Beruflich Dokumente
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307
B.V.. Amsterdam
Methylcyclohexane
zeolite Y catalysts
and methylcyclohexene
cracking over
and
Gerald S. Koermer* and Rostam J. Madon
Engelhard Corporation, Menlo Park, CN 40, Edison, NJ 08818 (U.S.A.), (tel. (+ l-908)2055011,
fax. (+ l-908)2055300
(Received 8 June 1990, revised manuscript received 24 August 1990)
Abstract
Naphthenes are an important class of molecules in fluid catalytic cracking. The cracking behavior of
the model naphthenes, methylcyclohexane and methylcyclohexene was investigated over rare earth Y
and USY zeolite catalysts. Initial products from methylcyclohexane are formed by a combination of
protolytic and /?-scission cracking plus isomerization, H- transfer, H+ transfer and dehydrogenation
reactions. Methylcyclohexane is a sensitive probe for characterizing the chemistry occurring on solid
acid surfaces. Methylcyclohexene is the key intermediate in the formation of aromatics from methylcyclohexane. Methylcyclohexene cracks at a slower rate than methylcyclohexane but overall conversion
is higher because hydride transfer reactions are fast.
cracking, methylcyclohexene
cracking, na-
phthene cracking.
INTRODUCTION
0166.9834/91/$03.50
B.V.
Nevertheless, the cracking chemistry of naphthenes is expected to be complex because a number of competing reactions such as cracking, hydride transfer, ring opening and isomerization can occur simultaneously. However this
rich chemistry should make naphthenes a sensitive probe for catalyst properties. In fact, there have been recent publications using cyclohexene as a test
molecule for hydrogen transfer [ 9,101. However this work was done at temperatures significantly lower than commercial cracking temperatures.
We have investigated the cracking behavior of the model naphthenes, methylcyclohexane (MCHA) and methylcyclohexene (MCHE), over zeolite Y catalysts. We report here (but see also refs. 11 and 12) the cracking chemistry of
these compounds and the utility of MCHA as a probe molecule. The cracking
chemistry provides insights into naphthene reactivity for both higher molecular weight and gasoline range naphthenes. Reaction product ratios allow us
to assess subtle differences among zeolite catalysts.
EXPERIMENTAL
Materials
Methylcyclohexane (99% ) and 1-methyl-1-cyclohexene
(97% ) were purchased from Aldrich and used without further purification.
Ultrastable Y (USY, Catalyst I) was prepared by standard hydrothermal
techniques [ 131 from particles of approximately 80% zeolite Y in a low surface
area, low activity y-alumina binder. After hydrothermal calcination and ammonium exchange, the zeolite unit cell size (UCS) was 24.53 A and the catalyst
Na,O content was 0.69%.
Rare earth Y (Catalyst III) was prepared by ion exchanging mixed rare earth
ions into approximately 80% zeolite Y bound with a low surface area alumina.
The rare earth (RE,O,) content of the catalyst was 7.2 wt.-%, the Na,O content was 1.41% and the UCS was 24.70 A.
Catalyst I was steamed in a fluidized bed at 732 C for 8 h at one bar of 100%
steam to give Catalyst II which had a UCS of 24.31 A. Steaming Catalyst III
in a fluidized bed at 732C for 8 h in 1 bar of 100% steam reduced the UCS to
24.45 A (Catalyst IV). Steaming reduced the absolute zeolite content of the
unsteamed material by lo-15%.
Catalysis
Catalytic results were obtained using a fixed bed glass tubular reactor [ 141
with a 32-mm internal diameter. Reactions were done at atmospheric pressure
and 500. Data was generated by two methods: (i) by holding time-on-stream
constant and changing the amount of catalyst (i.e. changing the catalyst-tooil ratio) to vary conversion and (ii) at constant cat/oil with a variable time-
309
(2)
ii
-0
(1)
CH,
methylpentanes, methylpentenes
311
RESULTS
AND DISCUSSION
Table 1 shows the observed initial products for MCHA cracking over catalysts I-IV at 500C. Fig. 1 contains plots of mol-% yield versus MCHA conversion for selected products from Catalyst I. In the following discussion, for
brevity, unless otherwise noted, Catalyst I results are used.
Inspection of Table 1 indicates that the products can be rationalized by a
combination of protolytic and j$scission cracking. In addition, both dehydrogenation mechanisms noted above seem to occur.
