Kinetics of toluene disproportionation modeling and experiments

ARTICLE
pubs.acs.org/IECR
Kinetics of Toluene Disproportionation: Modeling and Experiments

Marcos W. N. Lob~ao, Andre L. Alberton, Slvio A. B. V. Melo, Marcelo Embiruc-u,
Jose L. F. Monteiro, and Jose Carlos Pinto*,
Programa de Engenharia Industrial, Escola Politecnica, Universidade Federal da Bahia, Rua Aristides Novis, no 2, Federac-~ao,
Salvador, 40210-630 BA, Brasil
Pontifcia Universidade Catolica do Rio de Janeiro, Rua Marquês de S~ao Vicente 225-371 L, Rio de Janeiro, 22451-900 RJ, Brasil
Programa de Engenharia Qumica/COPPE, Universidade Federal do Rio de Janeiro, Cidade Universitaria, CP: 68502,
Rio de Janeiro, 21941-972 RJ, Brasil
ABSTRACT: This work presents modeling and experimental studies on the kinetics of toluene disproportionation in operation
ranges that include real industrial operation conditions. The inuence of reaction temperature, reactor pressure, feed composition,
and residence time on conversion of reactants and product selectivity was investigated. Experiments were performed according to a
sequential experimental design strategy, in order to provide maximum accuracy for model predictions. Statistical treatment of
parameter estimates and model adequacy was performed with the help of maximum likelihood principles. Excellent agreement
between model predictions and available experimental data was obtained in the full ranges of investigated experimental conditions.
derived from mechanisms that consider toluene adsorption3,6,19

or surface reaction3,20 as the RDS. In all these studies, the catalysts
used to promote toluene disproportionation were based on
Y-zeolites,3,15,20 ZSM-5 zeolites,4,5,10,12 and more commonly
H-mordenite.68,10,11,13,14,1618
As briey reviewed above, although the kinetics of toluene
disproportionation has been investigated by several researches,
distinct reaction mechanisms have been proposed and distinct
kinetic models have been derived. Discrepancies can possibly be
ascribed to the dierent analyzed catalyst types, operating
conditions, conversion levels, and coking of catalysts; nevertheless, it is certain that agreement has yet to be reached
regarding the kinetics of toluene disproportionation over heterogeneous catalysts.
It is important to emphasize that many works published in
the literature were performed at low pressures and not at
the relatively high pressures practiced in real industrial
environments.47,12,15,19,20 When the operation conditions
resembled the actual industrial operation conditions, simplied models based on pseudohomogeneous approach were
proposed, specially for the study of catalyst deactivation.810
However, the use of simplied kinetic models leads to a
poorer ts, when compared to the LHHW and ER expressions. 19 Besides, as one can observe in Table 1, many
studies were performed at low toluene conversions, reducing
the reliability of the models for prediction of real industrial
operation conditions.
Based on the previous paragraphs, the use of LHHW models
to t experimental data obtained at operation conditions that
resemble the actual industrial conditions seems appealing. For
this reason, the main objective of the present work is to
1. INTRODUCTION
Toluene disproportionation is an important chemical transformation for most reneries and chemical complexes, constituting the heart of economically relevant commercial
processes used for direct production of aromatic products
and indirect manufacture of polymer resins, synthetic bers,
and plasticizers.1 The toluene disproportionation reaction can
be represented as
2T a B X
R1
where T is toluene, B is benzene, and X is xylenes. Toluene

disproportionation is performed commercially with the help of
heterogeneous catalysts.1,2 One of the most important processes is the Tatoray process, where typical industrial conditions include temperatures of 350530 C, pressures of
1050 bar, and H2/aromatic ratios between 5 and 12/1.1,2
The high hydrogen to aromatic ratio is necessary to avoid the
catalyst deactivation.3
Reliable kinetic studies are very important for design, analysis,
and control of the industrial process. Although most toluene
disproportionation technologies are mature, kinetics of toluene
disproportionation over heterogeneous catalysts is not completely understood even in ranges of experimental conditions
normally employed by industrial processes. Table 1 presents a
summarized review about the kinetic models proposed in the
literature, including the experimental conditions and the conversion ranges investigated by the authors.
Dierent kinetic models have been used so far to describe
the catalytic disproportionation of toluene. Many authors
proposed a pseudohomogeneous kinetics of rst order4,5
or second order610 with respect to the toluene partial pressure in order to describe the reaction rates. Good ts have
been reported for LangmuirHinshelwood-Hougen-Watson
(LHHW) kinetic rate expressions, derived from mechanisms
that consider surface reactions1118 as the rate determining
step (RDS), and EleyRideal (ER) kinetic rate expressions,
r 2011 American Chemical Society
Received: July 17, 2011

Accepted: November 7, 2011
Revised:
October 11, 2011
Published: November 07, 2011
171
dx.doi.org/10.1021/ie2015526 | Ind. Eng. Chem. Res. 2012, 51, 171183
Industrial & Engineering Chemistry Research
ARTICLE
Table 1. Kinetic Studies of Toluene Disproportionation over Zeolites Catalyst (Adapted from Marques17)
year
ref
catalyst
P (bar)
T (C)
kinetic modelsa
XT (%)
1979
(3)
HY/AlF3/Cu
211.1
400500
e22
E-R reaction surface or toluene adsorption as rds
1981
(7)
modied mordenite
350450
<45
pseudohomogeneous 2nd order
1981
(11)
mordenite
919
400
e10
L-H reaction surface as rds
1985
(12)
HZSM-5
240300
e10
L-H surface reaction as rds
1987
(6)
mordenite
350450
e25
pseudohomogeneous 2nd order/E-R

toluene adsorption as rds
1987
(13)
mordenite
530
360430
<45
1990
1990
(20)
(4)
HY and HY-Ni
HZSM-5
3
1
340500
502562
e10
e10
E-R reaction surface as rds

pseudohomogeneous 1st order
1990
(14)
mordenite
5.140.5
-c
e10
L-H surface reaction as rds
1993
(15)
HY
240320
e8
1993
(16)
mordenite
19.629.4
430
e33
1994
(5)
modied HZSM-5
450500
e15
pseudohomogeneous 1st order
1994
(17)
mordenite
528
390434
<38
2000
(19)
HZSM-5
475
e25
E-R toluene adsorption as rds
2004
2004
(8)
(9)
mordenite
-c
28.59
31.2d
397451
347352d
<55
-c

