendations 199 I ) 1231
process must be stated ( e . g . partial pressure and purity o f g a s , method of

heating and i t s r a t e , g a s reacting f l u w r a t e , sample size).
2.2 Chemical composition
Catalytic materials a r e frequently composed of many c o m p o n e n t s and phases.

T h e r e f o r e , i t i s seldom adequate t o define a c a t a l y s t by merely s t a t i n g t h e
chemical c o m p o s i t i o n , e . g . 1% P t , 9 9 % Si02. Note that by c o n v e n t i o n t h e
s u p p o r t should be indicated clearly by using an oblique s t r o k e (solidus),
e . g . 1% Pt/Si02.
The term major active component may be used t o describe t h e active c o m p o n e n t ,
the proportion of which greatly exceeds that of the o t h e r s . Secondary
components added on purpose may be described a s a d d i t i v e s , whereas the term
impurities should be reserved for trace amounts o f other e l e m e n t s , o v e r which
the investigator (manufacturer) h a s little control. T h e u s e of the word
romoter implies that t h e additive imp7oves s o m e particular property o f t h e
c:talysts, and i t i s desirable to indicate this property when k n o w n (e.9.
a c t i v i t y , s e l e c t i v i t y , textural properties, r e s i s t a m e to sintering).The term
modifier i s used s o m e t i m e s in this c o n t e x t , but i s n o t r e c o m m e n d e d . The term
modifier i s used in a special and proper sense in the c o n t e x t of asymmetric
hydrogenation w h e n , for e x a m p l e , Raney nickel i s modified by optically active
tartaric acid in order t o impart t h e property o f asymmetry t o hydrogenation
reactions over the c a t a l y s t .
The action of adding a s m a l l amount of foreign atoms t o form a solid solution
in the lattice of a nonmetallic catalyst i s s o m e t i m e s called doping.
The description of t h e composition of a catalytic system should indicate t h e
crystallographic form o f the support (e.9. 'd -A1203, Ti02 - anatase). The
chemical composition should be unambiguously defined. Nhen specifying the
proportions of t h e active phase to the s u p p o r t , weights may be used provided
the stoichiometry i s clearly indicated ( e . 9 . C o 3 0 4 and M o o 3 , C o 9 S 8 and MoS2,
N i O , Pt).
2.3 Aggregate morphology
The solid obtained after the operations described in Section 2.1 (supp:orts,
intermediate s o l i d s , precursors o r catalysts) c a n be used as- s u c h i e . g .
powders) or shaped i n t o larger entities (beads, p e l l e t s , e x t r u d a t e s , rings).
In special c a s e s s t r u c t u r e s called monoliths are used a s s u p p o r t . Description
of t h e aqnregate morphology should include reference t o the c r y s t a l s t r u c t u r e
and details of the s h a p e of the particles of t h e various p h a s e s p r e s e n t ,
their arrangement in s p a c e (including .the voids o r pores) and the s h a p e o f
larger physically s e p a r a t e entities. The structure i s defined by t h e
distribution in space o f . t h e a t o m s or i o n s in t h e material part of the
c a t a l y s t , t h e texture i s defined by the detailed geometry of the void s p a c e
in the particles o f c a t a l y s t and by t h e spatial relationships between t h e
different phases p r e s e n t .
Certain materials used a s catalysts o r supports consist o f s p h e r o i d s smaller
than 10 nm in d i a m e t e r , cemented into larger entities. A p r i m a r y particle
should b e defined a s t h e s m a l l e s t discrete iuentifiable entity and t h e method
of identification should be mentioned (e.g. transmission electron m i c r o s c o p y ,
scanning electron microscopy). An assemblage o f such primary particles
exhibitin.g an identifiable collective behaviour (e.g. chemical nature o f t h e
aggregated primary p a r t i c l e s , texture o f the a g g r e g a t e , resistance to
mechanical separation upon grinding) constitutes an a g g r e g a t e . When describing
the aggregates the criterion of identification should be mentioned. Strongly
bonded aggregates a r e called agglomerates.
A collection o f l o o s e , u n a t t a c h e d , primary particles o r aggregates of
relatively small size i s usually called a p o w d e r . I t i s recommended t h a t t h e
word powder i s used if t h e largest dimension of t h e individual eri'tities i s
smaller than 1 m m . The s h a p e o f t h e particle should b e described (sphere,
flake) and the method o f i t s preparation specified ( c r u s h i n g , grinding
spray drying).
In the designation of larger aggregates tiro criteria may b e u s e d : s h a p e ,
referring t o geometrical d e f i n i t i o n , o r method of preparation. S p h e r i c a l ,
spheroidal or rounded aggregates obtained by beading or granulation a r e
called b e a d s , and aggregates of cylindrical s h a p e , f o r m e d by tableting
(tablet) o r extruding (extrudate) are described as cylinders. The term lump

is used to describe an aggregate of irregular shape, obtained usually by
crushing, but its form should be described as precisely as possible. A precise
description should be given when aggregates of other form, such a s rings o r
trilobes, are used. The dimensions (diameter, thickness, length, inner and
outer diameter of a ring) of the entity as defined above should be stated.
2.4 Forming operations
Depending upon the technology (e.g. fluidization, moving-bed o r fixed-bed)

and the conditions of the catalytic process, the shape and size of catalyst
entities may vary appreciably, e.g. powder, cylinders, beads. A general
problem is to make entities of dimensions larger than 1 mm from fine powder
particles o r precipitates. Materials which are difficult to shape are treated
with additives (e.g. flake graphite, starch, stearic acid, poly(acry1ic acid),
mineral oil, vegetable oil) usually in amounts of l-Swt.-%. Shaping additives
may act as lubricants, plasticizers, cements, porosity promoters (porogenic
additives). The powdered starting material mixed with the additives may be
dry, o r converted to a plastic pulp by addition of a suitable liquid.
One sometimes distinguishes:
If the material is of natural origin (natural molecular sieve, pumice) the

desired entity size is obtained by crushing and/or grinding and subsequent
size selection by sieving. Some catalysts are also obtained in this way from
synthetically prepared bulky masses (e.g. ammonia catalyst). Grinding may
take place in the absence (drv grinding) o r presence (wet grinding) of a
liquid, usually water.
In spray-drying a solution o r a slurry of the powder in suspension in water
is passed through a nozzle which sprays small droplets into hot air.
Spray-drying gives particles of almost identical shapes (spheres with a small
characteristic depression) and size which are used as such in fluid bed
operations. The dropping-in-oil method consists in introducting a sol or gel
as drops through a nozzle into a hot oil. Water from sol o r gel is evaporated
(chemical bonds may be formed at this stage) and the gel hardens, resulting
in the formation of beads. Depending on the relative densities the drops may
move downwards (oil drop p e r s e ) o r upwards. Granulation is a process of
aggregation by progressive humidifying in a rotating granulator. Generally,
aggregates of different size are kept in motion under a spray of liquid
(water or aqueous solution) in a hori6ontal rotating cylinder o r a pan
rotating around, an axis incline,d about 45 . The pan may be concave (hemispheric
granulator o r bow granulator o r cylindrical (flat granulator o r dish
granulator '1. Spheroidal particles o r granules are thus formed. In the method
of tabletin , the powder is firmly compressed in a die to be shaped into
small cylindgers (pellets), rings o r beads. In most cases some plasticizing
agents are added to the powder (talc, graphite, stearic acid). Another
technique of shaping larger entities from a powder is extrusion, in which a
paste is forced through a die to form a cylinder which is cut into small
pieces. The cross-section of the die may have different shapes (circular,
trilobe, toothed wheel, ring). The powder with the additives is first pulped
with a liquid, homogenized, kneaded and fed to the die by some pushing device
(screw, piston). The paste may be soft or stiff. The product is termed the
extrudate, of which the exact form-ee above) as well as the dimensions
should be specified.
2.5 Stability of catalyst systems
2.5.1 Physical stability

