TITTLE: Kinetics of Toluene alkylation with methanol catalyzed by HZSM-5,

ZM13 and MOR/ZSM-5 zeolites

NAME OF STUDENT: ALABI, WAHAB OLAIYA.

STUDENT LEVEL: Msc Chemical Engineering.

NAME OF SUPERVISOR: Prof.Sulaiman Al-Khattaf.

UNIVERSITY: King Fahd University of Petroleum and Minerals.

DATE OF SUBMISSION: 13th of Feb., 2012.

Abstract
Kinetic study of toluene alkylation with methanol was performed over pure
HZSM-5, MOR/ZSM-5(hybrid mordinite and HZSM-5), and ZM13 (composite
mixture of HZSM-5 and MCM-41 at PH 13). Experimental runs were carried out
using a fluidized bed reactor at temperatures of 300, 350 and 400 C and reaction
times of 3, 5, 7, 10, 13, 15 and 20 s. the rate of toluene methylation and toluene
disproportionation were study on the three catalyst(toluene alkylation is usually
accompanied by toluene disproportionation on acid catalyst). Based on the results
obtained, a simplified power law kinetic model consisting of three reactions was
developed to account for the overall transformation of toluene. Coke formation on
catalysts was evaluated using both reaction time and reactant conversion decay
functions. All parameters were estimated based on quasi-steady state
approximation. Estimated kinetic parameters were in good agreement with
experimental results. It was found that the order of alkylation ability of the
catalysts is; ZM13 > HZSM-5 > MOR/ZSM-5 ,while the reverse is for toluene
disproportionation (MOR/ZSM-5 > HZSM-5 > ZM13 ).Thus; alkylation of toluene
is most favorable on ZM13 due to combined effect of mesoporosity induced
through its synthetic route and acid content. Toluene/MeOH molar ratio of 1:1 is
suitable for toluene alkylation

Keywords: Toluene alkylation, disproportionation reaction, xylene, zeolite catalyst,

power law model, reaction time, reactant conversion

Kinetics of Toluene alkylation with methanol catalyzed by HZSM-5, ZM13

and MOR/ZSM-5 Zeolites
Introduction
Zeolites are highly amenable to industrial acid-catalyzed reactions due to their
unique properties, such as shape selectivity, high porosity, and thermal stability [14]. Its favorable activity has been attributed mostly to the brnsted acid sites. The
production of xylenes by the petrochemical industry has increased over the years
due to its numerous applications. P-xylene is an important precursor to terephthalic
acid and dimethyl terephthalate, both are key components of polyethylene
terephthalate (PET) production. o-xylene is used mainly in the synthesis of
phthalic acid anhydride while m-xylene is usually oxidized to isophthalic acid.
Among

the

recent

possible

routes

to

xylene

production

is

toluene

disproportionation. Nevertheless, co-formation of benzene has made this route less

viable. The study of another potential route with great economic interest is
alkylation of toluene. This route has the advantage of using methanol as the
alkylating agent which is a cheaper raw material and available in abundance [5].
The reaction mechanism of toluene methylation has been studied extensively, and
this has been summarized into two mechanistic approaches.
Attempts have also been made in the aspect of kinetic studies of toluene alkylation
reaction [6-11]. A comprehensive review showed efforts have been mainly focused
on obtaining kinetic data over archetype ZSM-5 catalysts using fixed bed reactor.
Recently, Al-Khattaf and co-workers [12-14] have reported the use of fluidized
bed reactor for different zeolite catalysts.
In the present study we examine the catalytic performance of HZSM-5,
ZM13 and hybrid MOR/ZSM-5 zeolite catalysts for toluene-methanol alkylation
reaction. Our approach involves obtaining extensive kinetic data as a function of

