Microporous and Mesoporous Materials 35–36 (2000) 21–30

www.elsevier.nl/locate/micromeso

Current views on the mechanism of catalytic cracking

A. Corma a, *, A.V. Orchillés b
a Instituto de Tecnologı́a Quı́mica, UPV-CSIC, Avenida de los Naranjos s/n, 46022 Valencia, Spain
b Departament d’Enginyeria Quı́mica, Universitat de València, Dr. Moliner, 50, 46100 Burjassot, Spain

Received 25 March 1999; received in revised form 12 July 1999; accepted for publication 13 July 1999

Dedicated to the late Werner O. Haag in appreciation of his outstanding contributions to heterogeneous catalysis and zeolite science

Abstract

The cracking mechanisms of hydrocarbons have been reviewed and the kinetic and thermodynamic implications
of the different steps, i.e. initiation, chain propagation, and termination, have been discussed. Although the cracking
mechanism of olefins and alkylaromatics is well established, the initiation step for the cracking of paraffins is still
under debate. The role of Brönsted-type active sites and also the possible influence of extra-framework Al species in
the case of zeolite catalysts, especially when commercial feeds and industrial conditions are employed, are presented.
The product distribution is determined by the number of propagation events occurring per initiation step, and this
can be controlled by carefully selecting the precise reaction conditions and the catalyst (including its composition and
pore topology). © 2000 Elsevier Science B.V. All rights reserved.

Keywords: Carbocations; Catalytic cracking of hydrocarbons; Cracking chain mechanism; Cracking mechanism; Paraffin activation

1. Introduction these areas that the work of Werner Haag has

It is fair to say that the catalytic cracking of
hydrocarbons ( FCC ) is one of the most important
processes in the oil refining industry. Owing to
this, and to the existence of detailed mechanistic
proposals that allow us to rationalize the results
obtained, it has been an active research field, with
more than 5000 articles published during the last
10 years alone.
However, despite the considerable advance-
ments in this area and the enormous amount of
work performed, there are still three general areas
where we still require more understanding. It is in
* Corresponding author. Tel.: +34-96-387-7800;
fax: +34-96-387-7809.
E-mail address: itq@upvnet.upv.es (A. Corma)
been most important:
$ What is the exact nature of the active sites?
$ What is the nature of the transition state?
$ Is there only one route or are there more routes
through which the reaction proceeds?
In this paper we will try to summarize the current
state of knowledge in this important field.
2. Catalytic cracking mechanism: the initiation step
The catalytic cracking of hydrocarbons is a
chain reaction that is believed to follow the carbo-
nium ion theory developed by Whitmore [1]. This
chain mechanism involves three elementary steps:
initiation, propagation and termination. The initia-
tion step is represented by the attack of an active
site on the reactant molecule to produce the acti-

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PII: S1 3 8 7 -1 8 1 1 ( 9 9 ) 0 0 20 5 - X
22 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30

