Chin. J. Chem. Eng.

, 15(3) 326332 (2007)

Kinetic Model and Simulation Analysis for Toluene

Disproportionation and C9-Aromatics Transalkylation*

XU Ouguan()a,**, SU Hongye()a, JI Jianbing()b, JIN Xiaoming()a

and CHU Jian()a
a
National Key Laboratory of Industrial Control Technology, Institute of Advanced Process Control, Zhejiang Uni-
versity, Hangzhou 310027, China
b
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032,
China

Abstract A new kinetic model for commercial unit of toluene disproportionation and C9-armatiocs transalkylation
is developed based on the reported reaction scheme. A time based catalyst deactivation function taking weight
hourly space velocity (WHSV) into account is incorporated into the model, which reasonably accounts for the loss
in activity because of coke deposition on the surface of catalyst during long-term operation. The kinetic parameters
are benchmarked with several sets of balanced plant data and estimated by the differential variable metric optimiza-
tion method. Sets of plant data at different operating conditions are applied to make sure validation of the model
and the results show a good agreement between the model predictions and plant observations. The simulation
analysis of key variables such as temperature and WHSV affecting process performance is discussed in detail, giv-
ing the guidance to select suitable operating conditions.
Keywords toluene disproportionation and C9-armatiocs transalkylation, kinetic model, catalyst deactivation func-
tion, parameter estimation, simulation analysis

1 INTRODUCTION sivity of reactants or available acid site number re-

As is well known, benzene (B) is a key raw ma-
terial for many intermediates of petrochemicals , and
xylenes (X) are important starting materials for the
production of synthetic fibers, plasticizers, and resin.
The convenient ways to get more valuable benzene
and xylenes from surplus toluene (C7) and trimethyl-
benzenes (C9) consists in the processes such as tolu-
ene disproportionation[1], toluene alkylation with
methanol[2] or toluene disproportionation and transal-
kylation with trimethylbenzenes[3]. The rapidly grow-
ing demand for benzene and xylenes urges develop-
ment of all mentioned processes above.
Reaction kinetics study has shown to be a crucial
research subject for process development which pro-
vides valuable data for reactor design, process opti-
mization, process control, and cycle length prediction.
The advantage of utilizing rigorous kinetic models as
compared to empirical approaches is related to the fact
that the prediction accuracy of rigorous models can be
significantly superior over a wide operating range,
hence researchers are in pursuit of kinetic model of
process industries. As to toluene disproportionation
(TDP), many kinetic models have been proposed over
several zeolites[47], but few models appeared for
toluene disproportionation and transalkylation with
trimethylbenzenes[8,9] although their reaction scheme
and mechanism were investigated widely[3,10,11].
Catalysis by zeolites always accompanies coke depo-
sition causing deactivation problem during long-term
operation[12], and two major mechanism of coke
deposition had been proposed for the catalyst fouling:
pore plugging and site coverage which reduced diffu-
spectively[7]. As far as catalyst decay is concerned,
only a few works[8,1315] can be found in the re-
ported literatures in spite of commercial use of zeo-
lites as catalysts for TDP and aromatics transalkyla-
tion to produce benzene and xylenes.
Zeolite catalyst is inevitably deposited by coke
with extending operation period, and the coke forma-
tion in the reactions is responsible for the loss of cata-
lyst activity and must be incorporated into kinetic
models. The purpose of this study is to develop a
practical kinetic model for industrial application tak-
ing catalyst deactivation into account under represen-
tative industrial operation regimes, namely at high
reaction pressure and wide conversion range. Sensitiv-
ity of process variables is analyzed based on the de-
veloped model. The kinetic scheme employed in this
modeling work is largely based on previously pub-
lished studies.
2 KINETIC MODEL DEVELOPMENT
The reaction scheme used here is mainly based
on Ref.[9] in addition to the side reaction concerning
C10-aromatics (C10A). The side reaction is considered
in the present work as the importance of C10A to the
react system, while it was neglected in others because
of relatively low concentration of C10A. Although a
certain quantity of C10A is in favor of preventing
transformation of C9-aromatics to C10A, more quantity
of C10A is forbidden in the system in terms of its great
effect on catalyst deactivation. The reaction scheme is
shown as follows.

Received 2006-06-15, accepted 2007-01-10.

