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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-
zene (EB) methylation on ZSM-5 and mordenite (MOR) was studied in a batch uidized-bed
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
methylation with methanol. A maximum ethyltoluenes yield of 22.0% was achieved during
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
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
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
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.
Nomenclature
Ci
Ei
ki
koi
MWi
ri
R
t
T
To
V
Wc
Whc
yi
Greek letters
catalyst deactivation constant
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
2.2.
Catalyst characterization
36
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 =
3.
3.1.
Catalytic test
(B)
% yieldi =
wt% of product i
100%
wt% of toluene in feed
% selectivity =
3.2.
Acidity results
3.3.
Catalytic activity
3.3.1.
Ethylation of toluene
37
Catalyst
ZSM-5
HZ80-6L
MOR
a
b
c
Smeso (m2 g1 )a
51.0
45.0
0.19
0.17
0.24
451
424
514
RC (%)c
0.09
0.08
0.05
100
85
100
Catalyst
Tb
L.T. (weak)
ZSM-5
HZ80-6L
MOR
a
b
c
0.354
0.307
0.04
H.T. (mediumstrong)
<300 C
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.
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
200
225
250
300
10
20
10
20
10
20
10
20
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 / %
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
39
50
40
30
20
10
0
100
200
300
400
Reaction temperature / C
Ethyltoluene selectivity / %
60
50
100
40
80
30
20
10
100
200
300
400
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
40
20
Toluene conv.
gases
EB
Bz
Total ET
50
40
30
20
15
10
10
0
ZSM-5
1:3
1:1
3:1
3.3.2.
Tol + EtOH
EB + MeOH
60
Methylation of ethylbenzene
MOR
HZ80-6L
41
200
225
250
300
10
20
10
20
10
20
10
20
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
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)
Ci =
yi Whc
MWi V
(2)
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
100
90
Tol + EtOH
EB + MeOH
80
70
60
50
40
4.1.
20
10
0
ZSM-5
MOR
100
90
Para-ethyltoluene selectivity / %
Alkylation only
30
HZ80-6L
r1 = k1 CT CE
Tol + EtOH
EB + MeOH
80
70
60
V dCT
= r1 exp(t)
Wc dt
(5)
50
V dCETol
= r1 exp(t)
Wc dt
40
30
4.2.
20
10
0
(4)
ZSM-5
MOR
HZ80-6L
E 1
i
ki = ki0 exp
1
T0
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)
(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
(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
E1 (kJ/mol)
56.4 4.9
21.2 6.4
0.102 0.002
0.040 0.034
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
(10)
(11)
27.9 5.8
133.3 34.7
123.3 32.6
0.08 0.02
Calk
(13)
CMET
Keq3
(14)
(12)
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
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
44
Table 11 Rate constants as a function of temperature evaluated for the ethylation of toluene ethylation over MOR based
on Scheme2b.
Temp C
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
k1
E1
k1
E1
1.0000
0.4948
0.9196
0.4948
1.0000
0.6338
Authors
0.9196
0.6338
1.0000
Catalyst
V dCT
= r1 exp(t)
Wc dt
0.81
0.92
1.04
1.27
Activation
energy (kJ/mol)
ZSM-5
ZSM-5
75
62
ZSM-5 supported
on monolith
ZSM-5
64
70
(15)
4.3.
(16)
(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)
(18)
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
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
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
46
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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