reaction conditions (both temperature and time) to estimate the kinetic parameters.
A power law kinetic model was developed to probe the kinetics of the reaction in a
fluidized bed reactor. The physico-chemical and acidic properties of the zeolite
catalysts were evaluated using analysis such as XRD, N2 adsorption, and Pyridine
FTIR (Py-IR).
Experimental Section
Catalysts Preparation
The calcined HZSM-5 with Si/Al ratio of 13.5 and surface area of 284 m2/g
was obtained from CATAL, UK. The uncalcined proton form of mordenite with
Si/Al ratio of 18.3 and surface area of 364 m2/g was obtained from Tosoh
Chemicals, Japan. The calcined form of mordenite was then physically mixed with
HZSM-5 in 1:1 ratio to form MOR/ZSM-5 catalysts. ZM13 is a composite of
HZSM-5 and MCM-41 which is obtained by the disintegration and assembly of the
former in the latter. The synthesis procedure involves disintegrating 2g of HZSM-5
using 0.7 M NaOH solution at a pH condition of 13 by gradual heating (without
stirring) at 100 oC for 24 h in the presence of CTAB (4.45%). The mixture was
cooled down and pH adjusted to 9.0 through the addition of dilute sulfuric acid
(2N). The mixture was then stirred for 24 h followed by ageing at 100 C for 24 h.
The solid product was filtered, washed thoroughly using distilled water, dried at
80oC overnight, then calcined at 550 C for 6 h to remove the surfactant. The
obtained composite was ion-exchanged thrice with 0.05M NH4NO3 solution at 80
o

C for 2 h then calcined at 550oC for 2 h.

Catalysts Characterization
Brunauer-Emmett-Teller (BET) technique was used to determine the surface
areas of the catalyst samples. This was achieved through the N2 adsorptiondesorption isotherm using Quantachrome AUTO-SORB-1 (model # ASI-CT-8).
Adsorption measurements were carried out after the samples had been heated at
100 C for 3 h in the presence of N2 gas stream.
Structural elucidation of the catalyst samples were examined using X-ray
power diffraction (XRD). Diffraction patterns were obtained on a Bruker D8
Advance X-ray powder diffractometer equipped with a graphite monochromator
and position sensitive detector using Cu K radiation in Bragg-Brentano
geometry.The XRD result in figure 1, BET and Acidity test result ;table 1
Catalytic Testing
In a typical experiment, 0.8g of catalyst sample which has already been
crushed and sieved to ~60 m was loaded into the catalyst basket of the riser
simulator, a bench scale fluidized bed reactor invented by de Lasa [23]. Before the
actual experimental runs, the catalyst was thermally activated at 620 C for 15 min
in the presence of Ar. A liquid mixture of the feedstock (toluene and methanol)
was injected into the reactor. Two thermocouples, one located in the catalyst bed
and the other on the outer wall of the reactor were used to monitor the reaction
temperature. Typically, the temperature difference recorded is negligible. The
temperatures for the catalytic reactions are 300, 350 and 400 C for 7 different
reaction times varying from 3 - 20 s. On the other hand, the reaction pressure
changes from 1 atm at the point of injecting the feedstock to ~2.5 atm at the end of
the reaction. This increase, monitored by the pressure transducer, is due to the
vaporization of the liquid mixture and the reacting species produced. The reactor
effluent was analyzed online using Agilent GC with FID (Agilent Chromatograph

Model 6890N), equipped with an HP-INNOWax capillary column (Polyethylene

glycol (PEG)) (length 60 m x internal diameter 0.32 mm x film thickness 0.50
m). During the course of the investigation, a number of runs were repeated to
check for reproducibility in the experiment results, which were found to be
excellent. Typical errors were in the range of 2 %.
The experimental results of the three catalysts at different temperatures and time
are shown in tables 2-4.
Kinetic Modeling
Reaction kinetic study is presented in this section, the purpose of which to
develop a simplified kinetic model for the detailed catalytic reaction. In particular,
emphasis is on the main reactions which took place during toluene alkylation with
CH3

CH3
CH3OH
Toluene

CH3
CH3

k2
Xylene
H 2O

k1

CH3OH

CH3

k3

TMB
H2O

CH3
CH3
Benzene

Xylene

methanol. The kinetic scheme employed therefore showed in details the main reactions as
presented in scheme 1:
Scheme 1: reaction network for toluene-methanol alkylation

Similar reaction scheme have been proposed by Serra et. al. [15] when
toluene-methanol alkylation reaction was catalyzed by solid acids. For the purpose

of developing the kinetic model, experimental data obtained for toluene/MeOH

molar ratio of 1:1 is used
Model Formulation
Power law model has been used to study the kinetics of the observed
chemical reactions. The governing equations for the riser simulator are simply
material balances for reactants and products of the chemical reaction similar to
batch reactor. In general, for each independent reacting species, the material
balance equation can be written as:
(1)

Where
system,

and

are the reaction rate and mole concentration of each species in the

is the volume of the reactor,

seconds, while

is the mass of the catalyst,

is time in

is the deactivation function to account for catalytic activity loss.

