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Journal of Natural Gas Chemistry 18(2009)2124

Highly selective ethylbenzene production through alkylation of dilute


ethylene with gas phase-liquid phase benzene and transalkylation feed
Shenglin Liu1 ,

Fucun Chen1 , Sujuan Xie1 ,

Peng Zeng2 ,

Xiyan Du2 ,

Longya Xu1

1.State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road No. 457, Dalian 116023,
liaoning, China; 2. China petroleum Engineering Co. Ltd, Fushun Company, Fushun 113006, liaoning, China
[ Manuscript received May 25, 2008; revised July 3, 2008 ]

Abstract
A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor
phase ethylene feed stream, benzene and transalkylation feed stream. Especially the product stream containing ethylbenzene was used to
heat the reactor vessel, which consisted of an alkylation section, an upper heat exchange section, and a bottom heat exchange section. In
such a novel reactor, vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between
the upper heat exchange section and the bottom heat exchange section. The process was demonstrated by the thermodynamic analysis and
experimental results. In fact, during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction, the
ethene conversion was above 95%, and the ethylbenzene selectivity was above 83% (only benzene feed) and even higher than 99% (benzene
plus transalkylation feed). At the same time, the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried
out under the reaction conditions of 140185 C of temperature, 1.62.1 MPa of pressure, 3.05.5 of benzene/ethylene mole ratio, 46 v%
of transalkylation feed/(benzene+transalkylation feed), 0.190.27 h1 of ethene space velocity, and 1000 g of 3998 catalyst loaded. Thus,
compared with the conventional ethylbenzene synthesis route, the transalkylation reactor could be omitted in this novel industrial process.
Key words: dilute ethylene; gas phase-liquid phase benzene; alkylation; ethylbenzene

1. Introduction
Development of the ZSM-5/ZSM-11 co-crystallized zeolite catalysts by Dalian Institute of Chemical Physics (DICP)
in China has made the technology of converting benzene with
dilute ethene in FCC (fluid catalytic cracking) off-gas to ethylbenzene (EB) commercialized [14]. This widens the traditional route of EB production, in which benzene can only react
with pure ethene [5]. The excellent sulfur- and water-resistant
catalyst with good regeneration characteristics ensures high
ethylene conversion, high ethylbenzene selectivity, and long
operation period. In recent years, the novel technology and
advantageous catalyst have been widely applied in China on
account of their virtue of anticorrosion, simplicity, and economic advantage as well as effective utilization of FCC offgas [6].
At present, DICP has developed three types of alkylation reactor systems for producing EB from the FCC offgas, namely, vapor phase reactor system, vapor phase-liquid
phase reactor system, and catalytic distillation system [7].

The vapor phase reactor system is comprised of multiple


fixed beds of zeolite catalyst and operates at 330450 C and
0.51.5 MPa. The main product is EB in this reaction of ethylene with benzene. Meanwhile, some undesirable byproducts are generated including xylene, diethylbenzene (DEB),
tri-ethylbenzene (TEB), and heavier aromatics through chain
and side reactions. Additionally, trace of propene and butene
in the FCC off-gas also reacts with benzene to produce polyethylbenzene (PEB), butylbenzene (BEB), and others [5,8
10]. These heavy aromatics, PEB and BEB will be diverted
to the fuel oil system via separation, and the DEB and TEB
mixture can be transformed into EB via a transalkylation reactor system. Only trace of xylene isomer products exists
as an impurity in the subsequent product. As their boiling
points are very close to that of EB, no feasible methods can
be used to separate them from the objective products. In the
vapor phase reactor system, the EB product typically contains
20003000 ppm of xylene isomers.
In order to minimize the formation of xylene isomers,
DICP developed the combination technology of vapor-phase

Corresponding author. Tel: +86-411-84379279; Fax: +86-411-84693292; E-mail: slliu@dicp.ac.cn; lyxu@dicp.ac.cn


This work is supported by the National 973 Project of China (2009CB623501).