Additional information can be extracted from the data. For example, the
amount of methane is slightly higher than the amount of cyclohexane. This
can be explained by considering that cyclohexyl carbocation, before desorbing
TABLE
for methylcyclohexane
I-IV at 500C
Catalyst
II
III
IV
Methane
Ethane
0.017
0.020
0.005
0.030
0.004
0.023
0.012
0.005
0.009
0.003
0.021
0.073
0.106
0.054
Ethene
Propane
Propene
Butanes
Butenes
Pentanes
Pentenes
Cyclohexane
2-Methylpentane
3-Methylpentane
Hexane
Methylcyclopentane
Dimethylcyclopentanes
Dimethylpentane
2Methylhexane
3-Methylhexane
n-Heptane
Heptenes
Methylcyclohexenes
Methylcyclohexadienes
Toluene
Xylenes
Hydrogen
Coke
0.186
0.083
0.060
0.007
0.011
0.027
0.022
0.005
0.002
0.042
0.004
0.012
0.146
0.131
0.100
0.045
0.007
0.018
0.012
0.017
0.004
0.001
0.040
0.003
0.016
0.019
0.152
0.030
0.156
0.219
0.258
0.122
0.092
0.005
0.034
0.090
0.125
0.073
0.205
0.194
0.097
0.066
0.063
0.010
0.008
0.034
0.021
0.004
0.001
0.051
0.005
0.014
0.021
0.146
0.206
0.106
0.058
0.033
0.002
0.035
0.018
0.005
0.052
0.028
0.073
0.006
0.066
0.003
0.027
0.003
0.113
0.058
0.010
0.010
0.020
0.018
0.004
0.001
0.035
0.005
0.017
0.023
0.167
0.250
0.080
0.006
0.040
0.022
0.024
0.003
Mole
% Yield
(A)
o-
10
20
40
30
Mole
50
60
Conversion
Methylcyclohexane
% Yield
6i@)
4+
_,
3-
/
2-
I,d
Ok
10
20
30
Methylcyclohexane
40
50
60
Conversion
Fig. 1. Plots of mol-% yield vs. methylcyclohexane conversion over Catalyst I at 500C. (A)
propene; (B) butenes; (C) heptane; (D) heptenes; (E) substituted cyclopentanes; (F) cyclohexane; (G) methylcyclohexenes; (H) toluene.
can react further to give methylcyclopentane, plus branched hexanes and hexenes derived from ring opening. Indeed, a marked instability of cyclohexane is
apparent in Fig. 1F even at conversion as low as 5%. If one adds the initial
selectivities of all C!, products detected, the ratio of C,/C, is lower than one,
indicating that C6 products could also be formed by reaction other than crack-
313
Mole
% Yield
OS&0
.^ Mole
10
20
30
Methylcyclohexane
Methycylcohexane
40
50
60
50
60
Conversion
% Yield
IO
20
30
40
Conversion
Mole
% Yield
_1
10
20
30
Methylcyclohexane
Mole
40
60
50
Conversion
% Yield
0.16
c
/
0.12
0.08
0.04
Y
0
10
20
30
Methycyclohexane
40
50
60
Conversion
Fig. 1.
20-b+
(5)
0
The open chain C7 products are also informative. Heptanes and heptenes
appear as primary products. Within experimental error, both heptane and heptenes are stable. Instability, if it occurs, is seen only at high MCHA conversions. This means that cracking products ( <6 carbons) come mostly from
cracking of C7 surface carbenium ions formed from ring opening, not from
315
Mole
*I
% Yield
40
Methylcyclohexane
Mole
50
60
Conversion
% Yield
7 (H)
6-
4
1
3
2-
lA
ok
10
20
%
30
Methylcyclohexane
40
50
60
Conversion
readsorption of heptanes or heptenes. If readsorption followed by cracking occurred extensively, heptane and heptenes would show marked curvature in the
selectivity curves, Figs. 1C and D. This is not observed. In addition, it seems
clear that little or no heptane is formed from saturation of heptenes by hydrogen transfer reactions but mostly by hydride transfer from MCHA to C!, carbenium ions derived from ring opening of MCHA. Of course heptanes, heptenes and cracked products can also be formed from dimethylcyclopentanes.
Our study does not address this or whether dimethylcyclopentanes crack more
readily than MCHA. Regardless of the precise precursor for the ring opened
316
C, carbenium ion, the fate of this cation can be approximated by looking at the
amount of cracking products and the amounts of heptenes and heptanes.
Cracked products come from J?-scission. Heptanes will reflect the amount of
H- transfer to the carbocation and heptenes reflect the amount of H+ transfer
from the ion to the catalyst. We will discuss the implications of these results
in the next section dealing with the use of MCHA as a probe molecule.