Granular catalysts have a grain size distribution which may be determined
by passing a sample through a series of graded sieves. The grain size
distribution is determined by the condition under which the materials were
precipitated or dried during catalyst preparation. Grains may be structurally
weak so that they undergo attrition ( s e e section 3 . 4 ) when in random contact
with other grains. Thus grain size distribution of a catalyst may change as
it is transported before use, or while it is in use. Fragmentation of catalyst
particles in the reactor, caused, for example , by thermal shock or carbon
build-up, may also occur.
To obtain a correct grain size distribution for a catalyst, a proper sampling

procedure should be adopted. For example, samples should be taken from various
depths within a container in order to determine whether the batch has been
rendered inhomogeneous by settling effects, and care must be taken to ensure
that the sieving process itself does not cause attrition. In the case of
tableted o r extruded catalysts the process of attrition may be inhibited by
binders used in their preparation.
Catalysts consisting of an active phase on an oxidic o r carbon support are
subject to a particular form of degradation in that attrition may result in
preferential loss of the active phase as fines.
Catalysts which have the capacity to adsorb water or carbon dioxide from the
air may exhibit weight instability due to climatic changes. Time and variation
of temperature o r pressure may, in principle, give rise to losses or gains
in weight due to changes in water content. Metal particles are susceptible
to sintering with a concomitant loss of dispersion.
2.5.2 Chemical stability
Most heterogeneous catalysts in the as-received state or in precursor form
possess a considerable degree of chemical stability whereas after activation
they are highly reactive. Two cases may be distinguished: (i) chemical
stability in air at ambient temperature and pressure, and (ii) chemical
stability at elevated temperatures of the catalyst in the as-received state.
Many oxides, sulfides, and metals react with air slowly at ambient temperature,
although such processes may be measurable only over long periods. For example,
supported nickel which has been passivated by exposure to air under conditions
which produce only surface oxidation may react further to give supported bulk
nickel oxide. Air contains water vapour and carbon dioxide and also hydrocarbon
impurities so that hydroxide or carbonate formation and hydrocarbon
contamination may occur. Catalysts consisting of an active phase supported
on a non-stoichiometric compound may undergo chemical change by reaction of
the support with oxygen of the air. Catalysts which contain a material that
is photosensitive, e.g. titania, may show enhanced chemical instability when
exposed to sunlight.
Catalysts subjected to heating in air may exhibit accelerated hydroxide or

carbonate formation, before a loss of water o r carbon dioxide could take
place. Phase changes may also occur, for example, in alumina by interaction
of a partially hydrated phase with water physically adsorbed in pores,
Elevated temperature may lead to measurable chemical reaction, between active
phases, o r between active phases and supports, o r to the segregation of
phases in systems that were formerly homogeneous, which greatly modify the
properties of the catalyst when activated. F o r example, nickel oxide and
silica may form nickel silicate, o r cobalt oxide and alumina may form cobalt
aluminate. In a nickel/silica hydrogenation catalyst, silicate formation
would reduce the amount of nickel formed under standard reduction conditions.
In a Co0-Mo03/A1203 hydrodesulfurization catalyst, coba,lt aluminate formation
would reduce the quantity of cobalt available to act as a promoter.
The nickel catalyst used in the hydrogenation of natural oils and edible fats
is a special example of a catalyst which is transported in a protected state.
In this case, the catalyst is protected by encapsulation in solid fat. The
fat melts when the catalyst is introduced into the reactor, so releasing the
active phase. Particular care must be taken to control the temperature
during the transport and handling of this material.
The action o f steam may have a deleterious effect on catalytic materials,
For example, transport of silica can lead to loss of support material o r to
the encapsulation of the active phase. Steaming may also change the pore
structure of the support. At somewhat lower temperatures the action of water
vapour may result in an irreversible decrease in the surface area.
3. PHYSICAL PROPERTIES
3.1 Total surface area
Many catalysts are porous solids of high surface area and with such materials
it is often useful to distinquish between the external and internal surface.
The external surface is usually regarded as the envelope surrounding discrete
particles or a g g l o m e r a t e s , but i s difficult to define precisely because solid

surfaces a r e rarely s m o o t h o n a n atomic s c a l e . I t c a n b e taken t o i n c l u d e a l l
the prominences plus t h e surface o f those c r a c k s , pores and c a v i t i e s which
are wider than they a r e deep. The internal s u r f a c e c o m p r i s e s t h e walls o f t h e
rest of t h e pores, c a v i t i e s and cracks. In practice, t h e demarcation i s likely
t o depend o n the methods o f assessment and t h e nature o f t h e pore s i z e
distribution. The total s u r f a c e area (A ) equals t h e s u m o f t h e external and
internal s u r f a c e areas. T h e rouahness c?f a solid surface mav b e characterized
by a roughness f a c t o r , i.e. t h e ratio o f t h e external s u r f a c e to t h e chosen
geometric surface.
Gas adsorption methods a r e often used t o determine the s u r f a c e area and pore
size distribution o f catalysts. The Brunauer-Emmett-Teller (BET) adsorption
method i s the most widely used standard procedure. ( S e e : P u r e and Applied
Chemistry 5 7 , 6 0 3 ( 1 9 8 5 ) 1.
3.2 Pore structure
Most catalysts o f high s u r f a c e area a r e t o s o m e extent porous. Porosity i s

a concept related t o texture and r e f e r s t o t h e pore s p a c e in a material. I t
c a n be defined a s t h e fraction o f t h e bulk volume that i s occupied by pore o r
void space. An open pore i s a cavity or channel communicating with t h e s u r f a c e
o f a particle, a s opposed t o a closed pore. Void i s the s p a c e o r interstices
between particles.
The pore s y s t e m s o f s o l i d s a r e o f many different kinds. T h e individual pores
may vary greatly both in s i z e and in s h a p e within a given s o l i d , and between
o n e solid and another. A feature o f special interest f o r many purposes i s t h e
width (w) of the pores, e.g. t h e diameter of a cylindrical pore, or the
distance between t h e s i d e s o f a slit-shaped pore.
It i s expedient to classify pores according t o their sizes:
(i) P o r e s with w i d t h s exceeding about 50 nm a r e called macropores;
(ii) P o r e s with w i d t h s not exceeding 2 nm a r e called micropores;
(iii) P o r e s of intermediate s i z e a r e called mesopores.
These l i m i t s a r e t o some extent arbitrary. I t i s worth emphasizing that
amongst s o l i d s a s a w h o l e a wide and continuous r a n g e of pore s i z e s i s t o be
f o u n d , from macropores through mesopores and micropores t o grain b o u n d a r i e s ,
cleavage planes and dislocations.
The total o r e v o l u m e , V , s o m e t i m e s called s ecific o r e volume when referred
to unit maEs, i s t h e t o t i 1 internal volume pe; unit m E s s o f catalyst. S o m e o f
this pore volume may be completely enclosed and thus inaccessible t o molecules
participating in a catalytic reaction. The total accessible pore volume i s
often derived from t h e amount o f vapour adsorbed at a relative pressure c l o s e
to u n i t y , by assuming that t h e pores a r e then filled with liquid adsorptive.
The accessible pore volume may be different for molecules o f different s i z e s .
I t may be useful t o determine t h e dead s p a c e by means o f a nonsorbable g a s
(normally helium) in conjuction with t h e determination o f T h e bulk volume o f
t h e catalyst by means o f a non-wetting liquid (mercury).
The pore-size distribution i s t h e distribution o f pore volume with respect t o
pore size. It i s a n important factor controlling the diffusion o f r e a c t a n t s
and products in t h e porous catalyst and t h u s a n essential property f o r i t s
characterization. T h e computation o f pore s i z e distribution i n v o l v e s a number
of assumptions and therefore reporting o f t h e data should always be
accompanied by a n indication of t h e method used f o r i t s determination. ( S e e :
P u r e and Applied Chemistry 5 7 , 6 0 3 ( 1 9 8 5 ) ) .
T h e pore geometry o f t h e majority of catalysts consists o f a n interconnected
three-dimensional network o f interparticle s p a c e s , pores or capillaries.
Usually capillary segments o f different s h a p e s and s i z e s a r e distributed over
the network in s o m e irregular fashion. lihen a solid i s formed by aggregation
o f p r i m a r y , non-porous particles, the detailed s h a p e s o f pores will depend on
the s i z e distribution o f t h e primary particles and o n their mode o f packing.
Platelets will tend t o form wedge-shaped pores o r slits. With s p h e r e s , t h e
closeness o f packing will depend o n t h e average number o f neighbours. Well
defined geometrical n e t w o r k s c a n be assigned t o s o m e c a t a l y s t s , e.g. zeolites,
some l a m e l l a r materials, and f i b r o u s silicates. However, t h e pore structure
o f many materials used a s catalyst supports present a highly irregular
geometry, far removed from simple models. This complexity imposes a s e r i o u s
limitation o n the reliability o f t h e methods o f calculation o f pore-size

distribution.
Some porous solids expand o n exposure t o t h e vapours o f adsorptives. This
phenomenon i s called swelling. By determining the length o r volume o f a
specimen o f t h e solid a t different vapour pressures t h e expansion isotherm
may be obtained. Rigid adsorbents, l i k e charcoal o r silica g e l , s w e l l by only
a f e w percent, but non-rigid adsorbents, l i k e agar-agar, may s w e l l t o several
times t h e original size. Provided t h e adsorption o c c u r s slowly t h e rigid
solid may accommodate t h e stresses, but if suddenly exposed t o high vapour
pressure t h e material may shatter.
3.3 Density
Several catalyst densities a r e used in t h e literature. True density may be

