Ind. Eng. Chem. Res.

2001, 40, 1337-1347

1337

A Fundamental Kinetic Model for the Catalytic Cracking of Alkanes

on a USY Zeolite in the Presence of Coke Formation
Hans C. Beirnaert, John R. Alleman, and Guy B. Marin*
Laboratorium voor Petrochemische Techniek, Universiteit Gent, Krijgslaan 281, B-9000 Gent, Belgium

The catalytic cracking of alkanes in the presence of deactivation by coke formation is presented.
Elementary reactions such as protonation, deprotonation, hydride transfer, isomerization,
scission, and protolytic scission are explicitly accounted for. A distinction is made between the
formation of primary coke by irreversible adsorption of hydrocarbons on catalytic sites and the
formation of coke by further growth on said primary coke. Termination of the coke growth occurs
when the coke molecules reach the dimensions of the zeolite pores. Primary coke molecules are
formed out of the reaction of an alkene with a carbenium ion on the catalyst surface. The degree
of coverage of the catalyst surface with carbenium ions is obtained from the pseudo-steadystate approximation. The deactivation effect of coke on each elementary reaction is modeled
with empirical exponential deactivation functions. These functions are expressed as a function
of the amount of primary formed coke, this being a measure for the amount of deactivated acid
sites. The kinetic parameters are estimated by regression of experimental data of 2,2,4trimethylpentane cracking on a USY zeolite catalyst between 698 and 723 K, a hydrocarbon
partial pressure between 7 and 15 kPa, and catalyst coke contents between 0.48 and 3.35 wt %.
The deactivation effect of coke on the various elementary reaction steps is different and increases
in the order deprotonation < protonation; protonated cyclopropane isomerization < (t,t) scission;
protolytic scission < hydride transfer on alkanes < scission in which secondary carbenium
ions are involved.
Introduction
Catalytic cracking of heavy oil fractions toward more
valuable light hydrocarbons is one of the most important
conversion processes in the oil refining industry. The
optimal and flexible operation of catalytic cracking units
requires accurate process models. Therefore, reliable
kinetic models must be available.
Recently, significant progress was made in the development of fundamental kinetic models for catalytic
cracking.1-11 The single-event kinetic modeling, developed by Froment and co-workers, takes into account the
detailed carbenium ion chemistry occurring on the
active sites of zeolite catalysts.12-15 The reaction rate
expressions are based explicitly on the elementary
reaction steps involved in the transformation of the
intermediates. This approach leads to rate coefficients
which are independent of the feedstock because of their
fundamental chemical nature. They can be determined
from experiments with typical key components and
simple mixtures of these. This approach was developed
first for hydrocracking on Pt-loaded Y zeolites14,15,17,18
and later on extended to catalytic cracking on Y zeolites.2,19 Dewachtere19 developed a single-event kinetic
model for catalytic cracking of alkanes, cycloalkanes,
and aromatics.
A very important aspect of catalytic cracking is coke
formation and its impact on the reaction kinetics. This
was not yet accounted for in the single-event kinetic
modeling. In the present paper, a single-event kinetic
* To whom correspondence should be addressed. E-mail:
Guy.Marin@rug.ac.be. Fax: +32 9 2644999.
Current address: UCB Chemicals, Pantserschipstraat 207,
B-9000 Gent, Belgium.

model for catalytic cracking of alkanes is constructed,

taking into account deactivation by coke formation.
Often, the deactivation effect of coke on the reaction
kinetics of catalytic cracking is taken into account by a
single deactivation function, describing the effect of coke
on the global catalyst activity.4,8,20 However, the effect
of coke on all reaction types involved in catalytic
cracking is not identical.21,22 The deactivation effect of
coke on a reaction depends on several aspects, such as
the amount of sites involved in the reaction, acid
strength distribution, site density, and texture of the
catalyst.23-26 Accounting for all of these effects on an
explicit basis is very difficult because of the complexity
of the resulting kinetic model and the amount of
structural catalyst properties to be determined. For that
reason, empirical deactivation functions are often used
when modeling the deactivation effect of coke on a
reaction. The resulting model is more reliable when the
deactivation function is expressed as a function of a
variable related to the cause of the deactivation, i.e.,
the coke content on the catalyst, and not as a function
of time on stream.23,27 This requires, however, a kinetic
model for coke formation.
The present model for coke formation is innovative
in the way that it reflects the fundamental carbenium
ion chemistry underlying the catalytic cracking process.
The coke formation is indeed considered as starting from
carbenium ions on the catalyst surface. The concentration of the carbenium ions on the catalyst surface is
obtained via the single-event modeling of the catalytic
cracking reactions as such.
Experimental Section
Reactor. The reactor setup consists of a combination
of an electrobalance and a recycle reactor. With the