vated complex that, in the gas phase or when using

liquid superacids, would correspond to the forma-
tion of a carbocation [2]. The chain propagation
is represented by the transfer of a hydride ion
from a reactant molecule to an adsorbed carbe-
nium ion. Finally, the termination step corres-
ponds to desorption of the adsorbed carbenium
ion to give an olefin whilst restoring the initial
active site.
In more detail, the initiation step, if one con-
siders an olefin as the reactant, corresponds to the
attack of one Brönsted acid site from the catalyst
to the double bond of the reactant olefin to form
a carbenium ion. This is certainly what occurs in
the gas phase [3], or in the presence of liquid Fig. 1. A concerted mechanism for charge isomerization [7].
superacids where the positive charge is stabilized
by the anion [4].
When this carbocation is formed it can
rearrange without increasing the branching of the
chain or can rearrange to generate a branched
carbocation. The former process is believed to
occur through a 1,2 hydrogen shift, whereas
branching isomerization occurs via a protonated
cyclopropane ring as the intermediate [5].
When the olefin interacts with solid acids, and,
more specifically, with zeolites, weak Brönsted acid
sites are already active and the reactions described
above can readily occur. Kazansky [6 ] proposed
that the activation of the reactant and the isomer-
ization process occurred in two steps. Firstly the
formation of a surface alkoxide by addition of a
proton from the zeolite, and in a second step the Fig. 2. Transition state of branching isomerization in linear
alkoxide decomposes to give the isomerized pro- butenes over zeolites. Distances in angstroms and angles in
duct. However, a mechanism like the one proposed degrees [7].
above involving highly stable alkoxide species also
involves activation energies much higher than be shown later, this can play an important role
those found experimentally. This problem has been during the cracking of linear paraffins and olefins.
recently revisited [7] and it has been shown that, A third reaction, which can occur when a proton
after protonation of the olefin, the charged isomer- has attacked an olefin, is the cracking of the CMC
ization process can occur via a concerted mecha- bond located in b position with respect to the
nism through the transition state given in Fig. 1. carbon supporting the positive charge (b scission)
The formation of this transition state involves [10,11]. During this process the formation of pri-
16.1 kcal mol−1; this is in good agreement with mary carbenium ions should be avoided, and this
the observed experimental values, which range occurs if 1,2 hydrogen shifts and branching isomer-
between 15 and 20 kcal mol−1 [8,9]. Branching ization take place prior to the CMC cracking
isomerization also occurs on zeolites, via a proton- process. For carbenium ions with a carbon number
ated cyclopropane ring (PCP) (Fig. 2) and, as will less than six, no rearrangements are possible that
 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30
can avoid the formation of primary carbenium
ions at some point of process cracking, whereas
octene cracking can proceed via tertiary carbenium
ion intermediates. This explains the dramatic
decrease with carbon number of the cracking rates
of C5–C8 olefins, as indicated by Buchanan et al.
[12].
A general agreement exists in the literature on
the nature of the active sites and the global mecha-
nism through which the cracking of olefins and
alkylaromatics occur. However, this is not the case
for the cracking of paraffins, where the initiation
step has been widely debated. It was first thought
that the presence of olefins, even at trace levels,
was necessary to initiate the cracking of a paraffin
[13,14]. In this mechanism the traces of olefins are
readily protonated and the carbenium ions formed
are able to abstract a hydride ion from a paraffin,
generating in this way the carbenium ion necessary
for the paraffin to keep reacting:
+H+ C
R–CHNCH–R∞  R–CH–CH –R∞
2 2
C are practically the same [25], and when the mecha-
R–CH−CH –R∞+CH –CH –CH –CH –CH 
2 3 2 2 2 3
C calculations [26 ] it is found that the lower activa-
R–CH –CH –R∞+CH –CH –CH–CH –CH –CH .
2 2 3 2 2 2 3
It was also claimed that the olefins necessary to
initiate the cracking of paraffins could be formed
by the direct attack of a proton on an HMC bond
of the paraffin to give H and an olefin in a similar
2
way as occurs in the presence of liquid super-
acids [15].
The formation of the first surface carbenium
ion was also proposed to occur by abstraction of
a hydride ion by a Lewis acid site of the catalyst
[16,17]. In all cases, regardless of the active site
involved, the authors always proposed that the
cracking of paraffins on solid acids occurred
through the formation of a carbenium ion as the
initiation step. It is surprising that the authors did
not take into consideration the paraffin cracking
mechanism, which was demonstrated to work in
liquid superacids, and which showed that the initia-
tion could also occur by direct protonation of a
CMC bond [4]. This remained so until 1984, when
Haag and Dessau [18] proposed that also on solid
acids the cracking of paraffins could be initiated
23
by the direct attack of a Brönsted acid site on a
CMC bond, forming a surface ‘carbonium ion
type’ activated complex [19,20]. When this carbo-
nium ion is formed it can crack via protolytic
cracking or even give hydrogen if the proton
attack takes place at a CMH bond. Using
3-methylpentane and n-hexane as reactants, Haag
and Dessau [18] proposed the reaction scheme and
the active sites for the initiation step in the cracking
of paraffins shown in Fig. 3.
It can be seen there that the protonic attack
occurs on the most nucleophilic centres of the
molecule, i.e. on the s CMC and CMH bonds
[21]. The protonation of the CMH bonds does
not occur on the primary carbon atoms, as is
demonstrated by the results from neopentane
cracking on Y zeolites [22], and H is mainly
2
obtained from paraffins containing tertiary carbon
atoms [23,24]. On the other hand, the formation
of carbonium ions and their rupture only obeys
statistical criteria and does not involve large ener-
getic barriers. In this way the rates of formation
of H , CH and C H during cracking of n-butane
4 2 6
nism is studied by means of molecular orbital
tion energy required for the protolytic cracking at
the central atom is compensated by the larger
activation entropy of the external bond. This com-
pensation makes equally probable the rupture of
any of the CMC bonds in n-butane.
After the introduction of protolytic cracking as
the initiation step it appeared that the mechanistic
problems for the cracking of paraffins were solved.
However, several points have been raised recently
that suggest further discussion is still needed to
resolve this matter fully. Firstly, Sommer and
coworkers [27–29] have produced an excellent
piece of work on the initiation and chain propaga-
tion steps during the reaction of isobutane with
deuterated liquid superacids using deuterated
solids at temperatures in the range of 20–200°C.
Their findings show that the H/D exchange
between the liquid superacid and isobutane takes
place in the primary as well as in the tertiary CMH
groups. The observed regioselectivity is in
agreement with the relative basicity of the s CMH
bonds. In this case a reaction scheme via the
formation of pentacoordinated ions can explain
24 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30