The rate equations for the elementary reactions can then be written as:
2

(2)
(3)
(4)

Rate constant which is a function of pre-exponential factor and activation energy

as defined by Arrhenius equation is expressed to incorporate temperature
dependence of the reaction given as:
1

(5)

Where

is the pre-exponential factor of reaction i and Ei is the energy of

activation of the reaction i.

is referred to as the centering temperature which is

the average of all the temperatures for the experiment. This was introduced to
reduce parameter interaction as postulated by Agarwal and Brisk [16]. Reactions
involving hydrocarbons inevitably yields coke deposit. Two catalyst deactivation
functions were investigated in this study: reaction (RT) and reactant conversion
(RC) expressed as
where

and

exp

exp

[17] and

[18];

are decay constants for their respective deactivation functions and

is the weight fraction of toluene, (

Expressing concentrations

).

in terms of weight fraction of each species

, which

are the measurable variables from the chromatographic analysis, we have:

(6)

Where

is the weight of feedstock injected into the reactor,

is the

molecular weights of the species.

Based on scheme 1, rate of reaction for toluene, benzene, xylene and TMB species
can thus be written as:

(7)

(8)

(9)

(10)

Model Assumptions
Summarized below are the assumptions taken into consideration for the model
formulation:
1. The reactor operates under isothermal condition
2. Toluene diproportionation is considered to have irreversible reaction path
and taken to be second order.
3. Effectiveness factor, , is been taken to be unity. Similar assumption was
used in previous works [12-14]
4. Isomers of xylene and TMBs are grouped together for a simplistic model
evaluation.
Model Parameter Evaluation
Using non-linear regression analysis combined with fourth order RungeKutta routine to numerically integrate the rate equations, the kinetic parameters for
the toluene-methanol alkylation reaction over the zeolite catalysts under study
were evaluated. The developed model provides approximate estimates of all the
kinetic parameters which are shown in tables 5 and 6. o Also, the R-squared value
of the regression is close to unity (0.99) and a parity plot of the weight fractions of
the reactive species (Figure 3) gave an excellent fit between the predicted and
experimental data, indicating the suitability of the proposed model. Extensive
studies have been reported on kinetics of toluene alkylation reaction with methanol
over ZSM-5 (modified and unmodified). In the present study, activation energy for

HZSM-5 has an approximate value of ~57 kJ/mol for toluene methylation reaction,
irrespective of the deactivation model employed. This value is very much
comparable with the works of previous authors as shown in Table 8. Vinek and
Lercher [19] reported an apparent activation energy of 50 55 kJ/mol for toluene
alkylation with methanol on H-ZSM-5, a value of 68 kJ/mol was reported by Rabiu
and Al-Khattaf [12] and most recently, Odedairo et al [13] estimated a value of 47
kJ/mol for similar reaction on ZSM-5. For a modified ZSM-5 with magnesium,
Sotelo et al. [20] obtained apparent activation energy of 60 kJ/mol. In general,
activation energy for alkylation of toluene with methanol reported by several
authors has been summarized by Mirth et. al. [21] to be typically in the range of 50
90 kJ/mol.
Both for ZM13 and MOR/ZSM-5, the apparent energy barriers for the
reactions are lower than that on HZSM-5. It has been established that apparent
activation energy is equivalent to half the summation of both intrinsic and
diffusion activation energies [22]. Intrinsic activation energy however is related to
acidity of the catalyst; high acid catalysts have low intrinsic energy. HZSM-5 is a
two-dimensional channel structure defined by 10 member ring, with a medium
pore of ~6 . This creates a steric effect on large molecules which imposes
diffusional constraint. We can therefore conclude that, the pore structure of
HZSM-5 plays more significant role in its reactivity despite having acid sites
(brnsted) of higher concentration and strength than ZM13. Methylation of toluene
on ZM13 has apparent activation energy of 15 kJ/mol while 21 kJ/mol is calculated
for MOR/ZSM-5 using time-on-stream catalyst deactivation model (table 5). On
the other hand, toluene disproportionation overcomes energy barrier of 20.3 kJ/mol
and 13.1 kJ/mol on ZM13 and MOR/ZSM-5 respectively. Similar activation
energies for both reactions have been estimated with marginal difference (table 6)