2007
(10)
mordenite and HZSM5
-c
300400
e30
2010
(18)b
mordenite
530
300380
<30
E-R: EleyRideal, L-H: LangmuirHinshelwood. b Also evaluating xylenes disproportionation. c Not reported. d Other investigated conditions not
reported.
investigate the kinetics of toluene disproportionation over a

commercial H-mordenite catalyst in a broader range of
experimental conditions, including the conditions normally
employed to perform the reaction in industrial sites. The
obtained experimental data are then used to build a kinetic
model in order to represent reaction rates in a wider range of
experimental conditions. A sequential experimental design
technique is used to select the experiments, to accelerate the
model building process, and to provide maximum accuracy
for model predictions.
estimated through minimization of the following objective

function (F)21,22
0
12
ipred i
iexp
Nexp Ny
yj xi , yj
x ,
B
C
F
1
@
A
i
i1 j1
y, j
where Nexp represents the number of experiments, Ny is the

number of response variables, y(i)
j is the response variable j for
(i)
(i)
is the standard deviation of variable y(i)
experiment i, y,j
j , and x
is the set of experimental design variables for experiment i. The
superscripts exp and pred represent the experimental value and
the value calculated with the model, respectively.
After minimization of the objective function and estimation of
the model parameters, it is possible to infer the uncertainties of
the parameter estimates. If the experimental errors are suciently small, the covariance matrix of parameter uncertainties,
V, can be calculated21,22
2
!T
!31
Nexp
1 yi
i
y
i
5
V 4
2
3 Vy
3
i1
2. PARAMETER ESTIMATION AND EXPERIMENTAL

DESIGN
Let us assume that a set of experiments has been performed.
The set of independent experimental conditions dened by the
analyst is represented here by x and named as the set of design
variables (reactor design, mass of catalyst, feed ow rates, reactor
temperature, and reactor pressure). The set of dependent
experimental conditions obtained by the analyst as the experimental results is represented here by y and named as the set of
response variables (outlet compositions). Variables x and y are
related to each other through the mass balance equations and the
kinetic model.
In order to analyze the available experimental data, the following hypotheses are assumed to be valid: (i) experimental
measurements are subject to random experimental errors, which
follow the normal distribution; (ii) experiments are well done, so
that gross and persistent errors are not present; (iii) the proposed
mathematical model is perfect, so that experimental measurements uctuate around model predictions; (iv) design variables
are well controlled and are not subject to signicant experimental
errors; and (v) experimental errors are not correlated to each
other. In this case, the set of kinetic parameters can be
where the matrix Vy(i) is the covariance matrix of experimental

uncertainties for experiment i. As it was assumed that experimental errors are independent
2
6
6
6
V i
y
6
4
172
y1 2
0
l
0
y2 2
l
0
333
333
0
l
333
yNy 2
3
7
7
7
7
5
dx.doi.org/10.1021/ie2015526 |Ind. Eng. Chem. Res. 2012, 51, 171183
ARTICLE
Table 2. Properties of the H-Mordenite Catalyst

parameter
value
acidity (mol NH3 3 g1)
0.225
pores volume (cm3 3 g1)
0.66
density (g 3 cm3)
surface area (m2/g)
1.33
330
Chemical composition
Si
18
Al
28
Fe, Zn, Ni, and Cu

Ca, Mg, K, Na
<0.2
<0.3
humidity
8.6
The diagonal elements of V represent the parameter uncertainties, while the nondiagonal elements of V represent the parameter correlations. Finally, the parameter uncertainties are transformed into uncertainties of model predictions as21,22

T
y
y
pred
Vy
4
V
3 3
Sequential experimental design strategies are used to select
experimental conditions that allow for discrimination of rival
models and/or estimation of model parameters with maximum
accuracy.21,2326 In short, experimental design techniques make
use of the available models to predict future experimental data
and infer the experimental conditions that can lead to the most
precise set of parameter estimates, avoiding the costs of performing experiments in regions where the information content is
low.2123 After selection of the experimental conditions, the
experiment must be performed and the model parameters must
be re-estimated. The procedure must be repeated iteratively until
attainment of the desired parameter precision or selection of the
best model candidate.
Several criteria can be used for design of experiments for
estimation of precise model parameters. The y-trace criterion
proposed by Pinto et al.27 is used in the present work. According
to this criterion, the optimal experimental condition is the one
that allows for minimization of the trace of matrix Vypred
presented in eq 4. As explained by Pinto et al.,27 this criterion
is focused on the model performance and does not necessarily
leads to the most precise set of model parameters but to the
lowest prediction uncertainties. As the trace of Vypred must be
calculated through model simulations, the eciency of the
experimental design technique depends strongly on the ability
of the model to predict the experimental data.
Figure 1. (A) Experimental apparatus and (B) reactor scheme.
into the reactor with the help of a metering pump (Whitey 1/3
HP), with ow rates in the range between 0 and 10 mL 3 min1.
The liquid stream was vaporized with the help of external
electrical resistances and mixed with the hydrogen stream. The
hydrogen/aromatic ratio (RHC) was set to 6 (in molar basis) in
all experiments.
A xed bed reactor was used to perform the reactions, as
illustrated in Figure 1B. The reactor was lled with three distinct
particle layers. The catalyst bed was placed between two beds of
silica of similar length. Silica particles presented the same average
diameter of catalyst particles. Experiments performed without
the catalyst (blank experiments) never led to any signicant
conversion of the reactants. The internal reactor temperature was
monitored and controlled with 3 type-J thermocouples placed at
the three solid layers, as shown in Figure 1B. The reactor was
placed in a vessel containing uidized alumina pellets and
electrical resistances for improved control of the reactor temperature. Additional details about the experimental apparatus can
be found elsewhere.13
3. METHODOLOGY
3.1. Experimental Setup and Procedure. The acidity, pore
volume, surface area, and chemical composition of the catalyst
are presented in Table 2. The catalyst used in the present work is
a commercial H-mordenite grade presenting low concentrations
of Ca, K, and Na, which indicate that hydrogen constitutes the
only compensation cation in the catalytic system. The catalyst
presents a low atomic Si/Al ratio of 0.62. Additional details on
the catalyst properties are described elsewhere.13
Reaction experiments were carried out in a laboratory unit, as
illustrated in Figure 1A. Aromatic compounds (toluene, benzene,
xylenes) kept in the liquid phase in a storage reservoir were fed
173
ARTICLE
where s represents a catalyst site and RDS indicates the rate

