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Ind. Eng. Chem. Res.

2004, 43, 4105-4111 4105

Alkylation of Benzene with Ethylene in a Packed Reactive

Distillation Column
Zhiwen Qi* and Ruisheng Zhang
UNILAB Research Center of Chemical Reaction Engineering, East China University of Science and
Technology, 130 Meilong Road, Shanghai 200237, China

The alkylation of benzene with ethylene suffers from heavy deactivation of the catalyst. However,
this problem can be solved by reactive distillation, as demonstrated through experiments guided
by modeling work. The simulations predict a very low liquid composition of ethylene in most of
the catalyst bed. The experiments explore a low feasible molar feed ratio of benzene to ethylene,
i.e., 1.5-2.0, at which ethylene can be fully converted, and the selectivity toward the desired
product is higher than 99.7%. After 408 h of use, the deactivation of the catalyst is slight except
for the upper part to a lesser extent. Therefore, a long life for the catalyst can be expected. One
additional advantage is that the byproducts toluene and xylene are not detected in this work,
which is favorable for the downstream separation process.

Introduction is applied in the conventional processes. The molar feed

ratio of benzene to ethylene (B/E) is generally about
Ethyl benzene (EB) is an important intermediate for 2-2.5 for processes using AlCl3, and it can even reach
styrene synthesis. In industry, EB is mainly manufac- 8-16 for processes using zeolite in the gas-phase
tured by the alkylation of benzene with ethylene via two reactor. In the Unocal-Lummus-UOP method, the feed
methods, i.e., the gas-phase method and the liquid- ratio is 4-10 at 2.79-6.99 MPa and 10 at 6.55 MPa.
phase method. The recently developed gas-phase method However, the large excess of benzene will result in
is the Mobil-Badger technology1 over the catalyst higher equipment investment costs and much greater
molecular ZSM-5. The gas-phase method employs mod- operating costs to separate benzene from the product
erate pressure (1.0-20.8 MPa) and high temperature and to recycle it to the reactors.
(573-773 K), which leads to higher energy consumption
and strict requirements for the apparatus. Moreover, To make use of the advantages of the liquid-phase
this method suffers from several disadvantages. For method, several publications have reported improve-
example, more byproducts are produced, especially ments of the reaction in the liquid phase3-9 and new
toluene at about 1000-2000 ppm, which is much higher types of reactors.10-13 Bellussi et al.3 found a higher
than the levels required by the downstream processes; activity and selectivity on β-zeolite than Y-zeolite.
the selectivity toward ethyl benzene is low, and the Gao10,11 and Shi et al.12,13 investigated this reaction
deactivation of the catalyst is so serious that it requires system under supercritical conditions over Y- and
periodic regeneration. β-zeolites. They studied the mechanism of the catalyst
The traditional liquid-phase methods are performed deactivation under different reaction conditions and
over catalyst AlCl3. The Unocal-Lummus-UOP tech- concluded that the catalyst deactivation will be serious
nology2 over a solid acid catalyst containing Y-zeolite if the liquid molar fraction of ethylene is higher than
is the most developed one that can improve the defects 0.1.
of the gas-phase method. The temperature is lower A technology making use of benefits of the liquid-
(<573 K), and the selectivity of ethyl benzene is higher. phase method will be favorable if it can reduce the feed
The main advantages are that the composition of B/E ratio and prolong the life of the catalyst. The main
toluene in the product is only 20-40 ppm and the life point is to acquire a low liquid composition of ethylene
of the catalyst is longer. The catalyst can run for 1 year such that the deactivation of the catalyst can be
under recycling diethyl benzene. However, the required depressed. Reactive distillation is suitable for overcom-
pressure is higher than 3.5 MPa. ing drawbacks of the liquid-phase method because two
One difficulty encountered in the alkylation of ben- functions, i.e., reaction and distillation, are integrated
zene with ethylene is that the formed EB is more in one single column. Two patents have demonstrated
reactive than benzene with respect to ethylene, which ideas to use enriched ethylene14 (or pure ethylene) and
leads to the production of diethyl benzenes (DEBs). The dilute ethylene15 sources. For the latter, the dry feed
DEBs are more reactive than EB and therefore have a gas should be pretreated by desulfurization and dehy-
tendency to form triethyl benzene (TEB). To limit these dration, and the feed B/E ratio is about 2.5. For the
polyalkylation reactions, a large excess of benzene with former, the feed B/E ratio could be as low as the
respect to ethylene at the entry of the alkylation reactor stoichiometric coefficient ratio, i.e., 1:1. Some benzene
and ethylene should be withdrawn with the lights at
* To whom correspondence should be addressed. Present
the overhead of the column. At such a low feed ratio,
address: Max-Planck-Institute for Dynamics of Complex the product quality and the catalyst life must be
Technical Systems, Sandtorstrasse 1, D-39106 Magdeburg, examined during a long-run test. So far, there is no
Germany. Tel.: +49-391-6110387. Fax: +49-391-6110542. sound process analysis available in the scientific litera-
E-mail: ture. In particular, a detailed process study based on a
10.1021/ie0342816 CCC: $27.50 © 2004 American Chemical Society
Published on Web 06/25/2004
4106 Ind. Eng. Chem. Res., Vol. 43, No. 15, 2004