Copyright 2009, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(08)60071-7

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alkylation with liquid-phase transalkylation and catalytic distillation technology one after another, where the xylene isomers amounts in the EB product are 10001500 ppm and
5001000 ppm, respectively. On the basis of our previous
study, we explore a new process, namely, gas phase dilute
ethene alkylation with gas phase-liquid phase benzene. In this
new process, the amount of xylene isomers in the EB product is less than 100 ppm, and the EB selectivity can be higher
than 99% by adding some transalkylation feed into the benzene feed in the alkylation reactor. Thus, the transalkylation
reactor can be omitted in comparison with the processes mentioned above. In this article, the new process will be discussed
in detail.

a reactor vessel having several sections, namely, an alkylation section 6, an upper heat exchange section 7, and a bottom
heat exchange section 5. Fixed-bed alkylation section 6 is an
isothermic reactor where vapor phase ethene reacts with vapor phase-liquid phase benzene to form liquid phase EB and
PEB. The heat of the reaction is used to vaporize benzene
and transfer to the transalkylation feed. Owing to the dilute
effect of methane, nitrogen, and hydrogen in the ethene feed,
the alkylation reaction is carried out at a temperature at least
10 C lower than the normal boiling temperature of benzene
at a given alkylation pressure, as long as the integrated vaporliquid phase is maintained between the upper heat exchange
section and the bottom heat exchange section.

2. Experimental
Zeolite SSY was provided by the Chinese Wenzhou
Huahua Group. -alumina was used as binder for the zeolite
in a weight ratio of 70 : 30 (zeolite: -alumina), and the product was formed into 1.6 mm extrudates. After burning off the
template at 550 C for 3 h in a muffle furnace, ammonium ion
exchanging, and some upgrade treatment, the catalyst 3998
was obtained. Then, the 3998 catalyst was crushed and sieved
into 1.2512.00 mm particles for the reaction evaluation.
Alkylation of benzene with ethene was performed in a
fixed-bed stainless steel tubular reactor of 30 mm i.d, which
was heated by six electrical furnaces. 1000 g of catalyst, diluted with 800 ml SiO2 of the same size, was loaded into the
reactor and activated in an atmospheric pressure of N2 flow at
550 C for 23 h. Then, the sample was cooled to the reaction temperature. As the temperature approached the reaction
value, the N2 pressure was increased to the desired value.
Subsequently, benzene or benzene plus transalkylation feed
were fed until the reaction zone was filled up with the feed.
As soon as the feed flow was adjusted to the desired value
and the desired pressure, the ethene feed was introduced
into the reactor via a gas mass flow controller. The reaction conditions were as follows: temperature = 140185 C,
pressure = 1.62.1 MPa,
n(Benzene)/n(C2H4 ) = 3.05.5,
WHSV of C2 H4 = 0.190.27 h1 . The gas reaction effluents
were analyzed by a Model GC-8A Shimadu GC equipped
with a TCD detector and a Poropak QS packed column (2 m
long and 3 mm i.d.). The liquid effluents were analyzed by
an Agilent 4890D GC equipped with a FID detector and a
CEC-5 capillary column (50 m long and 0.32 mm i.d.). The
selectivity of the product was calculated basing on ethene [7].
The reaction equilibrium temperature in the thermodynamic
analysis was calculated according to literature [7].
3. Results and discussion
3.1. Characteristics of alkylation of gas phase dilute ethene
with gas phase-liquid phase benzene
The EB synthesis apparatus through alkylation of gas
phase dilute ethene with gas phase-liquid phase benzene is
depicted in Figure 1. The EB production system comprises

Figure 1. Schematic diagram of EB synthesis through alkylation of gas


phase dilute ethene with gas phase-liquid phase benzene and transalkylation
feed. 1dilute ethene stream, 2fresh benzene stream, 3product stream,
4vent gas, 5bottom heat exchange section, 6alkylation section, 7
upper heat exchange section, 8condenser, 9heat exchanger, 10reflux
drum, 11transalkylation stream