* Supported by the National Creative Research Groups Science Foundation of China (No.60421002) and priority supported fi-
nancially by the New Century 151 Talent Project of Zhejiang Province.
** To whom correspondence should be addressed. E-mail: ogxu@iipc.zju.edu.cn
 Kinetic Model and Simulation Analysis for Toluene Disproportionation and C9-Aromatics Transalkylation 327

Main reactions: tivation function was not taken into account. In this
paper, the catalyst decaying function is incorporated
into the kinetic model and the net rate equations are
expressed as follows. A more detailed description of
kinetic modeling approach used in this work can be
(1) found in the reported paper[9].
Toluene disproportionation (reversible):
2 a a
r1 = k1 aTol B X (9)
K1

(2) 2 a a
r2 = k2 aTol B EB (10)
K2
Transalkylation of toluene with trimethyleben-
zenes (reversible):
a a
(3) r3 = k3 aTol aTMB X X (11)
K3

a a
r4 = k4 aTol aTMB EB EB (12)
K4
Dealkylation (irreversible):
(4) r5 = k5 aMEB (13)
r6 = k6 aPB (14)
Side reactions: Trimethylebenzenes diproportionation (reversi-
ble):
2 aX aC10 A
r7 = k7 aTMB (15)
K7
(5)
Hence the net rate equations of the key composi-
tions such as benzene (B), toluene (Tol), propylbenze
(PB), methylethylbenzene (MEB), trimethylbenzenes
(TMB), ethylbenzene (EB), xylenes (X), and C10A are
given by
(6) rB = 0.5r1 + 0.5r2 + r6 (16)
rTol = r1 + r2 + r3 + r4 r5 (17)
rPB = r6 (18)
rMEB = r5 (19)
(7) rTMB = r3 + r4 + r7 (20)
rEB = 0.5r2 + 2r4 (21)
Isomerization reactions of xylenes: rX = 0.5r1 + 2r3 + 0.5r7 (22)
rC10 A = 0.5r7 (23)
where r is reaction rate; a is mass fraction, %; is
catalyst deactivation function assumed to be uniform
for all reactions; k is reaction rate constant; and K is
chemical equilibrium constant.
(8) Catalysts for hydrocarbons catalysis are inevita-
bly deactivated by the coke deposition. In fact catalyst
decay has been widely discussed in many processes
such as catalytic cracking and catalytic reforming. A
time-based model was proposed by Jacob et al.[16]
A kinetic model for toluene disproportionation accounting for catalyst fouling in residue oil catalytic
and C9-aromatics transalkylation has been developed cracking. Taskar and Riggs[17] applied another model
by Liu[8] and Xu et al.[9], but unfortunately the deac- related to the amount of coke deposited on the surface
Chin. J. Ch. E. 15(3) 326 (2007)
328 Chin. J. Ch. E. (Vol. 15, No.3)

of catalyst to characterize deactivation as van Trim- yPX + yOX + yMX = 1 (35)

pont et al.[18] did during naphtha reforming, and the
reactant converted decay model was successfully then
used for xylene transformation in a riser simulator[19]. aPX = yPX aX (36)
In this work, a time-based empirical catalyst deactiva-
tion function is proposed taking hydrogen partial aOX = yOX aX (37)
pressure and weight hourly space velocity into account aMX = yMX aX (38)
as follows:
where y is mole fraction, %.
= exp( t ) Ph WHSV (24) The axial fixed-bed reactor with diameter of
where is catalyst deactivation constant; t is on 2.18m and length of 14.53m and the catalyst of
stream time, d; Ph is hydrogen pressure, kPa; is HAT-096 invented by Shanghai Research Institute of
pressure exponent; WHSV is weight hourly space ve- Petrochemical Technology are involved in the paper.
locity, h 1; and is space velocity exponent.

The reactor model can be described by the global ma-
As to hydrogen partial pressure, it can be obtained: terial balance equations as follows; the details about

Ph =
(mH 2 / HC ) P
t
(25)
the axial fixed-bed reactor and the reactor model
derivation can be seen in Xu et al.[9].
1 + (mH 2 / HC )Y H2 da j Rb2 da j
= , a j (0) = a j 0 (39)
whre mH 2 HC is molar ratio of hydrogen-to-hydrocarbons, dl WHSV Vc L c dt
1
molmol ; Pt is total pressure at reactor inlet, kPa; where Rb is radius of catalyst bed, m; l is dimen-
and YH 2 is purity of cycle hydrogen based on molar, %. sionless length of bed; L is length of catalyst bed, m;
Vc is catalyst volume, m3; is feedstock density,
The temperature dependence of the rate constant, kgm 3; c is catalyst density in the bed, kgm 3. Eq.(39)

k, is described by the Arrhenius equation as are solved by numerical algorithm of fourth-fifth order
E Runge-Kutta.
ki = k0i exp ai , ( i = 17) (26) Because of the huge pressure drop in the axial
RT fixed bed, the Ergun equation[20] is added with these
where k0 represents frequency factor; Ea represents equations
activation energy, kJmol 1; R represents gas constant,

