chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Experimental and kinetic studies of ethyltoluenes

production via different alkylation reactions
Luqman A. Atanda a , Abdullah M. Aitani a , Sulaiman S. Al-Khattaf a,b,
a

Center of Research Excellence in Petroleum Rening & Petrochemicals, King Fahd University of Petroleum &
Minerals, Dhahran 31261, Saudi Arabia
b Chemical Engineering Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

a r t i c l e

i n f o

a b s t r a c t

Article history:

Ethyltoluenes production via two alkylation reactions vis: toluene ethylation and ethylben-

Received 31 March 2014

zene (EB) methylation on ZSM-5 and mordenite (MOR) was studied in a batch uidized-bed

Received in revised form 21 October

reactor at a temperature range of 200300 C for reaction times of 520 s. Toluene ethylation

2014

with ethanol gave better yield and selectivity to ethyltoluenes on ZSM-5 compared with EB

Accepted 2 January 2015

methylation with methanol. A maximum ethyltoluenes yield of 22.0% was achieved during

Available online 13 January 2015

toluene ethylation whereas 7.3% yield was attained in EB methylation on ZSM-5. To achieve

Keywords:

tetraethyl orthosilicate (TEOS). While toluene conversion on silylated ZSM-5 (HZ80-6L) was

enhanced para-ethyltoluene selectivity, ZSM-5 was modied by silylation treatment using

Ethyltoluenes

decreased, 100% para-isomer selectivity was obtained due to the reduction of the effec-

Alkylation

tive pore channel and strength of acid sites. A comprehensive kinetic study of the toluene

Toluene

ethylation reaction is reported in this paper using the power-law approach for the model

Ethylbenzene

development. A satisfactory correlation between experimental data and the model result
was achieved. The required apparent activation energy for the alkylation step of toluene

Ethanol

ethylation reaction over ZSM-5, HZ80-6L and MOR catalysts was determined to be 70 kJ/mol,
63 kJ/mol and 28 kJ/mol, respectively.
2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1.

Introduction

Ethyltoluenes (ETs) are aromatic compounds useful for a wide

variety of applications in the petrochemical and chemical
industries. For example, p-ethyltoluene (p-ET) is used in the
synthesis of poly(p-methylstyrene) which are adaptable to
food packages subjected to thermal conditions (Canteniro,
1980; Forward et al., 1984). Poly(p-methylstyrene) has advantage over polystyrene due to its low density, higher glass
transition temperature, and ash point. It has also potential in the area of ame retardancy or ignition resistance
(Kaeding et al., 1981). Ethyltoluenes are usually produced via
alkylation of toluene with ethanol or ethylene (Walendziewski

and Trawczynski,
1991; Villareal et al., 2002; Parikh, 2008;
Manivannan and Pandurangan, 2010). Most often this reaction is conducted on medium pore zeolites especially ZSM-5,
because of its shape selective properties favoring paraselectivity. Further improvement of para-selectivity of ZSM-5
can be achieved by impregnation of the zeolite channels with
metal or non-metal oxides (Engelhardt et al., 1992; Parikh et al.,
1992; Zheng et al., 2003) and/or modication of the external

acid sites with a siliceous material (Hui et al., 2011; Cejka

and
Wichterlov, 2002) or by carbonaceous material in form of coke
deposit (Kaeding et al., 1984; Odedairo and Al-Khattaf, 2010).
The kinetics of toluene alkylation with ethylene has
been investigated in a xed bed reactor. Bhandarkar and

Abbreviations: DEB, diethylbenzene; EB, ethylbenzene; ET, ethyltoluenes; EtOH, ethanol; m-ET, meta-ethyltoluene; MOR, mordenite;
o-ET, ortho-ethyltoluene; TMB, trimethylbenzene; p-ET, para-ethyltoluene.

Corresponding author at: Center of Research Excellence in Petroleum Rening & Petrochemicals, P.O. Box 5040, King Fahd University of
Petroleum & Minerals, Dhahran 31261, Saudi Arabia. Tel.: +966 13 860 2029; fax: +966 13 860 4509.
E-mail addresses: abiola2kng@yahoo.com (L.A. Atanda), maitani@kfupm.edu.sa (A.M. Aitani), skhattaf@kfupm.edu.sa (S.S. Al-Khattaf).
http://dx.doi.org/10.1016/j.cherd.2015.01.001
0263-8762/ 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Nomenclature
Ci
Ei
ki
koi
MWi
ri
R
t
T
To
V
Wc
Whc
yi

concentration of specie i in the riser simulator

(mol/m3 )
apparent activation energy of the ith reaction
(kJ/mol)
apparent rate constant for the ith reaction
(m3 /kg of catalyst s)
pre-exponential factor for the ith reaction after
re-parameterization (m3 /kg of catalyst)
molecular weight of specie i
reaction rate
universal gas constant (kJ/kmol K)
reaction time (s)
reaction temperature (K)
average temperature of the experiment
volume of the riser (45 cm3 )
mass of the catalyst (0.81 g)
total mass of the hydrocarbon injected the riser
(0.162 g)
mass fraction of ith component

Greek letters
catalyst deactivation constant

Bhatia (1994) studied the kinetics of toluene alkylation

using LangmuirHinshelwoodHougenWatson (LHHW) and
the EleyRideal mechanism and demonstrated that the LHHW
model better represents the reaction mechanism. The surface reaction of the co-adsorbed toluene and ethanol on
unmodied HZSM-5 required approximately 62 kJ/mol activation energy for ET to be formed as reported by the authors.
Kinetic analysis of ethylation of toluene on HZSM-5 based
on LHHW mechanism was also reported by Lee and Wang
(1985) using ethylene as the alkylating agent. They concluded
that ethylene adsorption was the rate determining step of the
reaction mechanism and the estimated activation energy for
alkylation was 75.4 kJ/mol. Parikh (2008) reported the kinetics of the reaction using a monolith reactor on which ZSM-5
was wash-coated. He proposed a rate expression which indicates p-ET to be the primary product of the alkylation reaction.
o-Ethyltoluene was not accounted for due to negligible observable quantities while the net rate of m-ET formation was as
a result of the total rate of toluene consumption to form pET and the subsequent isomerization rate of p-ET to m-ET.
Activation energy of 64 kJ/mol was estimated for the alkylation reaction. It is noteworthy to point out that modied
ZSM-5 always has higher activation energy for alkylation when
compared to the unmodied ZSM-5. This variation has been
ascribed to lowering of acid strength after modication (Lnyi
et al., 1991; Bhandarkar and Bhatia, 1994).
Alkylation of ethylbenzene (EB) with methanol on the other
hand, has not been extensively reported in the literature. This
reaction was studied by Ko and Huang (1993) using different catalysts. The kinetics of the reaction was not studied
but they proposed a reaction network of EB on HY zeolite to
have undergone alkylation, disproportionation and dealkylation reactions. Inuence of acidity and basicity on the reaction
mechanism of methylation of EB was also investigated using
X type zeolites (Huang and Ko, 1993). Acidic zeolite favored
ring alkylation whereas side-chain alkylation was promoted
on basic zeolite. On KX zeolite which has mainly basic sites,