The cool dilute ethene feed is heated to the temperature


of the bottom heat exchange section at the heat exchanger
9, and then enters the bottom heat exchange section 5. Benzene and transalkylation feed from the upper reactor vessel are
heated to the desired reaction temperature via the upper heat
exchange section 7. The heated feeds mentioned above contact with the zeolite catalysts in the alkylation reaction section
6 to produce EB, DEB, and PEB, etc. Vaporizing benzene
and heated transalkylation feed mostly recover the heat of the
reaction. The benzene is condensed at the reactor vessel overhead 8 and 10. The top part of the alkylation catalyst bed 6
contains hydrogen, methane, nitrogen, ethane, benzene, original ethene, and trace of PEB, etc. The overhead gas from the
alkylation bed enters the upper heat exchange section 7, where
PEB is condensed by the reflux of benzene.
The reactor vessel overhead gas stream from the upper
heat exchange section 7 proceeds to condenser 8. The gas is
further cooled in reflux drum 10. Liquid and vent gas products
are separated in 10. Vent gas 4 proceeds to Pressure Swing
Adsorption (PSA) hydrogen recovery (not shown) or to a fuel
gas system, while the cool benzene from 10 and fresh benzene

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Journal of Natural Gas Chemistry Vol. 18 No. 1 2009

feed from 2, besides some transalkylation feed, are reheated


at the heat exchanger 9 and enter the reactor vessel. Liquid
products flow from the bottom of the reactor vessel containing benzene, EB, and PEB. Some products exchange heat with
the dilute ethene at exchange section 9, while the remaining
products are further separated into benzene, EB, TEB, DEB,
via PEB column (not shown). Benzene, TEB, and DEB are
recycled to reflux drum 10 from 2 and 11, respectively.
This novel process differs from that of catalytic distillation [11], in which the thermodynamic effect on ethene
conversion via simultaneous separation of EB product is insignificant. In the upper heat exchange section 7 in Figure 1,
almost no products such as EB, DEB etc. are detected, while
in the case of the catalytic distillation process, this section is
used to rectify the remaining products. For the bottom heat exchange section 5, the temperature is close to that of the heated
dilute ethene feed, but is lower than that of the alkylation reaction. As soon as the feed contacts with the gas of the heat
exchange section, the original material balance of the bottom
heat exchange section is broken and a new material balance
is found. Thus, in comparison with the catalytic distillation,
the reboiler can be omitted in this novel reactor vessel. Additionally, the ethene space velocity in the latter is larger than
that in the former, in which a lot of benzene is occupied in

the former reactor volume (a high benzene/ethylene ratio is


needed) under the similar ethene conversion and product selectivity. Owing to the high content of methane and hydrogen
in the ethene stream, the bubble point temperature in the dilute ethene and benzene is lower than the activity temperature
of the alkylation catalyst and the freezing point of benzene.
Therefore, the use of a liquid phase reaction system for dilute
ethene stream is impossible.
3.2. Thermodynamic analysis of the alkylation of gas phase
dilute ethene with gas phase-liquid phase benzene
Based on the schematic diagram of Figure 1, combined
with the knowledge of chemical equilibrium, material equilibrium, phase equilibrium, and heat energy equilibrium [12],
the thermodynamic analysis was studied and proposed with
the following assumptions: (1) The dilute ethene gas contains ethene 15 v%, propene 0.7 v%, N2 84.3 v%; (2) The
benzene/ethene mole ratio is 4, the benzene/(DEB+benzene)
mole ratio is 66.67 (DEB/(benzene+DEB) = 5 v%), the reaction pressure is 2.4 MPa, and the ethene feed is 1 mol; (3)
The ethene conversion is 100%, and the EB selectivity and
isopropyl benzene (IPB) selectivity are both 100%. The calculated results are shown in Figure 2.