defined a s t h e mass o f a powder o r particle divided by i t s volume excluding
all pores and voids. I n a strict physical s e n s e , this density c a n be calculated
only through X-ray o r neutron diffraction analysis o f single crystal samples.
The term apparent d e n s i t y h a s been used t o refer t o the mass divided by t h e
volume including s o m e portion o f t h e pores and v o i d s , and so values are
always smaller than t h e true density. This term should not b e used unless a
clear description i s given o f what portion o f t h e pores i s included in t h e
volume. So-called helium densities determined by helium expansion are
apparent densities and n o t true densities s i n c e t h e measurement may e x c l u d e
closed pores.
Bulk d;insity, or p a c k i n g d e n s i t y , includes all pores and voids (interparticle
spaces in i t s calculation. I t i s determined by filling a graduated c y l i n d e r ,
with or without tapping. It f o l l o w s that t h e value obtained i s dependent upon
the form o f t h e catalyst (powder, tablets, extrudates) because of the
different contribution o f interparticle void s p a c e t o t h e pore volume. Tap
density i s t h e apparent density o f a bed o f particles in a container o f stated
dimensions when a given amount o f powder i s vibrated or tapped under controlled
conditions. T h e u s e o f t h e term bulk density should be e n c o u r a g e d , accompanied
by t h e detailed description o f t h e conditions o f i t s determination.
Catalyst manufacturers a l s o define a n effective solid d e n s i t y , determined by
displacement of a given liquid (water, ethanol). Values obtained with
different liquidsmay vary s u b s t a n t i a l l y , depending o n the extent t o which the
molecules o f t h e liquid a r e able t o penetrate into the pores o f t h e catalyst.
The term p i e c e density i s sometimes used when t h e measurement i s performed
with a liquid which d o e s not substantially penetrate into t h e pores.
3.4 Mechanical strength
It i s desirable for commercial catalysts to have sufficient mechanical

strength so that l o s s e s during handling and u s e a r e minimized. Broken pieces
and f i n e s (fine powder) l o s t during handling o r produced during commercial
use c a n represent a significant e x p e n s e , especially f o r c a t a l y s t s containing
precious metals s u c h a s P t and R e - D e p e n d i n g o n the design o f the commercial
reactor, broken c a t a l y s t , or f i n e s , c a n l o d g e i n s u p p o r t s c r e e n s or in
containment s c r e e n s causing a restriction in t h e f l o w o f reactants and
products through t h e reactor. Various laboratory t e s t s have been designed t o
provide information concerning t h e ability o f a catalyst t o maintain i t s
physical integrity.
Crush strength i s defined a s t h e resistance o f formed catalysts t o compresive
forces. Measurements o f crush strength are intended t o provide a n indication
o f t h e ability of t h e catalyst t o maintain i t s physical integrity during
handling and use. When crush strength i s measured for s i n g l e pieces i t i s
called p i e c e crush s t r e n g t h , and when i t i s mesured f o r a bulk s a m p l e i t i s
called bulk crush strength. Other t e r m s which have been used f o r piece c r u s h
s t r e n g t h , but which a r e n o t recommended a r e static crush s t r e n g t h and s i n g l e
pellet crush strength.
Piece crush strength i s commonly measured by placing individual c a t a l y s t
pieces between t w o f l a t s u r f a c e s , applying a commpresive l o a d , and measuring
the f o r c e required to crush the piece. Best results a r e obtained f o r regular
s h a p e s , such a s beads and tablets. Crush strength measurement of extrudates
i s l e s s straightforward, and t h e results will vary greatly with particle
geometry and with the d e t a i l s o f t h e analytical procedures used. T h e procedure
used should b e described in detail. S o m e methods may be repeatable within a
single laboratory but irreproducible between laboratories.

Eulk c r u s h strength i s commonly measured by p l a c i n g a r e p r e s e n t a t i v e s a m p l e
in a c y l i n d e r , applying a constant f o r c e with a p i s t o n , and mesuring t h e
amount of f i n e s generated. Many different variants a r e possible and no
generally accepted method i s y e t available. T h e bulk crush s t r e n g t h i s defined
empirically and t h e r e s u l t s a r e expressed o n a n arbitrary scale. This
measurement may be applied to all catalyst shapes.
Attrition i s defined a s loss o f c a t a l y s t during handling o r use. Attrition
c a n occur by loss of f i n e s through a b r a s i o n , w h i c h i s w e a r i n g , g r i n d i n g , o r
rubbing of t h e particles with each other or with container w a l l s . Attrition
c a n also occur by loss of pieces due to b r e a k a g e s , which c a n be caused, by
impact o r collision o f particles with container walls. Numerous t e s t s have
been designed to measure t h e resistance o f c a t a l y s t particles t o attrition.
These t e s t s vary considerably i n complexity and s e v e r i t y . Their applicability
d e p e n d s o n the particular t y p e o f c a t a l y s t being tested.
A s i m p l e method t o measure attrition i s t o place a representative s a m p l e o f
the catalyst in a closed c o n t a i n e r , vibrate o r s h a k e t h e c o n t a i n e r , and t h e n
measure the amount o f f i n e s generated. Another relatively mild method i s t o
place a s a m p l e i n a drum having a single b a f f l e , r o t a t e t h e drum f o r a fixed
period o f t i m e , and then measure the amount o f f i n e s generated by s i e v i n g
through a standard s i e v e . Larger particles o f s i l i c a and alumina will hold
very f i n e particles o n their s u r f a c e and these stay attached during s i e v i n g ,
but c a n be removed by agitation in water.
More severe t e s t s are a'pplicable to c a t a l y s t s used in moving bed r e a c t o r s .
Some testsuse a high velocity stream of g a s to c a u s e atttrition o f t h e catalyst.
In s o m e t e s t s , a small-scale plant which s i m u l a t e s t h e c o m m e r c i a l plant i s
used. T h e amount o f attrition measured in all these t e s t s i s very d e p e n d e n t
o n the exact procedure used. Reproducibility among l a b o r a t o r i e s i s only
likely t o be possible if precise details of t h e method are g i v e n .
4. FINE STRUCTURE
4.1 Surface structure and topography
The catalyst particle i s usually a complex entity composerJ of,a p o r o u s s o l i d ,

serving a s the s u p p o r t for o n e o r more catalytically active phase(s). These
may c o m p r i s e c l u s t e r s , t h i n s u r f a c e mono- o r multilayers, or s m a l l crystallites.
The s h a p e , s i z e and orientation o f c l u s t e r s o r c r y s t a l l i t e s , t h e extension
and arrangement o f different c r y s t a l f a c e s together with m a c r o d e f e c t s s u c h a s
s t e p s , k i n k s , e t c . , a r e parameters describing t h e s u r f a c e topography. T h e
type o f a t o m s and their mutual positions at the s u r f a c e o f t h e active phase
or o f the s u p p o r t , and the t y p e , concentration and mutual positions o f point
defects (foreign a t o m s in lattice positions, i n t e r s t i t i a l s , v a c a n c i e s ,
d i s l o c a t i o n s , etc.) define t h e surface structure.
T h e determination of t h e s u r f a c e structure of solid i s possible using a

variety o f experimental m e t h o d s , t h e methods c h o s e n being dependent o n ,the
specific information r e q u i r e d . Information o n s u r f a c e elemental composition
'is also desirable.
With single c r y s t a l s the symmetry of the surface structure and t h e presence
of features, s u c h a s s t e p s , c a n b e obtained using l o w energy electron
diffraction (LEED). F o r r e a l c r y s t a l s , s u r f a c e topography c a n b e i n v e s t i g a t e d
by conventional optical microscopy and various o t h e r microscopic t e c h n i q u e s ,
such a s scanning electron microscopy ( S E M ) , transmission electron microscopy
(TEN), scanning transmission electron microscopy (STEM), high r e s o l u t i o n
electron microscopy ( t l R E M ) , and analytical electron microscopy (AEM).
T h e basic concept in examining samples by S E M i s that t h e intensity o f
t h e radiation emerging from each region o n t h e surface i s characteristic
of the topography o f t h e r e g i o n . Local variation i n s u r f a c e topography,
i.e. orientation o f t h e surface with respect t o t h e electron beam
gives r i s e to contrast in S E M . T h e accompanying X-ray s i g n a l s generated
may be used to provide information o n chemical composition (energy
dispersive analysis by X-rays, EDAX). T h e local environment of atoms
(coordination n u m b e r , nature o f coordinating a t o m s and atom-to atom distances)
c a n be dotermined from an anaiysis of the extended X-ray absorption f i n e