determining steps. According to the mechanism presented in R3,
the following rate expressions could be derived for toluene and
xylenes disproportionation reactions
The outlet stream was condensed, and samples of the liquid

stream were analyzed with the help of a CG-25 gas chromatograph equipped with a thermal conductivity detector (TCD).
Hydrogen was used as the carrier gas. The chromatograph
columns were made out of bentona 34 on chromosorb P, suitable
for separation of aromatic compounds.28
A reference experiment was performed every three experiments in order to guarantee that no signicant deactivation of the
catalyst had occurred. Whenever observed conversion deviations
were larger than 5% for the reference experimental condition, the
catalyst bed was replaced and the previous three experiments
were discarded. Experiments performed with catalysts of dierent sizes and with dierent ow-rates13,29 indicated that the
external and internal resistance to mass transfer were not
signicant at the analyzed operation conditions.
3.2. Modeling. The starting point of this work was the study
developed by Krahl,13 who investigated the gas phase disproportionation of toluene on a commercial H-mordenite catalyst
and proposed LHHW kinetic rate expressions to fit the obtained
experimental data. As observed experimentally, the product
distribution could be described very well by the kinetic model
derived from the following reaction mechanism
2T a B X
R1
2X a T TMB
R2
r1
r2
k2 3 KX2 3 PX2 PT 3 PTMB =KEX

1 KT 3 PT KX 3 PX KB 3 PB KTMB 3 PTMB 2
where r1 and r2 are the reaction rates for toluene and xylenes,
respectively; k1 and k2 are kinetic rate parameters; Kj is the
adsorption equilibrium parameter for component j; Pj is the
partial pressure of component j (j = T, X, B, TMB); and KET and
KEX are the reaction equilibrium constants for toluene and
xylenes disproportionation, respectively.30 The kinetic rate parameters (k1 and k2) and adsorption equilibrium parameters (Kj) can
be described as function of the reactor temperature
where TMB is a pool of trimethylbenzenes. The author proposed

several reaction mechanisms and derived a number of LHHW
and ER kinetic models to explain the available data, but the best
results were obtained with the following reaction scheme
T s a Ts
2Ts a Bs Xs RDS
Bs a B s
Xs a X s
2Xs a Ts TMBs RDS
TMBs a TMB s
k1 3 KT2 3 PT2 PB 3 PX =KET

1 KT 3 PT KX PX KB 3 PB KTMB 3 PTMB 2
ki PFi 3 eEi =R 3 TK , i 1, 2
Kj
eSj =R Hj =R 3 TK , j T, X, B, TMB
bar 1
where PFi is the pre-exponential factor, and Ei is the activation

energy for reaction i; Sj is the entropy and Hj is the enthalpy
of adsorption for component j, and TK is the reactor temperature. Correlation between pre-exponential factors and activation energies can be minimized if the rate expressions are
reparameterized as3133
R3

TK Tr
TK
2
e
r1
3 PT PB3 PX =KET
!0

12
TK Tr
TK Tr
TK Tr
TK Tr
mol
A
B
A
B
A
B
A
B
T
T3
X
X3
B
B3
TMB
TMB 3
B
C
TK
TK
TK
TK
gcat 3 h 3 bar 2
B
C
e
e
e
B1 e
C
P
P
P
P
T
X
B
TMB C
3
3
3
3
B
bar
bar
bar
bar
@
A
A1 B1 3
9

TK Tr
TK
2
e
r2
3 PTMB =KEX
3 PX PT
!0

12
TK Tr
TK Tr
TK Tr
TK Tr
mol
A
B
A
B
A
B
A
B
T
T3
X
X3
B
B3
TMB
TMB 3
B
C
TK
TK
TK
TK
gcat 3 h 3 bar 2
B
C
e
e
e
B1 e
C
P
P
P
P
T
X
B
TMB
3
3
3
B
C
bar
bar
bar
bar
@
A
A2 B 2 3
10
where A1, B1, A2, B2, AT, BT, AX, BX, AB, BB, ATMB, and BTMB are
the parameters that must be estimated and Tr is a reference
temperature, made equal to 666.9 K in order to minimize the

correlation between the parameter estimates.3133 The values of
174
ARTICLE
Table 3. Sequence of Designed Experiments in the Temperature of 360 C, with y-Trace Criterion
aromatic molar fractions in the feed
P (bar)
(gcat 3 h/garomatic)
31.19
0.0563
30.54
0.1000
30.82
0.2300
30.93
yT
yB
aromatic molar fractions outlet