G(E) 0
G(P) 0
G(B) 5.50102
G(o-DEB) 2.76107
G(p-DEB) 2.77107

G(N) 5.62
G(EB) 2.97105
G(m-DEB) 8.05107
G(i-PB) 1.84108

L(B) 3.60
L(o-DEB) 1.08103
L(p-DEB) 1.23103

L(EB) 1.75102
L(m-DEB) 2.92103
L(i-PB) 2.08105

Condenser

35 C

Hin = 374162 J

Hout = 186785 J

G(P)0

G(E) 0
G(B) 3.65
G(o-DEB) 1.08103
G(p-DEB) 1.27103

G(N) 5.62
G(EB) 1.76102
G(m-DEB) 2.92103
G(i-PB) 2.08105

Heat exchange section II

G(E) 0
G(P) 0
G(B) 3.96
G(o-DEB) 1.37103
G(p-DEB) 1.60103

169 C

Alkylation reaction

G(P) 4.67102

151 C reflux
L(B) 3.60
L(o-DEB) 1.39102
L(p-DEB) 1.62102

L(EB) 1.76102
L(m-DEB) 3.51102
L(i-PB) 2.08105

Hin = 649546 J
Hout = 649540 J
+ L(CB) 4.00 and L(CDEB) 0.06

G(N) 5.62
G(EB) 6.92102
G(m-DEB) 3.67103
G(i-PB) 1.21104

L(B) 3.90
L(o-DEB) 1.42102
L(p-DEB) 1.66102

L(EB) 6.92102
L(m-DEB) 3.59102
L(i-PB) 1.21105

174 C

Hin = 2828582 J

Hout = 2828573 J

G(E) 1.0
G(B) 2.61
G(o-DEB) 1.00103
G(p-DEB) 1.10103

G(N) 5.62
G(EB) 0.24
G(m-DEB) 2.50103
G(i-PB) 7.70103

L(B) 5.49
L(o-DEB) 1.38102
L(p-DEB) 1.61102

L(EB) 1.24
L(m-DEB) 3.47102
L(i-PB) 5.44102

Heat exchange section I


170 C in
G(E) 1.0
G(P) 4.67102
G(B) 0
G(o-DEB) 0
G(p-DEB) 0

170 C

Hin = 495043 J

Hout = 567415 J

G(N) 5.62
G(EB) 0
G(m-DEB) 0
G(i-PB) 0

L(B) 2.88
L(o-DEB) 1.28102
L(p-DEB) 1.50102

L(EB) 1.0
L(m-DEB) 3.22102
L(i-PB) 4.67102

Figure 2. Thermodynamic results for the alkylation of gas phase dilute ethene with gas phase-liquid phase benzene. Gamount in gas phase (mol), Lamount
in liquid phase (mol), Henthalpy. Eethene, Ppropene, NNitrogen, Bbenzene, EBethylbenzene, DEBdiethylbenzene, PBpropylbenzene,
CBcool benzene, CDEB-cool diethylbenzene

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Shenglin Liu et al./ Journal of Natural Gas Chemistry Vol. 18 No. 1 2009

As shown in Figure 2, the dilute ethene gas requires


72.372 kJ (567.415495.043 kJ) to be heated to 170 C from
35 C before entering the bottom heat exchange section I,
and the required heat can be obtained from heat exchanger
9 shown in Figure 1. Similarly, before entering the upper
heat exchange section II, the feeds including benzene and EB,
etc, after being cooled in the condenser 8 and reflux drum 10
shown in Figure 1 need to be heated to 151 C. Thus, the reaction equilibrium temperature is 174 C besides the addition
of benzene of 4.00 mol and DEB of 0.06 mol (both are 35 C)
to the reactor section via the cool feeds absorbing the isothermic reaction heat. In addition, heat energy of 187.377 kJ can
be recovered, when the vent gas from the upper heat exchange
section II of 169 C is cooled to 35 C in the condenser.
When the dilute ethene feed of 170 C contacts with the
materials of the bottom heat exchange section I, the original
material balance is broken and a new material balance begins
to form. During the reaction process, alkylation of ethene with
benzene produces EB and DEB, while propene reacts with
benzene to obtain IPB; thus the amount of IPB produced is
equal to that of the propene feed (0.047 mol). In the meantime, the liquid products reach equilibrium with the gas products. The benzene amount increases in contrast to that of EB,
DEB, and PB via the heat exchange in the heat exchange section II. After being cooled in the condenser, the vent gas contains very little EB, DEB, and PB (<3105), and benzene
of 0.055 mol, which are further recovered in condenser 8 in