35

carbanion and carbonium ion mechanism governed the alkylation and dealkylation reactions, respectively. Free radical
mechanism leading to the formation of dehydrogenation and
demethylation products also took place.
In this paper, we report the ethylation of toluene using a uidized batch reactor whereas previous studies have reported
the use of xed bed reactor. We seek to exploit the advantages
of uidized bed over xed bed such as the ease of catalyst
regeneration as well as the elimination of temperature and
concentration gradients. p-Ethyltoluene is considered to be of
promising industrial interest, hence, the effect of silylation in
enhancing para-selectivity of ZSM-5 was examined. This study
also focused on detailed kinetic investigation of the reaction.
A systematic kinetic analysis of the alkylation reaction was
conducted to account for the toluene ethylation reaction as
well as the concomitant isomerization taking place. A power
law model is employed to develop the mathematical expressions representing the reaction rates for the proposed reaction
mechanisms.

2.

Experimental

2.1.

Materials

Na forms of ZSM-5 (Si/Al molar ratio 80) and mordenite (Si/Al

molar ratio 180) were obtained from Tosoh chemicals, Japan.
The samples were ion exchanged with NH4 NO3 to replace
the Na+ with NH4 + , then followed by calcination at 600 C for
2 h to obtain the proton (H+ ) form. HZ80-6L was prepared by
chemical liquid deposition as reported by Zheng et al. (2006).
A suspension of parent ZSM-5 zeolite (Si/Al = 80) in n-hexane
was heated until reux at 70 C. TEOS solution was added to
the stirred heated mixture and silylation was continued for 2 h
at 70 C with reux and stirring. Excess n-hexane was removed
by evacuation. The sample was dried at 100 C for 24 h and then
calcined at 550 C for 4 h. Silylation treatment was conducted
six times using the same procedure to obtain six layers of TEOS
deposition (4 wt% SiO2 ) on the parent zeolite.
Toluene (99.6%), ethanol (99.9%), EB (99.8%) and methanol
(100.0%) were obtained from SigmaAldrich and no further
attempt was made to purify the chemicals.

2.2.

Catalyst characterization

Powder X-ray diffraction (XRD) patterns were recorded on

a Shimadzu powder diffraction system using Cu K radiation ( = 0.154 nm, 45 kV and 35 mA). The XRD patterns were
recorded in the static scanning mode from 1.2 to 60 (2) at a
detector angular speed of 0.01 /s and step size of 0.02 .
The textural properties of the zeolite samples were characterized by N2 adsorption measurements at 196 C using
Quantachrome Autosorb 1-C analyzer. Samples were outgassed at 220 C under vacuum (105 torr) for 3 h before N2
physisorption. The BET specic surface areas were determined from the desorption data in the relative P/P0 range from
0.060.3, assuming a value of 0.164 nm2 for the cross-section
area of the nitrogen molecule. The pore size distribution
(PSD) was calculated from the adsorption branch using the
BarrettJoynerHalenda (BJH) method, and the maximum of
the PSD was considered as the average pore size. t-Plot analysis was used to determine the micropore surface area and
pore volume.
Temperature-programmed desorption of NH3 (NH3 -TPD)
was conducted using Quantachrome Autosorb 1-C/TCD to

36

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

determine total acid sites on the catalyst samples. Samples

were pretreated at 450 C in a ow of helium (25 ml min1 ) for
2 h. This was followed by the adsorption of ammonia (5 vol.%
in helium) at 100 C for 30 min. Samples were then purged in
a helium stream for 2 h at 120 C in order to remove loosely
bound ammonia (i.e. physisorbed and H-bonded ammonia).
The samples were then heated linearly from 100 to 700 C at
a heating rate of 10 C/min in a ow of helium (25 ml min1 )
while monitoring the evolved ammonia using TCD.
Infrared spectroscopy of adsorbed pyridine was used to
determine the types of available acid sites (i.e. Brnsted
and/or Lewis acid sites). The measurements were conducted using a Fourier transform infrared using Nicolet
FTIR spectrometer (Magna 500 model). The samples in the
form of a self-supporting wafer (ca. 60 mg in weight and
20 mm in diameter) were obtained by compressing a uniform layer of the powdered samples. The wafer was then
mounted in an infrared vacuum cell equipped with KBr
windows (Makuhari Rikagaku Garasu Inc., Japan), and preheated under vacuum (ca. 103 torr) at 450 C for 2 h. The
adsorption temperature of pyridine was 150 C. For a quantitative characterization of acid sites, the following bands and
absorption coefcients were used: pyridine (PyH+ ) band at
1545 cm1 , = 0.078 cm mol1 ; pyridine (PyL) bands at 1461

and 1454 cm1 , = 0.165 cm mol1 (Gil et al., 2008; Zilkov

et al., 2009).

2.3.

(A)

1700

1600

1500

1400
-1

wavenumber (cm )
Fig. 1 FTIR of chemisorbed pyridine onto (A) ZSM-5 and
(B) HZ80-6L.
% para-selectivity =

wt% of p-ET in product

100
wt% of ET in product

3.

Results and discussion

3.1.