Figure 1. Packed reactive distillation column and the stage model.

systematic combination of experimental and model- r3 ) 0.000 85 exp(-20 643/RT)CE1.77CEB0.35 (2c)

based investigations is fully missing.
In this contribution, as the most important feature The chemical equilibrium constant for reaction 1d is
of this reaction system, the liquid composition of eth-
ylene at different feed B/E ratios is first investigated
through simulations. The influence of important operat- K ) xBxDEB/xEB2 (3)
ing conditions (the feed B/E ratio and the molar flow
rate ratio of the reflux to the benzene feed rf) is At 571.15 K, K is 0.883.9 At arbitary temperature T,
predicted. Then, experiments over Y-zeolite are carried K can be obtained from the relation

( ) ( )
out under the guide of the simulation results. The
product quality and the life of the catalyst are inspected, K 1 1 1
ln ) - (4)
and a feasible feed ratio is recommended on the basis K571.15 R T 571.15
of the experimental results.
Process Simulation
Reaction Network
For modeling, the packed reactive distillation column
In the process of the alkylation of benzene with is divided into several stages, and each stage consists
ethylene several chemical reactions can take place, of certain differential elements, as shown in Figure 1.
which are The coordinate is directed from top to bottom. The vapor
and liquid feeds are processed between the stages and
C6H6 + C2H4 f C6H5C2H5 (1a) are taken into account in the stage boundary conditions.
For one element, the model is described by a set of
C6H6 + 2C2H4 f C6H4(C2H5)2 (1b) differential-algebraic equations. In the model, several
assumptions are used: (1) The solid and liquid phases
C6H5C2H5 + C2H4 f C6H4(C2H5)2 (1c) are treated as one phase. (2) The temperatures of the
different phases are the same at certain column heights.
C6H6 + C6H4(C2H5)2 T 2C6H5C2H5 (1d) (3) Mass-transfer resistance exists only at the vapor-
liquid interface. (4) The vapor and liquid phases are in
phase equilibrium at their interface. (5) The catalyst is
C6H5C2H5 + C2H4 f CH3C6H4C3H7 (1e) averagely distributed in the reactive section. (6) The
heat loss along the column is not considered in the
C6H5C2H5 + C2H4 f (CH3)2C6H3C2H5 (1f) element model.
For one element, the component mass balances in the
and further polyalkylation and transalkylation of the liquid and vapor phases are
alkylated benzenes with ethylene and benzene, respec-
tively. d(Lxi) NR
The consecutive and parallel side reactions can gener-
ate several different byproducts. Because the sum of
- (aAc)nLi - Ac ∑ νikrk
ethylene, benzene, ethyl benzene and diethyl benzene (i ) 1, ..., NC - 1) (5)
is generally higher than 99 mol % and the kinetics for
other side reactions are not available, only these four d(Vyi)
components are considered in the process simulations. 0)- + (aAc)nVi (i ) 1, ..., NC - 1) (6)
The results do not deviate substantially, as compared dz
The kinetics for reactions 1a-1c are taken from the At the vapor-liquid interface, nVi ) nLi ) cVi kVi (yVi - yIi ).
literature9 The mass balances are completed by the summation
r1 ) 0.084 exp(-9502/RT)CE1.0CB0.32 (2a) NC NC

