Applied Catalysis A: General 196 (2000) 225–231

n-Butane isomerization over H-mordenite: role of the

monomolecular mechanism
P. Cañizares ∗ , A. de Lucas, F. Dorado
Department of Chemical Engineering, Faculty of Chemistry, University of Castilla-La Mancha, Campus Universitario s/n,
13004 Ciudad Real, Spain
Received 14 June 1999; received in revised form 20 October 1999; accepted 21 October 1999

Abstract
Isomerization of n-butane over several H-mordenite and Pd/H-mordenite samples with different Si/Al ratios is studied.
1,1,1,3,3,3-Hexamethyldisilazane was injected to obtain catalysts with poisoned external Brönsted acid sites. In the absence
of metal, isomerization activity was virtually suppressed for the poisoned non-dealuminated mordenite catalysts. However,
dealuminated samples were more resistant to the poisoning, and showed a higher selectivity to isobutane. For these samples,
the reaction order with respect to n-butane was close to 1 for isobutane and close to 2 for pentanes, and turnover frequency
(TOF) was not dependent on acid site density. No significant behaviour changes were observed for samples modified with Pd.
It is proposed that isomerization of n-butane over the dealuminated samples can take place via monomolecular mechanism.
©2000 Elsevier Science B.V. All rights reserved.
Keywords: Mordenite; n-Butane isomerization; Bimolecular/monomolecular isomerization mechanism

1. Introduction C8 carbenium ions, by isomerization and ␤-scission,

Skeletal isomerization of n-butane is thought to pro-
ceed via bimolecular reaction route, involving the for-
mation of C8 carbenium ions [1,2]. The first step is
the formation of a butylcarbenium ion via (i) protona-
tion of butane by a Brönsted acid site and subsequent
abstraction of H2 , (ii) hydride abstraction by a Lewis
acid site, or (iii) protonation of trace olefins formed by
thermal cracking [3,4]. Then, C8 + ions can be formed
either by reaction of the butylcarbenium with an olefin
forming an octylcarbenium ion or by reaction with
an alkane forming an octylcarbonium ion. Finally, the
∗ Corresponding author. Tel.: +34-926-295300;
fax: +34-926-295318.
E-mail address: pcanizar@inqu-cr.uclm.es (P. Cañizares).
yield n- and i-butane, and by disproportionation, yield
propane and pentane [2].
Since a large molecule (C8 carbenium ion) has to be
formed, isomerization of n-butane could be sterically
inhibited in mordenite micropores [5,6]. In this way,
only those sites that are located outside the microp-
ore system of the zeolite will effectively contribute to
the catalyst activity [7]. This is a consequence of the
general principle that bimolecular encounters are ex-
tremely unlikely in one-dimensional micropores [8].
As stated by Liu et al. [5], this fact may easily ex-
plain the striking difference in catalytic performance
for n-butane isomerization between Pt/ZrO2 –SO4 and
Pt/H-mordenite catalysts, with roughly the same num-
ber of acid and exposed Pt sites and similar acid
strength of the Brönsted acid sites. Their pore geo-