10.1021/ie000497l CCC: $20.00 2001 American Chemical Society

Published on Web 02/01/2001

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Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

electrobalance, the mass increase of the catalyst is

measured continuously. At the end of the experiment,
the catalyst is flushed at pretreatment conditions and
the final amount of coke is obtained from the mass
difference of the catalyst before and after the experiment. The reactor is operated gradientlessly at high
conversion by external recirculation, with online gas
chromatographic analysis of the effluent. A detailed
description of the reactor setup is given elsewhere.21
Catalyst. The catalyst is a commercial USY zeolite,
LZ-Y-20 of Union Carbide. This is a Y zeolite, dealuminated by steaming, in which the aluminum removed
from the framework remains in the zeolite as extraframework aluminum (Si/Al framework ) 30 mol/
mol; total Si/Al ) 2.6 mol/mol).28 The steaming treatment results in a secondary pore structure of mesopores.
For each experiment this catalyst was brought to a
reproducible activity by the following pretreatment:
heating in an inert flow of nitrogen at a rate of 5 K/min
up to 773 K and remaining at that temperature for 1 h
before establishing the reaction conditions.
Conditions. Eleven experiments with 2,2,4-trimethylpentane were performed. The space time was varied
between 16.5 and 81.1 kgs/mol, the partial pressure
between 6.8 and 15 kPa, and the temperature between
698 and 748 K. At each set of conditions, the gas effluent
composition was followed as a function of time. In total
64 compositions were used for the parameter estimation.
The experiments were executed in the absence of
diffusional limitations.
Catalytic Cracking Reactions
Single-Event Approach. In this section the principles of the single-event kinetic model for alkane
catalytic cracking are briefly discussed.
The very large number of global reactions occurring
in the catalytic cracking of hydrocarbons consists of a
limited number of types of elementary steps on the
carbenium ion level: protonation; deprotonation; protolytic scission; hydride transfer; hydride shift, methyl
shift, and protonated cyclopropane (PCP) isomerization;
and scission. The present model only includes protolytic scission of an alkane yielding a carbenium ion
and a smaller alkane; protolytic dehydrogenation is not
considered. In the cracking of alkanes, the initial
carbenium ions feeding the catalytic cycle are formed
through protolytic scission. The formation of carbenium
ions through protonation reactions dominates if alkenes
are present in the feed. Figure 1 shows the various types
of elementary steps on the carbenium ion level involved
in the catalytic cracking of alkanes. Figure 2 schematically represents the reaction network for the catalytic
cracking of isooctane. It illustrates, for instance, how
the global cracking reaction of isooctane into isobutane
and isobutene consists of the consecutive elementary
steps of (a) hydride transfer generating the isooctyl
carbenium ion; (b) (t,t) scission leading to isobutene
and the isobutyl carbenium ion; and (c) desorption of
the latter by hydride transfer with another carbenium
ion, leading to isobutane.
The first step in the reaction of hydrocarbons is the
formation of carbenium ions on the Brnsted acid sites
of the catalyst surface by protonation of alkenes or by
protolytic scission of an alkane with the formation of a
smaller alkane and a carbenium ion. The carbenium
ions can undergo a limited number of elementary
reactions: scission with formation of an alkene and a

Figure 1. Types of elementary steps involved in the catalytic

cracking of alkanes.

Figure 2. Schematic representation of the catalytic cracking

reaction network of isooctane. The various global reactions consist
of a limited number of elementary steps.

smaller carbenium ion or isomerization reactions such

as hydride shift, methyl shift, or PCP isomerization. An
adsorbed carbenium ion can act as a Lewis acid site and
may undergo hydride transfer with an alkane, resulting
in the desorption of the carbenium ion as an alkane and
the formation of a carbenium ion out of the first alkane.
Deprotonation of a carbenium ion leads to an alkene
and the regeneration of the Brnsted acid site.
The formation of primary carbenium ions is only
considered for protolytic cracking. These unstable ions
do not undergo any isomerization or cracking reactions
but only desorb via hydride transfer or deprotonation.
In all other reactions, only secondary and tertiary
carbenium ions are involved.
For a given feedstock, a complete reaction network
can be generated via these elementary steps.11,12 The
reacting hydrocarbon species are represented by Bool-

Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1339

ean relation matrices. The elementary reaction steps

can be represented by changes of these matrices. The
structure of all fed and formed hydrocarbon species is
stored in a more compact vector notation, from which
the sparce Boolean relation matrices can always be
generated.15
The reaction rate of an elementary step is given by
the product of the corresponding rate coefficient and the
concentration of the reacting species of either a molecule
or a carbenium ion. Transition state theory can be used
to show that these elementary step rate coefficients k
are multiples of single-event rate coefficients, k :15,17

k ) nek

(1)

where ne is the number of single events associated with

the elementary step. The latter can be calculated from
the global symmetry numbers, gl, of the reactant and
the transition state:15,17

ne ) gl,r/gl,*

(2)

The number of single-event rate coefficients could be

significantly reduced on the basis of some simplifying
assumptions and thermodynamic constraints:2,11,13-15,17,18
(a) Only one rate coefficient for hydride transfer on
alkanes is considered.
(b) The single-event deprotonation coefficients are
assumed to be independent of the structure.19 This
results in a single deprotonation rate coefficient for each
type of carbenium ion. Thermodynamics then imply that
the single-event protonation coefficients are dependent
on the type of the formed carbenium ion and on the
structure of the alkene. They can be calculated out of
the protonation rate coefficient of a reference alkene.
By a judicious choice of the reference alkenes, only two
independent single-event protonation rate coefficients
are retained, k Pr(s) and k Pr(t).19
(c) For the protolytic scission of alkanes, proceeding
via carbonium ions as intermediates, it is assumed that
the single-event rate coefficients are only dependent on
the carbenium ion type formed (primary, secondary, or
tertiary).
(d) The single-event reaction rate coefficients for
surface reactions between carbenium ions depend only
on the carbenium ion type of the reactant and the
product, resulting in four rate coefficients for hydride
shift, methyl shift, PCP isomerization, and scission
((s,s), (s,t), (t,s), (t,t)).
With the above assumptions, the number of singleevent rate coefficients for the modeling of the catalytic
cracking of alkanes could be limited to 25.
Rate Equations for the Elementary Reactions.
The reaction rate of an elementary step, for instance,
the (s,s) scission of a secondary carbenium ion R1+ is
given by

r ) nek (s,s)R1+(s,s)