structure (EXAFS), and that o f surface atoms by using s u r f a c e EXAFS (SEXAFS),
glancing angle o r reflection EXAFS (REFLEXAFS) o r c r i t i c a l a n g l e EXAFS.
4.2 Surface area of different phases
For any given catalytic reaction t h e active s u r f a c e area i s normally o n l y

a s m a l l fraction o f the area o f the active component (active phase). T h e t e r m
active s i t e s i s often applied t o the s i t e s effective f o r a particular
heterogeneous catalytic r e a c t i o n . T h e t e r m s active s i t e and a c t i v e c e n t r e a r e
often used a s s y n o n y m s , but active c e n t r e may a l s o b e u s e d t o d e s c r i b e a n
ensemble of s i t e s at which a catalytic reaction t a k e s place. T h e r e i s evidence
that the centres required f o r s o m e catalytic reactions a r e composed o f a
collection of several metal a t o m s (ensemble). This a p p e a r s t o b e t h e c a s e f o r
such r e a c t i o n s . a s , for e x a m p l e , hydrogenolysis, hydrogenation o f C O , and
certain deuterium-exchange processes with hydrocarbons.
I t i s frequently convenient to describe the chemical properties o f a c a t a l y s t
surface by reference to surface sites. A surface s i t e may be c o m p o s e d of o n e
o r more surface atoms o r i o n s and may a c t a s a n active s i t e f o r a given
catalytic r e a c t i o n , or may be inactive. I t i s . characterized by t h e c h e m i c a l
reactivity o f these a t o m s o r i o n s and by their spatial arrangement a t t h e
surface. The s i t e density i s t h e number of s i t e s per unit s u r f a c e area.
However, i t i s expedient to extend t h e use of this term to c a s e s w h e r e surface
area h a s n o clear s i g n i f i c a n c e . I n these c a s e s t h e s i t e density i s r e f e r r e d
to unit m a s s or unit volume o f the c a t a l y s t .
I n supported catalysts the surface area o f t h e active phase i s d i f f e r e n t f r o m
t h e total s u r f a c e a r e a . I n - t h e particular c a s e of supported metal c a t a l y s t s
several techniques may be used t o estimate t h e s u r f a c e area o f .the active
phase and t h e number o f exposed metal atoms. (Note, h o w e v e r , that t h i s d o e s
not necessarily provide a measure o f t h e active surface area). T h e method
used most often i s based on selective chemisorption o f appropriately c h o s e n
probe molecules ( H C O , N 2 0 ) , t h e chemisorption d'ata obtained under w e l l
defined c o n d i t i o n s &king then compared with t h e total surface area determined
from t h e analysis o f physical adsorption data. H o w e v e r , a s s u m p t i o n s .must b e
made regarding the stoichiometry o f the interaction o f t h e probe molecule
with t h e surface metal a t o m s and o f t h e number o f surface metal a t o m s per
unit s u r f a c e area. This method provides consistent measurements o f t h e surface
area of metal particles but i s . n o t generally applicable t o nonmetal catalysts.
A variation o f t h i s method c o n s i s t s i n the titration o f a n adsorbed s p e c i e s
(e.g. oxygen) by a r e a c t a n t (e.g. - H 1. I t i s still necessary t o make s o m e
assumptions concerning t h e stoichiomezry o f t h e titration reaction.
The degree o f dispersion i s defined a s t h e fraction (percentage) o f t h e total
metal a t o m s which a r e s u r f a c e atoms. (The term fraction exposed (percentage
exposed) i s synonymous with t h e degree of dispersion).
Several physical m e t h o d s may b e used to provide indirect e s t i m a t e s of t h e
degree of dispersion. S i z e s o f particles, or o f single k r y s t a l l i t e s , or o f
magnetic domains d e t e r m i n e d , r e s p e c t i v e l y , by electron m i c r o s c o p y , X-ray
line b r o a d e n i n g , and magnetization measurements, c a n be used f o r t h i s purpose
but, in all c a s e s , assumptions must be introduced i n t o t h e c a l c u l a t i o n s ?
An alternative means o f description i s to use t h e mean diameter o f primary
p a r t i c l e s a s obtained from low-angle X-ray scattering, broadening o f X-ray
diffraction lines o r EXAFS. It may a l s o be possible to u s e these techniques
to determine the grain s i z e of t h e s u p p o r t , o r o f t h e c a t a l y s t particles i n
g e n e r a l , providing t h e s e materials a r e sufficiently c r y s t a l l i n e . T h e particle-
s i z e distribution may be measured directly using o n e o f t h e microscopic
techniques or indirectly by using a sedimentation method.
4.3 Surface elemental composition of different phases
The chemical nature a n d composition o f catalyst s u r f a c e s a r e essential

parameters f o r understanding catalvtic reactivity. Electron s D e c t r o s c o p i e s .
mainly Auger Electron S p e c f r o s c o p i (AES), X-ray' Photoelectron Spectroscop;
(XPS), Secondar Ion Mass Spectroscop (SIMS) and Ion Scattering S p e c t r o s c o y
CISs) allow sucyh information to be o E t a i n e d . AES and X P S are most likely
provide m c a n i n g f u l . d a t a if t h e s u r f a c e region o f t h e solid i s homogeneous
70
over a depth several t i m e s the inelastic mean f r e e path of t h e emitted
electrons.
In catalysis it i s important not only to be able to study t h e s u r f a c e r e g i o n

of the catalyst i t s e l f , but also any adlayer that may be present. The l a t t e r
may arise from adsorption o r preferential segregation o f o n e c o m p o n e n t f r o m
the bulk to the s u r f a c e . The spatial distribution o f t h e e l e m e n t s a t the
surface c a n be obtained f r o m scanning AES. E x p e r i m e n t s , in which t h e s u r f a c e
i s progressively e r o d e d , e . g . , by ion-bombardment, with s u r f a c e a n a l y s i s by
A E S , X P S or I S 5 carried- out- after various t i m e s , m a y provide concentration:
depth profiles of the chemical s p e c i e s .
4.4 Surface chemical characterization
T h e activity o f a catalyst depends o n the n a t u r e , t h e n u m b e r , t h e s t r e n g t h

and t h e spatial arrangement o f t h e chemical bonds that a r e transiently created
between the reactants and the s u r f a c e . T h e objective of the chemical
characterization o f t h e surface i s a detailed description o f t h e adsorbate-
adsorbent bonds that a given catalyst will develop when contacted with a
given reaction mixture. Therefore, chemical characterization should be
done in s i t u in the c o u r s e of the reaction itself. H o w e v e r , because o f
experimental limitations, this i s seldom possible and c a t a l y s t s u r f a c e s a r e
usually characterized by m e a n s o f s e p a r a t e experiments. I t i s important t o
characterize t h e catalyst s u r f a c e both before and after i t s u s e i n a reaction.
The pretreatment o f the c a t a l y s t , before t h e chemical characterization
e x p e r i m e n t s , must be selected so that the relevant surface properties a r e a s
similar a s possible to ,those existing during ,the catalytic r e a c t i o n . When t h e
chemical constitution of t h e surface o r i t s structure a r e n o t significantly
modified by the reaction' i t s e l f , the same pretreatment c a n be used for t h e
characterization e x p e r i m e n t s a s for t h e catalytic tests.
Ideally,, the probe molecules used in t h e chemical clpracterization experiments
should s i m u l a t e as closely a s possible the behaviour o f t 9 e a c t u a l r e a c t a n t s .
This i s rarely possible and so simple probe molecules ( H 2 , 0 C O , NO) a r e
u s e d instead. S o m e additional information about the nature o f ti;l'e s u r f a c e may
be obtained using thermal analysis m e t h o d s , e . g . , c a l o r i m e t r y , temperature-
programmed d e s o r p t i o n , temperature-programmed r e a c t i o n .
When a catalytic reaction modifies the s u r f a c e properties o f the catalyst in
a way which c a n n o t be simulated in the absence of r e a c t a n t s , or when l a r g e
series o f similar c a t a l y s t s are to be c o m p a r e d , i t i s convenient t o
characterize a given c a t a l y s t by its activity in a n a p p r o p r i a t e , p r o b e - r e a c t i o n
4.4.1 Acid-base s i t e s
An acid-base s u r f a c e c o n t a i n s individual acidic and basic s i t e s which may
interact together. On a given s u r f a c e , o n e type (acidic or basic) may prevail
but both are always present (conjugate acidic and basic pairs). Examples o f
such surfaces a r e found in metal o x i d e s , sulfides and o t h e r compounds. T h e
description of acidic and basic surface properties requires t h e determination
of the nature (Lewis or Brdnsted), the d e n s i t y , t h e l o c a t i o n , and t h e strength
distribution of s i t e s . It i s important t o distinguish between the number o f
acid ( o r base)'sites and t h e acid ( o r base) s t r e n g t h d i s t r i b u t i o n .
Acidic and basic s i t e s a r e usually generated during t h e c a t a l y s t s y n t h e s i s
but many pretreatments c a n c h a n g e the n u m b e r , the nature and/or t h e strength
of the sites. Such c h a n g e s may r e s u l t , for i n s t a n c e , from: decomposition o f
ammonium o r organic c a t i o n s , ion e x c h a n g e , reduction or oxidation o f c a t i o n s ,
hydration-dehydration, dehydroxylation by r e a g e n t s in s o l u t i o n , up,on heating
or evacuation, water decomposition o n polarizing c a t i o n s , s t e a m i n g , exposure
to various g a s e s , ( e . g . C 1 C 0 2 ! H 2 S , F2),,;treatment with chemicals
(dealumination). T h e r e f o r e , &e choice of speci%ic and defined c o n d i t i o n s f o r
characterization i s of major importance.
No r i g o r o u s practi'ca? definition of acid strength e x i s t s outside o f very
dilute aqueous solutions t i h e r e activity coefficients c a n b e assumed t o b e
unity. Each method o f measuring the acid strength o f s u r f a c e s i t e s i s l i a b l e
to give somewhat different a n s w e r s , the results being q u a l i t a t i v w a t best.
The dielectric constant of t h e m e d i u m , in which the acid or base probe i s used
influences the measured acid-base strength.
In general t e r m s , an acidic s i t e may be defined, a s a site on which a b a s e is
chemically a d s o r b e d , and basic s i , t e a s a site on which an acid is chemically
adsorbed. A Brdnsted acid s h o w s a tendency to donate a proton and the Brdnsted

