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Documente Cultură
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].
Copyright 2009, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(08)60071-7
22
Shenglin Liu et al./ Journal of Natural Gas Chemistry Vol. 18 No. 1 2009
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
23
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
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
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
24
Shenglin Liu et al./ Journal of Natural Gas Chemistry Vol. 18 No. 1 2009
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.
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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