(3)

where R1+ is the fractional coverage of the Brnsted acid

sites with R1+. The total concentration of the Brnsted
acid sites is incorporated in the single-event rate coefficient k (s,s). The deactivation function, , expresses the
decrease of the reaction rate due to coke formation.
The fractional coverage of the Brnsted acid sites with
a carbenium ion can be derived by applying the pseudosteady-state approximation to the latter, expressing that
the disappearance rate of R1+ by deprotonation and

hydride transfer with alkanes, coke, and aromatic

precursors is equal to its formation rate by protonation
of alkenes, protolytic cracking of alkanes, and hydride
transfer of an alkane P1 with adsorbed carbenium ions:

j (ne)Depk Dep(s)Dep(s) +

R1+

par

(ne)HtfPP + Rarom

Htf /carb) )
j)1
k Pr(s)Pr(s)(1 - carb)(ne)PrK
(OjSOref)PO +
j
k Proto(s)Proto(s)(1 - carb)(ne)ProtoPP +
j
R1+(k HtfHtf

(ne)Htfk HtfHtfPP1carb (4)

This balance explicitly accounts for the formation of
alkanes via hydride transfer reactions involved in the
formation of aromatics and coke via the last term on
the left-hand side. Below it is explained how the
arom
corresponding alkane formation rate, RHtf
, can be
obtained from eq 21. Note that the surface reactions are
assumed to proceed on a much smaller time scale than
the adsorption and desorption reactions, so that only
the latter have to be considered in the balance. Solution
of eq 4 leads to the following expression for the fractional
coverage of the Brnsted acid sites with R1+:
R1+ )

(n )

k Pr(s)Pr(s)(1 - carb)

(OjSOref)POj
e PrK

(ne)av,Depk Dep(s)Dep(s) + k HtfHtf

)(n )

(ne)HtfPPj + Rarom
Htf /carb

k Proto(s)Proto(s)(1 - carb

e ProtoPPj

(ne)av,Depk Dep(s)Dep(s) + k HtfHtf

(n )

e HtfPPj

Rarom
Htf /carb

k HtfHtfcarb(ne)HtfPP1
(ne)av,Depk Dep(s)Dep(s) + k HtfHtf

(n )

e HtfPPj

(5)
+

Rarom
Htf /carb

where (ne)av,Dep is the average number of single events

of the elementary deprotonation steps of R1+.
The total fractional coverage of the Brnsted acid
sites, carb, is calculated as the sum of the fractional
coverages with carbenium ions Ri+, given by equations
similar to eq 5, leading to an implicit equation in carb:

carb )

ions

(6)

Rate Equations for the Global Reactions. Global

reactions consist of a number of elementary steps, as
illustrated in Figure 2. On a molecular level, the global
reaction rates are calculated by summation of the
reaction rates of the elementary reaction steps which
transform carbenium ions formed out of the reacting
molecule into carbenium ions which desorb to the
product molecule. For example, the reaction rate for the
scission of an alkane P1 into an alkene O and an
alkane P2 is obtained from a summation of rates of
elementary -scission reactions, which transform secondary or tertiary carbenium ions formed out of P1 into
secondary or tertiary carbenium ions which desorb to
P2.

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Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

The lumping coefficients LC are independent of the

value of the single-event rate coefficients. They only
depend on the generated reaction network and the lump
composition. They can be calculated from
par
LC(m,n)
)

yi,L (ne)Htf(ne)

m,n

Figure 3. Schematic representation of the relumping for the

scission of the lump of alkanes L1 into alkenes and the lump of
alkanes L2. A fraction D(n) of the product carbenium ions desorbs
through hydride transfer to alkanes of lump L2; the other product
carbenium ions deprotonate to alkenes.

Practically, a certain degree of lumping between

molecules may be necessary. For instance, the exact
composition of complex feed mixtures is not always
known because of the limits of chemical analysis techniques. Moreover, the solution of the continuity equations for all components in the reaction mixture can lead
to excessive calculation times, especially at higher
carbon numbers. Single-event modeling enables one to
calculate the reaction rates between lumps in a rigorous
way. The reaction rate between two lumps is found by
the summation of the rates of all elementary reaction
steps which transform carbenium ions, formed out of
molecules of the first lump, into ions, which desorb to
molecules of the second lump. This so-called relumping
is illustrated in Figure 3 for the scission of a lump of
alkanes L1 into alkenes and a lump of alkanes L2. The
corresponding reaction rate is calculated as19
par
r(L1fO + L2) ) LC(s,s)
F(s,s)k (s,s)(s,s)PL1 +
par
F(s,t)k (s,t)(s,t)PL1 +
LC(s,t)
par
LC(t,t)
F(t,s)k (t,s)(t,s)PL1 +
par
F(t,t)k (t,t)(t,t)PL1
LC(t,t)