Figure 1. Liquid bottom products existing in the reactor vessel contain benzene, EB, and PEB, while the amount of gas
phase plus liquid phase DEB is equal to the value of input liquid feed DEB (0.06 mol). This indicates that addition of some
DEB to the feed can suppress the generation of DEB during
the alkylation of ethene with benzene.
3.3. Life-test of 3998 catalyst for alkylation of gas phase dilute ethene with gas phase-liquid phase benzene
In order to demonstrate the feasibility of the novel
process and the rationality of the thermodynamic analysis, the 3998 catalyst was used for the alkylation
of gas phase ethene with gas phase-liquid phase benzene under the following reaction conditions: temperature = 140185 C, pressure = 1.62.1 MPa, benzene/ethene
mole ratio = 3.05.5, ethene space velocity = 0.190.27 h1 ,
3998 catalyst loaded = 1000 g. During the1010 hour-time-onstream, the ethene conversion was above 95%, the IPB selectivity was above 99%, and the EB selectivity was 80%. At
the same time, the xylene content in the products was less
than 100 ppm. If adding 46 v% transalkylation feed to the
benzene feed, the EB selectivity could exceed 99%, indicating
that the transalkylation reactor may be omitted. In conclusion,
this novel process is rational and the 3998 catalyst shows high
catalytic activity, selectivity, and good stability. Up to now,
the 3998 catalyst and this novel process have been expanded
to industrial scale with the production of 1000 ton/year EB.

Table 1. Reaction performance of 3998 catalyst


T
( C)
140160
153172
156175
157175
160178
171181
178182
170181
175184
174185
174185

P
(MPa)
1.6
2.0
2.0
1.8
2.0
1.9
2.0
2.1
1.8
2.1
2.1

WHSV
(h1 )
0.27
0.26
0.23
0.21
0.20
0.20
0.19
0.20
0.19
0.20
0.20

Benzene/ethene
(mol ratio)
3.0
3.9
4.7
5.5
5.2
4.1
4.2
4.1
4.6
4.2
4.1

TOS
(h)
1
151
260
348
424
658
674
700
854
978
1010

Ethene conv.
(%)
97.2
96.5
96.5
98.3
98.1
96.6
98.4
97.5
95.9
96.3
97.4

Xylene
(ppm)
40
0
0
28
18
0
0
5
0
0
10

i-PB sele.
(%)
99.3
99.6
99.3
99.1
99.9
99.4
99.1
99.1
99.1
99.5
99.5

EB sele.
(%)
88.1
89.8
83.6
83.8
83.1
100.7
101.3
99.7
99.9
99.5
99.9

Ethylation sele.
(%)
88.1
98.7
98.6
97.9
98.1
99.5
99.6
99.4
99.1
99.2
99.8

FCC off-gas feed (v%): H2 15%20%, N2 15%18%, O2 0.30%0.50%, COx 3.0%4.0%, CH4 27%30%, C2 H4 15%20%, C2 H6 14%17%, C3 H6
0.04%1.0%, C3 H8 0.50%1.0%, H2 S 100500 ppm, H2 O 10001500 ppm. Transalkylation feed (wt%): EB 1.01%, DEB 89.78%, TEB 9.21%
Benzene + (46) v% transalkylation feed during the 6581010 h time-on-stream; EB selectivity = EB in the products/(EB in the products + DEB + TEB +
EB in the feed) 100% (w/w)

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