Aromatics formation is also an important process. The selectivity to hydrogen is not sufficient to account for the yields of MCHE, methylcyclohexadiene
and toluene by direct dehydrogenation. However, as a first approximation, hydride and proton transfer between saturated naphthenes, unsaturated naphthenes, carbenium ions and the catalyst surface seem to be responsible for
most of the unsaturated naphthenes and aromatics. We note that MCHE (Fig.
lG), and methylcyclohexadiene are unstable primary products. Whereas toluene, (Fig. 1H) is a stable primary and secondary product. While MCHE is
easily rationalized as a primary product, methylcyclohexadiene and toluene
are much more difficult to explain. The formation of toluene by hydrogen
transfer requires three consecutive bimolecular reactions with intermediate
desorption and readsorption of MCHE and methylcyclohexadiene. Thus, as
observed, MCHE and methylcyclohexadiene are unstable products. This multistep bimolecular process for aromatics formation should have a very low frequency factor. The surprising appearance of toluene even at very low conversion could be due to the confined space in the zeolite cavities that produces
high concentrations of reactants and relatively long residence times for the
molecules in the pores. Also one must take into account the faster rate of dehydrogenation of MCHE and methylcyclohexadiene compared with the initial
dehydrogenation of MCHA to MCHE. This can be deduced from the magnitude of Catalyst I initial selectivities to MCHE (0.092 ), methylcyclohexadiene
(0.005) and toluene (0.058). In any case MCHE is clearly a key intermediate
in the reaction chemistry of MCHA. The importance of MCHE as an intermediate will be discussed further in the section on MCHE reactions.
Methylcyclohexane as a catalyst probe molecule
Our results suggest that initial product ratios from MCHA cracking can be
used as a sensitive probe to characterize and quantify the chemistry occurring
on a catalyst surface. Based on the previous discussion, the ratio of cracking
products to (MCHE + 2 (methylcyclohexadiene) + 3 (toluene ) + 3 (xylenes)
+ 6 (coke) -hydrogen)
should reflect cracking relative to hydride transfer.
In addition, the ratio of cracking products to heptenes should mirror cracking
relative to H+ transfer to the catalyst. Finally, the ratio of heptenes to heptane
should give the relative rate of proton transfer to hydride transfer for surface
heptenium ions formed from either C5 or C, ring opening.
If the above ratios are indeed diagnostic for catalyst performance, these ra-
317
tios should vary in reasonable ways as the unit cell size (UCS) of Y zeolite in
the catalyst is changed. We assessed this by determining the ratios for catalysts
I through IV. The zeolite UCS varied from 24.70 to 24.31 A. The results are
shown in Figs. 2-4.
Fig. 2 plots the ratio of cracking/H- transfer vs. UCS. The ratio increases
as unit cell size decreases. This is consistent with previous work showing that
Cracking/Hydride
Transfer
3-P
,i-
24.3
24.4
24.5
A_
24.6
24.7
+ 3 (toluene)
Cracking/Heptenes
3.5
2.5 -
2
24.3
24.4
24.5
24.6
I
24.7
+6 (coke) - hydrogen)
vs.
318
Heptenes/Heptane
1.3
, i_
24.3
24.4
24.5
24.6
24.7
319
TABLE 2
Initial molar selectivities for methylcyclohexene cracking over Catalyst I at 500C
Product
I.S.
Methane
Ethane
Ethene
Propane
Propene
Butanes
Butenes
Pentanes
Pentenes
Hexanes
Hexenes
Methylcyclopentanes
Dimethylpentanes
Dimethylcyclopentanes
Cyclohexane
Heptane
Heptenes
Methylcyclohexane
Methylcyclohexadiene
Toluene
Xylenes
Hydrogen
Cg aromatics
Coke
0.010
0.003
0.020
0.006
0.088
0.040
0.060
0.010
0.013
0.028
0.012
0.003
0.001
0.013
0.034
0.050
0.087
0.290
0.020
0.245
0.052
0.004
0.002
0.029
and isomerization products from MCHA and MCHE. These rates were generated from plots of time-on-stream vs. the sum of yields for products of each
class [ 151.
Clearly the rate of cracking and ring opening for MCHE is less than the rate
of hydrogen transfer. In addition, the rate of MCHE cracking is slower than
that of MCHA. The relative cracking rates are surprising since alkenes generally crack as much as two orders of magnitude faster than their saturated
analogs [ 211.