Textural properties of catalysts

Catalytic test

Experiments were conducted on a riser simulator, a bench

scale uidized bed reactor invented by de Lasa (1991). It is
operated in a batch mode under high gas phase circulation rates as well as intense catalyst mixing conditions and
pre-determined reaction times, thereby simulating various
locations of riser/downer type reactor units. In a typical experiment, 0.8 g of the catalyst sample which has already been
crushed and sieved to 60 m was loaded into the catalyst
basket of the reactor. Before the catalytic activity test, thermal activation of the catalyst was done in the presence of Ar
at 620 C for 15 min. The reactant feed is a mixture of toluene
and ethanol (1:1) for ethylation reaction, EB and methanol (1:1)
for methylation reaction. For both reactions, the feed mixture
is of 1:1 molar ratio.
All experimental runs were conducted at atmospheric
pressure and under isothermal condition. The reactor efuent
was analyzed in an Agilent model 6890N gas chromatograph
with a ame ionization detector and a capillary column
Innowax, 60 m cross-linked methyl silicone with an internal
diameter of 0.32 mm. Reproducibility check of the experimental runs was performed. Typical errors were found to be in
the range of 2%. The terms for toluene or EB conversion,
product yield, ET selectivity and p-ET selectivity are dened as
follows:
% toluene (T) or EB conversion
=

(B)

T (or EB) in feed T (or EB) in product

100
T (or EB) in feed

% yieldi =

wt% of product i
100%
wt% of toluene in feed

% selectivity =

wt% of ethyltouene (ET) in product

100
wt% of aromatic in product

Textural properties of the catalyst samples are presented in

Table 1. By applying the multiple-point BET model on the
adsorption branches of the N2 -isotherm, the BET areas and
pore volumes were calculated. As shown in Table 1, HZ806L exhibited lower BET area and pore volume compared to
ZSM-5. The estimated micropore volume obtained from the
t-plot method also show reduction for the modied ZSM-5
which may be due to partial pore blockage of the zeolite pore
channels by the deposited silica. From the XRD results, relative crystallinity of ZSM-5 reduces from 100% to 85% after the
silylation treatment indicating that the incorporated silica is
amorphous.

3.2.

Acidity results

Table 2 shows the acid properties of the catalyst samples.

The total concentration of acid sites measured by NH3 -TPD
on modied zeolite (HZ80-6L) was lower compared to the parent zeolite (ZSM-5). In addition, FTIR of chemisorbed pyridine
showed reduced peak intensities (Fig. 1) as well as reduction in
the quantied Brnsted and Lewis acidities (Table 2) after silylation treatment. It can thus be concluded that the introduced
silica was partly deposited onto the acid sites of the zeolite
sample, reducing the number of available acid sites that can
interact with the probe gases (ammonia and pyridine).

3.3.

Catalytic activity

3.3.1.

Ethylation of toluene

Temperature and time dependence of toluene conversion is

shown in Fig. 2A and B for the alkylation of toluene with
ethanol on both ZSM-5 and MOR. Expectedly, conversion
of toluene rose with increase in temperature and time. At
reaction conditions of 300 C and 20 s, toluene conversion of

37

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Table 1 Textural properties of the catalysts.

SBET (m2 g1 )

Catalyst
ZSM-5
HZ80-6L
MOR
a
b
c

Smeso (m2 g1 )a

Vmicro (cm3 /g)a

51.0
45.0

0.19
0.17
0.24

451
424
514

Vmeso,N2 (cm3 /g)b

RC (%)c

0.09
0.08
0.05

100
85
100

Obtained from t-plot.

Pore volume in the range of 4100 nm derived from N2 adsorption.
Relative crystallinity derived from XRD measurements.

Table 2 Acid sites properties of the catalysts.

NH3 -TPD (mmol g1 )a

Catalyst
Tb

L.T. (weak)

ZSM-5
HZ80-6L
MOR
a
b
c

0.354
0.307
0.04

H.T. (mediumstrong)

<300 C

FTIR-chemisorbed Pyr. (mmol g1 )

300450 C

1.00
0.95

>450 C

0.194
0.187

0.16
0.12

0.205
0.158
0.270

0.165
0.131
0.05

0.040
0.027
0.22

L.T. and H.T. correspond to low- and high-temperature NH3 desorption peak, respectively.
Total number of acid sites is based on the amount of NH3 desorbed above 300 C (i.e. H.T. region).
Strong acid sites of Brnsted and Lewis nature, respectively.

approximately 30.8% and 33.3% was achieved on ZSM-5 and

MOR, respectively. In contrast to toluene conversion, reaction temperature has negligible effect on ethanol conversion
which was in the range of 8087% after 20 s of reaction time for
all temperatures. The only exception is with MOR catalyst at
200 C where ethanol conversion is 52.6%. Noteworthy is the
fact that ethanol conversion is higher than toluene conversion. This is because of the reactivity of ethanol to undergo
both alkylation and dehydration reactions. The total ET yield
also increased with toluene conversion or temperature (Fig. 3A
and B) on both catalysts but selectivity reduced. Maximum
value of total ET yields of 22% and 14.6% was recorded at 300 C
and 20 s for ZSM-5 and MOR, respectively.
Activity results of the alkylation of toluene with ethanol
over ZSM-5 and MOR are detailed in Tables 3 and 4. The
reaction product comprises mainly of ET isomers and small
to insignicant amount of other observed products. Typical
alkylation reaction of aromatic compounds is governed by
carbenium ion type mechanism involving the direct

orthopara attack of the alkylation agent on the benzene

ring followed by positional isomerization (Perez, 1978;
Manivannan and Pandurangan, 2009). Fig. 4 presents a plausible reaction pathway for toluene alkylation with ethanol.
Ethanol is protonated by the Brnsted acid site of the zeolite
sample to form ethyl oxonium ion which is then transformed
to ethyl cation. This subsequently reacts with toluene at
both the ortho- and para-positions of the benzene ring to
form ET. The reaction takes place at these positions because
the methyl group of toluene is an orthopara director and
electrophilic attack of ethyl cation occurs at ortho and para
positions.
The isomer distribution of ET on ZSM-5 favors both p- and
m-ETs in higher quantities than o-ET as shown in Fig. 5A.
For example, ET isomers distribution at 300 C, 20 s for p-ET,
m-ET and o-ET is 27.5%, 61.4% and 11.1%, respectively. This
distribution is near equilibrium concentration of 33.7% (p-ET),
49.9% (m-ET) and 16.3% (o-ET) at 330 C as reported by Lee
and Wang (1985). The excess concentration of m-ET above

Table 3 Catalytic performance of ZSM-5 in toluene alkylation with ethanol.