when catalyst deactivation by reactant conversion model is used. These kinetic

parameter results are quite similar to the experimental observation in which
methylation of toluene is best favored on ZM13. Due to aforementioned diffusion
limitation which has been assumed to influence the apparent activation energy of
HZSM-5, the order of toluene methylation, ZM13 > MOR/ZSM-5 > HZSM-5 and
toluene disproportionation, MOR/ZSM-5 > ZM13 > HZSM-5 follows a different
pattern from the one proposed earlier. Xylene methylation on HZSM-5 has high
activation energy of 70 kJ/mol (RT model). This further confirms the effect of
diffusion limitation of large molecules within its pores. TMBs are more bulky
molecules, larger than both xylene and toluene, hence higher barrier to overcome.
Values of 15.2 kJ/mol and 17.8 kJ/mol are estimated respectively for MOR/ZSM-5
and ZM13, both possessing larger pores.
Conclusion
Detailed kinetic data were obtained employing a fluidized bed reactor (riser
simulator) for toluene/MeOH molar ratio 1:1. Power law model was used to
evaluate the kinetic parameters based on time-on-stream (TOS) and reactant
conversion (RC) catalyst decay function. Similar results were obtained for both
and deactivation due to coke deposit was accounted to be fairly minimal, but not
negligible. The apparent activation energies of toluene methylation and
disproportionation reactions on HZSM-5 have higher values compared to ZM13
and MOR/ZSM-5. The order of activation energies for toluene methylation is
HZSM-5 (56.1 kJ/mol) > MOR/ZSM-5 (20.8 kJ/mol) > ZM13 (14.6 kJ/mol)
whereas the order of toluene disproportionation is HZSM-5 (54.8) > ZM13 (20.3)
> MOR/ZSM-5 (13.1)
References
(1) Davis, M. E. Acc. Chem. Res. 1993, 26, 111115.

10

(2) Corma, A.; Martinez, A. Catal. Rev.Sci. Eng. 1993, 35, 483570.
(3) De Vos, D. E.; Dams, M.; Sels, B. F.; Jacobs, P. A. Chem. Rev.2002, 102, 36153640.
(4) Sartori, G.; Maggi, R. Chem. Rev. 2006, 106, 10771104. Use of solid catalysts in friedelcrafts acylation reactions.
(5) A.B. Halgeri, Bull. Catal. Soc. India 2 (2003) 184193.
(6) Wei, J. A mathematical theory of enhanced para-xylene selectivity in molecular sieve
catalysts. J. Catal. 1982, 76, 433.
(7) Hashimoto, K., Masuda, T., Kawase, M., Karge, H. G., Weitkamp, J., Eds. Zeolites as
Catalysts, Sorbents and Detergent Builders. Stud. Surf. Sci. Catal. 1989, 46, 485.
(8) Young, L. B.; Butter, S. A.; Kaeding, W. W. Selectivity in xylene isomerization, toluenemethanol alkylation and toluene disproportionation over ZSM-5 zeolite catalysts. J. Catal. 1982,
76, 418.
(9) Kaeding, W. W.; Chu, C.; Young, L. B.; Weinstein, B.; Butter, S. A. Selective Alkylation of
Toluene with Methanol to Produce para-Xylene. J. Catal. 1981, 67, 159.
(10) Bhat, Y. S.; Halgeri, A. B.; Prasada Rao, T. S. R. Kinetics of Toluene Alkylation with
Methanol on H-ZSM-8 Zeolite Catalyst. Ind. Eng. Chem. Res. 1989, 28, 890-894
(11) Ramakrishna, M.; Subhash, B.; Musti, S. R. Kinetics of Deactivation of Methylation of
Toluene over H-ZSM-5 and Hydrogen Mordenite Catalyst. Ind. Eng. Chem. Res. 1991, 30, 281(12). Al-Khattaf S, Rabiu S, Tukur NM, Alnaizy R (2008) Chem Eng J 139:622
(13) Kinetics of Toluene Methylation over ZSM-5 Catalyst in a Riser Simulator, S. Rabiu and S.
Al-Khattaf, Ind. Eng. Chem. Res. 2008, 47, 39-47
(14) Toluene Disproportionation and Methylation over Zeolites TNU-9, SSZ-33, ZSM-5, and
Mordenite Using Different Reactor Systems, T. Odedairo, R.J. Balasamy, and S. Al-Khattaf, Ind.
Eng. Chem. Res. 2011, 50, 31693183.
(15) Serra, J.M.; Corma, A.; Farrusseng, D.; Baumes, L.; Mirodatos, C.; Flego, C.; Perego, C.,
Catal. Today, 2003, 81, 425 436.
(16) Agarwal, A. K; Brisk, M. L.; Agarwal, A. K; Brisk, M. L. Ind. Eng. Chem. Process Des.
Dev. 1985, 24, 203
(17) Weekman, V. W. Ind. Eng. Chem. Process Des. Dev. 1968, 7, 90-95.
(18) Al-Khattaf, S.S.; de Lasa, H.I. Ind. Eng. Chem. Res, 2001, 40, 5398.
(19) Vinek, H.; Lercher, J. J. Mol. Catal. 1991, 64, 2339.