base to accept a proton. A Lewis acid i s able to accept a n electron pair and
a Lewis base to donate a n electron pair. The Lewis acid c a n b e , f o r i n s t a n c e ,
a coordinatively unsaturated aluminium i o n i n alumina or s i l i c o a l u m i n a t e s ,
a cation such a s Na(1) o r Ca(I1) in z e o l i t e s , e t c .
The acid o r base strength i s defined by comparing the interaction between t h e
s i t e s and reference (probe) molecules. F o r e x a m p l e , the acid s t r e n g t h i s t h e
ability o f t h e site t o c o n v e r t a n adsorbed reference neutral b a s e i n t o i t s
conjugate acid. This process may be monitored by following t h e c o l o u r c h a n g e s
o f t h e indicators or by s u c h techniques a s IR o r , NMR spectroscopies. S e v e r a l
criteria must be considered in t h e selection of the& probes: their pK v a l u e
must be adapted to the acidity o r basicity o f t h e surface under s t u d y ; t h e
size o f t h e probe molecules should ensure that all sites are readily
accessible; f i n a l l y , t h e probe should be selected so that i t s interaction
with t h e surface i s easily studied by t h e available experimental techniques.
Catalytic test reactions a r e sometimes used for t h e evaluation o f a c i d - b a s e
properties of catalysts. F o r e x a m p l e , dehydration of propan-2-01 i s a
convenient test for weak s u r f a c e acidity.
Since acidic o r basic s i t e s may interact with each o t h e r , the s i t e density
ought t o be determined. M o r e o v e r , a n attempt should be made t o describe t h e
site l o c a t i o n , particularly in the c a s e o f microporous acid catalysts
(zeolites).
4 . 4 . 2 Redox s i t e s
Redox s i t e s may be separated into two c a t e g o r i e s , namely (i) s i t e s
incorporating atoms . w h i c h , in the presence o f t h e r e a c t a n t s , 'are oxidized or
r e d u c e d , and (ii) s i t e s able to from a charge-transfer complex by interaction
with an electron acceptor o r an electron donor.
I n the c a s e of surface s i t e s incorporatinqatoms, 'the valence s t a t e s and their
eventual variation in the c o u r s e o f the reaction can be studied by
spectroscopic methods such a s electron P a r a m a g n e t i c resonan.ce ( E P R ) , XPS,ultra-
violet photoelectron (UPS), I R , and near-edge X - r a y ( X A N E S ) spectroscopies.
(see Note b )
Quantitative information on the number of s i t e s may be obtained from a

volumetric o r gravimetric study o f the adsorption o f oxidizing o r reducting
molecules. Adsorption calorimetry c a n be used to determine t h e e n e r g e t i c s of
the site d i s t r i b u t i o n , a s in t h e c a s e of acidic and basic s i t e s .
The formation of a charge-transfer complex i s related t o the ionization
potential f L , ) of the e l e c t r o n - d o n o r , t o t h e electron affinity
electron acckptor and to t h e dissociation energy (Ed)o f t h e comple%a:
(r
) of the
A + D = A D = A - + D+
The number of ionized s p e c i e s i s given by Ni exp [ -(Ei - -ea