yX
RHC
yT
yX
7.06
0.9749
0.0117
6.43
0.9524
0.0228
6.15
0.8991
0.0519
0.3630
6.21
0.8697
0.0685
30.87
0.3900
6.53
0.8587
0.0671
30.14
0.1497
6.16
0.0797
0.8422
30.22
0.2500
6.03
0.1211
0.7616
30.22
10.18
0.0970
0.1496
0
0
0
0
1
1
5.98
6.03
0.0574
0.024
0.8863
0.9519
10.18
0.2503
5.94
0.0314
0.9375
5.30
0.1994
5.94
0.0128
0.9736
5.20
0.2989
5.97
0.0199
0.9603
5.30
0.4000
6.07
0.0264
0.9469
30.22
0.0996
0.6081
0.3919
6.12
0.5968
0.0050
30.12
0.1991
0.6081
0.3919
5.98
0.5840
0.0113
30.12
0.2988
0.6081
0.3919
6.05
0.5733
0.0165
the kinetic parameters presented in eqs 9 and 10 can be recovered

from the estimated parameter values as
PF1 eA1 2 3 AT B1 2 3 BT
11a
E1 B1 2 3 BT 3 R 3 Tr
11b
PF2 eA2 2 3 AX B2 2 3 BX
11c
E2 B2 2 3 BX 3 R 3 Tr
11d
Sj R 3 Aj Bj , j T, X, B, TMB
11e
Hj Bj 3 R 3 Tr , j T, X, B, TMB
11f
3.3. Numerical Procedures. The set of ordinary eqs 12a-12d

was solved numerically with a fourth-order RungeKutta
method.35 The relative precision of the integration was always
better than 1.0 105. Model parameters were estimated as
described in Section 2, using the well-known GaussNewton
method.21,22 Distinct initial guesses were used in order to avoid
local minima. The relative precision of the estimation step was
always better than 1.0 104. All numerical procedures were
implemented in Fortran.36
3.4. Experimental Design. As the number of model parameters to be estimated was high, it was convenient to group the
model parameters in terms of the reactor temperature. Analyzed
reaction temperatures were equal to 360, 380, 404, and 431 C,
based on the work of Krahl.13 For the temperature level of
360 C, sixteen experiments were carried out, including the data
reported by Krahl,13 which were generated without the proposition of statistical experimental designs. For temperatures of 380,
404, and 431 C, the following experimental design procedure
was adopted:
(i) a set of initial experiments was selected, including data
reported by Krahl;13
(ii) the set of experiments was performed;
(iii) model parameters were estimated and the results evaluated;
(iv) for a given temperature, the experimental design procedure was interrupted when suciently low prediction
errors had been obtained;
(v) otherwise, a new experiment was designed, as described in
Section 2, before returning to step (ii).
Some experiments were also performed for feeds containing
mixtures of toluene and benzene, in order to estimate the
parameters KB and KX independently. Experimental conditions
are presented in Tables 36.
In order to perform step (iv), it was assumed that reaction
conditions could be manipulated in the following ranges:
the total pressure (P) could assume the values of 5, 10, and
30 bar, which are typical values of real industrial operations;1,2
The reactor was described as a standard plug ow reactor

(PFR), which was supported by the high Peclet number (above
80) and the large ratio between the reactor diameter and the
catalyst pellet diameter (higher than 20).34 Thus, the individual mass balance equations could be written as
1 dyT
r2
r1
M 3 d
2
12
1 dyX
r1
r2
3
M d
2
0

3 3 yB 2 3 y0T y0X 2 3 yT yX
yB
3
12b
yTMB 1 yB yT yX
12d
12c
where y T, yX, yB, and yTMB are the molar fractions of species T,
X, B, and TMB, respectively, considering only the aromatics
species; is the spatial time (in gcat 3 h/garomatic); and M is the
mean molecular weight of the aromatic feed. The terms y 0T, y0X,
and y0B represent the feed conditions of yT, y X and yB.
175
ARTICLE
P (bar)
30.55
0.3590
30.68
0.1900
30.42
0.1070
30.97
0.0516
30.97
yT
yB

yX
RHC
yT
yX
5.82
0.7472
0.1182
5.91
0.8369
0.0802
6.51
0.8954
0.0509
6.61
0.9496
0.0236
0.0475
5.96
0.9468
0.0258
30.24
0.2667
0.6041
0.3959
6.61
0.5516
0.0361
30.14
0.1005
0.6041
0.3959
6.66
0.5795
0.0169
5.399
5.399
0.3992
0.1999
1
1
0
0
0
0
6.25
6.10
0.9685
0.9810
0.0167
0.0099
10.28
0.2975
5.89
0.9562
0.0219
10.28
0.1051
6.53
0.9796
0.0104
30.14
0.2574
6.09
0.2215
0.5558
30.14
0.0998
6.09
0.1308
0.7429
30.24
0.1497
6.09
0.1599
0.6833
10.38
30.12
0.1497
0.0500
0
0
0
0
1
1
6.02
6.04
0.0756
0.0624
0.8525
0.8775
Initial Set of Experiments
Designed Experiments
P (bar)
30.14
0.4060
31.05
0.3590
30.93
0.2350
30.90
31.54
0.0977
0.0512
30.14
30.24
yT
yB

yX
RHC
yT
yX
6.56
0.6216
0.1713
5.90
0.6379
0.1693
6.49
0.7074
0.1410
1
1
0
0
0
0
5.99
6.20
0.8354
0.9013
0.0820
0.0499
0.1008
0.6046
0.3954
6.09
0.5449
0.0343
0.2608
0.6092
0.3908
6.35
0.5015
0.0586
5.50
0.3992
6.24
0.9442
0.0289
5.40
0.1995
6.08
0.9688
0.0152
10.28
0.2961
5.96
0.9077
0.0464
10.28
0.1009
6.14
0.9575
0.0212
30.14
30.24
0.2514
0.1499
0
0
0
0
1
1
6.06
6.13
0.2493
0.2309
0.4790
0.5298
30.14
0.0988
6.07
0.1880
0.6224
10.78
0.1494
6.07
0.1378
0.7301
30.22
0.0499
6.06
0.1282
0.7477
the spatial time () could assume the values of 0.05, 0.1,