(10)

The F factors are given by

F(m,n) )
k HtfHtfcarbD(n)
par lumps

(ne)av,Depk Dep(m)Dep(m) + k HtfHtf

LCHtfPLj + Rarom
Htf /carb

j)1

(11)

where m and n are the carbenium ion types, either

secondary or tertiary.
The factor D(n), which is the fraction of carbenium
ions which desorbs by hydride transfer to alkanes
belonging to lump L2, is calculated from
D(n) )
par lumps

k HtfHtf

LCHtfPLj + Rarom
Htf /carb

j)1

par lumps

(ne)av,Depk Dep(m)Dep(m) + k HtfHtf

LCHtfPLj + Rarom
Htf /carb

j)1

(12)

with summations over all lumps of alkanes in the

reaction mixture. The other fraction of the product ions
desorbs toward alkenes by deprotonation.

(13)

The summation in eq 13 extends over all -scission

reactions which transform carbenium ions of type m,
formed out of the lump L1, into carbenium ions of type
n, which desorb to alkanes of lump L2. The factor (ne)Htf
is the number of single events of the hydride transfer
reaction from which the reactant ion is formed, and (ne)
the number of single events of the elementary -scission
reaction. The lumping coefficient LCHtf is calculated
from

LCHtf )

i yi,L (ne)Htf
1

(14)

with the summation extending over all alkanes of the

lump Lj.
Equations which are similar to those above can be
derived for the other global reactions necessary to
describe the catalytic cracking of acyclic hydrocarbons.
These reactions are, for the lumps of alkanes, hydride
transfer/protolytic scission/PCP isomerization/ scission
and, for the lumps of alkenes, protonation/PCP isomerization/ scission. Hydride transfer of lumps of alkanes
results in the transformation of alkanes into alkenes
by hydride transfer followed by deprotonation. Protonation of lumps of alkenes transforms alkenes into
alkanes by protonation, followed by hydride transfer.
Protolytic scission converts alkanes into smaller alkanes
and carbenium ions, which can desorb as alkanes or as
alkenes. PCP isomerization of lumps of alkanes or
alkenes results in the formation of carbenium ions with
a different degree of branching, desorbing as alkanes
or as alkenes. Finally, scission converts lumps of
alkanes or alkenes into smaller alkenes and carbenium
ions, which can desorb as alkanes or as alkenes. The
net rates of formation of the different lumps, necessary
for the solution of the corresponding continuity equations, are found by summation of these global reaction
rates.
Coke Formation
Reactions. Coke formation is assumed to start from
alkenes in the gas phase. Small alkenes such as
isobutene readily undergo consecutive elementary reaction steps such as protonation, deprotonation, alkylation, isomerization, hydride transfer, and ring closure,
leading to macromolecules, which cannot diffuse out of
the supercages of the USY zeolite.22,29-31 Coke molecules
are not chemically inert but interact with the cracking
reactions and continue to grow until the dimensions of
the growing molecules reach the dimensions of the
zeolite pores. Coke growth is terminated by steric
hindrance.
This reaction route is modeled by two consecutive
reactions: the formation of primary coke by site coverage, followed by coke growth on the primary coke
molecules. The formation of primary coke by irreversible
adsorption on catalyst sites is considered to start from
carbenium ions on the catalyst surface. In this way, the
coke formation is linked with the cracking reactions.

Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1341

This is reflected in the kinetic equations and will be

discussed below. The primary coke can further grow
through alkylation with an alkene from the gas phase,
according to an Eley-Rideal reaction mechanism. The
termination of the coke growth is also accounted for in
the kinetic model.
The simplified modeling by two consecutive reactions
implies that the kinetic parameters for coke formation
will show a certain dependence on the composition of
the reaction mixture, in contrast to the single-event rate
parameters.
Rate Equations. The formation of a primary coke
by site coverage is considered to proceed through the
reaction of an alkene in the gas phase with a carbenium
ion on the catalyst surface. The rate of formation of a
primary coke is therefore proportional not only to the
alkene partial pressure, Pol, but also to the degree of
coverage of the catalyst surface with carbenium ions,
carb, as obtained from eq 6:

dCs/dt ) RCs ) kscarbPolC

(15)
s

The presence of carb and Pol in this equation makes a

simultaneous modeling of the coke formation and the
kinetics of the cracking reactions necessary.
The deactivation function, , accounts for the deactivation effect of coke on the reaction rate. An empirical
exponential deactivation function is used:

Cs ) exp(-RsCs)

(16)

It is expressed as a function of the amount of coke

formed by site coverage, Cs, and not as a function of the
total coke content, CC. In the absence of diffusional
limitations within the catalyst particles and of effects
of pore blockage, Cs is proportional to the amount of
deactivated acid sites.32,33
Coke growth cannot continue indefinitely. It is terminated by sterical constraints once the coke molecule
has reached the dimensions of the pore volume. Analogous to work by Beyne and Froment26 and Devoldere
and Froment,34 this termination is explicitly taken into
account. In this respect, the kinetic model considers the
amount of coke, Csg, involved in the site coverage which
is still active for further growth.
In agreement with the coke formation mechanism, the
rate of coke growth is proportional to the alkene partial
pressure and to the amount of coke still susceptible to
growth, Csg:

dCg/dt ) RCg ) kgPolCsg

(17)