= N * E - -d
E )/(a)]
In the case of s o m e paramagnetic m o l e c u l e s , the formation of a charge-transfer
complex c a n be determined by EPR either d i r e c t l y , when t h e electron o f ' t h e
donor molecule i n t e r a c t s with t h e nuclear s p i n o f t h e electron-acceptor s i t e ,
or indirectly by observation o f the electron delocalisation i n t h e probe
molecule. Both (methods c a n yield quantitative information about the
distrubution o f electron donor o r electron acceptor s i t e s when a r a n g e o f
probe molecules having different electron affinities or ionization e n e r g i e s
a r e used.
5. CATALYTIC PROPERTIES
5.1 General considerations
In heterogeneous c a t a l y s i s a fluid (liquid or gas) i s brought i n t o c o n t a c t
with a solid c a t a l y s t , which effects a c h a n g e o f chemical composition of t h e
fluid ideally without itself entering i n t o the stoichiometric equations.
Catalysis by s o l i d s c a n be observed only through the c h e m i c a l c h a n g e i n t h e
fluid which i s in contact with the c a t a l y s t , t h e system being e i t h e r closed
o r o p e n . The system i s called o p e n when it exchanges matter and energy with
its surroundings. T h e quantitative measure o f catalytic properties i s t h e n
based o n the material balance of the system (the system could b e defined a s a
catalyst b e d , catalyst p a r t i c l e , an element of ,active s u r f a c e or a n active
site) -to which reactants are introduced and products r e m o v e d , preferably a t
Note b: Near-edge X-ray spectroscopy is abbreviated in some parts of the world, particularly in USA,
as NEXASS.
t h e s t e a d y s t a t e , when t h e c a t a l y s t i s n e i t h e r a n e t s o u r c e n o r a s i n k o f
m a t e r i a l . The c r i t e r i o n u s e d t o d e f i n e t h e s t e a d y s t a t e s h o u l d b e s t a t e d .
Q u a n t i t a t i v e d e s c r i p t i o n o f c a t a l y t i c p r o p e r t i e s r e q u i r e s t h a t t h e system
under c o n s i d e r a t i o n be unambiguously d e s c r i b e d with respect t o system
b o u n d a r i e s (mass o f c a t a l y s t m , a r e a o f c a t a l y t i c s u r f a c e A , or v o l u m e o f
p o r o u s c a t a l y t i c p a r t i c l e V )-‘and c o n d i t i o n s s u c h as c o m p o s i % i o n , p r e s s u r e ,
t e m p e r a t u r e , p r e v a i l i n g at+ t h e boundary ( c o n t r o l v a r i a b l e s ) . A s e t o f d a t a
c h a r a c t e r i z i n g a c a t a l y s t must p e r m i t t h e p r e d i c t i o n o f m a t e r i a l b a l a n c e o f
t h e s y s t e m c o n t a i n i n g t h e c a t a l y s t a t s t e a d y s t a t e u n d e r a t l e a s t one s e t o f
c o n t r o l v a r i a b l e s . I t i s sometimes p o s s i b l e t o r e p r e s e n t a number of
e x p e r i m e n t a l o b s e r v a t i o n s by r a t e e q u a t i o n o r a set o f r a t e e q u a t i o n s which
may o r may n o t b e b a s e d o n a m e c h a n i s t i c m o d e l . The m o d e l h a s t o f u l f i l t h e
above c r i t e r i a w i t h i n a c e r t a i n r a n g e o f v a l i d i t y w h i c h s h o u l d b e i n d i c a t e d .
The c a t a l y t i c s y s t e m s h o u l d b e c h a r a c t e r i z e d w i t h r e s p e c t t o t h e r a t e o f
c h e m i c a l change ( a c t i v i t y ) and w i t h r e s p e c t t o product composition ( s e l e c t i v i t y ) .
5.2 Catalytic activity
5.2.1 Reaction r a t e
We d i s t i n g u i s h i n t e g r a l a n d d i f f e r e n t i a l characteristics of catalytic
p r o p e r t i e s . One o f t h e i n t e g r a l c h a r a c t e r i s t i c s i s t h e e x t e n t o f r e a c t i o n 15.
G e n e r a l l y , a n y c h e m i c a l r e a c t i o n , w h e t h e r o v e r a l l or an e l e m e n t a r y s t e p , c a n
be r e p r e s e n t e d b y a s t o i c h i o m e t r i c e q u a t i o n :
where V i s t h e s t o i c h i o m e t r i c c o e f f i c i e n t o f component B . , t a k e n p o s i t i v e
when Bi-i i s a p r o d u c t a n d n e g a t i v e when i t i s a r e a c t a n t 4 The c h e m i c a l
c h a n g e - o c c u r r i n g i n t h e c o u r s e o f t h e r e a c t i o n may b e d e s c r i b e d b y % ( i n m o l ) :
ci - n.
-1 0
E=
- -
Vi
-
-A
where q oa n d ci a r e t h e a m o u n t s o f s u b s t a n c e Bi ( i n m o l e s ) a t t i m e z e r o
and a t - a n y - t i m e , r e s p e c t i v e l y . I t i s an -extensive q u a n t i t y a t t a i n e d
under s p e c i f i e d c o n d i t i o n s .
An a l t e r n a t i v e e x p r e s s i o n i s i t s d i m e n s i o n l e s s f o r m , h a v i n g a v a l u e b e t w e e n
z e r o a n d u n i t y , c a l l e d f r a c t i o n a l c o n v e r s i o n or d e g r e e o f c o n v e r s i o n .
The d r a w b a c k o f i n t e g r a l c h a r a c t e r i s t i c s s u c h a s e x t e n t o f r e a c t i o n or d e g r e e
o f c o n v e r s i o n i s t h a t v e r y many c o n t r o l v a r i a b l e s s u c h a s t h e r e a c t o r t y p e ,
f e e d c o m p o s i t i o n , t i m e , t e m p e r a t u r e , e t c . , i n f l u e n c e t h e v a l u e s o b t a i n e d and
have t o be s t a n d a r d i z e d . Moreover, w i t h h i g h c o n v e r s i o n , a g r e a t d i f f e r e n c e
i n c a t a l y t i c a c t i v i t y u s u a l l y leads t o only s m a l l differences i n t h e conversion
values.
A d i f f e r e n t i a l c h a r a c t e r i s t i c w h i c h demands a l o w e r d e g r e e o f s t a n d a r d i z a t i o n
i s t h e r e a c t i o n r a t e . The r a t e o f a c h e m i c a l r e a c t i o n w i t h r e s p e c t t o compound
B a t a g i v e n p o i n t i s d e f i n e d as t h e r a t e o f f o r m a t i o n o f B i n moles p e r u n i t
t i m e p e r u n i t volume. I t c a n n o t be measured d i r e c t l y and i s d e t e r m i n e d f r o m
t h e r a t e s o f c h a n g e o f some o b s e r v a b l e q u a n t i t i e s s u c h a s t h e amount o f
s u b s t a n c e , c o n c e n t r a t i o n , p a r t i a l p r e s s u r e , w h i c h a r e s u b j e c t t o measurements.
R e a c t i o n r a t e s a r e o b t a i n e d f r o m o b s e r v a b l e q u a n t i t i e s by use of the
c o n s e r v a t i o n e q u a t i o n s r e s u l t i n g f r o m t h e mass balance for t h e g i v e n r e a c t o r t y p e .
The c o n s e r v a t i o n e q u a t i o n f o r c o m p o n e n t B i , f o r any system, can be w r i t t e n as

F = Ei + F. + (dci/dt)
- i-
,O - -1,c -
where Fi,o = f l o w r a t e of c o m p o n e n t Bi i n t o t h e s y s t e m i n m o 1 . s - I
-
= f l o w r a t e o f component B y o u t of t h e system i n m o 1 . s - I
Ei
FT = r a t e o f c o n s u m p t i o n o f component Bi
-1, c
system i n mo1.s-I
- by reaction inside the
-
t = time
For an ideal gradientless f l o w reactor (continuous stirred tank reactor C S T R )

in t h e steady s t a t e t h e conservation equation reduces to
r
- = - -
v1
.-' (EL)O - E p Q
-
where r i s the reaction r a t e in m o 1 . s - l per unit amount o f c a t a l y s t and 0
i s t h e a m o u n t o f catalyst.
For a n ideal p l u g f l o w reactor t h e mass balance i n t h e s t e a d y s t a t e g i v e s
r
- = - Y.-ldX/d(Q/F. )
-1- -1,o
Lihere i s the fractional c o n v e r s i o n , and the term x ( i n u n i t s o f time per
amount o f catalyst per a m o u n t o f reactant)
x=Q / F-190
.
i s called the s p a c e time. The inverse of t h e s p a c e time i s t h e s p a c e velocity

-
v = E/Q
frequently expressed in h-l (gas or liquid hourly s p a c e v e l o c i t y , G H S V or
L H S V , respectively), if t h e quantities of c a t a l y s t and r e a c t a n t s a r e expressed
in the s a m e units.
In the c a s e of ideally stirred batch reactor the mass balance l e a d s t o t h e
expression
r = V-1. -1 (dni/dt)/Q
- - -
As t h e true s t a t e variable o f t h e system t h e r a t e r d e p e n d s only o n t h e
temperature and concentration if it i s derived from data f r e e o f _heat and
mass transfer effects.
T h e reaction r a t e under specified c o n d i t i o n s (composition, t e m p e r a t u r e ,
pressure) i s a measure o f the catalytic activity o f t h e s o l i d f o r c o n v e r s i o n
o f B under these conditions. The amount o f c a t a l y s t Q to which t h e reaction
rate i s referred may be expressed by t h e mass (E 1) volume (1) o r t h e s u r f a c e
area (Ac) of the' solid catalyst. Correspondincgly t h e val6es bbtained a r e
mass-specific r a t e r i n mo1.s-'.kg-l
-m-
volume-specific r a t e Lv in m o 1 . s - l
area-specific r a t e rA- in m o 1 . s - 1 . m - 2
-
I n s p i t e o f the fact that i t was previously recommended t h a t r be called t h e
specific activity o f the c a t a l y s t ( s e e P u r e Appl.Chem. 6, 71 (1976)) t h e
uqe of t h i s term i s now discouraged.
A rate equation d e s c r i b e s t h e observed dependence o f t h e r a t e o f reaction o n
the composition o f the fluid phase at the boundary of t h e system under
consideration (e.g., c a t a l y s t p a r t i c l e , element o f surface). The coefficie'nts
of the r a t e equation must be given in proper units so that a material balance
of the system under consideration c a n be predicted unambiguously within t h e
range of control variables over which validity o f t h e r a t e equation i s
postulated. These r a t e coefficients k (the experim&tal r a t e constants) may
be .taken to characterize the catalytic activity.
F o r a single elementary r e a c t i o n ,
-
k = -
A.exp[-E/(O)]
where 4 is the pre-exponential factor and i s the activation energy. Where
an overallcatalytic .reaction o b e y s the Arrhenius equation o v e r a certain range
o f temperatures t h e experimentally determined energy i s a n apparent activation
energy.
A r a t e equation in t e r m s o f t h e local composition o f reacting fluid i n contact
with t h e surface o f the catalvticallv active material may be called t h e
"intrinsic" r a t e e q u a t i o n ; t h e c o e f f i c i e n t s in t h i s e q u a t i o n a r e "intrinsic"
r a t e coeffic,,;nts. The local concentrations of reactants and p r o d u c t s a t the
catalytic surface in general cannot b e observed and have to be inferred from
the observable composition at t h e boundary o f a larger s y s t e m , t h e observed