However, the total rate of reaction of MCHE exceeds that for MCHA because the transformation of MCHE to aromatics, methylcyclohexadiene and
MCHA is very fast. Also noteworthy is the relatively high coke yield from
MCHE and the lower hydrogen yield compared to MCHA.
The key to understanding MCHE cracking chemistry is the hydrogen transfer reaction. Rapid hydrogen transfer occurs for several reasons. First, MCHE
is both an alkene and a naphthene, thus it can fulfill two roles. MCHE can act
as both a hydrogen donor and acceptor. Protonation of MCHE leads to a high
320
0.5
Mole
% Yield
(n)
0.4
% Methylcyclohexene
Mole
I2
Conversion
% Yield
(6)
10 -
8-
8-
10
20
30
% Methylcyclohexene
40
50
60
Conversion
Fig. 5. Plots of mol-% yield vs. percent methylcyclohexene conversion over Catalyst I at 500C.
(A) methylcyclohexadiene; (B ) toluene.
321
TABLE 3
Initial rate constants (s-l)
Cracking
Isomerizationa
Hydrogen transfer
Ring opening
Methylcyclohexene
0.104
0.006
0.045
0.032
0.049
B
0.107
0.032
Another reason for rapid hydride transfer in this system is the formation of
a relatively stable [ 221 allylic delocalized carbocation from MCHE.
Thirdly, the axial hydrogens adjacent to the double bond in MCHE are held
by the cyclohexenyl ring in a conformation that makes them coplanar with a
p orbital of the methylcyclohexene double bond. This stabilizes the developing
positive charge in the C-H sp3-s bond as the hydride is being transferred. The
net result is a relatively low activation energy for hydride transfer from an
unsaturated naphthenic ring.
The resulting allylic carbenium ion loses a proton to give methylcyclohexadiene which quickly again transfers a hydride and then eliminates a proton
to give toluene. The high reactivity of methylcyclohexadiene can be seen from
Fig. 5. Toluene formation is thermodynamically favorable and toluene is comparatively very stable. Thus the overall process is fast and essentially
irreversible.
A simplified reaction pathway for MCHE reaction is shown in Fig. 6. MCHA+
(I) is formed by protonation of MCHE. A hydride is then transferred to
MCHA+ from MCHE to give the allylic carbenium ion II and MCHA. Ion II
then loses a proton to the surface to give methylcyclohexadiene. Methylcyclohexadiene gives up a hydride to another MCHA+ to form intermediate III,
which quickly loses a proton to give toluene. Since /z3>> k_,; k, >> k_,; and k6
>> k_6, the process is irreversible. Cracking, ring opened products and ring
isomerization products arise from MCHA or I.
The role of allylic carbenium ions in strong acid zeolite catalysis has been
invoked [ 181 but not well studied. However there is evidence for allylic carbenium ion formation from propene oligomers in mordenites and HNaY zeolites [ 231. In naphthene systems, allylic carbenium ions seem to play a more
important role than in straight chain alkanes or alkenes.
It is interesting to compare the cracking chemistry of MCHE to its acyclic
C, analogue, heptene. Heptene cracking chemistry has been reported for HY
and ZSM-5 zeolites [ 24,251. These reports indicate that heptene cracking gives
no aromatics or cyclic hydrocarbons as initial products. In contrast, aromatics
322
CRACKING6 ISOMERIZATION
Fig. 6. Simplified reaction scheme for inital reaction of methylcyclohexene over zeolite catalysts.
and dehydrogenation products dominate MCHE reactivity. The lack of aromatics from heptene suggests that the first and most difficult step in the aromatization of acyclics is the cyclization of the carbenium ion [ 261. The absence
of dialkenes as initial products from acyclic alkenes [ 261 suggests that allylic
carbenium ions, while they may form, are of much less consequence in acyclic
systems than in naphthenic systems.
Our data suggest hydride transfer cannot be the slow step that controls
cracking at least in the MCHE system. Previous reports [27] have suggested
that chain transfer via hydrogen transfer is the slow step in alkane cracking.
In the MCHA/MCHE system, MCHE has a much higher hydrogen transfer
rate than MCHA. Nevertheless, the cracking rate is lower for MCHE than for
MCHA. This means that hydrogen transfer does not control cracking. As Fig.
6 illustrates, for MCHE feed, hydrogen transfer actually suppresses cracking
by converting methylcyclohexyl carbocation to less reactive MCHA. MCHA
cannot compete with MCHE for adsorption sites and thus is relatively stable
at low conversions of MCHE.
CONCLUSIONS
323
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