Reaction temp. ( C)
Reaction time (s)
Toluene conversion (%)
Ethanol conversion (%)
Product yield (%)
p-ET
m-ET
o-ET
Total ET
Gases
Benzene
EB
Xylenes
TMBs
DEBs
ET selectivity (%)
ET composition (%)
p-ET
m-ET
o-ET

200

225

250

300

10

20

10

20

10

20

10

20

5.8
65.9

13.7
79.7

7.4
67.6

18.8
81.8

17.3
66.6

25.9
84.2

24.2
68.6

30.8
80.2

2.4
3.3
0.2
5.9
14.4

0.1

0.2
95.2

4.3
7.2
0.5
12.0
13.4
0.1
0.2
0.2

0.4
96.0

2.8
3.9
0.2
6.8
14.7

0.1

0.2
95.8

5.4
10.4
1.0
16.8
10.5
0.1
0.4
0.4

0.6
91.8

4.6
9.4
0.9
14.9
8.7
0.1
0.4
0.3

0.4
92.5

6.2
12.9
1.5
20.6
10.3
0.2
0.7
0.6
0.1
0.6
90.4

5.3
11.7
1.8
18.8
8.2
0.3
0.8
0.8
0.1
0.5
88.3

6.1
13.5
2.4
22.0
10.5
0.5
1.2
1.2
0.2
0.7
85.3

41.0
55.9
3.10

35.9
60.0
4.10

40.4
56.6
3.10

32.1
62.3
5.60

31.2
63.0
5.80

30.3
62.5
7.20

28.4
61.9
9.70

27.5
61.4
11.1

38

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Table 4 Catalytic performance of MOR in toluene alkylation with ethanol.

Reaction temp. ( C)

200

225

250

300

Reaction time (s)

10

20

10

20

10

20

10

20

Toluene conversion (%)

Ethanol conversion (%)
Product yield (%)
p-ET
m-ET
o-ET
Total ET
Gases
Benzene
EB
Xylenes
TMBs
DEBs
ET selectivity (%)
ET composition (%)
p-ET
m-ET
o-ET

6.9
47.7

22.2
52.6

14.0
69.4

23.7
85.2

10.6
57.7

24.5
79.0

22.4
64.6

33.3
84.3

0.7
1.4
3.3
5.4
9.5

100

1.0
2.5
5.1
8.6
16.3

100

1.1
3.1
4.6
8.8
10.5

100

2.1
6.1
4.6
12.8
10.8
0.1
0.2
0.1

96.9

1.1
3.5
2.8
7.4
8.4
0.1
0.2
0.2

93.6

2.5
7.3
2.9
12.5
7.6
0.3
0.9
1.0

0.2
83.9

2.3
5.9
1.7
9.9
6.9
0.4
1.2
1.6

0.4
73.3

3.6
8.7
2.4
14.7
6.8
0.8
2.0
2.8
0.1
0.8
69.3

12.9
26.0
61.1

12.0
29.1
58.9

12.8
34.9
52.3

16.4
47.8
36.1

14.3
47.7
38.0

19.9
56.6
23.5

23.2
59.4
17.4

24.4
59.4
16.2

40

30

100

100

20
15
10
5
0
0

12

16

80

80

60

60

40

40

20

20

Selectivity / %

25
Conversion & Yield / %

Toluene conversion / %

200 C
225 C
250 C
300 C

35

20

Reaction time / s
0
100

40

0
400

100

100

25
20
15
10
5

80

80

60

60

40

40

20

20

Selectivity / %

Conversion & Yield / %

Toluene conversion / %

30

300

Reaction temperature / C

200 C
225 C
250 C
300 C

35

200

0
0

12

16

20

Reaction time / s
Fig. 2 Catalytic activity of (A) HZSM-5 and (B) MOR, for
alkylation of toluene with ethanol. Reaction conditions:
temperature = 200300 C, reaction time = 520 s,
toluene/EtOH molar ratio = 1:1. Experimental data (data
points), model predicted values (solid lines).

0
100

200

300

0
400

Reaction temperature / C

Fig. 3 Temperature effect on the activity of (A) ZSM-5 and

(B) MOR at 20 s reaction time. () toluene conversion, ()
ethyltoluene selectivity, () ethyltoluene yield.

39

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Fig. 4 Reaction pathway for toluene ethylation with ethanol.

50
40
30
20
10
0
100

200

300

400

Reaction temperature / C

Ethyltoluene selectivity / %

60

equilibrium value is ascribed to the isomerization of p-ET

on the external surface of the crystal (Parikh, 2008). Fig. 5B
shows that the ET isomer distribution on MOR differs from
that obtained on ZSM-5, especially at low temperatures. At
200 C, isomerization is slow, and therefore a high selectivity
of o-ET (60%) was observed. However, o-ET selectivity drops
with rise in temperature to a near equilibrium value of 16%
at 300 C. With increase in temperature, isomerization rate
occurs to a great extent, thereby resulting in increased concentration of m-ET in the ET isomer distribution. Thus, it can
be assumed that m-ET is produced mainly from the isomer
ization of o-ET. Cejka
et al. (1991) also reported that m-ET is
mainly formed from o-ET previously generated by preferential
alkylation of toluene with ethylene on a H-Y zeolite catalyst.
The yield of p-ET also increases with temperature, arising
from direct alkylation of toluene with ethanol. Therefore, over
solid acid catalysts where no shape selectivity are expected,
ortho-position is preferentially attacked, and the initial stage
of alkylation involves o-ET formation (Coughlan et al., 1982;
Manivannan and Pandurangan, 2010).

50

100

40

80

30

20

10
100

200

300

400

Xylene isomer distribution / %

Ethyltoluene selectivity / %

60

m-xylene
o-xylene
p-xylene

60

40

20

Reaction temperature / C
Fig. 5 Ethyltoluene selectivity as a function of temperature
on (A) ZSM-5 and (B) MOR at 20 s reaction time. () para, ()
ortho, () meta.

MOR

ZSM-5

HZ80-6L

Fig. 6 Xylene isomer distribution over the zeolite catalysts

at 300 C and 20 s.