0926-860X/00/$ – see front matter ©2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 9 9 ) 0 0 4 7 7 - 9
226 P. Cañizares et al. / Applied Catalysis A: General 196 (2000) 225–231
metry is very different: mordenite has one-dimensional
micropores, whereas Pt/ZrO2 –SO4 has a wide distri-
bution of pore sizes.
For C5+ hydrocarbons, it is admitted that iso-
merization occurs via monomolecular mechanism.
This different mechanism is related to the fact that
monomolecular isomerization of n-butane would in-
volve a very unstable primary carbenium ion as an
intermediate.
However, Garin et al. [9] reported that n-butane
isomerization could occur through a monomolecular
mechanism over ZrO2 –SO4 based catalysts. More re-
cently, Tran et al. [10] showed that the reaction or-
der for n-butane isomerization over an H-mordenite
with a framework Si/Al ratio of 80 was close to 1
(suggesting a monomolecular mechanism), whereas
for an H-mordenite with a framework Si/Al ratio of
6.6, it was close to 2. The greater significance of the
monomolecular mechanism found for the more dealu-
minated samples is related to their low acid site den-
sity, and could also depend on the acid site strength.
The monomolecular mechanism could take place if
the catalyst had acid sites strong enough to catalyse
this very difficult reaction. It is well known that, after
mordenite dealumination, the strength of the Brönsted
acid is increased. But at the same time, mesopores are
formed during dealumination, which might favour the
bimolecular mode due to lower geometrical restric-
tions.
In this work, catalytic isomerization of n-butane
over several H-mordenite and Pd/H-mordenite sam-
ples with different Si/Al ratios is investigated
to clarify whether the monomolecular mecha-
nism plays a significant role. The catalysts were
tested both fresh and selectively poisoned with
1,1,1,3,3,3-hexamethyldisilazane to suppress the ac-
tivity of those Brönsted acid sites that were not
located in the micropore system.
2. Experimental
2.1. Catalysts preparation and characterization
Non-dealuminated Na-mordenite was supplied by
PQ, with a framework Si/Al ratio of 5.5. Conversion
to the protonated forms was carried out through am-
monium nitrate exchange and subsequent decomposi-
tion under nitrogen at 510◦ C for 5 h. Depending on
the dealumination level required, dealumination was
carried out by steaming at 400–600◦ C for 4–6 h, fol-
lowed by HCl treatment at 50–100◦ C for 4–24 h with
a liquid/solid ratio of 15 ml/g. The HCl concentra-
tion was 1–5 M. After filtration and rinsing, the re-
sultant catalyst was dried at 120◦ C overnight. Metal
free catalysts were then calcined under flowing air at
500◦ C for 4 h. On the other hand, palladium loaded
catalysts were obtained after dealumination by ion ex-
change with a palladium tetra-ammonium hydroxide
solution. After drying the solid at 120◦ C for 14 h, it
was calcined in a flow reactor (0.7 cm height bed) un-
der the following conditions: weight of catalyst, 1 g;
air flow-rate, 20 l/h; temperature increase from room
temperature up to 180◦ C at 1◦ C/min, 1 h at 180◦ C;
increase in temperature at the same rate up to 450◦ C
(which was maintained for 2 h), and finally, cooling
down to room temperature. These samples were re-
duced in situ at 400◦ C for 2 h before each experimental
run.
Pore size distributions were determined by nitro-
gen adsorption at 77 K. The total acid site density
of the catalysts was measured by temperature pro-
grammed desorption of ammonia (TPDA). For the poi-
soned samples, the signal due to the poison desorp-
tion was determined previously and subtracted from
the TPDA profiles. The nature of the acid sites was de-
termined by Fourier transform infrared (FTIR) experi-
ments. No Lewis acid sites were observed by pyridine
chemisorption, as found previously by other workers
[10,11]. Thus, strong Brönsted acid site density can be
drawn directly from the TPDA measurements. This is
an important result, as FTIR experiments for the poi-
soned samples are difficult to carry out (the poison
would be removed during the vacuum pretreatment
step). A detailed description of all these techniques is
given elsewhere [6,12]. Pd dispersion was measured
by volumetric hydrogen chemisorption, following the
method described by Kip et al. [13].
The most relevant characteristics of the catalysts
are given in Table 1. Catalysts have been identified
by a letter and a number. The letter refers whether
the catalyst is fresh (F) or poisoned (P). The num-
ber indicates the framework Si/Al ratio. If the cata-
lyst has been loaded with palladium, the symbol Pd is
added.
 P. Cañizares et al. / Applied Catalysis A: General 196 (2000) 225–231 227

Table 1
Characteristics of the mordenite samples
Sample Framework Si/Al Strong Brönsted acid BET surface area Pore volume (␮l/g)
ratio sites (mmol/g)a (m2 /g)
Mesopores (>10 Å)b Micropores (<10 Å)c

F-5.5 5.5 0.691 525 50 186

P-5.5 5.5 0.462 – – –
Pd/F-5.5d 5.5 0.693 499 50 180
Pd/P-5.5d 5.5 0.464 – – –
F-17 17 0.225 561 97 233
P-17 17 0.132 – – –
F-50 50 0.082 549 111 227
P-50 50 0.049 – – –
Pd/F-50d 50 0.082 538 115 220
Pd/P-50d 50 0.048 – – –
F-66 66 0.069 551 104 229
P-66 66 0.038 – – –
Pd/F-66d 66 0.073 555 103 233
Pd/P-66d 66 0.040 – – –
a NH3 desorbed above 350◦ C.
b Determined by the BJH method.
c Determined by the t-plot method.
d Pd content and Pd dispersion for all Pd-containing catalysts were 0.95 wt.% and 100%, respectively.