0.15, 0.2, and 0.25 gcat 3 h 3 garomatic1, in order to allow for
wide variation of conversions;
feed could be composed of pure toluene or xylenes or mixed
charges of toluene/benzene with molar ratios of 9/1, 8/2, 7/
3, 6/4, 5/5 and toluene/xylenes with molar ratios of 7/3, 5/
5 in order to allow for estimation of parameters associated
with the adsorption constants of chemical species

independently.
Only new experimental conditions could be designed in step
(iv), which means that selection of replicates was forbidden. It is
also important to emphasize that experiments performed with a
pure xylenes feed can allow for improved estimation of the
parameters associated to the products.
176
ARTICLE
P (bar)
30.88
0.0911
20.61
0.1650
15.27
0.3990
31.30
0.0298
30.76
yT
yB

yX
RHC
yT
yX
5.94
0.7164
0.1361
6.23
0.6978
0.1410
6.10
0.6058
0.1783
5.77
0.8709
0.0612
0.2500
5.96
0.5676
0.1943
20.86
0.0387
5.60
0.8939
0.0507
20.57
0.2860
6.27
0.6078
0.1772
5.59
5.63
0.0590
0.3790
1
1
0
0
0
0
6.35
5.62
0.9691
0.8216
0.0149
0.0886
15.35
0.0490
6.01
0.8943
0.0515
15.21
0.2320
5.64
0.6910
0.1485
10.69
0.0540
6.27
0.9288
0.0365
5.67
0.2200
6.11
0.8930
0.0533
10.36
0.3770
6.51
0.6964
0.1479
10.53
0.1950
5.46
0.7946
0.0968
30.14
30.14
0.1518
0.2328
0.5
0.5
0.5
0.5
0
0
6.12
6.14
0.4187
0.3985
0.0485
0.0602
30.14
0.2007
0.6011
0.3989
6.06
0.4597
0.0770
30.12
0.1000
6.05
0.2476
0.4883
30.12
0.1495
6.03
0.2546
0.4675
10.18
0.0998
6.07
0.1692
0.6653
30.22
0.0499
6.09
0.2051
0.5872
5.20
10.18
0.0996
0.1505
0
0
0
0
1
1
5.96
6.03
0.0991
0.2095
0.8086
0.5843
5.20
0.1497
5.96
0.1265
0.7538
4. RESULTS
First, replicated experiments were performed in order to
determine the experimental uncertainty of response variables
(conversions of toluene and xylenes). For all experimental runs,
three samples were collected for chromatographic analysis. Besides, for one predened standard condition of = 0.08 gcat 3 h 3
garomatic1, T = 431 C, P = 30 bar and pure feed of toluene,
replicates of the whole experiment were performed. Based on the
previous steps, it was observed that a suitable value for the
standard deviations for toluene and xylenes molar fractions were
approximately equal to T X 1 102. It must be
emphasized that the experimental error is of fundamental
importance for evaluating model adequacy and parameter signicance, as described in Section 2. It is true that experimental
errors may depend on the experimental conditions;37 however,
the determination of experimental uncertainties in all investigated conditions is not possible in most kinetic studies.38 Besides,
as shown below, the excellent agreement between predicted and
observed values strongly suggests that the hypothesis of constant
experimental variability is appropriate.
Tables 36 present the experimental results for each analyzed
temperature level, including the initial set of experiments and the
sequentially designed experiments. Although the main focus of
the present work was the analysis of the toluene disproportionation, the xylenes disproportionation was also investigated
because the y-trace criterion indicated that feeding of pure

xylenes could lead to improved estimation of model parameters
(such as the adsorption constants KX and KTMB). As one can also
see in Tables 36, sequentially designed experiments led to
experimentation at distinct pressure, residence time, and feed
composition levels, allowing for good exploration of the experimental region.
Although experiments were grouped in terms of the reactor
temperatures, obtained model parameters and experiments were
used afterward for more involving estimation of parameters for
the nonisothermal case. Parameter values and their respective
standard deviations are presented in Tables 79. Table 7 shows
the parameter values obtained at each particular temperature
level after the end of the sequential design procedure.
The trajectories of model parameters for the designed experiments are presented in Figure 2. It can be observed that the
determinants of the covariance matrix of parameter uncertainties
tend to decrease as additional experimental results are accumulated, indicating the improved precision of parameter estimates.
The oscillatory behavior of the determinant values can be
associated with signicant changes of the parameter estimates,
as dierent experimental conditions are inserted into the experimental set. Figure 2 also indicate that parameter uncertainties
approach minimum limiting asymptotic values, justifying the
interruption of the sequential experimental design.
177
ARTICLE
Table 7. Estimated Kinetics Parameters for Individual

Temperatures
parameter
mean
standard value
Table 8. Estimated Kinetic Parameters and Respective Standard Deviations and Coecients of Variation
coecient of variation (%)a
parameter
Temperature of 360 C
k1KT2
3.359 104
2.907 104
86.54
KT
k2KX2
9.094 103
2.675 103
1.150 101
2.191 104
1265
8.191
KX
2.379 101
2.909 102
12.23
KB
3.167 101
2.374 101
74.96
KTMB
4.555 101
2.654 101
58.27
k1KT2
1.154 103
1.996 104
17.30
KT
6.438 102
3.025 102
46.99
2
1.781 103
12.53
KX
KB
4.751 101
2.044 101
5.192 102
6.993 102
10.93
34.21
KTMB
4.466 101
1.329 101
29.77
k2KX
1.422 10
2.80 10
2.68 104
9.60
1.08 101
2.15 102
19.90
2
2.64 10
2.40 103
9.09
KX
3.75 101
3.98 102
10.63
KB
KTMB
1.45 101
9.42 101
4.01 102
1.34 101
27.56
14.24
k1KT
KT
k2KX
k1KT
1.358 10
2
6.140 10
4
A1
5.980
0.071
1.18
B1
AT
30.700
1.960
1.450
0.132
4.72
6.73
BT
12.900
2.760
21.40
A2
4.160
0.057
1.37
B2
27.200
1.180
4.34
AB
1.290
0.151
11.71
BB
7.410
3.350
45.21
AX
1.130
0.075
6.67
BX
ATMB
0.021
0.584
1.470
0.176
7067.31
30.14
BTMB
17.800
3.010
16.91
Table 9. Pre-Exponential Factors, Activation Energies, and