1 1
8.314Jmol K ; and T is reaction temperature, K. dP (1 ) 2 (1 )
= 1.75105 3 G + 1.50103 3 G
And for chemical equilibrium constant K, dz g d p g d p
M M
K1 = K ep1 B 2 X (27) (40)
M Tol
where is bed void fraction; is viscosity of gas
M B M EB passing through the bed, Pas; g is density of gaseous
K 2 = K ep2 2
(28) mixture through the reactor, kgm 3; dp diameter of

M Tol
catalyst particle, m; G is superficial mass velocity of
gases, kgm 2s 1.

M X2
K3 = K ep3 (29)
M Tol M TMB
2
3 MODEL PARAMETERS ESTIMATION
M EB 3.1 Catalyst deactivation parameters estimation
K 4 = K ep4 (30)
M Tol M TMB In the commercial operation of catalytic reactors,
the effects of catalyst inactivation are often encoun-
M X2 M C10 A tered by increasing the catalyst temperature with time
K 7 = K ep7 2
(31) on stream in order to achieve a constant conversion of
M TMB
reactant to products[21]. Hence the loss of catalyst
where M denotes molecular weight, gmol 1; Kep de-

activity is compensated by the raised reaction tem-
notes thermodynamic constant, and is determined by perature during long-term operation. In this case, Sz
G pe and Levenspie[22] derived an important condition
K epi = exp i , ( i = 14,7) (32) for the extremal policy as follows:
RT
where G is Gibbs free energy, kJmol 1.
d (k )
=0 (41)
As to PX isomerization, the concentration of iso- dt
mers [PX (p-xylene), MX (m-xylene), OX (o-xylene)]
which means that the effective rate constant should be
can be determined by the following:
kept unchanged during the entire process.
y As mentioned earlier, rate constants obey Ar-
K ep5 = OX (33)
yMX rhenius law and Eq.(41) can be rewritten as
y E
K ep6 = PX (34) k0 exp a = C (42)
yMX RT
June, 2007
 Kinetic Model and Simulation Analysis for Toluene Disproportionation and C9-Aromatics Transalkylation 329

Table 1 Operating conditions and feedstock composition

Time on stream, Reaction temperature, Reaction pressure, H2/HC, WHSV, H2 purity,
Date
molmol 1 h1

d MPa %
20050401 69 347.56 3.12 7.64 1.11 84.75
20050404 72 348.56 3.12 7.56 1.12 84.53
20050412 80 349.67 3.13 7.58 1.17 84.40
20050418 88 351.61 3.13 6.92 1.24 83.74
20050430 98 352.07 3.13 7.66 1.18 82.51
Components in feedstock (w, %)
Date
B Tol PB MEB TMB EB PX MX OX C10A Non-aromatics
20050401 0.01 58.28 1.98 12.78 22.77 0.03 0.06 0.15 0.92 2.65 0.37
20050404 0.00 58.71 2.18 13.33 21.87 0.01 0.01 0.03 0.33 3.12 0.41
20050412 0.03 58.80 2.05 13.33 22.45 0.00 0.01 0.01 0.20 2.58 0.54
20050418 0.01 59.64 1.90 12.73 22.57 0.00 0.01 0.01 0.26 2.49 0.38
20050430 0.00 60.12 1.84 12.87 22.35 0.01 0.01 0.02 0.25 2.50 0.03