 
2.2. Catalyst activity measurements a0 (butane) − a(butane)
x(%) = 100
a0 (butane)
The experiments were carried out in a flow-type where a0 and a are inlet and outlet amounts of n-butane
apparatus designed for continuos operation. This (in mmol), respectively.
apparatus consisted of a gas feed system for each Selectivities to individual products are defined as
component nitrogen and n-butane (≥99.95% purity,  
significant impurities being isobutane (max 400 ppm) ap
S(%) = 100
and propane (max 100 ppm)) with individual control a0 (butane) − a(butane)
by mass flow meters, a fixed-bed downflow reactor,
where ap stands for the individual product.
and an exit gas flow meter. The reactor was a quartz
The yield of a product is given by the equation
tube with an internal diameter of 4 mm. The weight
 
hourly space velocity (WHSV) was selected between ap
0.5 and 12 h−1 to yield different initial conversion Y (%) = 100
a0 (butane)
levels, but always lower than 10%. Partial pressures
of N2 and n-butane were 0.9 and 0.1 bar, respectively. The rate of transformation of n-butane into an indi-
Catalysts were pretreated in situ as described above, vidual product is defined as the number of millimoles
and then cooled to reaction temperature (250◦ C) of n-butane transformed into that product per hour and
under nitrogen. In order to minimize the influ- per gram of catalyst.
ence of deactivation, short values of time-on-stream
were chosen (0.5–10 min depending on WHSV). 2.3. Poisoning experiments
Reaction gas products were analyzed on line by a
Hewlett-Packard gas chomatograph, using a fused For the poisoning experiments, 0.1 ml of 1,1,1,3,3,3-
silica PLOT Al2 O3 /KCl column and an FID detec- hexamethyldisilazane was evaporated into the re-
tor. Conversion and selectivities were obtained from action mixture stream. 5 min after injection, the
the product distribution. The n-butane conversion is catalyst activity was measured as described above.
defined as the ratio 1,1,1,3,3,3-Hexamethyldisilazane is a selective poison
228 P. Cañizares et al. / Applied Catalysis A: General 196 (2000) 225–231

of Brönsted acid sites [14,15], mainly those sites that
are located at the outer zeolite surface or in accessible
mesopores, as it is large enough to hardly enter the
micropore channel system. The poison remains on the
surface and only above 450◦ C does it slowly desorb
or decompose. Thus, catalysts were never treated at
temperatures higher than 450◦ C after being poisoned.
3. Results and discussion
Table 2 shows the product selectivity of the samples
at approximately 8% conversion. It is remarkable that
product distribution was practically constant for con-
version values between 1 and 10%, not being affected
by deactivation.
For the non-poisoned samples, n-butane was always
mainly transformed into isobutane, propane and pen-
tanes. A small quantity (≤4%) of methane and ethane
was also obtained. Isomerization is the main reaction
over F-17, F-50 and F-66 catalysts, while dispropor-
tionation (formation of propane and pentanes) is the
main reaction over F-5.5.
For the poisoned samples, an abrupt change in prod-
uct distribution is observed. Isomerization is virtually
suppressed over P-5.5, and a relatively high selectivity
to light paraffins is obtained. However, P-17, P-50 and
P-66 had a higher selectivity to isobutane than their
non-poisoned parent catalysts. Finally, pentanes were
obtained in a very low quantity over the poisoned cat-
alysts.
With regard to the Pd-loaded catalysts, only mi-
nor changes were observed upon Pd incorporation. A
small increase in selectivity to isobutane and a corre-
sponding decrease in selectivity to propane and pen-
tane were the most significant changes in comparison
with their non-Pd-containing palladium parent cata-
lysts.
The big change in product distribution between the
non-dealuminated sample (F-5.5) and the dealumi-
nated zeolites (F-17, F-50 and F-66) has been re-
ported previously and explained in two different ways.
Asuquo et al. [2] related the high disproportionation
selectivity for the non-dealuminated mordenite to its
high density of Brönsted acid sites. However, Tran
et al. considered this explanation to be unlikely [10].
They pointed out that the theoretical acid density of a
non-dealuminated mordenite is only about 1.5 times
greater than that of a dealuminated mordenite with a
framework Si/Al ratio of 10, but a very different prod-

Table 2
Product selectivity for the mordenite catalystsa
Catalyst Selectivity (%)