Entropies of Adsorption and Enthalpies of Adsorption Recovered from the Parameter Estimates Presented in Table 5
parameter
PF1 (mol 3 gcat1 3 h1 3 bar2)
E1 (J 3 mol1)
1
1
ST (J 3 K
3 mol )
HT (J 3 mol1)
0.05
KT
2.983 101
1.959 102
0.07
PF2 (mol 3 gcat1 3 h1 3 bar2)
k2KX2
6.248 102
3.774 103
0.06
E2 (J 3 mol )
KX
2.963 101
5.865 102
0.20
1
2
KB
4.484 10
KTMB
1.324
4.113 10
1.745 101
coecient of variation (%)a
Coecient of variation is calculated as the standard deviation divided

by the mean value multiplied by 100.
2
standard deviation
3
mean
1
1
1
SB (J 3 K
3 mol )
HB (J 3 mol1)
SX (J 3 K1 3 mol1)
0.09
0.13
HX (J 3 mol1)
Coecient of variation is calculated as the standard deviation divided

by the mean value 100.
STMB (J 3 K1 3 mol1)

HTMB (J 3 mol1)
As one can see in Table 7, all parameters could be obtained

with good precision (except KT at 360 C). Precision of model
parameters was better at higher temperatures, probably as a
consequence of the higher sensibility of response variables with
respect to the experimental conditions presented in Tables 36.
Besides, the number of experimental runs was higher at 431 C.
Table 8 presents the values and precisions of parameters
estimated with all available experimental data. As one can
observe, most parameters could be estimated with very good
precision. Good estimation was obtained for parameters A1 and
B1, related to k1 3 KT2; A2 and B2, related to k2 3 KX2; AT and BT,
related to KT; and ATMB and BTMB, related to KTMB, whose
coecients of variation fell between 1.18% to 21.40%. Good
estimation was obtained for parameter AB, but BB was estimated
with coecient of variation of 45%. Parameter AX was estimated
precisely, but parameter BX could not be estimated with good
precision. Figure 3 presents the ratio between the kinetic
and adsorption constants at temperatures of 431 and 360 C.
One can observe the much larger variations of the kinetic rate
constants, showing the higher sensitivity of kinetic rate constants
to temperature (and the highest precision as a consequence) as
compared to the adsorption constants. On the other hand, the
mean
17.12
27.17 103
90.96
71.53 103
101.33 109
151.04 103
50.88
41.09 103
9.57
115.33
143.13
98.69 103
parameter KB was not very sensitive to the experimental conditions, which explains the large uncertainty of BX. Since the
parameter KX did not vary signicantly in the analyzed experimental range, a single constant value could be adopted for this
parameter in the temperature range investigated here.
Table 9 presents the parameters PFi, Ei (i = 1,2), Sj, and Hj
(j = T,B,X,TMB) that correspond to the values presented in
Table 8. It can be observed in Table 9 that there are some
apparent thermodynamic inconsistencies in the estimated entropy and enthalpy of adsorption for several compounds. According to the literature,39 spontaneous adsorption must be
exothermic (H < 0) as the entropy of adsorption is negative
(S < 0). Apparent thermodynamic inconsistencies have been
reported in other kinetic studies40,41 and used to discard the
investigated models.4246 It must be pointed out, however, that
constraints can be imposed on the estimation problems in order
to avoid such thermodynamic inconsistencies,18 which means
that numerical procedures can be used to force the proposed models
to obey the imposed constraints. Nevertheless, as extensively
discussed by Pinto et al.,38 there may be no fundamental theoretical
basis for implementation of similar procedures, since the kinetic
178
ARTICLE
Figure 2. Determinant of covariance matrix of parameter uncertainties

as function of the number of designed experiments (for T = 431 C, the
rst design experiment was 18).
Figure 4. Experimental output molar fractions for (A) toluene feed and
(B) xylenes feed.
eventually obtained for all estimated model parameters when