11

(20) Sotelo, J. L.; Uguina, M. A.; Valverde, J. L.; Serrano, D. P. Ind. Eng. Chem. Res. 1993, 32,
2548-2554.
(21) Mirth, G.; Lercher, J. A. J. Catal.1991, 132, 244252
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List of Figures
Figure 1:

XRD pattern of zeolites: a) HZSM-5, b) MOR/ZSM-5, c) ZM13

List of Figures
Figure 1:

XRD pattern of zeolites: a) HZSM-5, b) MOR/ZSM-5, c) ZM13

Figure 2:

Catalytic activity of A) HZSM-5, b) MOR/ZSM-5, c) ZM13. reaction

conditions: temperature = 300 400 C, reaction time = 3 20 s,
toluene/MeOH molar ratio = 1:1

Figure 3:

Parity plot of toluene conversion for the three zeolite samples

List of Tables
Table 1:

Physicochemical and acid properties of the three zeolites samples

Table 2:

Product

distribution

of

toluene

alkylation

with

methanol

alkylation

with

methanol

with

methanol

(toluene/MeOH ratio = 1:1) on HZSM-5

Table 3:

Product

distribution

of

toluene

(toluene/MeOH ratio = 1:1) on MOR/ZSM-5

Table 4:

Product

distribution

of

toluene

(toluene/MeOH ratio = 1:1) on ZM13

alkylation

12

Estimated kinetic parameters for toluene-methanol (1:1) reaction over

Table 5:

HZSM-5, MOR/ZSM-5 and ZM13 catalysts using TOS model

Estimated kinetic parameters for toluene-methanol (1:1) reaction over

Table 6:

HZSM-5, MOR/ZSM-5 and ZM13 catalysts using RC model

Activation energies for toluene alkylation with methanol reported in

Table 7:

literatures

Intensity (a.u.)

(c )

(b )

(a )
10

20

30

40

50

60

70

2 T h e ta

Figure 1: XRD pattern of zeolites: a) HZSM-5, b) MOR/ZSM-5, c) ZM13

13

36

Toluene conversion / %

45

300 C
0
350 C
0
400 C

32
28

40
35

24

30

20

25

16

20

12

15

10

4
0

300 C
0
350 C
0
400 C

A
2

10

12

14

16

18

20

22

Reaction time / s
36

12

14

16

18

20

22

Reaction time / s
0

300 C
0
350 C
0
400 C

32

Toluene conversion / %

10

28
24
20
16
12
8
4
0

C
2

10

12

14

16

18

20

22

Reaction time / s

Figure 2: Catalytic activity of A) HZSM-5, b) MOR/ZSM-5, c) ZM13. Reaction conditions:

temperature = 300 400 C, reaction time = 3 20 s, toluene/MeOH molar ratio = 1:1

14

40

Predicted

30

20

10

10

20

30

40

Experimental

Figure 3: Parity plot of toluene conversion for the three zeolite samples

15

Table 1: Physicochemical and acid properties of the three zeolites samples

Brnsted acid sites

Lewis acid sites

(mmol/g)

(mmol/g)

L/B ratio

Si/Al

Surface

Samples

ratio

Area (m2/g)

150 C

400 C

150 C

400 C

(400 C)

ZSM-5

13.5

284

0.4497

0.3296

0.2093

0.1305

0.40

MOR/ZSM-5

22

364

0.5381

0.4278

0.0447

0.0321

0.08

ZM13

12

468

0.3541

0.2658

0.2380

0.1448

0.54

16

Table 2: Product distribution of toluene alkylation with methanol (toluene/MeOH ratio = 1:1) on
HZSM-5
Reaction Toluene
time (s) Conv.
(%)