CH4 C2 H6 + C2 H4 b C3 H8 + C3 H6 c i-C4 H10 C4 H8 d C5 H10 e,f

F-5.5 3.3 0.4 58.5 23.6 0.1 14.1
P-5.5 22.9 27.5 44.9 3.1 0.0 1.6
Pd/F-5.5 3.7 0.6 55.8 27.1 0.4 12.4
Pd/P-5.5 22.5 27.8 45.7 2.9 0.0 1.1
F-17 3.0 0.3 22.6 60.5 0.1 13.5
P-17 5.3 6.4 10.5 77.5 0.0 0.3
F-50 2.6 0.2 20.6 63.2 0.0 13.4
P-50 4.4 5.4 8.7 81.4 0.0 0.1
Pd/F-50 2.7 0.2 18.8 66.5 0.0 11.8
Pd/P-50 4.8 5.1 8.1 81.9 0.0 0.1
F-66 2.1 0.2 19.9 68.7 0.0 9.1
P-66 3.9 4.6 7.6 83.8 0.0 0.1
Pd/F-66 2.5 0.1 19.1 69.4 0.0 8.9
Pd/P-66 3.0 5.1 7.3 84.6 0.0 0.0
a Conversion ∼
= 8%.
b Ethane and propane were mainly obtained.
c Ethane and propane were mainly obtained.
d All isomers.
e n-C H + i-C H .
5 10 5 10
f Hexanes or higher were not obtained.
 P. Cañizares et al. / Applied Catalysis A: General 196 (2000) 225–231
uct distribution is obtained over these zeolites. They
associated the high disproportionation selectivity for
the non-dealuminated mordenite with the absence of
mesopores, and therefore, with the much longer diffu-
sion pathway for organic molecules. Thus, while the
reactant molecules diffuse through the channels, they
could undergo many successive intermolecular reac-
tions with a preferential formation of propane (butanes
and pentanes are very reactive compared to propane
and can be transformed into this product). Indeed,
mesopores are obtained in mordenites after dealumi-
nation [16–20], which could reduce the diffusional
limitations.
However, there is another interesting question to be
taken into account. It is well known that, after dea-
lumination, the strength of the Brönsted acid sites is
increased. This strengthening has been accounted for
from topological Al density [21], or using Monte Carlo
simulation [22], and by means of molecular orbital
calculation [23]. It could be thought that these stronger
Brönsted acid sites might stabilize the highly unstable
primary carbenium ions, thus allowing a monomolec-
ular mode for n-butane isomerization. Therefore, we
suggest that the higher selectivity to isobutane for
dealuminated mordenites may be due not only to the
presence of mesopores but also to a non-negligible
contribution of the monomolecular mechanism (very
selective to isobutane) to that reaction.
The experiments with the poisoned samples seem
to confirm this hypothesis. Under inert gas atmo-
sphere, isomerization of n-butane via bimolecular
mechanism could be expected to be favoured [10].
However, this mechanism may be sterically inhibited
in mordenite micropores as commented above. In
that case, bimolecular mechanism would take place
mainly over the mordenite external surface and in
mesopores, whereas monomolecular mode might take
place inside the micropore system. After poisoning
with 1,1,1,3,3,3-hexamethyldisilazane, those Brön-
sted acid centers that are located outside the zeolite
and in the mesopores are deactivated, but those cen-
ters that are located in the micropore system remain
unaffected, as was reported in a previous work [7]. As
pentanes were scarcely obtained after poisoning, it is
concluded that the bimolecular pathway is virtually
suppressed in the mordenite one-dimensional pore
system, which is in agreement with previous works
[5,6]. Hence, isobutane is formed over P-17, P-50
229
Fig. 1. Reaction order with respect to n-butane for i-C4 and C5
formation over P-17 catalyst.
and P-66 samples via a monomolecular mechanism,
thus indicating that these mordenites certainly have
very strong acid sites capable of catalyzing this very
difficult reaction.
To further confirm this conclusion, the reaction
order with respect to n-butane for the formation of i-
butane over P-17 was calculated by carrying out
n-butane transformation experiments under various
n-butane pressures from 0.05 to 0.15 bar (Fig. 1). A
reaction order of 1.17 was found, which certainly
suggests a monomolecular mechanism. On the other
hand, the reaction order with respect to n-butane for
the formation of pentanes was of 1.9, which seems
to be a reasonable result, as pentanes still have to be