simple reaction mechanisms and usual adsorption models are
proposed.
The results presented so far illustrate typical problems of
kinetic studies related to the precise estimation of the model
parameters. Moreover, obtained results suggest that the evaluation of phenomenological aspects based solely on the parameter
values of models tted to available data should be performed very
carefully. Thermodynamic inconsistency strongly suggests that
the proposed model is likely to be incorrect, from the phenomenological point of view; nonetheless, even if all parameters are
thermodynamic consistent, this does not guarantee that the
proposed model is phenomenologically correct. Actually, if one
is not interested in the fundamental phenomenological aspects of
the proposed model, it seems reasonable to focus primarily on
the predictive capacity of the proposed models.
It can be observed in Table 10 that activation energies reported
in the literature lie in the range between 43 and 118 kJ/mol, while
the value obtained in the present work is close to 27 kJ/mol.
However, for complex models, such as the LHHW model used
here, parameter estimates are correlated to each other, making
comparison with previously published material questionable, as
extensively discussed by Pinto et al.38 Even when very simple
models are compared to each other, dierent parameter values can
be found, depending on the analyzed experimental range and
operation conditions. For example, Gnep and Guisnet11 found
that the kinetics of disproportionation depended strongly on the
catalyst type and on its pretreatment. Particularly, it was found that
the reaction order decreased with the wet-air or dry-air pretreatment of the mordenite catalyst prepared from uorinated alumina,
making the interpretation of kinetic orders doubtful.
Figure 3. Ratio between model parameters at the maximum temperature of 431 C and the minimum temperature of 360 C.
model is a necessary simplication of reality. Thus, the proposition of kinetic models is almost always the result of arbitrary
assumptions, so that thermodynamic consistency can eventually
constitute a numerical trick of the kinetic formalism, especially
when it can be corrected with the help of numerical techniques at
the expense of the quality of the model t. In this sense, one could
always argue that the quality of model tting is more important
than the thermodynamic consistency of estimated parameters if
the extensive investigation of the experimental region has been
carried out. This point of view is adopted in this work. Therefore,
the proposed modeling procedure privileges the model t and
the regression analysis of the model parameters. In fact, excellent
agreement is reached between model predictions and the experimental data, as shown in Figure 4 in wide ranges of toluene and
xylenes conversions. One can also observe that systematic
deviations and outliers cannot be identied in Figure 4, as
assumed in Section 2.
It must be clear, though, that thermodynamic consistency
should be expected in exact phenomenological kinetic models,
which are rarely available, especially when the reaction mechanisms are complex. If thermodynamic consistency is not obtained
for a given kinetics, either the model hypotheses are not adequate
(reaction network, choice of the rate determining step, etc.) or the
adopted adsorption theory is not the most appropriate. In such
case, other models might be tested by the analyst, if the analyst is
not satised with the obtained model performance, although it
cannot be guaranteed that thermodynamic consistency will be
179
ARTICLE
Table 10. Activation Energies for Toluene

Disproportionation
ref
activation energy (kJ/mol)
this work
27.17
(3)
(4)
88.00
118.71
(5)
64.79
(7)
60.61
(8)
104.50
(9)
102.00
(10)
54.22
(12)
84.85
(13)
(14)
117.04
43.47
(19)
99.00
(20)
87.78
Figure 7. Experimental (symbols) and simulated (line) toluene conversions with feed of toluene+H2 at 10 bar as a function of spatial time
for several temperatures.
Figure 8. Experimental (symbols) and simulated (line) toluene conversions with feed of toluene+H2 at 5 bar as a function of spatial time
for several temperatures.
Figure 5. Experimental (symbols) and simulated (line) toluene conversions with feed of toluene+H2 at (A) 30 bar as a function of spatial
time for several temperatures.
Figure 9. Experimental (symbols) and simulated (line) conversions at

431 C with feed of toluene+H2 at several pressures.
Figure 6. Experimental (symbols) and simulated (line) toluene conversions with feed of toluene+benzene+H2 at 30 bar as a function of
spatial time for several temperatures. (For T = 431, yT = 0.5, and yBZ =
0.5 and for other temperatures yT = 0.6 and yBZ = 0.4).
accurate matrix inversions demanded by the parameter estimation procedure is feasible only when the reparametrization is
performed. Particularly, pre-exponential factors and activations
energies of the Arrhenius equation are correlated strongly,
demanding reparametrization for achievement of good parameter estimation.3133 In the present problem, the estimation
of model parameters without reprarametrization was not possible, so that it was not possible to determine the standard
deviation of the original model parameters, such as the activation
energy and pre-exponential factors presented in Table 9. The
alternative technique of error propagation could be used but
It is important to emphasize that reparametrization makes the

estimation of model parameters easier, since the correlations
between parameters can be signicantly reduced (and sometimes
removed). However, reparameterization does not lead to improvement of model predictions, as the model remains essentially the same. Despite that, reparameterization is appealing for
numerical and statistical reasons.3133 In fact, in some cases
180
ARTICLE
Figure 12. Experimental (symbols) and simulated (line) conversions as

a function of spatial time for several temperatures at 5 bar with feed of
xylenes+H2.

xylenes+H2.
of toluene conversions with respect to pressure decreases. This

can be explained in terms of eqs 9 and 10, as reaction rates
increase with the square of the system pressure when the partial
pressures are close to zero and are insensitive to pressure changes
when the partial pressures grow to innity. Similar results are
observed in Figures 58.
Similarly, Figures 1012 present xylenes conversions for
experiments carried out with pure xylenes in the feed. As one
can observe in Figures 1012, the eects of operation conditions
on xylenes disproportionation are very similar to the eects
observed for toluene disproportionation over H-mordenite. The
comparison between Figures 5 and 10, Figures 7 and 11, and
Figures 8 and 12 indicates that the rates of xylenes disproportionation are always higher than the rates of toluene disproportionation for similar experimental conditions. This can only be
explained in terms of the parameter values in the investigated
experimental ranges, given the relative complexity of the kinetic
rate expressions and the thermodynamic reversibility of the
reactions. A possible mechanistic explanation can be related to
a simple statistical eect, as xylene molecules present two methyl
groups available for disproportionation, while toluene molecules
present only one methyl group. A second eect can be related to
the well-known electron-donor eect of methyl groups, which
can lead to more eective adsorption of xylene molecules onto
the catalyst.
Based on the available experimental results, it is possible to
perform sensitivity analyses regarding the inuence of the
analyzed experimental conditions on the conversion of toluene
and/or xylenes in specied experimental regions. For instance,
when Figures 5 and 9 are compared, an increase of 10 bar has
approximately the same impact on toluene conversion as an
increase of 50 C, at the contact time of 0.3 (h 3 gcat/gAromatic).
However, it is important to emphasize that the sensitivity to
experimental conditions change in the analyzed experimental
range. For this reason, the kinetic rate expressions obtained in the
present work can be used in the near future for more involving
optimization and sensitivity analysis studies.
As shown in Figures 412, excellent model ts to experimental data can be obtained in all cases. Therefore, the model
presented here can be used successfully for representation of
obtained experimental data in the investigated operation range.
Therefore, the model can be used with condence for simulation,
process design, process control, and interpretation of industrial
and laboratorial reactors.