Fig. 3. Protolytic cracking of 3-methylpentane and n-hexane via pentacoordinated carbonium ions [18].

the mechanism of activation and isotopic exchange
(Fig. 4).
On the contrary, with a solid acid catalyst, or
even with solid superacids, the H/D exchange only
occurs on the primary hydrogen of the isobutane.
Then, this behaviour can only be explained if one
assumes that isobutene is formed firstly and this
becomes protonated (see Fig. 5). In other words,
the formation of an olefin will be the first step
instead of the direct attack of the proton on a
CMC bond. Finally, the same authors conclude
that, at lower temperatures on solid acids, the
activation mechanism of paraffins has not yet been
clearly demonstrated without ambiguities.

Fig. 4. Exchange and protolysis equilibria of isobutane in DF–SbF [27–29].

5
 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30
Fig. 5. Catalytic cycle of H/D exchange on solid acids [AH ]
[27–29].
Moreover, it has been suggested [15–17] that
the presence of Lewis acid or electron acceptor
sites in many solid acids (and certainly in zeolites
where they are associated with partially coordi-
nated framework Al, or extra-framework Al
( EFAL) species [30]) can enhance the dehydroge-
nation of paraffins, thus forming olefins that can
initiate, or at least enhance, the cracking reaction.
In isobutane cracking, this possibility was firstly
postulated by McVicker et al. [31], who proposed
an initiation step based in the generation of a
radical cation over zeolite electron acceptor sites.
In this way, isobutene formation was assumed to
occur by decomposition of a surface-bound isobu-
tane radical cation. This hypothesis could have a
renewed interest with the work done by the groups
of Sommer and Dumesic [32]. We will return to
this point later.
Recently, Kissin [33,34] has proposed a new
paraffin cracking initiation mechanism in which
Brönsted acid sites are involved. The author firstly
noted a different product distribution when crack-
ing olefins and isoalkanes with the same structure.
Thus, although the product distribution obtained
during cracking of olefins is consistent with a b
scission mechanism, this is not the case for the
isoparaffins. More specifically, a larger amount of
short chain products are produced during the
cracking of isoalkanes. To explain this, the author
proposes that the cracking occurs at the CMC
25
Fig. 6. Proposed mechanism of alkane cracking [33,34].
bond in the a position with respect to the active
sites, which is always located on the tertiary carbon
( Fig. 6). This mechanism predicts large amounts
of olefins, which implies the formation of molecu-
lar H . Although this is an interesting proposal, it
2
is unfortunate that the working temperature used
by the author was far too low (150°C ) and,
furthermore, the amount of H produced was not
2
determined experimentally.
In conclusion, current knowledge certainly sug-
gests that Brönsted active sites intervene in the
initiation step for the cracking of olefins and
alkylaromatics, and also in the possible protolytic
cracking of paraffins. However, the generation of
olefins from paraffins by Brönsted and Lewis acid
sites has also to be considered as an initiation or,
at least, as a complementary initiation mechanism
during the cracking of paraffins.
If one now tries to use this accumulated knowl-
edge on the cracking mechanism generated from
more fundamental studies using pure compounds
to explain what is occurring during the cracking
of commercial feeds, one must also consider the
following. In commercial units the temperature at
which the feed encounters the catalyst is quite high
(~700°C ); moreover, the zeolite is not a ‘pure’
Brönsted acid catalyst. In addition, a large amount
of dispersed EFAL also exists on the surface of
the zeolite crystals. This EFAL presents Lewis
acidity, and will be the first type of site that will
encounter the large reactant molecules present in
the feed. It can thus be expected that, in accordance
26 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30
with the opinion of McVicker et al. [31] and
Corma and coworkers [30,37], besides protolytic