The deactivation function is assumed to be in- k0 and parts of them are shown in Table 1. The fre-
variable in a certain day. This is absolutely reasonable quency factors are optimized by the differential vari-
because of the catalysts stable performance during able metric optimization method and the estimated
long-term operation. The function is supposed to be results are listed in Table 2. The detail procedures
1 at the conditions of t = 0 and T0 = 614.53K , then about parameter estimation can be found in Xu et al.[9].
E
k0 exp a = C (43) Table 2 Kinetic parameters of the model
RT0 Reaction ki, s1 k0i, s1 Eai, kJmol1
Substituting Eq.(24) into Eq.(42) and combining 1 326.222 9.1061010 102
Eq.(43), then rearranging, leads to the following 13
relationship 2 36.221 9.53410 150
3 554.664 5.7121010 96.77
1 1
Ea
t + ln Ph + ln WHSV = (44) 4 22.799 6.0011013 150
R
T0 T 5 227.994 6.1261010 101.8
Parameters can be estimated by the least square
6 381.221 3.2631010 95.8
method with large number of data from commercial
unit. In this case, the deactivation function becomes 7 5.369 3.213109 106

= exp(0.0006t ) Ph0.0022 WHSV 1.3781 (45)

In fact hydrogen prevents catalyst from coke
deposition in the commercial unit, but the hydrogen
pressure seems to have no effect on catalyst deactiva-
tion from the top equation. While the estimation of
pressure exponent above is reasonable, because the
hydrogen pressure is kept stable by and large during
operation and its hard to consider its function in the
empirical correlation. So the deactivation function
could be
1.3781
= exp(0.0006t ) WHSV
3.2 Kinetic parameters estimation
To decrease the difficulty of parameter estimation,
activation energies (Ea) are taken from the reported
paper[8,9] and only 7 frequency factors (k0) need to be
estimated. Nine sets of assay data first reconciled by
material balance from a commercial unit in Sinopec
Zhenhai Refining & Chemical Company Limited at
different operating conditions are applied to determine
4 MODELING RESULTS
4.1 Model validation
In order to demonstrate the efficiency of the de-
veloped model, two important performance indexes
are introduced, namely deviation (E) and average ab-
solute error (Eaae) as below
E = a j a j (47)
11
Eaae = a j a j (48)
j =1
(46)
where a j and a j denote the concentration of com-
ponent j and corresponding model output respectively.
The model is confirmed by simulation at different
operating conditions with the estimated parameters, and
the predictions are consonant with plant observations
greatly. The deviations vary from 1.79% to 1.24%
(by mass), while those from the model[9] developed
previously vary from 1.09% to 2.51% (by mass),
which convinces the better fitness of the proposed
Chin. J. Ch. E. 15(3) 326 (2007)
330 Chin. J. Ch. E. (Vol. 15, No.3)

model. The advantages of the model considering
catalyst fouling can also be seen from average abso-
lute errors. Details are shown in Table 3.
The simulation result of composition profile
through the reactor is shown in Fig.1. The plot is based
on the operating conditions from date of 20051004 in
Table 3. As shown in the plot, toluene disproportiona-
tion and C9-aromatics transalkylation result in de-
crease of feedstock, and at the same time lead to the
increase in products such as benzene and xylenes,
which agrees with the tendency observed in the com-
mercial unit quite well.

Table 3 Comparison of model prediction and plant observation

Time on stream, Reaction temperature, Reaction pressure, H2/HC, WHSV, H2 purity,
Date
d MPa molmol1 h1 %
20050122 0 341.38 3.11 7.90 1.04 88.66
20050701 159 353.80 3.13 8.05 1.15 83.29
20051004 252 357.79 3.14 7.10 1.29 81.56
Components in feedstock (w, %)
Date
B Tol PB MEB TMB EB PX MX OX C10A Non-aromatics
20050122 0.00 65.81 1.57 11.64 19.02 0.00 0.01 0.01 0.28 1.64 0.01
20050701 0.00 59.76 1.89 12.71 22.10 0.01 0.01 0.02 0.24 3.20 0.03
20051004 0.00 59.74 1.82 12.28 22.23 0.02 0.02 0.01 0.28 3.55 0.04
Components in reactant (w1, %) Average Pressure
Date absolute
B Tol PB MEB TMB EB PX MX OX C10A Non-aromatics drop, MPa
error, %
20050122 Ref.[9] 10.14 42.66 0.35 5.58 8.79 1.69 6.53 14.57 6.21 1.61 1.87 0.71
This
work 11.12 41.41 0.32 4.46 8.48 1.92 6.82 15.22 6.49 1.61 2.14 0.40 0.02