formed through a bimolecular mechanism. It should
be emphasized that both monomolecular and bi-
molecular mechanisms can co-exist, but we conclude
that, under especially favourable conditions (presence
of strong acid centers and absence of mesopores),
the monomolecular mode is more relevant than the
bimolecular mechanism.
On the other hand, as no isobutane is obtained over
the P-5.5 sample, it can be concluded that such very
strong acid centers do not exist (or they are very
scarce) on that mordenite, which is consistent with
the next nearest neighbour (NNN) theory. This well
known theory predicts that the intrinsic acid strength of
230 P. Cañizares et al. / Applied Catalysis A: General 196 (2000) 225–231
Fig. 2. TOF vs. strong Brönsted acid site density over dealuminated
mordenites.
an acid site is dependent on the number of aluminium
atoms in the next nearest neighbourhood [24]. The
O–H bond strength is thought to decrease (meaning
an increase in the acid strength) until all NNN-atoms
are silicon [25,26]. Barthomeuf calculated this critical
framework Si/Al ratio for different zeolites, finding a
value of 9.4 for mordenite [21]. Therefore, the mini-
mum framework Si/Al ratio to have acid centers strong
enough to catalyze the monomolecular reaction would
be of 9.4, which is in agreement with our results and
with those obtained previously [7,10].
Further evidence of the monomolecular mechanism
role over the dealuminated samples can be obtained
by plotting the turnover frequency (TOF) versus
strong Brönsted acid site density (Fig. 2). It can be
observed that TOF is practically independent of acid
site density for the poisoned samples, which strongly
suggests a monomolecular mechanism. Therefore, it
can be concluded that this mechanism is not negligible
over dealuminated mordenites even under nitrogen.
Furthermore, this finding seems to confirm that the
bimolecular mechanism is sterically impeded inside
the mordenite micropore system.
As found previously [10], TOF is increased with
acid site density for the non-poisoned dealuminated
samples. Bimolecular n-butane transformation, which
requires at least two close acid sites [27], is clearly
very dependent on the acid site density. Obviously, if
the external surface and the mesopore system are not
deactivated, the bimolecular mode can play a role,
and hence, this TOF increase is an expected result.
At this point, the importance of the mesopores on
the dealuminated samples should be remarked. As
there are no steric restrictions in the mesopores, the
bimolecular mechanism should be favoured. More-
over, it seems that the bimolecular mode is more
selective to isobutane if it takes place in the meso-
pores [10]. The presence or absence of mesopores in
mordenite-based catalysts is hence very important to
understand the catalytic performance of this zeolite,
as far as n-butane isomerization is concerned.
For the Pd-containing catalysts, no drastic changes
are observed. The products obtained over these cat-
alysts are similar to those over H-mordenite. Just a
slight increase in selectivity to isobutane and a de-
crease in selectivity to propane and pentanes are ob-
served, which is in agreement with results reported
by Asuquo et al. [28]. According to these workers,
the metal, under inert atmosphere, does not induce
any major changes in the mechanistic pathway. This
is consistent with the fact that the acid properties of
the samples are hardly influenced by the metal (Table
1). Furthermore, when TOF is plotted versus strong
Brönsted acid site density for the Pd-containing cat-
alysts (Fig. 2), the trend is very close to their parent
catalysts, which strongly suggests that the presence of
the metal does not involve any change in mechanism.
We can now speculate about a conceptually good
catalyst for n-butane isomerization based on mor-
denite. To favour a (selective) bimolecular mecha-
nism, Brönsted acid site density should be as high
as possible, and the presence of mesopores would be