cracking, a ‘radical’ type of cracking and dehydro-
genations will also occur on this EFAL and olefins
will be generated, even if one starts from a purely
paraffinic feed. These olefins can, at the very least,
enhance the rate of paraffin cracking by adsorbing
on Brönsted acid sites and form a ‘carbenia sur-
face’ [35], which can activate paraffins by hydride
abstraction just as Lewis acid sites would do.
Good support for this idea comes from the work
of Schuette and Schweizer [36 ], who enhanced the
cracking rate of industrial feeds by introducing
Lewis acidity via the introduction of active
alumina.
Therefore, if we wish to understand better what
is occurring during the cracking in industrial units,
further research under more realistic experimental
conditions and feeds is required. This has been
attempted by carrying out the cracking of n-
heptane and vacuum gasoil on USY zeolites with
a similar unit cell size but with different contents
of EFAL [37]. It has been observed that when
EFAL is removed, while preserving the unit cell
size of the USY zeolite, gasoil conversion is
decreased and lower selectivities to liquid distillates
are obtained. These experiments clearly showed
that, at least for gasoil cracking, the Lewis acidity
associated with EFAL is also intervening in the
reaction.
3. Cracking mechanism: chain propagation
Regardless of the initiation and cracking mecha-
nism, when the CMC bond is broken a ‘carbenium-
like ion’ is left on the surface. This can either
desorb, giving one olefin or one paraffin when the
cracking occurs via protolytic or b-scission respec-
tively, or can interact with one molecule of reac-
tant. For the case of a paraffin the interaction with
a carbenium ion has been studied theoretically
[38–40], and it has been traditionally proposed
that chain propagation will occur when a carbe-
nium ion abstracts a hydride ion from a reactant
paraffin, and while the former will desorb as a
paraffin, the reactant molecule will be converted
into a carbenium ion that will be able to either
Fig. 7. Hydride transfer between different carbenium ions and
paraffins in the gas phase: (1) (C H MHMC H )+; (2)
2 5 2 5
(C H MHMC H )+; (3) (tert-C H MHMtert-C H )+; (4)
3 7 3 7 4 9 4 9
(C H MHMtert-C H )+ [39].
3 7 4 9
isomerize and/or crack, therefore keeping the reac-
tion chain going. When this interaction was care-
fully studied in the gas phase [39], it was found
that a stable carbocation intermediate is formed
( Fig. 7). This presents a CMHMC bond that is
bielectronic and tricentric, and whose geometry
changes depending on the carbon atoms
implicated.
Similar results have been obtained when the
hydride transfer process occurs between a paraffin
and a carbenium ion adsorbed on a zeolite cluster.
At this point it should be possible to write a
general mechanism for paraffin cracking [18,41] in
which the initiation step occurs through a mono-
molecular reaction where the ‘carbocation’ is
formed. This will be followed by a bimolecular
chain transfer reaction that corresponds to the
hydride transfer between an adsorbed ‘carbenium
ion’ and a reactant molecule:
After the hydride transfer has occurred and a
‘carbenium ion’ of the reactant molecule is formed,
it sometimes becomes difficult to visualize a
b-scission without involving a primary carbenium
ion. Thus, owing to the high instability of primary
carbenium ions, a search has been made for alter-
native cracking routes that avoid the formation of
primary carbocations. In this way Sie [42,43] has
proposed a new mechanism for the cracking of
carbenium ions that involves the participation of
 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30
PCP structures [44]. The mechanism is presented
in Fig. 8.
This mechanism not only avoids the participa-
tion of primary carbenium ions, but also can
explain the high yield of isoparaffins obtained
during the cracking of n-paraffins.
There is no doubt that the product distribution
observed during cracking of paraffins will depend
on the relative contribution of protolytic and
b-scission mechanisms of CMC rupture. Then, if
most of the cracking occurs through a bimolecular