r2 ) 0.603 exp(-15 396/RT)CE CB 1.3 0.33

(2b) ∑
xi ) 1, ∑
yi ) 1 (7a,b)
Ind. Eng. Chem. Res., Vol. 43, No. 15, 2004 4107

Table 1. Simulation Conditions: Column Configurations

and Operating Conditions
parameter value
total number of stagesa 8
reactive stage stages 2-6
stripping stage stage 7
catalyst amount 48 g
pressure 1.8 MPa
benzene feed position stage 2
ethylene feed position stage 6
benzene feed flow rate 1.55 × 10-3 mol/s
ethylene feed flow rate 3.87 × 10-4 mol/s
distillate flow rate 0
rfb 10
a Including condenser and reboiler. b Flow rate ratio of the reflux

to the benzene feed.

At the vapor-liquid interface, thermodynamic equilib-

rium between the two phases is assumed

yIi ) KixIi (i ) 1, ..., NC) (8)

The distribution coefficient, Ki, comprises fugacities in

both phases and activity coefficients in the liquid phase.
From eqs 5 and 6 one can obtain the total mass
balance as
dL dV
- Ac ∑ ∑ νikrk

The energy balances in the liquid and vapor phases are

0) - (aAc)eL (10) Figure 2. Composition and temperature profiles of components
in the liquid phase. P ) 1.8 MPa, B/E ) 3.9, rf ) 10.
0)- + (aAc)eV (11) important message about the compositions in the liquid
phase. The liquid molar fraction of ethylene is very low
At the vapor-liquid interface, e ) eL ) eV. The overall (about 0.0003-0.001) in the reactive section except for
energy balance is the upper part (about 0.01), which illustrates the
conjunct effect of chemical reaction and distillation in
d(Lh) d(VH) the reactive distillation column. Because of the large
0) - (12) difference of boiling points between ethylene and the
dz dz
other components (>250 K at 1.8 MPa), ethylene has
To solve the model equations, the Newton-Raphson very strong potential to concentrate in the reactive
method is used. The initial values of variables (including section. However, the fast reaction of ethylene with
the possible feeds) at the upper boundary of each stage benzene consumes much of the ethylene as it is being
are given and then are intergrated to the lower bound- concentrated along the reactive zone toward the top of
ary. The residuals between the new calculated and the column. Moreover, because benzene is lighter than the
former-step values at each boundary are used to gener- alkylated benzenes (difference of boiling points > 75 K
ate the new values. The calculation continues until the at 1.8 MPa), the latter will be continuously removed
residuals are smaller than the given accuracy. toward the bottom of the column during the course of
The vapor-liquid equilibrium is calculated using the the reaction through the simultaneous distillation. As
Benedict-Webb-Rubin-Starling (BWRS) model. The a result, the liquid phase in the reactive zone contains
parameters for the BWRS model and for enthalpy are mainly benzene (molar fraction of about 0.9), and the
taken from Aspen. The mass transfer coefficients are local ratio of benzene to ethylene is higher than 50,
taken from the in-house report on the applied packing16 which is much higher than the feed ratio. Consequently,
the further consecutive polyalkylation and transalkyl-
kVi ) biV 0.7 (13) ation reactions can be greatly depressed such that the
concentrations of the polyalkylated benzenes can be
where the parameters bi are 0.0003 for ethylene and maintained at a very low level, which is favorable not
0.000 01 for benzene, ethyl benzene, and diethyl ben- only for a high selectivity toward the desired product
zene. but also for suppressing the deactivation of the catalyst.
By using the above model, the experimental packed In addition, by reactive distillation, the heat released
reactive distillation column (Figure 5; for details see the by the reaction is continuously removed by liquid-phase
Experiment section) is simulated at steady state. The evaporation during the reaction process, which results
corresponding configurations and operating conditions in a much better temperature profile of the reactor for
are listed in Table 1. From Figure 2a, one can infer an control, as shown in Figure 2b.
4108 Ind. Eng. Chem. Res., Vol. 43, No. 15, 2004

Figure 3. Influence of the molar flow rate ratio of the reflux to

the benzene feed (rf) on the liquid composition of ethylene. P )
1.8 MPa, B/E ) 3.9.

Figure 5. Experimental packed reactive distillation column for

alkylation of benzene with ethylene.