The termination of coke growth corresponds to the

formation of nonreactive coke by reaction of a gas-phase
alkene with coke which is still susceptible to growth.26
The rate of termination is therefore proportional to both
the alkene partial pressure and Csg. The net production
rate of coke, which is still active for further growth,
follows from the difference between the formation rate
of a primary coke and the termination rate due to
sterical constraints:

dCsg/dt ) RCsg ) kscarbPolCs - ktCsgPol

(18)

The total amount of coke on the catalyst is given by

the sum of both contributions of site coverage and coke
growth, of which the respective evolutions in time are
obtained by integration of eqs 15 and 17:

CC ) Cs + Cg

(19)

Correspondingly, the total coke formation rate is the

sum of both site coverage and coke growth rates:

RC ) RCs + RCg

(20)

Hydride Transfer Involved in the Formation of

Aromatics and Coke. The hydride transfer involved
in the formation of aromatics and coke significantly
enhances the formation rate of alkanes because of the
fact that in these reaction paths hydride transfer with
carbenium ions is frequently occurring.22 This is accounted for in the kinetic model by considering the
alkane formation rate through said hydride transfer
arom
, such as, for instance, in the carbereactions, RHtf
nium ion balance equation (4). Because of the limited
selectivity for aromatics and coke formation in the
reaction of acyclic hydrocarbons on a USY zeolite
catalyst, no single-event approach was used to model
the reaction path toward these reaction products. The
arom
is calculated based on the
alkane formation rate RHtf
observed formation rate of monoring aromatics and the
calculated formation rate of coke.
In the formation of a molecule with one aromatic ring
out of an acyclic molecule, four hydride transfer steps
are involved: one in the formation of the allylic carbenium ion out of which a cycloalkane is formed and three
in the aromatization of the latter, proceeding as a
sequence of hydride transfer and deprotonation steps.
This is illustrated in Figure 4.
To quantify the hydride transfer in the coke formation, the H/C ratio of the coke molecules must be known
and a molecular mass of the coke molecules has to be
assumed. Pyrene was taken to represent a typical coke
molecule (H/C ) 0.625, MW ) 202 g/mol). Its properties
are quite in agreement with the results of Dimon et al.,35
who found H/C ratios of the coke molecules between 0.4
and 0.8, by characterization of the coke formed out of
propene at 723 K on a USY zeolite. The formation of
pyrene out of acyclic molecules is accompanied by the
desorption of 12 carbenium ions as alkanes.
Hence, the total amount of alkanes formed by hydride
transfer on aromatic and coke precursors follows from
the rate of formation of monoring aromatics and coke

Rarom
Htf ) 4Rarom + 12RC,mol

(21)

whereby the molar coke formation rate, RC,mol, is

obtained by eq 20, considering the molecular mass of
pyrene as a typical coke molecule.
The choice of another coke model molecule could
result in a different number of associated carbenium ion
desorption steps, i.e., a different coefficient of RC,mol in
eq 21, a different molar coke formation rate, and
ultimately a slightly different alkane formation rate,
arom
. A heavier coke model molecule would result not
RHtf
only in a higher number of desorption steps but also in
a lower molar coke formation rate, with both effects
compensating for each other.
The activity of all carbenium ions for hydride transfer
is assumed to be identical, so that the rate of disappearance of R1+ by the hydride transfer involved in the
formation of aromatics and coke is given by

R1+Rarom
Htf /carb

(22)

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Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 4. Reaction scheme for the formation of a molecule with

one aromatic ring out of an acyclic molecule, involving four hydride
transfer reaction steps.

This carbenium ion disappearance rate is included in

the carbenium ion balance equation (4), from which the
degree of coverage, R1+, is calculated.
Deactivation Functions for the Cracking Reactions. The deactivation functions, i(Cs), in the expressions for the elementary reaction rates, for instance, eq
3, account for the decrease in the reaction rates due to
the decreased number of catalyst active sites as a result
of site coverage by coke molecules. Different empirical
exponential deactivation functions are considered for
each type of elementary reaction:

i(Cs) ) exp(-RiCs)

(23)

Kinetic Parameter Estimation. The optimal values

of the kinetic parameters were determined by minimization of the following objective function with the
Rosenbrock algorithm:36
m-1

S)

wj(Xij,exp - Xij,cal)2 +

j)1
i)1
11

(CCi,exp - CCi,cal)2

i)1

wm

(24)

with m the number of responses, n the number of

observations (64), Xij the responses which are the molar
conversions to lump j for experiment i, and CCi the total
coke content for experiment i. The experimental responses are determined at various effluent analysis
times.21
Only the final coke content for each experiment is
taken into account in the objective function. The final
coke content is determined after flushing the catalyst
with inert gas at reaction temperature.
The weight factors wj were determined as19

wj )

( )
n

(25)