xylenes+H2.
would lead to unrealistic estimation of parameter uncertainties,

since the original nonlinear transformations in eq 11 must be
linearized when error propagation is performed. For this reason,
it is dicult to compare the data presented in Table 10 based on
rigorous statistical grounds.
Figures 58 show toluene conversions as functions of the
spatial time at dierent temperatures and pressures. As shown in
Figures 58, the increase of temperature signicantly increases
toluene conversions in all the investigated experimental conditions. A comparison between Figures 5 and 6 for similar pressures
and temperatures reveals that the presence of benzene reduces
the conversion of toluene very signicantly. According to eq 9,
the increase of the partial benzene pressure leads to reduction of
the reaction rates because of both the adsorption term in the
denominator and the thermodynamic equilibrium term in the
numerator. According to Figure 6, the inuence of temperature is
much less pronounced when benzene is present in the feed.
Particularly, when temperatures are in the range between 404
and 431 C, toluene conversions are essentially constant because
of the higher amounts of benzene in the feed in the experiment
performed at 431 C.
The inuence of pressure on toluene conversions can be
visualized in Figure 9, where the toluene conversions at 431 C
are presented as functions of the spatial time at dierent
pressures. Figure 9 clearly shows that the increase of the pressure
leads to signicant increase of toluene conversions. As observed
in Figure 9, with the increase of reaction pressure, the sensitivity
181
ARTICLE
4. CONCLUSIONS
The kinetics of toluene and xylenes disproportionation over a
commercial H-mordenite catalyst has been investigated with the
help of sequential experimental design procedures in a wide
range of operation conditions. The inuence of reaction temperature, reactor pressure, feed composition, and residence time
on conversion of reactants and product selectivity was investigated. Experiments were performed according to a sequential
experimental design strategy, in order to provide maximum
accuracy for model predictions. Statistical treatment of parameter estimates and model adequacy was performed with the
help of maximum likelihood principles. Excellent agreement
between model predictions and available experimental data was
obtained in the full ranges of investigated experimental conditions, although thermodynamic consistency of parameter estimates was not observed in some cases.
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AUTHOR INFORMATION
Corresponding Author
*Phone: 55-21-25628337. Fax: 55-21-25628300. E-mail: pinto@

peq.coppe.ufrj.br.
ACKNOWLEDGMENT
The authors thank CNPq Conselho Nacional de Desenvolvimento Cientco e Tecnologico, CAPES Coordenac-~ao de
Aperfeic-oamento de Pessoal de Nvel Superior, and FAPERJ
Fundac-~ao Carlos Chagas Filho de Apoio a Pesquisa do Estado do
Rio de Janeiro, for providing scholarships and supporting this work.
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Kinetics of toluene disproportionation modeling and experiments

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Kinetics of toluene disproportionation modeling and experiments

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ARTICLE

Kinetics of Toluene Disproportionation: Modeling and Experiments

derived from mechanisms that consider toluene adsorption3,6,19

where T is toluene, B is benzene, and X is xylenes. Toluene

Received: July 17, 2011

dx.doi.org/10.1021/ie2015526 | Ind. Eng. Chem. Res. 2012, 51, 171183

Industrial & Engineering Chemistry Research

E-R reaction surface or toluene adsorption as rds

pseudohomogeneous 2nd order

L-H reaction surface as rds

L-H surface reaction as rds

pseudohomogeneous 2nd order/E-R

L-H reaction surface as rds

E-R reaction surface as rds

L-H surface reaction as rds

L-H reaction surface as rds

L-H reaction surface as rds

pseudohomogeneous 1st order

L-H reaction surface as rds

E-R toluene adsorption as rds

pseudohomogeneous 2nd order

mordenite and HZSM5

pseudohomogeneous 2nd order

L-H reaction surface as rds

investigate the kinetics of toluene disproportionation over a

estimated through minimization of the following objective

where Nexp represents the number of experiments, Ny is the

2. PARAMETER ESTIMATION AND EXPERIMENTAL

where the matrix Vy(i) is the covariance matrix of experimental

dx.doi.org/10.1021/ie2015526 |Ind. Eng. Chem. Res. 2012, 51, 171183

Industrial & Engineering Chemistry Research

Table 2. Properties of the H-Mordenite Catalyst

acidity (mol NH3 3 g1)

pores volume (cm3 3 g1)

surface area (m2/g)

Fe, Zn, Ni, and Cu

Figure 1. (A) Experimental apparatus and (B) reactor scheme.

dx.doi.org/10.1021/ie2015526 |Ind. Eng. Chem. Res. 2012, 51, 171183

Industrial & Engineering Chemistry Research

where s represents a catalyst site and RDS indicates the rate

The outlet stream was condensed, and samples of the liquid

k2 3 KX2 3 PX2 PT 3 PTMB =KEX

where TMB is a pool of trimethylbenzenes. The author proposed

k1 3 KT2 3 PT2 PB 3 PX =KET

where PFi is the pre-exponential factor, and Ei is the activation

temperature, made equal to 666.9 K in order to minimize the

dx.doi.org/10.1021/ie2015526 |Ind. Eng. Chem. Res. 2012, 51, 171183

Industrial & Engineering Chemistry Research

aromatic molar fractions outlet

the kinetic parameters presented in eqs 9 and 10 can be recovered

3.3. Numerical Procedures. The set of ordinary eqs 12a-12d

The reactor was described as a standard plug ow reactor

dx.doi.org/10.1021/ie2015526 |Ind. Eng. Chem. Res. 2012, 51, 171183

Industrial & Engineering Chemistry Research

aromatic molar fractions outlet

Initial Set of Experiments

aromatic molar fractions outlet

Initial Set of Experiments

the spatial time () could assume the values of 0.05, 0.1,

with the adsorption constants of chemical species

dx.doi.org/10.1021/ie2015526 |Ind. Eng. Chem. Res. 2012, 51, 171183

Industrial & Engineering Chemistry Research