Table 2. Comparison of Simulated and Experimental

Results: Temperature Profile (K)
Figure 4. Influence of the feed B/E ratio on the liquid composition
of ethylene. P ) 1.8 MPa, rf ) 10. stripping
reactive sections section bottom
Figure 3 illustrates the influence of the molar flow (mol/mol) T1 T2 T3 T4 T5 T6 T7
rate ratio of the reflux to the benzene feed, rf, on the 1.7 simu 196.4 211.4 214.8 217.4 219.8 221.5 252.3
ethylene composition profile. In general, a higher rf exp 204.7 216.0 217.1 218.2 218.6 219.1 251.8
2.1 simu 202.8 213.2 214.6 215.5 216.4 219.6 230.9
value is favorable for achieving a lower liquid composi- exp 208.0 216.0 216.2 217.3 217.6 218.2 229.4
tion of ethylene in the reactive section. Because more 3.9 simu 206.9 215.4 216.3 216.9 217.5 218.3 225.6
benzene is refluxed inside the column at higher rf, much exp 209.7 216.2 216.4 216.4 216.6 217.1 225.1
of the concentrated ethylene can be consumed. Conse- 5.7 simu 210.7 214.8 215.2 216.1 216.9 217.5 219.2
quently, the composition of ethylene in the reactive zone exp 214.2 216.1 216.3 216.4 216.4 216.9 218.6
does not change dramatically with respect to rf. This Table 3. Comparison of Simulated and Experimental
feature implies that the column can be operated at a Results: Composition of Bottom (mol %)
relatively low rf value, e.g., 10 in the later Experiment
B/E benzene ethyl benzene diethyl benzene
The influence of the feed B/E ratio is predicted in (mol/mol) simu exp simu exp simu exp
Figure 4. At relatively high feed B/E ratios (2-6), 1.7 48.59 47.34 48.23 48.88 3.17 3.08
decreasing the B/E ratio essentially does not change the 2.1 55.82 54.98 41.85 43.24 2.33 1.52
ethylene profile. However, at low values of B/E (<2), 3.9 76.71 75.98 21.25 22.61 2.04 1.25
5.7 83.27 82.99 15.81 16.37 0.93 0.58
the liquid composition of ethylene is significantly en-
hanced. Especially at the feed ratio of their stoichio- organized to explore the influence of the feed B/E ratio
metric coefficients as suggested by the patent,14 i.e., B/E on the product quality and on the deactivation of the
) 1:1, the liquid molar fraction of ethylene will reach catalyst.
0.15 at the upper part of the reaction zone, which will
lead to a serious deactivation of the catalyst. The Experiment
simulation results, e.g., the temperature profile and the
bottom compositions, are compared to the experiment The packed reactive distillation column for benzene
(see Figure 2b and Tables 2 and 3), which shows an alkylation is illustrated in Figure 5. The column in-
acceptable agreement. cludes two parts: the reactive section at the upper part
As studied by Gao,10 the deactivation of the catalyst and the nonreactive section at the lower part. The outer
could be reduced at ethylene molar fractions lower than diameter of the column is 50 mm. The catalyst, i.e., 48
0.1 in the liquid phase. From the above simulation g of cylinder-type Y-zeolite offered by the Institute of
results, a wide range of the feed B/E ratio (>1.5) could Petroleum Processing Shanghai, is averagely distrib-
be applied. In the next section, an experiment is uted in four segments of high effective packing16 with
Ind. Eng. Chem. Res., Vol. 43, No. 15, 2004 4109

Table 4. Experimental Results: Product Compositiona

B/E composition in bottom (mol %)

(mol/mol) B EB IPB MPB DEB DMEB TEB 4EB EBP TMA selectivity (%)
1.7 47.34 48.88 0.006 0.020 3.08 0.034 0.412 0.203 0.011 0.017 99.5
2.1 54.98 43.24 - 0.005 1.52 0.009 0.163 0.062 0.010 0.003 99.8
3.9 75.98 22.61 - 0.003 1.25 - 0.105 0.045 0.009 - 99.8
5.7 82.99 16.37 - 0.002 0.58 - 0.046 0.009 0.009 - 99.9
a IPB ) isopropyl benzene, MPB ) methyl propyl benzene, DMPB ) dimethyl propyl benzene, 4EB ) tetraethyl benzene, EBP )