2
Xij,exp

i)1

whereby, if a ) 1, all responses have the same contribu-

tion to the residual sum of squares, S, or, if a ) 0, all

responses have the same weight, meaning that larger
responses contribute to a larger extent to S. An acceptable value for a is 0.2.
The weight factors wm were determined in such a way
that the contribution of cokes to the residual sum of
squares is about the same as the contribution of the gasphase products.
To reduce the correlation between the preexponential
factors and the activation energies of the rate coefficients, reparametrization was applied according to
Kittrell.37
Experimentally, the composition of the isomers with
an identical degree of branching was found to be
independent of conversion. This implies that hydride
shift and methyl shift are faster than the global 2,2,4trimethylpentane conversion, so that an equilibrium
composition is measured for these isomers and the rate
of interconversion between these isomers cannot be
calculated. Therefore, all hydrocarbons with the same
degree of branching are lumped, resulting in 38 molecular components and lumps: 19 alkane lumps, 18
alkene lumps, and coke. Because no significant amount
of tribranched C8 isomers was measured, the lump
composition of tribranched C8 alkanes is not the equilibrium composition but only 2,2,4-trimethylpentane.
The molar conversions of the different molecular
components and lumps are calculated by solution of the
corresponding continuity equations valid for the perfectly mixed flow reactor:

Xi - Ri(P,T,Cs,Csg) W/FiC8 ) 0,

i ) 1, ..., 37

(26)

with Ri the formation rate of lump i, calculated from

the reaction rates between lumps, such as, for instance,
that given by eq 10. Because the mean residence time
is small with respect to the time at which the effluent
is analyzed, the effects of accumulation are negligible.
Hence, the continuity equations form a set of algebraic
equations.
The continuity equations (26) are coupled with the
kinetics of coke formation, described by eqs 15-18. The
complete set of equations is integrated progressively for
time intervals [ti, ti+1]. Initially, i.e., on time zero, no
coke is present on the catalyst, and the olefin partial
pressure and total fractional coverage of the catalyst
surface carb are calculated. The set of eqs 15-18 is then
integrated from time zero to time t1, resulting in values
for coke formed by site coverage Cs and for the amount
of coke which is still susceptible to growth Csg on time
t1. This allows the calculation of the olefin partial
pressure and carb on time t1. This procedure is repeated
for every time interval [ti, ti+1].
For the calculation of the responses, the reactor
pressure, the temperature, the 2,2,4-trimethylpentane/
nitrogen ratio in the feed, the space time, and the times
on stream for the effluent analyses are used as independent variables.
The estimation of preexponential factors and activation energies for all single-event rate coefficients would
lead to an excessive amount of parameters. Therefore,
the temperature effect on protonation was neglected,
and one single activation energy was estimated for
hydride transfer, deprotonation, PCP isomerization,
scission, and protolytic scission. Because (t,t) scission
is important in the 2,2,4-trimethylpentane cracking, it
was possible to estimate the temperature dependence
of the related rate coefficient separately.

Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1343

Table 1. Estimatesa for the Arrhenius Parameters of the
Elementary Steps during the Catalytic Cracking of
2,2,4-Trimethylpentane, Together with the Values of the
Rate Coefficient at 748 K
reaction

Aa

E (kJ/mol)

k (748 K)

Htf
Pr(s)
Pr(t)
Dep(p)
Dep(s)
Dep(t)
PCP(s,s)
PCP(s,t)
PCP(t,s)
PCP(t,t)
(s,s)
(s,t)
(t,s)
(t,t)
Proto(p)
Proto(s)
Proto(t)

1.11 100
6.38 100
1.11 103
3.04 1017
2.91 1012
1.18 1012
2.62 100
3.59 100
4.24 10-1
1.58 101
8.97 109
4.24 1010
1.90 108
9.47 105
2.86 102
1.11 103
1.45 104

47.3

5.73 10-4
6.38 100
1.11 103
7.77 107
7.43 102
3.02 102
5.94 10-2
8.11 10-2
9.61 10-3
3.56 10-1
8.33 101
3.92 102
1.76 100
2.27 101
2.60 10-6
1.01 10-5
1.32 10-4

137.6
137.6
137.6
23.8
23.8
23.8
23.8
115.2
115.2
115.2
66.4
115.4
115.4
115.4

Units: mol/(kg s) or mol/(kg s kPa) for hydride transfer,

protonation, and protolytic cracking.

The number of deactivation constants was limited to

7: one for hydride transfer, one for protonation and PCP
isomerization, one for deprotonation of primary and
secondary carbenium ions, one for deprotonation of
tertiary carbenium ions, one for (s,s), (s,t), and (t,s)
scission, one for (t,t) scission, and one for protolytic
cracking.
Four parameters were necessary for the modeling of
coke formation: the deactivation constant Rs, the factor
kt/kg, and the rate coefficients for site coverage, ks, and
coke growth, kg. The ratio kt/kg can be considered as a
measure for the degree of polymerization of the coke
formed by growth of a primary coke. The temperature
effect on these rate coefficients could not be estimated.
However, this does not mean that the calculated coking
rate will be temperature-independent, because the
calculated surface coverage and the alkene partial
pressure depend on the reaction temperature.
The total amount of kinetic parameters was 34. The
optimal values are given in Tables 1-3. The values of
the single-event rate coefficients at 748 K are also
included in Table 1. All parameter estimates are significant, as appeared from the corresponding t values.
The preexponential factors of (s,t) and (t,s) PCP isomerization were fixed at the values given in Table 1.
Because these values did not influence the residual sum
of squares, these rate coefficients could not be determined from experiments with 2,2,4-trimethylpentane.
Parity plots for the global conversion, the coke content, and several reaction products are given in Figure
5. These plots show that the kinetic model is able to fit
the experimental data very well.
Assessment of the Kinetic Parameter Values.
The values of the reaction rate coefficients within each
reaction family can be explained by the stability of the
carbenium ions involved. Table 1 clearly shows that the
protonation and protolytic cracking rate coefficients
increase with the stability of the formed carbenium
ion: (p) < (s) < (t). In contrast, the rate coefficients for
deprotonation of less stable primary and secondary
carbenium ions are higher than that for the deprotonation of a tertiary carbenium ion. The rate coefficient
for (s,t) scission, whereby a more stabilized carbenium
ion is formed out of a secondary carbenium ion, is higher
than the rate coefficients for the other -scission reac-