40

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

20

Toluene conv.
gases
EB
Bz
Total ET

50

40

30

20

15

10

10
0

ZSM-5

1:3

1:1

3:1

Toluene:EtOH molar ratio

Fig. 7 Inuence of toluene:EtOH molar ratio on the
formation of ethyltoluenes over MOR at 300 C and 20 s.
Silylation treatment of ZSM-5 was conducted using TEOS as
the silica source, in order to improve para-isomer selectivity.
Table 5 shows the catalytic performance of the modied ZSM5 (HZ80-6L) for alkylation of toluene with ethanol. Addition
of silica greatly enhanced p-ET selectivity and yield, however,
toluene conversion was reduced. For example, at reaction conditions of 300 C and 20 s, toluene conversion, p-ET yield and
selectivity on ZSM-5 are 30.8%, 6.1% and 27.5%, respectively,
whereas on HZ80-6L, values of 18.8%, 13.5% and 77.1% for
toluene conversion, p-ET yield and selectivity, respectively,
were achieved. It is suggested that 100% p-ET in the ET isomer
distribution is caused by two reasons: one is the reduction of
pore mouth and the other is coverage of acid sites on the external surface of zeolite (Kaeding et al., 1984). The reduction of
pore mouth prevents diffusion of m- and o-ET out of the pores,
and coverage of outer surface acid sites suppresses the isomerization of p-ET on the external surface. These reasons can
also be extended to why p-xylene is the only isomer of xylene
produced from the disproportionation reaction of toluene over
HZ80-6L as shown in Fig. 6.
The molar ratio of toluene:ethanol was varied to investigate
the effect of concentration of the alkylating agent on ethyltoluene formation. Fig. 7 shows that with the increase in molar
ratio of toluene to ethanol, total ethyltoluene formation goes
through a maximum at 1:1. At low toluene:ethanol ratio, high
reactivity of ethanol led to huge gaseous hydrocarbon formation which include ethylene, ethane and diethyl ether. On the
other hand, high toluene:ethanol ratio promotes disproportionation of toluene to benzene and its successive alkylation to
ethylbenzene. From this result, the most suitable molar ratio
of toluene:ethanol appears to be 1:1.

3.3.2.

Tol + EtOH
EB + MeOH

Total ethyltoluene yield / %

Toluene conversion & product yield / %

60

Methylation of ethylbenzene

In order to investigate an alternate route to producing ETs,

methylation of EB is conducted. The idea is to look at the
simultaneous effect of increasing the alkyl substituent on the
aromatic ring and reduction of the alkylating agent size in
comparison with toluene ethylation. It was found that the
catalytic alkylation of EB with methanol gave a variety of
products on both ZSM-5 and MOR. Most signicant of the
products are DEB, ET, toluene and benzene (Table 6). Ko and

MOR

HZ80-6L

Fig. 8 Comparison of total ethyltoluene yield via toluene

ethylation and EB methylation reactions at 300 C and 20%
aromatic conversion.
Huang (1993) has proposed the reaction paths for the EBmethanol reaction which can be adapted in this study to
describe the observed product mixture. The primary reaction
steps are methylation and disproportionation of EB to give ET
and DEB/benzene, respectively. Benzene and toluene may be
as a consequence of dealkylation of EB and ET, respectively,
which is inuenced by temperature. Benzene can further react
with methanol to give toluene and the presence of xylene suggests that toluene subsequently undergoes either methylation
or disproportionation reaction. The multiple reactions taking
place leading to a wide range of alkyl aromatics suggest this
reaction route is non-selective toward ET formation. The scope
of this study therefore will not include detailed investigation
of EB-methanol reaction mechanism.
The activity of all the catalysts in terms of conversion for
the ethylbenzene methylation reaction (Table 6) is similar to
that of toluene ethylation reaction. Ethylbenzene conversion
increases with both reaction time and temperature whereas
methanol conversion seems to be unaffected by temperature. Ethylbenzene conversion on ZSM-5, MOR and HZ80-6L at
300 C and 20 s is 40.4%, 54.5% and 26.6%, respectively with a
corresponding methanol conversion of 85.9%, 86.3% and 85%.
Fig. 8 compares the yield of total ET produced at 300 C reaction
temperature and 20% aromatic conversion via both toluene
ethylation and EB methylation reactions. Taking ZSM-5 as
an example, approximately 20% ET yield was formed during
toluene ethylation reaction while about 4.4% yield of ET was
produced in the methylation reaction of EB. Similar trend of
alkylation reaction inuencing ET yield was observed in other
zeolite samples as well. This is caused by the difference in
the stability of attacking carbocation. Ethyl cation is more stable than methyl cation. Accordingly, the formation of ethyl
cation from ethanol is easier than that of methyl cation from
methanol. This can explain why the total yield of ET is higher
from alkylation of toluene with ethanol than from alkylation
of EB with methanol. The selectivity to total ETs and p-ET
at 300 C and 20% aromatic conversion are plotted and presented in Fig. 9A,B. Fig. 9A clearly shows that selectivity to ET
is much higher in the toluene ethylation reaction on all the
catalyst samples. It was however found out that p-ET selectivity is similar irrespective of the type of alkylation reaction.
This means that the choice of alkylating route does not have
much variation on para-isomer distribution. A look at the p-ET

41

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Table 5 Catalytic performance of HZ80-6L in toluene alkylation with ethanol.

Reaction temp. ( C)

200

225

250

300

Reaction time (s)

10

20

10

20

10

20

10

20

Toluene conversion (%)

Ethanol conversion (%)
Product yield (%)
p-ET
m-ET
o-ET
Total ET
Gases
Benzene
EB
Xylenes
TMBs
DEBs
ET selectivity (%)
ET composition (%)
p-ET
m-ET
o-ET

3.3
64.3

3.8
85.3

3.7
65.8

9.5
85.5

6.2
68.8

10.3
83.8

13.5
71.8

18.8
86.7

3.8

3.8
16.0

0.1
0.1

95.0

5.3

5.3
20.6

0.2
0.1

94.6

5.7

5.7
12.5

0.2
0.2

93.4

10.4

10.4
14.5
0.1
0.6
0.4

90.4

7.7

7.7
11.3
0.1
0.5
0.3

89.5

11.4

11.4
11.7
0.2
0.8
0.6

87.7

11.0

11.0
12.0
0.4
1.3
0.8

82.1

13.5

13.5
14.7
0.7
2.0
1.3

77.1

100

100

100

selectivity on ZSM-5 for example for both alkylation reactions

was approximately 27% and this value is close to the equilibrium value (Kaeding et al., 1984).