necessary. However, bimolecular mode is restricted
inside the micropore system, where there are many
acid centers. Hence, the monomolecular mode should
be favoured simultaneously. Therefore, the Si/Al ra-
tio should be high enough to have a maximum acid
strength, and in consequence, to catalyze this very
difficult reaction. Dealuminated mordenite with a
framework Si/Al ratio about 15 would then be a good
catalyst, and in fact, it has been found to have the
maximum activity with a high selectivity to isobutane
[7,10].
The repeatedly observed low TOF and isobutane
selectivity for non-dealuminated mordenite can be
 P. Cañizares et al. / Applied Catalysis A: General 196 (2000) 225–231
easily explained in similar terms. Due to its weaker
acidity, it cannot catalyze the monomolecular mode.
Due to the absence of mesopores, the bimolecular
mode is sterically restricted and is not selective to
isobutane. Of course, ‘restricted’ does not mean ‘for-
bidden’. Some bimolecular intermediates may still be
formed in the micropore system, so that isobutane
and pentanes could be obtained. But, as no mesopores
are present, while these molecules diffuse through
the channels, they undergo intermolecular reactions
with a preferential formation of propane, as explained
above.
4. Conclusions
n-Butane isomerization over dealuminated mor-
denites can take place through both bimolecular and
monomolecular mechanisms, even under nitrogen.
Bimolecular mode is sterically inhibited in the mor-
denite one-dimensional micropore system. Therefore,
it is clearly favoured by the presence of mesopores,
having a higher selectivity to isobutane. Monomolec-
ular mode takes place when the framework Si/Al
ratio (related to the acid strength) is high enough to
catalyze this very difficult reaction. Under nitrogen,
the presence of palladium has no influence on the
reaction mechanism.
References
[1] H. Krannila, W.O. Haag, B.C. Gates, J. Catal. 135 (1992)
115.
[2] R.A. Asuquo, G. Eder-Mirth, J.A. Lercher, J. Catal. 155
(1995) 376.
[3] R. Shigeishi, A. Garforth, I. Harris, J. Dwyer, J. Catal. 130
(1991) 423.
231
[4] M. Guisnet, N.S. Gnep, D. Aittaleb, Y.J. Dojomet, Appl.
Catal. A: Gen. 87 (1992) 255.
[5] H. Liu, G.D. Lei, W.M.H. Sachtler, Appl. Catal. A: Gen. 137
(1996) 167.
[6] P. Cañizares, A. de Lucas, F. Dorado, A. Duran, I. Asencio,
Appl. Catal. A: Gen. 169 (1998) 137.
[7] P. Cañizares, A. de Lucas, F. Dorado, D. Pérez, Appl. Catal.
A: Gen., in press.
[8] R. Kopelman, Science (Washington) 241 (1988) 1620.
[9] F. Garin, L. Seyfried, P. Girard, G. Maire, A. Abdulsamad,
J. Sommer, J. Catal. 151 (1995) 26.
[10] M.T. Tran, N.S. Gnep, G. Szabo, M. Guisnet, J. Catal. 174
(1998) 185.
[11] M. Guisnet, P. Ayrault, G. Datka, Polish J. Chem. 71 (1997)
1445.
[12] P. Cañizares, A. de Lucas, J.L. Valverde, F. Dorado, Ind. Eng.
Chem. Res. 36 (1997) 4797.
[13] B.J. Kip, F.B.M. Duivenvoorden, D.C. Koningsberger, R.
Prins, J. Catal. 105 (1987) 26.
[14] A.J. Rosmalen, M.C.G. Hartman, J.C. Mol, J. Catal. 66 (1980)
112.
[15] J. Houzvicka, V. Ponec, Appl. Catal. A: Gen. 145 (1996)
95.
[16] J. Scherzer, J.M. Bass, J. Catal. 28 (1973) 115.
[17] R. Dutartre, L.C. de Menorval, F. di Renzo, D. McQueen,
Microporous Mater. 6 (1996) 311.
[18] S. Moreno, G. Poncelet, Microporous Mater. 12 (1997) 197.
[19] I.V. Mishin, T.R. Brueva, G.I. Kapustin, Kinet. Catal. 38
(1997) 574.
[20] C.A. Henriques, J.L.F. Monteiro, P. Magnoux, M. Guisnet, J.
Catal. 172 (1997) 436.
[21] D. Barthomeuf, Stud. Surf. Sci. Catal. 38 (1988) 177.
[22] T.D. Ding, P.C. Sun, Q.H. Jin, B.H. Li, J.Z. Wang, Zeolites
14 (1994) 61.
[23] T. Teraishi, Microporous Mater. 5 (1995) 233.
[24] L.A. Pine, P.J. Maher, W.A.J. Wachter, J. Catal. 85 (1984)
2887.
[25] W.J. Mortier, J. Catal. 55 (1978) 138.
[26] P.A. Jacobs, Catal. Rev. Sci. Eng. 24 (1982) 415.
[27] C. Bearez, F. Chevalier, M. Guisnet, React. Kinet. Catal. Lett.
22 (1983) 405.
[28] R.A. Asuquo, G. Eder-Mirth, K. Seshan, J.A.Z. Pieterse, J.A.
Lercher, J. Catal. 168 (1997) 292.