b-scission mechanism, high yields of branched
products will be obtained. On the contrary, if
protolytic cracking dominates, then more lineal
paraffins, methane, ethane and even ethylene and
H will be produced.
2
Based only on the product distribution
obtained, some authors [16,17] have made a pro-
posal to evaluate the contribution of both types
of cracking mechanism taking place on a given
catalyst and with a given reactant. However, a
deep consideration of all the reactions occurring
during the cracking of paraffins indicates that,
when reactants with more than four carbon atoms
are used, it becomes impossible to determine the
exact contribution of the protolytic and b-scission
mechanism to the final product distribution
27
obtained if only product distribution data are used
in the procedure [45]. Nevertheless, one may use
isobutane as a reactant molecule to test the ability
of different catalysts to carry out both monomolec-
ular protolytic cracking and bimolecular cracking.
Isobutane, in addition to the tertiary carbon, has
a tertiary CMH bond that can easily react by
either a proton attack or by a hydride transfer
reaction [24].
As a consequence, isobutane gives H , CH , n-
2 4
butane, propane and i-butene as the primary pro-
ducts. Among them, only H and CH are gener-
2 4
ated by the protolytic route, whereas the rest of
the products are obtained by the bimolecular path-
way involving hydride transfer and b-scission. It
is then easy, in this case, not only to find the
relative contribution of each of those two mecha-
nisms on a given catalyst [23,24,46 ], but also to
calculate a ‘chain length’ (number of chains per
initiating event) by means of the ratio between the
bimolecular propagation and the monomolecular
reaction [24]. It is obvious that the ‘chain length’
will depend on the average lifetime of the carbe-
nium ion or its concentration on the catalyst
surface, and this in turn will be a function of the
nature of the reactant and the catalyst. More
specifically, in the case of zeolites there is an
28 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30
Fig. 8. Proposed mechanism of acid-catalysed cracking of
normal paraffins [42].
increase in the ‘chain length’ when the framework
Si/Al ratio is increased [23,24]. On the other hand,
detailed kinetic studies, including connecting cata-
lytic cycles, have also allowed the separation of
protolytic cracking from the other reactions. In
this way the rate kinetic constants for the different
groups of reactions occurring during catalytic
cracking have been able to be calculated [47,48].
4. Cracking mechanism: chain termination
The chain transfer is terminated when the sur-
face ‘carbenium ions’ are desorbed and the
Brönsted acid site of the catalyst is regenerated
[24,41]. This step is just the reverse of the adsorp-
tion of one olefin and could be written as:
C H+C H +H+.
3 7 3 6
With this simple step, the cracking chain mecha-
nism is completed.
5. Influence of the catalyst and operation variables
on the reaction mechanism
Haag and Dessau [18] found that the activation
energy was higher for the protolytic than for the
b-scission mechanism. Thus, it can be expected
that the monomolecular mechanism will predomi-
nate at high reaction temperatures. Moreover,
the monomolecular character of the protolytic and
the bimolecular nature of b-scission will make the
former predominant at low partial pressures of
hydrocarbon and lower levels of conversion. These
conclusions were supported by the work of Riekert
and Zhou [49], who observed an induction period
during paraffins cracking (which is typical of bimo-
lecular reactions) only at reaction temperatures
below 200°C. In an analogous way, Lukyanov
et al. [50] have only observed an important contri-
bution of the hydride transfer on the cracking of
n-hexane with ZSM-5 at reaction temperatures
below 400°C.
Furthermore, since the bimolecular hydride
transfer leading to a b-scission mechanism involves
a larger transition state than the unimolecular
protolytic cracking, it appears that the pore size
of the zeolite used as the catalyst can introduce a