3-ethylebp biphenyl, TMA ) R,R,γ-trimethyl anthracene.

a total height of 1200 mm. In the nonreactive section, reaction experiment, nitrogen is first introduced to
φ-type stainless Cannon packing (φ ) 3 mm, height ) exhaust the air inside the column. Then, 800 cm3 of
400 mm) is installed. benzene is pumped into the column. During the heating
Benzene (supplied by Shanghai Feida Chemicals and to reach the given system pressure, the inert gas
purified before application to guarantee a purity higher (nitrogen) is expelled by adjusting the valve over the
than 99.95 wt %) is pumped into the column at the top condenser. After the system reaches steady state for 2
of the catalyst part after being preheated. Ethylene h, benzene is fed into the column at the specified flow
(supplied by Shanghai Institute of Chemical Technology rate and ethylene is regulated to the column at an
with a purity higher than 99.95 wt %) is introduced at amplitude of 0.8 cm3/s until the assigned flow rate is
the bottom of the reactive section. Both the gas and the reached. The product is vented from the reboiler and is
liquid flow rates are measured through mass flow cooled. No any distillate is withdrawn.
gauges (Brooks 5950 TR). Two in-house-manufactured The experiments are operated continuously with a
ring-type distributors are applied for good distribution total time of 408 h. During the whole experiment, the
of the feeds in the catalytic packing. flow rate of benzene is fixed at 1.55 × 10-3 mol/s, and
It is worth noting that the difference of the boiling the flow rate of ethylene is regulated correspondingly.
temperature between ethylene and other components For each of the first three runs (B/E ) 5.7, 3.9, 2.1), it
is very large, e.g., 183.5 K at the normal atmosphere takes about 8-12 h to reach a steady state. After
and 251.2 K at the investigated pressure compared with operating at steady state for 12 h, the flow rate of
benzene. Therefore, very slight change of the ethylene ethylene is regulated for the next run. For the last run
composition in the liquid phase will leads to an obvious (i.e., B/E ) 1.7), the operating time is 330 h.
variation of the boiling point of the liquid mixture. In
this work, the concentration of ethylene inside the
Experimental results and discussions
column is not measured because of its strong evapora-
tion and the high system pressure. Instead, the com- Experimental Results. By using GC-MS, the ex-
positions, especially ethylene, in the liquid phase are perimental products are analyzed, and the structures
estimated by simulation compared with the measured of the compounds are determined. Before the installa-
temperature. For this purpose, several thermocouples tion of the catalyst into the packing, a preliminary
are installed at important positions of the column (T1- experiment is carried out by introducing benzene and
T7 in Figure 5). ethylene into the column. No product can be detected.
The column, including the condenser and reboiler, is For B/E ) 1.7-5.7 and P ) 1.8 MPa, the experimental
covered with heat-insulating material. Before the reac- results are shown in Table 4. Ethylene is fully con-
tion experiments, the overall heat effectiveness of the verted, and the selectivity toward EB, DEB, and TEB
column (i.e., the ratio of the heat-exchange duty of the is higher than 99.5%. The principal alkylated benzene
condenser to that of the reboiler) is measured, which is product is EB. In addition, there are other polyalkylated
about 0.84 at the investigated conditions. During the products including DEB, TEB, tetraethyl benzene, and
experiment, the flow rate of the cooling agent for the 3-ethyl diphenyl. At lower feed B/E ratios, the composi-
condenser is determined to maintain the molar flow rate tion of byproducts increases, and even more byproducts
ratio rf at about 10. The system pressure is measured are produced. For example, at B/E ) 1.7, dimethyl ethyl
and controlled through a pressure controller with the benzene, isopropyl benzene, and the multi-ring sub-
aid of an electric heater wrapping the reboiler. stance R,R,γ-trimethyl anthracene are found, the latter
The samples of bottom product are analyzed by gas two of which are not detected at B/E ) 2.1. In other
chromatograph and mass spectrograph GC-MS (Turbo- words, when the feed B/E ratio is too low, more high-
Mass, PE). Because diethyl benzene and triethyl ben- boiling alkylated benzene compounds are formed, which
zene can be transalkylated to ethyl benzene,15 EB, DEB, is harmful to the catalyst. It is worth noting that the
and TEB together are taken as the desired product. The byproducts toluene and xylene, normally produced in
selectivity is defined as other reactors, cannot be detected in this work.
xEB + xDEB + xTEB Deactivation of the Catalyst. One of most impor-
β) (14) tant features of the alkylation of benzene with ethylene
1 - xB is the deactivation of the catalyst, which leads to
practical problems in industry. After running for 408 h
In the experiments, the feasibility of prolonging the in reactive distillation, the apparent color of most
catalyst life and product quality at different feed B/E catalyst (80%, at the lower part of the reactive section)
ratios is studied. The extent of catalyst deactivation is changes slightly compared to that of fresh catalyst. Only
characterized by the content of carbon in the catalyst. a minor part (20%, upper part of the reactive section)
The experiments are carried out at different feed shows some color change. As studied by Gao,10 the
ratios of benzene to ethylene (B/E ) 5.7 f 3.9 f 2.1 f extent of catalyst deactivation for this reaction system
1.7) and at a constant pressure of 1.8 MPa. Before the can be characterized principally by the content of carbon
4110 Ind. Eng. Chem. Res., Vol. 43, No. 15, 2004