tions. The same trends were observed by Dewachtere19

for the catalytic cracking of acyclic hydrocarbons on a
RE-Y zeolite.
The high activation energy for deprotonation implies
that the surface coverage with carbenium ions has a
negative temperature dependence. This was expected
because the measured initial coke formation decreases
with increasing temperature. Also remarkable is the
significant difference in the activation energy between
the (t,t) scission and -scission reactions where
secondary carbenium ions are involved.
Table 2 reveals that the deactivation effect of coke is
not identical for the different elementary reactions. The
estimated deactivation constants increase in the order

RDep(p)+Dep(s) , RDep(t) < RPr+PCP , R(t,t) < RProto <

RHtf < R
Protonation reactions are found to be more deactivated
than deprotonation reactions. This is in accordance with
preferential coke formation on the strongest acid sites
of the zeolite.30,31,38,39 The formation of rather unstable
primary and secondary carbenium ions by protonation
of olefins requires indeed strong acid sites and is
therefore strongly deactivated by coke formation. Furthermore, scission, protolytic scission, and hydride
transfer to alkanes are more sensitive to deactivation
than protonation and PCP isomerization. Also, (t,t)
scission is less deactivated by coke than the -scission
reaction, in which secondary carbenium ions are involved and which need stronger acid sites to stabilize
the transition state.
The selectivity changes observed during the experiments with 2,2,4-trimethylpentane are caused by a
combination of two effects, viz., the different sensitivity
for deactivation of the elementary reactions and the
concentration changes in the continuously stirred tank
reactor (CSTR). Figure 6 illustrates that the kinetic
model is able to describe these selectivity changes:
while the isobutane formation is strongly deactivated,
the isobutene formation remains more or less unaffected.
The parameters for coke formation are listed in Table
3. The high value for the deactivation constant Rs shows
that in the 2,2,4-trimethylpentane conversion the coke
formation by site coverage is strongly deactivated. The
high value for kt/kg indicates that coke growth is limited
in the USY zeolite. This is also illustrated in Figure 7.
This is not very surprising because the alkylation
reaction between coke molecules and the branched
isobutene molecule, which is the most important alkene
in the reaction mixture of 2,2,4-trimethylpentane, will
be sterically hindered in the supercages of the USY
zeolite. Probably, coke growth will mainly occur in the
secondary mesopore structure of the zeolite. Termination of coke growth results in the increasing difference
between Csg, the amount of coke formed by site coverage
which is still active for growth, and Cs, the amount of
coke formed by site coverage (Figure 7).
Experimentally, a strong dependence between the
coking rate and the 2,2,4-trimethylpentane conversion
was observed. The kinetic model is not fully capable of
describing this dependence, as is clearly shown in Figure
8: at low space times, the amount of coke is overestimated, while at high space times, it is underestimated.
The overestimation of the coking rates at low conver-

1344

Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

Figure 5. Experimental versus calculated values for the 2,2,4-trimethylpentane conversion, the coke content, and the conversions to
isobutane, isobutene, propene, and isopentane. Calculated values obtained with a relumped kinetic model based upon a single-event
approach for the cracking reactions, taking into account the deactivation by coke formation and a lumped kinetic model for coke formation,
as represented by the continuity equations (15), (17), (18), and (26) and considering the parameter values of Tables 1-3. Experimental
values obtained from 2,2,4-trimethylpentane conversion on a USY zeolite catalyst with W/F ) 16.5-81.1 kgs/mol, PiC8 ) 6.8-15 kPa,
and T ) 698-748 K.

sions explains the slight deviation of the parity plot for

the 2,2,4-trimethylpentane conversion in Figure 5. A
more detailed kinetic modeling of the coke formation,
based on the single-event approach, would probably
remediate this bias. For that purpose, the formation of
allylic carbenium ions, alkylation, and ring closure need
to be incorporated in the single-event kinetic model.
This would lead to a kinetic model for coke formation
with parameters which would be independent of the

feedstock. At the same time, this approach would lead

to kinetic expressions for the formation of aromatic
compounds out of acyclic hydrocarbons, because the
same elementary reaction steps are involved.
Conclusions
A kinetic model for the catalytic cracking of alkanes
in the presence of coke formation was applied to 2,2,4-

Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001 1345

Figure 6. Experimental and calculated conversion to isobutane

(9) and to isobutene (2) as a function of time on stream in a CSTR
reactor. Experimental conditions: 2,2,4-trimethylpentane conversion on a USY zeolite catalyst at T ) 723 K, PiC8 ) 6.8 kPa, and
W/F ) 44 kgs/mol. Calculated lines are obtained as described in
the caption of Figure 5.