Obser. 10.76 40.15 0.02 4.60 8.72 2.35 6.76 15.50 6.56 2.70 1.90 0.029
20050701 Ref.[9] 9.39 38.53 0.27 4.74 9.73 2.25 7.06 15.75 6.72 3.12 2.45 0.26
This
work 9.76 38.30 0.36 4.60 10.09 2.25 7.03 15.69 6.69 3.13 2.10 0.23 0.032

Obser. 9.36 38.38 0.02 4.52 10.72 2.12 7.20 16.00 6.75 3.00 1.92 0.029
20051004 Ref.[9] 9.33 38.28 0.26 4.55 9.80 2.38 7.07 15.77 6.73 3.47 2.38 0.52
This
work 9.40 38.13 0.46 5.37 10.86 2.13 6.70 14.96 6.38 3.50 2.11 0.60 0.037

Obser. 8.58 37.53 0.02 4.09 10.86 2.01 7.50 16.75 7.06 3.43 2.15 0.029
Note: Obser. represents plant observations.

Figure 1 Profile of main component through reactor

Tol; MEB; TMB; EB; MX;

B; PB; PX; OX; C10A; non-aromatics

June, 2007
 Kinetic Model and Simulation Analysis for Toluene Disproportionation and C9-Aromatics Transalkylation
4.2 Simulation analysis
The kinetic model is useful for simulation analy-
sis of process variables, giving the guidance to select
suitable operating conditions. The effect of variables
such as on-stream time, reaction temperature, and
weight hourly space velocity on the process perform-
ance is investigated below.
The coke deposition on the catalyst surface is no-
ticed during long time operation. Activity of the catalyst
is reduced because of coke formation and the reaction
temperature must be raised to compensate the loss in
activity in order to maintain conversion at a certain level.
As expected, more coke accumulates as time goes on.
Generally speaking, the higher temperature is
favorable to the main reactions for their endothermic
character. As indicated in Fig.2, the same trend of total
conversion and temperature appears, but the conver-
sion goes no further in spite of increase in temperature
because of thermodynamic control reactions. Mean-
while, higher temperature causes more rapid catalyst
fouling; hence, balance between conversion and reac-
tion temperature should be kept during operation.
Figure 2 Effect of reaction temperature on
total conversion
WHSV affecting the reaction severity is relative
to the residence time with catalyst. The higher WHSV
results in the less severity of reaction and more depo-
sition of coke on the catalyst, which means that the
total conservation will be reduced. But fortunately it
will be compensated by increased reaction tempera-
ture. The typical relationship between temperature,
deactivation function and WHSV is shown in Fig.3.
As observed, deactivation function is decreased
markedly from 0.98 to 0.73 with WHSV varying from
1.04 to 1.29. At the same time, temperature is in-
creased to 358.03 from 341.38. Gain about 1 is
provided when 1t of feedstock is introduced.
Figure 3 Relationship between temperature,
deactivation function and WHSV
331
5 CONCLUSIONS
A rigorous kinetic model taking deactivation
function into account is developed and simulation re-
sults show validation of the model that supports reac-
tor design, process optimization and process control.
The simulation analysis of variables to process per-
formance is studied in the paper and the results indi-
cate the importance of maintaining the operating con-
ditions that would achieve a proper balance between
severity and catalyst activity, which directs our selec-
tion.
NOMENCLATURE
a mass fraction, %
a model output mass fraction, %
dp diameter of catalyst particle, m
E deviation
Ea activation energy, kJmol1
G superficial mass velocity of gases, kgm2s1
G Gibbs free energy, kJmol 1
K chemical equilibrium constant
Kep thermodynamic constant
reaction rate constant, s 1
k
k0 frequency factor, s1
L length of catalyst bed, m
l dimensionless length of bed
mH 2 HC molar ratio of hydrogen-to-hydrocarbons
Ph hydrogen pressure , kPa
Pt total pressure at reactor inlet , kPa
gas constant, 8.314Jmol 1K 1
R
Rb radius of catalyst bed, m
r reaction rate , h1
T reaction temperature, K
t on stream time, d
Vc catalyst volume, m3
WHSV weight hourly space velocity, h1
w eomponents in feedstock, %
w1 components in reactant, %
YH 2 purity of cycle hydrogen based on molar, %
y mole fraction, %
catalyst deactivation constant, d1
pressure exponent
space velocity exponent
bed void fraction
viscosity of gas passing through the bed, Pas
feedstock density, kgm3
c catalyst density in the bed, kgm3
g density of gaseous mixture through the reactor, kgm3
catalyst deactivation function
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