Table 5. Relationship between Catalyst Activity and problems and can provide great savings in investment
Carbon Content10 and operating costs.
carbon content catalyst Second, because the boiling points of xylene and ethyl
(wt %) activity benzene are close (2.16-8.22 K of normal boiling points),
5.60 0.99 they are difficult to separate to obtain high-purity ethyl
9.63 0.91 benzene through traditional distillation. In the reactive
10.43 0.83 distillation process, xylene and toluene are not pro-
duced, which can improve the product quality and
Table 6. Element Analysis of Carbon in Catalyst
simplify the downstream separation processes.
C As mentioned in the Introduction, the main problem
reaction conditionsa (wt %) ref in the alkylation of benzene with ethylene in the liquid
fresh catalyst 0.00 phase is the serious deactivation of the catalyst, the
under benzene at 523.15 K and 6.5 MPa for 8 h 1.29 10 mechanism of which was presented by Gao.10 Because
this work, about 80% catalyst for 408 h 1.77 of the high liquid composition of ethylene, coke is formed
this work, about 20% catalyst for 408 h 5.63
supercritical reaction for 60 h 6.81 10
by the polymerization of ethylene to high-boiling com-
liquid reaction for 14 h 10.37 10 ponents (so-called precoking) and by the alkylation of
under ethylene at 523.15 K and 6.5 MPa for 10 min 14.40 10 ethyl benzene to polyalkylated benzene, further leading
vapor reaction for 5 h 15.90 10 to a multi-ring substance. The former dominates the
a The catalysts for all experiments are the same. formation of coke, especially when the molar fraction
of ethylene is higher than 0.1 in the liquid phase. The
coke covers the active center on the catalyst surface and
blocks the micropores inside the zeolite, which leads to
catalyst deactivation. Therefore, the key to prolonging
the catalyst life is to reduce the liquid composition of
ethylene. In other words, an approach is strongly needed
to keep a higher ratio of benzene to ethylene in the local
liquid phase at a low feed B/E ratio.
In the reactive distillation process, the composition
profiles in the liquid phase are determined not only by
the properties of components but also by the reaction
kinetics. In addition, feasible operating conditions are
helpful. As mentioned in the Process Simulation section,
under the experimental conditions tested, the joint effect
of concentrating ethylene toward the top of the column
and consuming ethylene in the reactive section results
Figure 6. Carbon content of the catalyst along the catalyst bed.
in a low liquid composition of ethylene. The local molar
ratio of benzene to ethylene on the catalyst surface is
much higher than the feed ratio. Meanwhile, because
inside the catalyst. The relationship between the cata-
the alkylated products are the higher-boiling compo-
lyst activity and the carbon content is given in Table 5.
nents, they can be continuously removed from the
The catalyst samples at different positions are analyzed
reactive zone as soon as they are formed. The high local
and compared with other kinds of reaction process, as
B/E ratio and low composition of alkylated benzenes in
shown in Table 6. The profile of carbon content in the
the reactive zone can significantly slow the formation
reactive section is illustrated in Figure 6.
of coke and hence prolong the life of the catalyst. The
As can be seen from Table 6, the activity of the important advantage of reactive distillation is that the
catalyst is not particularly sensitive to benzene (carbon composition profiles in the liquid phase are not strongly
content of 1.29 wt % at pure benzene for 8 h) but is very dependent on the feed ratio. Therefore, the feed B/E
sensitive to ethylene (carbon content of 14.40 wt % at ratio could be relatively lower. However, one should
pure ethylene for only 10 min). Compared to other realize that at too low of a feed B/E ratio, e.g., close to
reaction processes, the extent of the catalyst deactiva- the stoichiometric coefficient ratio of 1:1, the liquid
tion in reactive distillation is slight. For most of the composition of ethylene will increase dramatically. As
catalyst, after 408 h, the carbon content is only slightly a result, more byproducts will be formed, and the
higher than the case under pure benzene. For the most deactivation of the catalyst will become serious. Taking
deactivated catalyst in this work, the mean carbon into account the deactivation of the catalyst and product
content is only 5.63 wt % and the activity is about 99 quality, the recommended feed B/E ratio is about 1.5-
wt %, which are much better than the results obtained 2.0.
with other reaction processes, especially the liquid-
phase-based reactor using the same catalyst. The ex-
pected life of the catalyst in reactive distillation can be
longer than 1 year according to the deactivation rate. The alkylation of benzene with ethylene in a packed
Discussion. From the above experimental and simu- reactive distillation column is carried out by the aid of
lation results, the technology of reactive distillation mathematical simulations. The influence of the molar
provides several benefits for the alkylation of benzene feed ratio of benzene to ethylene is investigated. The
with ethylene. First, the feasible feed ratio of benzene deactivation of the catalyst is analyzed and compared
to ethylene is lower than that required by the liquid- to that observed in other reaction processes.
phase-based reactor (normally 4-10), and ethylene is The experiments demonstrate the feasibility of alkyl-
fully converted. The benefit from this low feed B/E ratio ation of benzene with ethylene in reactive distillation
can reduce the subsequent separation and recovery at low feed ratios of benzene to ethylene. The recom-
Ind. Eng. Chem. Res., Vol. 43, No. 15, 2004 4111