100

100

100

100

100

was dened for all reactions. Using the rst order rate reaction
for a batch reactor and employing the power law rate equation,
the rate of reaction can be written as:
V dCi
= ri exp(t)
Wc dt

4.
Kinetics of the toluene ethylation
reaction
The reaction kinetics for the toluene ethylation reaction is
studied using a riser simulator whose operation is similar to a uidized bed batch reactor. Mathematical models
representing the rates of chemical reactions are developed
based on the observed product distribution. In formulating
the model, isothermal operating condition is assumed given
the design of the riser simulator unit and the relatively small
amount of reacting species. The rate of reaction for alkylation
was assumed to follow simple second-order kinetics and a
pseudo-rst order reaction kinetic was assumed for all species
involved in the reactions. Catalyst deactivation is taken to be
a function of reaction time, and a single deactivation function

(1)

where ri and Ci are the reaction rate and mole concentration

of each species in the system, V is the volume of the reactor, Wc is the mass of the catalyst, t is time in seconds, while
exp(t) is the reaction time catalyst deactivation function
which accounts for catalytic activity loss and is known as
the catalyst.
Mole concentration, Ci , can be expressed in terms of weight
fraction of each species yi , which are the measurable variables
from the chromatographic analysis, we have:

Ci =

yi Whc
MWi V

(2)

Table 6 Catalytic performance of EB alkylation with methanol at 20 s reaction time.

Reaction temp. ( C)
Catalyst samples
EB conversion (%)
Methanol conversion (%)
Product yield (%)
p-ET
m-ET
o-ET
Total ET
Gases
Benzene
Toluene
Xylenes
TMBs
DEBs
ET selectivity (%)
ET composition (%)
p-ET
m-ET
o-ET

250

300

ZSM-5

MOR

HZ80-6L

ZSM-5

MOR

HZ80-6L

29.5
84.5

40.9
72.3

13.7
82.3

40.4
85.9

54.5
86.3

26.6
85.0

2.1
4.7
0.6
7.3
6.8
2.1
1.5
1.6
1.6
9.3
31.2

2.1
5.6
2.3
9.8
3.1
4.4
3.1
1.7
1.0
3.4
41.9

2.6

2.6
9.5
1.6
1.4
0.8

6.1
20.8

2.0
4.7
0.7
7.4
9.2
5.5
4.5
3.1
1.9
11.1
22.1

2.8
6.5
1.7
10.9
5.9
3.8
4.1
3.4
2.0
6.9
35.1

2.6

2.6
15.5
5.4
4.1
1.6

6.9
12.6

28.6
63.7
7.7

21.0
55.8
23.2

27.0
63.3
9.7

25.4
59.4
15.2

100

100

42

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

100

Total ethyltoluene selectivity / %

90

Tol + EtOH
EB + MeOH

80
70
60
50

Scheme 1 Toluene ethylation reaction to ethyltoluenes.

40

4.1.

The main reaction pathway of toluene alklylation with ethanol

is to alkylated products, i.e. the ET isomers. The ET isomers are
grouped as a single product represented with Scheme 1. All
other products were neglected as a result of the insignicant
side reaction effects.
Therefore, reaction rate for the alkylation reaction is:

20
10
0

ZSM-5

MOR

100
90

Para-ethyltoluene selectivity / %

Alkylation only

30

HZ80-6L

r1 = k1 CT CE

Tol + EtOH
EB + MeOH

For the reacting species, rate of toluene consumption is:

80
70

60

V dCT
= r1 exp(t)
Wc dt

(5)

rate of ETs formation

50

V dCETol
= r1 exp(t)
Wc dt

40
30

4.2.

20
10
0

(4)

ZSM-5

MOR

HZ80-6L

Fig. 9 Comparison of (A) total ethyltoluene selectivity and

(B) para-ethyltoluene selectivity, via toluene ethylation and
EB methylation reactions at 300 C and 20% aromatic
conversion.

where Whc is the weight of feedstock injected into the reactor,

MWi is the molecular weights of the species.
The reaction rate, ri , is a function of the rate constant and
the concentration of the reacting species. The rate constant,
ki , can be expressed in terms of temperature dependent Arrhenius equation as:

 E 1
i

ki = ki0 exp

1
T0

Alkylation with isomerization

This scheme considers a two-step reaction pathway for the

formation of the ET isomers, neglecting other side reactions.
The rst step of the reaction is alkylation followed by isomerization reaction. For ZSM-5, p-ET is preferentially formed in
the channel intersections of the zeolite during the initial alkyl
et al., 1991). The p-isomer then diffuses out
ation step (Cejka
of the zeolite pores and isomerizes toward m-ET upon contact
with acid sites on the zeolite external surface (Paparatto et al.,
1987). Furthermore, a rearrangement of the methyl group on
the m-ET can simultaneously occur, shifting either to the para
or ortho position to give p-ET or o-ET as shown in Scheme 2a,

et al. (1991).
also proposed by Cejka
The rate equations for the alkylation and isomerization
reactions can then be written as:
r1 = k1 CT CE


(3)

where ki0 is the pre-exponential factor of reaction i and

Ei is the energy of activation of the reaction i. T0 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 (1985).
Two reaction schemes have been proposed for the alkylation of toluene with ethanol: Scheme 1 involves the direct
formation of ethyltoluenes by alkylation of toluene with
ethanol; Scheme 2 involves a two step reaction of alkylation
with successive isomerization. The rate equations for the
elementary reactions are derived using these schemes as discussed below:

(6)

r2 = k2

CPET

CMET
Keq1

CMET

COET
Keq2


r3 = k3

(4)


(7)


(8)

where Keq1 and Keq2 are the equilibrium constants for isomerization of p-ET to m-ET and m-ET to o-ET, respectively,
calculated from Alberty (1985).
The rate of reaction for each reacting species can then be
written as:
rate of toluene consumption

V dCT
= r1 exp (t)
Wc dt

(9)

43

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

(a)

(b)

Scheme 2 (a) Toluene ethylation and concurrent isomerization on ZSM-5. (b) Toluene ethylation and concurrent
isomerization on MOR.
Table 7 Estimated kinetic parameters for toluene
ethylation using Scheme 1.
Catalyst
ZSM-5
MOR

k1 (m6 /kgcat s) 102

2.76 0.4
2.41 0.7

E1 (kJ/mol)
56.4 4.9
21.2 6.4

Table 10 Estimated kinetic parameters for toluene

ethylation on MOR using Scheme 2b.