Figure 7. Calculated evolution of CC, Cs, Cg, and Csg as a function

of time on stream in a CSTR reactor, obtained as described in the
caption of Figure 5. Experimental conditions: 2,2,4-trimethylpentane conversion on a USY zeolite catalyst at T ) 723 K, PiC8 )
6.8 kPa, and W/F ) 44 kgs/mol.

Table 2. Estimates of the Deactivation Constants

Coupled with the Elementary Steps of the Kinetic Model
for Catalytic Cracking of 2,2,4-Trimethylpentane
reaction

R [(wt %)-1]

Htf
Pr + PCP
Dep(p) + Dep(s)
Dep(t)
(s,s) + (s,t) + (t,s)
(t,t)
Proto

0.653
0.148
0.031
0.127
0.825
0.407
0.445

Table 3. Estimates for the Kinetic Model of Coke

Formation Involved in the Catalytic Cracking of
2,2,4-Trimethylpentane
parameter
%)-1]

Rs [(wt
kt/kg
ks [kg (100 kgskPa)-1]
kg [(skPa)-1]

value
1.951
2.573
5.23 10-3
7.52 10-5

trimethylpentane cracking on a USY zeolite catalyst.

The cracking reactions were modeled by a fundamental
kinetic model, taking into account elementary reactions
such as protonation, deprotonation, hydride transfer,
isomerization, scission, and protolytic scission. Coke
formation was described as the formation of a primary
coke out of carbenium ions on the catalyst surface,
followed by coke growth. Coke formation and cracking
kinetics are linked with each other. The deactivation
effect of coke on each elementary reaction was modeled
with empirical exponential deactivation functions, expressed as a function of the amount of primary formed
coke. The parameter values indicated that the deactivation effect of coke is strongly dependent on the nature
of the elementary reactions. The kinetic model describes
the kinetic data very well, except the strong effect of
conversion on the coking rate. This shows that there is
a need for a more detailed kinetic model for coke
formation, based upon the single-event approach. Such
an approach would also lead to kinetic expressions for
coke formation with parameters which are independent
of the feedstock, as is the case for the kinetics of the
cracking reactions.

Figure 8. Experimental and calculated evolution of the total coke

content as a function of time on stream in a CSTR reactor.
Experimental conditions: 2,2,4-trimethylpentane conversion on
a USY zeolite catalyst at T ) 723 K, PiC8 ) 6.8 kPa, and W/F )
16.5 (b), 43.6 (9), and 89.7 ([) kgs/mol. Full lines are calculated
as described in the caption of Figure 5.

Acknowledgment
The authors are grateful to the Fonds voor Wetenschappelijk Onderzoek Vlaanderen (FWO-N) for financial support of part of the research.
Nomenclature
Roman Symbols
A ) preexponential factor, reaction dependent
CC ) total coke content, wt %
Cg ) coke formed by growth, wt %
Cs ) coke formed by site coverage, wt %
Csg ) coke formed by site coverage which is still active for
growth, wt %
k ) single-event rate coefficient, reaction dependent
k ) elementary step rate coefficient, reaction dependent
kg ) rate coefficient for coke growth, (s kPa)-1
ks ) rate coefficient for coke formation by site coverage,
kg/(100 kg s kPa)-1
kt ) rate coefficient for termination of coke growth, (s
kPa)-1

1346

Ind. Eng. Chem. Res., Vol. 40, No. 5, 2001

K
iso(O1,O2) ) modified equilibrium coefficient of the isomerization reaction between O1 and O2 (without global
symmetry number)
LC ) lumping coefficient
ne, (ne)s ) number of single events (of elementary steps s)
Pi ) partial pressure of component i, kPa
Rarom ) formation rate of aromatics, mol/(kg s)
RC ) coking rate, kg/(100 kg s)
RC,mol ) molar coke formation rate, mol/(kg s)
RCg ) formation rate of coke by growth on a primary coke,
kg/(100 kg s)
RCs ) formation rate of a primary coke by site coverage,
kg/(100 kg s)
RCsg ) formation rate of coke which is still active for growth,
kg/(100 kg s)
Rarom
) global desorption rate of carbenium ions to alHtf
kanes due to hydride transfer
with aromatics and coke formation, mol/(kg s)
T ) temperature, K
Xij ) molar conversion of lump j in experiment i
yi,Li ) mole fraction of component i in lump Li
W/F ) space time, kgs/mol
wi ) weight factor of response i
Greek Symbols
R ) deactivation constant, (wt %)-1
) surface coverage
gl,r ) global symmetry number of the reactant
gl,* ) global symmetry number of the transition state
) deactivation function
Subscripts
) scission
cal ) calculated
carb ) carbenium ions
Dep ) deprotonation
exp ) experimental
Htf ) hydride transfer
iC8 ) 2,2,4-trimethylpentane
ol ) alkenes
PCP ) PCP isomerization
Pr ) protonation
Proto ) protolytic scission
Superscripts
) in the feed
par ) alkanes

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Received for review May 17, 2000

Revised manuscript received November 9, 2000
Accepted November 28, 2000
IE000497L