Gas

Benzene pxylene

Yield (%)
m-xylene oxylene

Total
xylene

TMBs

300 C
1.07
2.18
3.05
3.97
6.54
7.85
9.65

0.38
0.40
1.28
1.40
1.59
1.74
1.85

0.34
0.65
0.83
0.86
1.15
1.27
1.37

0.82
1.24
1.82
2.16
2.57
2.76
3.05

0.78
1.70
2.14
2.46
3.12
3.48
4.00

0.30
0.52
0.81
0.96
1.22
1.36
1.58

1.90
2.46
4.77
5.58
6.91
7.60
8.63

0.28
0.32
0.41
0.45
0.52
0.55
0.63

2.35
5.48
8.84
12.92
15.76
18.30
21.67

0.95
1.38
1.75
2.17
2.48
2.76
3.14

0.75
1.07
1.60
1.94
2.32
2.50
3.34

1.28
1.87
2.36
2.94
3.37
3.73
4.05

1.73
2.64
3.58
4.55
5.39
6.07
6.98

0.65
1.00
1.39
1.77
2.13
2.42
2.83

3.66
5.51
7.33
9.26
10.89
12.22
13.86

0.36
0.45
0.61
0.74
0.88
0.96
1.27

9.76
1.74
1.78
2.11
3
15.73
2.54
2.51
3.13
5
21.09
3.20
3.01
3.86
7
25.15
3.45
3.82
4.22
10
28.92
3.66
4.31
4.82
13
29.63
3.78
4.73
4.90
15
30.14
3.88
5.29
5.06
20
a
TMB all isomers of TMB, catalys/feed ratio = 5

3.51
5.38
6.88
8.07
9.32
9.75
9.86

1.38
2.11
2.69
3.29
3.83
4.08
4.08

7.00
10.62
13.43
15.58
17.97
18.73
19.00

0.52
0.68
0.76
0.99
1.11
1.17
1.44

3
5
7
10
13
15
20
350 C
3
5
7
10
13
15
20
400 C

17

Table 3: Product distribution of toluene alkylation with methanol (toluene/MeOH ratio = 1:1)
on MOR/ZSM-5
Reaction Toluene
time (s) Conv.
(%)

Gas

Benzene pxylene

Yield (%)
m-xylene oxylene

Total
xylene

TMBs

300 C
3
5
7
10
13
15
20

5.26
12.12
18.31
22.25
25.47
26.61
34.13

0.60
0.85
1.81
2.19
2.23
2.67
3.83

2.46
3.63
4.76
5.67
6.44
6.64
8.88

1.08
1.80
2.42
2.79
3.35
3.58
4.14

2.22
3.76
4.99
5.85
6.98
7.26
8.76

0.95
1.59
2.10
2.47
2.92
3.06
3.67

4.25
7.14
9.51
11.11
13.25
13.90
16.57

1.03
1.73
1.92
2.37
2.64
2.70
3.33

17.17
21.55
25.91
31.97
34.65
35.98
38.72

1.94
2.32
3.11
3.75
4.22
4.33
4.84

4.47
5.38
6.67
7.64
8.82
8.69
10.19

2.03
2.57
3.02
3.79
4.02
4.26
4.50

4.34
5.56
6.47
5.25
8.57
9.02
9.71

1.90
2.40
2.80
3.50
3.70
3.91
4.19

8.27
10.53
12.29
12.54
16.29
17.19
18.40

1.88
2.25
2.54
3.19
3.25
3.42
3.90

3.92
5.67
5.77
8.15
8.50
9.24
9.24

1.77
2.56
2.60
3.65
3.86
4.16
4.09

7.52
10.87
11.07
15.60
16.31
17.72
17.61

1.78
2.49
2.36
3.31
3.53
3.74
3.76

350 C
3
5
7
10
13
15
20
400 C
16.10
2.19
4.33
1.83
3
23.48
2.95
5.78
2.64
5
24.87
3.45
6.37
2.70
7
33.47
4.25
8.01
3.80
10
35.60
4.81
8.81
3.95
13
37.25
5.19
9.02
4.32
15
38.27
5.39
10.03
4.28
20
a
TMB all isomers of TMB, catalyst/feed ratio = 5

18

Table 4: Product distribution of toluene alkylation with methanol (toluene/MeOH ratio = 1:1) on
ZM13
Reaction Toluene
time (s) Conv.
(%)