0.102 0.002
0.040 0.034

Table 8 Estimated kinetic parameters for toluene

ethylation on ZSM-5 using Scheme 2a.
Pre-exponential factor
k1 (m6 /kgcat s) 102
k2 (m3 /kgcat s) 101
k3 (m3 /kgcat s) 104
Activation energy (kJ/mol)
E1
E2
E3
Deactivation constant

2.24 0.4
1.06 0.4
5.95 3.8
69.9 6.4
44.7 16.7
81.5 45.1
0.16 0.023

rate of p-ET formation

V dCPET
= (r1 r2 ) exp(t)
Wc dt

(10)

rate of m-ET formation

V dCMET
(r2 r3 ) exp(t)
Wc dt

(11)

27.9 5.8
133.3 34.7
123.3 32.6
0.08 0.02

Calk

(13)
CMET
Keq3


(14)

(12)

Table 9 Estimated kinetic parameters for toluene

ethylation on HZ80-6L using Scheme 2a.

k1 (m6 /kgcat s) 102

E1 (kJ/mol)

r1 = k1 CT CE

r2 = k2

V dCMET
r3 exp(t)
Wc dt

2.10 0.5
4.44 2.9
4.40 3.3

In the case of MOR, the reaction scheme for the ET isomer

formation is represented by Scheme 2b. The alkylation reaction proceeds by direct attack on both the paraortho positions
of toluene. Due to the non-selective nature of MOR, both oand p-ETs are produced primarily from direct alkylation reaction and m-ET was formed through successive isomerization
reaction. Therefore, o-ET and p-ET are grouped together as
products of direct alkylation reaction in the reaction scheme
shown below:
The rate equations for the alkylation and isomerization
reactions can then be written as:

rate of o-ET formation

Kinetic parameters

Pre-exponential factor
k1 (m6 /kgcat s) 102
k2 (m3 /kgcat s) 102
k2 (m3 /kgcat s) 102
Activation energy (kJ/mol)
E1
E2
E2
Deactivation constant

Values
1.33 0.5
62.7 14.9
0.12 0.06

where Calk is the combined concentrations of the product of

direct alkylation (i.e. CPET and COET ) and Keq3 is the equilibrium
constant for the isomerization of alkylated products to m-ET.
Unlike in ZSM-5, the equilibrium constant is estimated at each
reaction temperature. This is because of the strong inuence
of temperature on the ET isomer distribution in relation to
their non-equilibrium composition.
The rate of reaction for each reacting species can then be
written as:

44

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Table 11 Rate constants as a function of temperature evaluated for the ethylation of toluene ethylation over MOR based
on Scheme2b.
Temp C

k1 (m6 /kgcat s) 102

k2 (m3 /kgcat s) 102

k2 (m3 /kgcat s) 102

200
225
250
300

1.15
1.64
2.27
3.97

0.25
1.38
6.43
93.2

0.31
1.49
6.20
73.5

Table 12 Correlation matrix for parameters of toluene

ethylation over ZSM-5 based on Scheme 1.

k1
E1

k1

E1

1.0000
0.4948
0.9196

0.4948
1.0000
0.6338

Authors

0.9196
0.6338
1.0000

Catalyst

Lee and Wang (1985)

Bhandarkar and Bhatia
(1994)
Parikh (2008)
Present work

V dCT
= r1 exp(t)
Wc dt

0.81
0.92
1.04
1.27

Table 15 Comparison of activation energy obtained

with reported values in literature.

rate of toluene consumption

Keq3 (k2 /k2 )

Activation
energy (kJ/mol)

ZSM-5
ZSM-5

75
62

ZSM-5 supported
on monolith
ZSM-5

64
70

(15)

4.3.

Model parameter evaluation

rate of alkylated products formation

V dCalk
= (r1 r2 ) exp(t)
Wc dt

(16)

rate of m-ET formation

V dCMET
= r3 exp(t)
Wc dt

(17)

Adapting Scheme 2a to HZ80-6L, whose ET isomer composition consists solely p-ET, k2 and k3 0. The rate equations
for the toluene consumption and p-ET formation respectively
can be written as:
rate of toluene consumption

V dCT
= r1 exp(t)
Wc dt

(9)

rate of p-ET formation

V dCPET
= r1 exp(t)
Wc dt

(18)

The intrinsic kinetic parameters for both reaction

Schemes 1 and 2 were estimated using non-linear regression
analysis together with fourth order RungeKutta routine
to numerically integrate the rate equations. The developed
models provide approximate estimates of all the kinetic
parameters which are reported in Tables 711. The crosscorrelation matrices of Schemes 1 and 2a for ZSM-5 are given
in Tables 12 and 13, and that of Scheme 2b for MOR is reported
in Table 14. Most of the correlation coefcients are at low
level with very few at moderate level. This is indicative of low
level parameter interaction, which implies that the estimated
kinetic parameters are statistically valid and reliable (Agarwal
and Brisk, 1985). In addition, parity plot of the experimental
data and predicted values shown in Fig. 10AC gives a good
correlation with a R2 value of the regression close to unity
(0.99). This also conrms the suitability of the proposed
model.
From Scheme 1, activation energy of 56.4 kJ/mol was estimated for the alkylation of toluene to ETs on ZSM-5 whereas,
26.1 kJ/mol of energy is required for the same reaction on MOR
(Table 7). The huge difference in the activation energy can be

Table 13 Correlation matrix for parameters of toluene ethylation over ZSM-5 based on Scheme 2a.
k1
k1
E1
k2
E2
k3
E3