shape selectivity effect that will control the relative
extension of the protolytic and b-scission mecha-
nisms. On the other hand, we must take into
account that bimolecular mechanisms are favoured
at higher site density and higher adsorption capac-
ity. Thus, an increase of the framework Si/Al ratio
of zeolite will have a negative effect on the rate of
bimolecular cracking. All of this will certainly be
reflected by the product distribution obtained.
Giannetto et al. [51] concluded that bimolecular
cracking is more restricted in Y zeolites with a
high Si/Al ratio. Haag and Dessau [18] found that
protolytic cracking is more favourable in a 10MR
zeolite, such as ZSM-5, than in a 12MR zeolite,
such as FAU. Mirodatos and Barthomeuf [52]
 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30
Fig. 9. Variation of cracking selectivity as a function of zeolite
structure [53].
further supported these findings and proposed that
protolytic cracking is favoured when small-pore
zeolites and/or zeolites with highly tortuous pores
are used. Wielers et al. [53] showed that the
cracking mechanism ratio (CMR), defined as the
ratio C +C /isobutane (which is directly propor-
1 2
tional to the ratio of protolytic to b-scission mecha-
nism), increased with decreasing zeolite pore
diameter during n-hexane cracking ( Fig. 9). In an
analogous way, when a protolytic versus hydride
transfer ratio was obtained on the basis of the
paraffins and olefins produced during cracking of
n-heptane [54], it was also found that this ratio
increases when decreasing the pore dimensions of
the zeolite ( Fig. 10).
The ratio of the protolytic versus the b-scission
mechanism is important not only from a funda-
mental standpoint, but has important implications
for a real FCC unit. Indeed, the product distribu-
tion obtained by a purely protolytic cracking will
be very similar to that obtained by a radical-
type mechanism, i.e. larger H , CH , C and
2 4 2
29
Fig. 10. Protolytic/hydride transfer ratio versus pore dimen-
sions in n-heptane cracking over different zeolites. (&) USY;
(+) ZSM-5; (×) Mordenite; (#) Beta; ($) MCM-22; (%)
CIT-1; (6) SSZ-24; (+) NU-86; ()) NU-87; (1) Ferrierite;
(n) ITQ-4.
olefin/paraffin production. Moreover, it will pro-
duce less branched products and lower selectivity
to gasoline and diesel.
On the other hand, the bimolecular mechanism
will give less dry gas, more gasoline and diesel,
lower olefins, and probably more catalytic coke.
Thus, catalyst manufacturers can utilize this
knowledge and modify the zeolite Y present in the
catalyst by stabilizing it with a higher or lower
framework Si/Al ratio depending on whether a
high yield of olefins and LPG olefins is desired
instead of a higher yield of distillates with a low
yield of gases respectively. Moreover, it is well
known that the introduction of ZSM-5 as a zeolite
additive should, in addition, contribute to increase
the ratio of protolytic versus b-scission cracking,
therefore augmenting the olefinicity of LPG and
gasoline, but decreasing the gasoline yield.
6. Conclusions
It has been discussed that although the cracking
mechanism of olefins and alkylaromatics is well
established, the activation step for paraffins still
needs further work to reach the required level of
understanding. From our current knowledge it
30 A. Corma, A.V. Orchillés / Microporous and Mesoporous Materials 35–36 (2000) 21–30
appears that the most probable activation route,
at least at high reaction temperatures, involves the
attack of a proton from the catalyst on a CMC
bond or on a CMH bond, especially if there are
tertiary hydrogen atoms present. However, it has
been shown that the role of EFAL species, particu-
larly when working with commercial feeds and
industrial conditions, cannot be neglected.
Finally, the product distribution observed is
highly dependent on the chain propagation mecha-
nism, and more specifically on the number of
propagation events per initiation step. This param-
eter can be controlled by the reaction conditions,
as well as by the nature (composition and topol-
ogy) of the catalyst-zeolite used.
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