Yield (%)
m-xylene
oxylene

Total
xylene

Gas

Benzene

pxylene

TMBs

2.45
6.83
9.80
11.38
14.02
14.66
19.17

0.78
1.26
1.50
1.71
1.85
1.89
2.37

0.31
0.44
0.50
0.52
0.54
0.62
0.81

1.50
2.15
2.60
3.14
3.50
3.44
3.75

2.03
3.21
3.92
4.37
5.17
5.37
6.63

0.99
1.45
1.79
2.20
2.51
2.53
2.91

4.52
6.81
8.31
9.71
11.18
11.34
13.29

0.57
0.80
0.99
1.18
1.39
1.46
1.77

7.44
11.16
14.68
19.10
21.86
23.73
26.74

1.18
1.55
1.94
2.31
2.55
2.68
3.00

0.53
0.73
0.79
1.03
1.14
1.29
1.55

1.87
2.41
2.94
3.50
3.85
3.94
4.32

3.35
4.37
5.41
6.75
7.46
7.84
8.86

1.38
1.82
2.25
2.83
3.14
3.32
3.78

6.60
8.60
10.60
13.08
14.45
15.10
16.96

0.87
1.07
1.28
1.59
1.80
1.95
2.26

4.34
5.85
7.40
8.15
8.93
9.75
10.29

1.82
2.46
3.07
3.54
3.90
4.28
4.59

8.42
11.30
14.10
15.64
17.14
18.66
19.73

1.04
1.36
1.75
1.86
2.02
2.21
2.41

300 C
3
5
7
10
13
15
20
350 C
3
5
7
10
13
15
20
400 C
11.43
1.56
0.79
2.26
3
16.55
2.07
1.04
2.99
5
20.91
2.47
1.30
3.63
7
24.50
2.82
1.79
3.95
10
26.74
2.87
2.03
4.31
13
28.62
3.12
2.42
4.63
15
31.88
3.19
2.64
4.85
20
a
TMB all isomers of TMB, catalyst/feed ratio = 5

19

Table 5: Estimated kinetic parameters for toluene-methanol (1:1) reaction over HZSM-5,
MOR/ZSM-5 and ZM13 catalysts using TOS model
k1

E1

k2

E2

k3

E3

m6/kgcat.s

(kJ/mol)

m6/kgcat.s

(kJ/mol)

m6/kgcat.s

(kJ/mol)

( 102)

( 102)

( 102)

HZSM-5
values

0.66

54.8

4.50

56.7

1.99

70.0

0.0052

95% CL

0.05

4.7

0.18

3.1

1.45

52.7

0.0039

MOR/ZSM-5
values

3.50

13.1

5.25

20.8

18.29

15.2

0.04

95% CL

0.26

3.0

0.53

7.8

2.49

10.3

0.008

ZM13
values

0.65

20.3

9.09

14.6

10.29

17.8

0.01

95% CL

0.06

5.9

0.31

2.3

0.16

11.7

0.005

Table 6: Estimated kinetic parameters for toluene-methanol (1:1) reaction over HZSM-5,
MOR/ZSM-5 and ZM13 catalysts using RC model
k1

E1

k2

E2

k3

m6/kgcat.s

(kJ/mol)

m6/kgcat.s

(kJ/mol)

m6/kgcat.s

( 10 )

E3

(kJ/mol)

( 10 )

( 10 )

HZSM-5
values

0.76

57.4

5.29

57.1

2.48

65.8

0.60

95% CL

0.11

4.9

0.68

3.1

1.66

48.7

0.40

MOR/ZSM-5
values

8.45

18.2

12.83

23.3

44.52

19.3

2.84

95% CL

2.15

3.5

2.95

7.7

11.60

10.1

0.06

ZM13
values

1.11

23.8

15.20

17.1

17.08

20.5

1.65

95% CL

0.22

5.7

2.51

2.3

3.68

11.2

0.50

20

Table 7: Activation energies for toluene alkylation with methanol reported in literatures
Author

Activation Energy (kJ/mol)

Catalyst

Temperature range (C)

Bhat et. al.19

61

HZSM-8

400 - 450

Sotelo et al.21

60

Mg-Modified ZSM-5

460 - 540

Vinek et al.41

50-55

HZSM-5

300 - 500

Rabiu et.al.23

68

ZSM-5

375 - 450

Odedairo et al.24

47

ZSM-5

300 - 400

Present study

57

HZSM-5

300 - 400