1.0000
0.4736
0.8552
0.1614
0.3186
0.0359
0.9116

E1
0.4736
1.0000
0.6254
0.1196
0.1124
0.2305
0.6649

k2
0.8552
0.6254
1.0000
0.2571
0.2293
0.0658
0.9395

E2
0.1614
0.1196
0.2571
1.0000
0.0626
0.0009
0.1791

k3
0.3186
0.1124
0.2293
0.0626
1.0000
0.1238
0.2425

E3
0.0359
0.2305
0.0658
0.0009
0.1238
1.0000
0.0675

0.9116
0.6649
0.9395
0.1791
0.2425
0.0675
1.0000

Table 14 Correlation matrix for parameters of toluene ethylation over MOR based on Scheme 2b.
k1
k1
E1
k2
E2
k2
E2

1.0000
0.3137
0.3683
0.1234
0.3284
0.0839
0.9385

E1
0.3137
1.0000
0.2365
0.1244
0.2114
0.1119
0.3485

k2
0.3683
0.2365
1.0000
0.5847
0.9748
0.6111
0.3710

E2
0.1234
0.1244
0.5847
1.0000
0.6111
0.9521
0.1019

k2
0.3284
0.2114
0.9748
0.6111
1.0000
0.6677
0.3300

E2

0.0839
0.1119
0.6111
0.9521
0.6677
1.0000
0.0669

0.9385
0.3485
0.3710
0.1019
0.3300
0.0669
1.0000

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

40

200 C
225 C
250 C
300 C

Predicted value

30

20

10

A
0
0

10

20

30

40

Experimental data
40

200 C
225 C
250 C
300 C

Predicted value

30

20

10

B
0
0

10

20

30

40

45

analysis of sorption accompanied by chemical reactions on

zeolites. This is because apparent activation energy is half the
summation of intrinsic and diffusion activation energies, i.e.
Eapp = (Ei + Ed )/2 (Levenspiel, 1999). Intrinsic activation energy
is dependent on acid strength of the catalyst. Since both catalysts have similar acid content, the energy requirement of
the molecules to freely move, Ed , is therefore the main factor
inuencing the Eapp . According to Scheme 2a, the activation
energy of alkylating toluene to p-ET over ZSM-5 is 69.9 kJ/mol
(Table 8) whereas HZ80-6L (silylated ZSM-5) gives a value of
62.7 kJ/mol as shown in Table 9. Isomerization of p-ET to mET and m-ET to o-ET require apparent activation energies of
44.7 kJ/mol and 81.5 kJ/mol, respectively. This suggests that
isomerization of p-ET to m-ET occurs with relative ease compared to that of m-ET to o-ET. This is may be because m-ET
is thermodynamically more stable, hence, higher energy is
required to shift the methyl group from meta to ortho position. Table 15 shows a comparison of activation energy for the
alkylation step reported by some authors. These values are
close in magnitude to that calculated in our present study.
Scheme 2b represents the proposed reaction pathway for
the ET isomer distribution over MOR. The estimated apparent
activation energies are given in Table 10. p- and o-ETs, being
the product of the alkylation step, requires activation energy of
27.9 kJ/mol. Meanwhile, successive isomerization of the alkylated products requires 133.3 kJ/mol of energy. The parameters
for the backward isomerization reaction (k2 and E2 ) were
also determined and given in Table 10. Since the ET isomer
distribution over MOR is temperature dependent, the ratio of
the rate constants of the forward and backward isomerization (k2 /k2 ) was used to compute the equilibrium constant
as a function of temperature and the values are tabulated in
Table 11.

Experimental data

5.

40

200 C
225 C
250 C
300 C

Predicted value

30

20

10

C
0
0

10

20

30

40

Experimental data
Fig. 10 Parity plot of toluene conversion on (A) ZSM-5
(Scheme 1), (B) ZSM-5 (Scheme 2a) and (C) MOR (Scheme 2b).

related to the channel size of the zeolite pores. ZSM-5 has pore
sizes whose channel diameter is close to kinetic diameters
of the aromatic molecules, thereby hindering free mobility.
Meanwhile, MOR is a large pore size zeolite with appreciable mobility of the reacting molecules. Hence, reaction kinetic
constants are inuenced by diffusion. Similar conclusion has
been deduced by Palekar and Rajadhyaksha (1986) in their

Conclusion

Alkylation of toluene with ethanol has been investigated using

a uidized bed reactor operated in batch mode. Shape selectiveness of ZSM-5 favored more yield of p-ET as compared
to MOR. Further improvement of p-ET selectivity on ZSM-5
was achieved via silylation treatment which involves silica
deposition. The use of TEOS as the silica source to modify
ZSM-5 proved to be an effective way of enhancing para-isomer
selectivity, eliminating undesired isomer yields. The results
of the pyridine FTIR and NH3 -TPD showed that deposited silica resulted in partial coverage of acid sites on the external
surface, which are responsible for para-isomer isomerization.
Reduction in the pore openings of ZSM-5 channels was evident
from the N2 adsorption analysis. These two factors combined
contributed to the enhanced para-isomer selectivity.
Methylation of EB in comparison with ethylation of toluene
under the same reaction conditions resulted in a wide spectrum of products. Side products such as DEB, benzene, toluene
and xylene are found in higher amounts. This is an indication
that in tandem with EB methylation, disproportionation of EB
due to alkyl side chain cracking is occurring, hence, this route
is not selective toward ET formation.
Kinetics of the toluene alkylation reaction modeled by
power law is well represented by the two-step reaction mechanism. The activation energy for p-ET formation on ZSM-5
and silylated ZSM-5 (HZ80-6L) is 70 kJ/mol and 63 kJ/mol,
respectively whereas, lower energy of 28 kJ/mol is necessary for the alkylation of toluene with ethanol over MOR.

46

chemical engineering research and design 9 5 ( 2 0 1 5 ) 3446

Zeolites with MFI structure (ZSM-5 and HZ80-6L) require

higher activation energy for the initial alkylation step compared to MOR, which can be ascribed to diffusional constraint
arising from pore channel dimension.

Acknowledgment
The authors are grateful to King Abdulaziz City for Science
& Technology (KACST) for nancial support of this research
through Project No. AR-34-22. The authors also appreciate the
support from the Ministry of Higher Education, Saudi Arabia in establishment of the Center of Research Excellence in
Petroleum Rening & Petrochemicals at KFUPM. The authors
are also grateful to the advice of Professor Hideshi Hattori
and to Mr. Mariano Gica for his assistance in catalyst activity
testing.

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