r a t e of reaction and t h e kinetics o f mass transfer between t h e boundary o f
the larger system and t h e active surface under consideration.
T h e turnover frequency, N, (the term turnover number i s discouraged) i s
defined a s the number o f molecules reacting per active s i t e i n unit time. I t
i s necessary t o specify t h e method used to estimate t h e number o f active
sites. Usually, t h e number of active s i t e s will be assumed t o be equivalent
to t h e number o f s u r f a c e a t o m s , derived, in t h e c a s e o f metals, f o r e x a m p l e ,
from measurements of t h e chemisorption of a specified adsorptive.
5 . 2 . 2 Measurement of activity parameters
Rates o f reaction depend in general o n t h e composition and o n t h e temperature
of the fluid surrounding the catalytically active s o l i d . These quantities
must b e observed simultaneously for a catalyst particle i n order t o describe
its catalytic activity.
Simultaneous measurements o f t h e r a t e of c h a n g e , temperature and composition
o f the reacting fluid c a n be reliably carried o u t only in a reactor where
gradients o f temperature and/or composition o f the fluid phase a r e absent or
vanish in t h e limit o f suitable operating conditions. The determination o f
specific quantities s u c h a s catalytic activity from observations o n a r e a c t o r
system where composition and temperature depend o n position i n t h e reactor
requires that t h e distribution of reaction r a t e , temperature and composition
in the reactor a r e measured o r obtained from a mathematical m o d z l l representing
the interaction o f chemical reaction, mass-transfer and heat-transfer i n t h e
reactor. The model and i t s underlying assumptions should bs specified when
specific r a t e parameters a r e obtained in this way.
The spatial distribution o f composition and temperature within a catalyst
particle o r in t h e fluid in contact with a catalyst s u r f a c e result from t h e
interaction of chemical r e a c t i o n , mass-transfer and heat-transfer i n t h e
system which in t h i s c a s e i s the catalyst particle. Only composition and
temperature at t h e boundary o f t h e system a r e then fixed by experimental
conditions. Knowledge o € local concentrations within the boundaries of t h e
system i s required f o r t h e evaluation o f activity and o f a r a t e equation.
ThLy c a n be computed o n t h e basis o f a suitable mathematical model if t h e
kinetics o f heat- and mass-transfer a r e known or determined separately. I t i s
preferable that experimental conditions f o r determination o f r a t e parameters
should b e chosen so that gradients o f composition and temperature in the
system c a n be neglected.
The effectiveness factor o f a porous catalyst i s t h e r a t i o o f the r a t e o f
reaction t o the hypothetical r a t e which would be expected i f fluid composition
and temperature i n the pores corresponded t o composition and temperature in
the fluid surrounding t h e porous aggregate.
5.3 Selectivity
Very often a reactant o r a s e t of reactants may simultaneously undergo several

parallel r e a c t i o n s , giving different individual products, P . , which r e a c t
further in consecutive reactions t o give different secondary 'products, P . . .
A commonly encountered situation i s the parallel-consecutive reaction netw&.
--------,
p --------
-
i 'pLi
I t i s sometimes advantageous t o consider not t h e individual p r o d u c t s , but t h e
s e t s o f products, resulting f r o m reactions o f a given type, e,.g., hydrogenation,
hydrogenolysis, e t c . I n what follows the symbol P . will designate either t h e
individual product or a s e t o f products. I n the latter c a s e each s e t o f
products will have t h e s a m e elemental composition a s t h e reactant ( o r s e t o f
reactants) 8 .
Selectivity may be determined in the integral or differential mode. Integral
selectivit depends o n t h e overall extent o f t h e reaction (degree of
d and o n the type o f reactor used even if heat and mass transfer
effects a r e eliminated. I t may be called reactor selectivity f o r t h e formation
o f product P , from t h e s e t o f reactants B when i t i s calculated a s t h e mole
fraction o f .- P i in the products (exluding unconverted feed) a t the exit o f
the reactor: -
n.
-1
(S.) = :
-1 R
- 1 n-
i
when t h e feed stream consist o f t h e s e t o f reactants B .
An alternative expression i s t h e ratio between the mass o f P i in t h e products
and t h e total mass o f products generated from 8 . -
The y i e l d ( Y ) o f product P i i s defined as:
-
Amount o f B converted into P i Number o f molecules o f B converted into P i
-
Y =j
Amount o f B introduced Number o f molecules o f B introduced

The conversion ( X ) o f r e a c t a n t B i s defined as:
Amount o f B reacted Number o f molecules o f B reacted
x=--
Amount o f B introduced Number o f molecules o f B introduced
Alternative expressions f o r yield and coniersion c a n be obtained using masses
o f P i and 8 , respectively.
-
On this basis yield = (selectivity ) x (conversion).
Selectivity i s generally a function of conversion and will depend o n the
system under consideration if t h e relative extents o f consecutive and parallel
reactions depend o n t h e spatial distribution o f composition and o n t h e
residence time in the reactor.
Differential selectivity, o r intrinsic selectivity of a catalytically active
surface with respect to t h e formation o f product P i from r e a c t a n t B may be
evaluated a s t h e ratio o f t h e r a t e o f reaction r: -resulting in product P ,
and t h e s u m o f t h e r a t e s o f all reactions r..C o & e q u e n t l y , the d i f f e r e n t i a 4
selectivity depends only o n temperature a d t h e actual concentrations o f
reactants but not o n t h e reactor type u s e d , and i s more suitable for the
discussion of t h e correlation o f catalytic properties with t h e structure and
chemistry o f t h e catalytic system.
I f t h e effects of operating variables o n selectivity a r e t o be expressed,
instead o f reaction r a t e s r . in t h e expression for differential selectivity
the corresponding r a t e equat4ons are introduced,
5.4 Relative activities
For a rapid characterization o f a s e r i e s o f catalysts i t is sometimes

advantageous t o determine their relative activities a t given reaction
conditions. T h e methods o f determining relative activities may be fairly
simple, but they should only b e applied t o a family o f similar catalysts in
which c a s e the mechanism o f t h e test reaction c a n be assumed not t o c h a n g e .
Then i t i s possible t o compare the v a l u e s , e.g., o f the time variable necessary
t o obtain the s a m e degree o f conversion with t h e same starting reaction
mixture. This i s more justified than comparing the conversions obtained at th::
s a m e reaction time or s p a c e time. The alternative is to determine t h e
temperature at which different catalysts give t h e s a m e degree o f conversion
under t h e s a m e initial composition and time v a r i a b l e ; this approach i s closer
t o t h e operation o f a n industrial reactor. The reciprocal values 1/1 are
compared, although t h e relationship between 1/1and t h e relative activities
i s n o t rigorously linear even f o r reactions with t h e s a m e mechanism and
activation energy.
5.5 Inhibition of the catalytic action
5.5.1 T y p e s o f inhibitory substances

The activitv o f Practicallv all catalvsts c a n be oartiallv or totallv
inhibited b y inhibitory o r deactivating substances, i n ' a broad'sense. I n whai
f o l l o w s such a substance will b e indicated by Is. This c a n b e caused by:
adsorption of more strongly than reactants o n active s i t e s (as);change o f
-
as due to reaction with Is: restriction of physical access due to formation
of a (semi) impervious layer of &.
The IS may (i) be present in the tants as impurities, (ii) come from
other sources (equipment, etc.) o r be formed during the course of the
reaction (by transformation of intermediary o r final products, etc.).
Ideally, the characterization of catalysts with respect to inhibition should
involve 3 types of information:
1. nature of the & acting on the catalyst,
2 . adequate relationship between the quantity of IS and catalytic properties,
3 . time-dependent effects on activity, selectivity, etc., due to the presence,
or a modification of concentration, of & (decreases of catalytic activity
with time, total o r partial recovery of catalytic properties after removal
of & from the feed, etc.).
-
IS may be classified into three categories:
Poisons (true poisons) are characterized by their propensity to attach very
strongly, by a truechemical bond (e.g. covalent) to the surface atoms or
ions constituting the catalytically active sites. Poisons act in minute
quantities. Typical poisons of metals are S, As, etc. In most cases, activity
and/or selectivity cannot be recovered without a drastic change in operating
conditions (most often a regeneration). Recovery, if at all, takes place very
slowly and/or only partially.
Inhibitors have a transient effect (inhibition). All catalytic properties can
be recovered after the supply of the inhibitor to the catalyst has been
stopped, without othel-wise changing the operating conditions. Inhibitors act
in minute quantities, have a reversible effect pi71 correspond to more or
less strong bonding.
Fouling agents, o r mechanical inhibitors are bound by neither covalent nor
other strong bonds to the active centres: the interaction is usually of the
van der Waals, H-bond, or sometimes ionic, type. They form protective layers
o r block pores, thus physically impeding access of reactants to the active
centres. The fouling agents causing real problems are those which have a long
standing effect and do not disappear spontaneously. Carbon deposits act,
partially or totally, this way. Other examples are vanadium and nickel sulfide
deposits in hydrotreating catalysts.
Fouling agents act in quantities equivalent to several layers spread over the
catalyst surface or to pore volume; they may according to different cases,
have a rapidly reversible, an only slowly reversible, o r an irreversible
effect .
5 . 5 . 2 Characterization of catalyst response to inhibitory substances
In principle, sensitivity to inhibition (by poisons, inhibitors o r fouling
agents) depends on the whole catalytic reaction system: nature of catalyst,
degree of ageing (in particular, nature and degree of poisoning, modification
of activity and selectivity by inhibition and fouling), operating conditions,
etc. Accordingly, the activity and selectivity of a catalytic reaction depends
on all the previous history of the catalyst.
Sensitivity to the deactivating influence of impurities, reaction products o r
intermediates is expressed in different ways depending on the category of
deactivating agent (poison, inhibitor, fouling agent).
5.5.2.1 Poisons
Sensitivity to poisons depends on:
-number of active centres in the catalyst: when it is small, the
catalyst may be inhibited by a small amount of poison;
-strength of adsorption of the poison on the active centres;
the weaker is the adsorption of poison, the lesser is the sensitivity
of the catalyst to poison;
-the effectiveness of adsorbed poison for inhibiting the catalytic
activity;
the latter decreases sometimes on adsorption of small amounts of
poison on active centres more than in proportion to the fraction of
active centres covered by the poison.
Sensitivity to poisons may be defined by:

1. the minimum amount of poison X per unit amount of catalyst
required to eliminate the catayytic activity (sometimes called the
lethal dose). If the number of active centres per unit mass of
catalyst, X t , is known, the quantity XE/XL should be recommended
as the measure of the sensitivity of the catalyst to the poison in
question.
2 . the initial ratio of the fractional decrease in the catalytic
activity (o(= (a - a )/a ) to the amount of poison attached to
the catalyst per'uniT'mas8, g/n (where so is the actPvity of the
catalyst in the absence of p o i a n and a is the activity in the
presence of poison). This ratio may be-Pcalled initial sensitivity.
Sometimes the ratio o(/c is used instead, where c is the
concentration of the poQson in the feed. This defynition is not
encouraged.
5.5.2.2 Inhibitors
There is actually a whole spectrum of possible phenomena, between very strong
irreversible poisoning and normal competition between molecules for a given
site (this competition leading to a decrease of activity). Inhibitors, as
defined above, correspond to a behaviour intermediate between those just
mentioned. The sensitivity to inhibitors can thus be expressed either as in
the case of true poisons, o r as in the case of competition. In the latter
formulation, for example, the value or relative value, of the adsorption
coefficient could characterize the inhibitor.
It is advisable to define also the rate at which activity decays when the
catalyst is contacted with a given concentration of inhibitors, or recovers,
after addition of the inhibitor is discontinued.
5.5.2.3 Fouling agents
The inhibiting influence of fouling agents is not a simple function of the
quantity of deposited substance. The reason is that the relationship between
this quantity w and activity depends on the' nature and texture of the
catalyst, the naqure and concentration of the feed constituents, temperature
and operating conditions, and the rate of build-up of the fouling deposit.
Vith this restriction the sensitivity to fouling agents is defined as the
quantity necessary to bring about a given effect on activity o r selectivity.
5.6 Time-dependent characteristics
The composition, structure, texture, surface state, activity and selectivity

of catalysts change continuously, at rapid o r slow rates according to
conditions, with time-on-stream. This change is characteristic of each
catalyst, and depends on its formulation, preparation and previous history.
Deactivation is one aspect. Another is the usually rapid changes that
catalytic activity and selectivity undergo in the first few minutes, hours
or sometimes days of operation: this may be called the initial adjustment to
catalytic operation. A third aspect is the response to changing operating
conditions (response to change).
The time-dependent changes of a catalyst are due to processes belonding to
6 main categories:
(a) poisoning;
(b) inhibition;
(c) fouling;
(d) sintering;
(e) chemical reactions;
(f) remodelling of the surface.
Poisoning, inhibition and fouling have already been defined. Sintering refers
to the diminution of dispersion. All phases present in a catalyst (active
phases, modifiers, support) potentially can undergo sintering.
Chemical reactions comprise reaction with feed intermediates o r final products
and reaction between catalvst comoonents. Thev mav result in the addition of
material to the catalyst o'r its loss, by formatibn of a volatile compound.
Remodelling refers to changes of the surface which do not involve any of the
previous processes: migration of active species inside a catalyst pellet,
change of shape (independently from change of total surface area developed)

of crystallites of a given phase, change in the number of steps, kinks on a
surface, changes in surface/bulk composition ratio.
5.7 Regeneration
The performance of deactivated catalysts can often be improved by regeneration.

Deactivation results from inhibition, from fouling and from sintering and all
of these may be reversed - at least in part - with some catalysts.
It follows that regeneration may consist of either (i) removal of IS;
sometimes poisons, most often inhibitors o r fouling agents, e.g., c x e
(hydrogenation catalysts, e.g., selective hydrogenation of pyrolysis gasoline)
o r (ii) redispersion of the active species (platinum catalysts) or (iii) both
(hydrodesulfurization o r catalytic reforming catalysts).
REFERENCES
1. Pure and Appl.Chem. -31, 579 (1572)

. -2 . P -
46, 7 1 (1976)
3 . Pure and Appl.Chem. -
5 7 , 6 0 3 (1965)

Unit-I Haber-True and App Density, Mechanical Strength

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Pure &App/. Chem., Vol. 63, No. 9, pp, 1227-1246,1991.

INTERNATIONAL UNION OF PURE

Prepared for publication by

2. CATALYST FORMULATION AND METHOOS OF ITS PREPARATION 1229

2.1 Methods of Preparation

3.1 Total Surface Area

4.1 Surface Structure and Topography

5.1 General Considerations

Many catalysts consist o f a n active component o r components ( s e e 2.2)

process o f impregnation i s carried o u t by percolation o f t h e impregnating

process must be stated ( e . g . partial pressure and purity o f g a s , method of

Catalytic materials a r e frequently composed of many c o m p o n e n t s and phases.

(tablet) o r extruding (extrudate) are described as cylinders. The term lump

Depending upon the technology (e.g. fluidization, moving-bed o r fixed-bed)

If the material is of natural origin (natural molecular sieve, pumice) the

2.5.1 Physical stability

To obtain a correct grain size distribution for a catalyst, a proper sampling

Catalysts subjected to heating in air may exhibit accelerated hydroxide or

particles or a g g l o m e r a t e s , but i s difficult to define precisely because solid

Most catalysts o f high s u r f a c e area a r e t o s o m e extent porous. Porosity i s

limitation o n the reliability o f t h e methods o f calculation o f pore-size

Several catalyst densities a r e used in t h e literature. True density may be

It i s desirable for commercial catalysts to have sufficient mechanical

single laboratory but irreproducible between laboratories.

The catalyst particle i s usually a complex entity composerJ of,a p o r o u s s o l i d ,

T h e determination of t h e s u r f a c e structure of solid i s possible using a

c a n be dotermined from an anaiysis of the extended X-ray absorption f i n e

For any given catalytic reaction t h e active s u r f a c e area i s normally o n l y

The chemical nature a n d composition o f catalyst s u r f a c e s a r e essential

In catalysis it i s important not only to be able to study t h e s u r f a c e r e g i o n

T h e activity o f a catalyst depends o n the n a t u r e , t h e n u m b e r , t h e s t r e n g t h

adsorbed. A Brdnsted acid s h o w s a tendency to donate a proton and the Brdnsted

Quantitative information on the number of s i t e s may be obtained from a

The number of ionized s p e c i e s i s given by Ni exp [ -(Ei - -ea

5.2 Catalytic activity

The c o n s e r v a t i o n e q u a t i o n f o r c o m p o n e n t B i , f o r any system, can be w r i t t e n as

For an ideal gradientless f l o w reactor (continuous stirred tank reactor C S T R )

i s called the s p a c e time. The inverse of t h e s p a c e time i s t h e s p a c e velocity

the observable composition at t h e boundary o f a larger s y s t e m , t h e observed

Very often a reactant o r a s e t of reactants may simultaneously undergo several

Amount o f B introduced Number o f molecules o f B introduced

For a rapid characterization o f a s e r i e s o f catalysts i t is sometimes

5.5.1 T y p e s o f inhibitory substances

Sensitivity to poisons may be defined by:

The composition, structure, texture, surface state, activity and selectivity

change of shape (independently from change of total surface area developed)

The performance of deactivated catalysts can often be improved by regeneration.

1. Pure and Appl.Chem. -31, 579 (1572)

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