mended feed B/E ratio is 1.5-2.0. Ethylene can be fully EB ) ethyl benzene
converted, and the selectivity toward the desired prod- TEB ) triethyl benzene
uct can be higher than 99.5%. No toluene and xylene
are detected in this work. After a long running time, Literature Cited
the catalyst deactivation is slight, and the expected life (1) Chen, N. Y.; Garwood, W. E. Industrial Application of
of the catalyst is much longer than in other reaction Shape-Selective Catalyst. Catal. Rev. 1986, 28 (2-3), 185.
processes. (2) Peterson, M. A. Presented at the Unocal Technology 1991
Symposium, Phuket, Thailand, Nov 6-8, 1981.
(3) Bellussi, G.; Pazzuconi, G.; Perego, C.; Girotti, G.; terzoni,
Nomenclature G. Liquid-Phase Alkylation of Benzene with Light Olefins Cata-
lyzed by β-Zeolites. J. Catal. 1995, 157, 227.
a ) specific vapor-liquid interfacial area, m2/m3
(4) Hendriksen, D. E.; Lattner, J. R.; Janssen, M. J. G.
Ac ) column cross section, m2 Alkylation Process Using Zeolite Beta. U.S. Patent 6,002,057,
B/E ) molar ratio of feed flow rates of benzene to ethylene, 1999.
mol/mol (5) Cavani, F.; Arrigoni, V.; Bellussi, G., Process for Alkylating
c ) molar density, mol/m3 Aromatic Compounds. European Patent EP 0,432,814,A1, 1991.
C ) concentration, mol/m3 (6) Nacamuli, G. J.; Innes, R. A.; Zones, S. I. Liquid-Phase
e ) energy flux through the vapor-liquid interface, kJ/ Alkylation or Transalkylation Process Using Zeolite Beta. U.S.
m2‚s Patent 4,891,458, 1990.
H, h ) enthalpies for the vapor and liquid phases, (7) Du, Y., Wang, H.; Chen, S. Study on Alkylation of Benzene
with Ethylene over β-Zeolite catalyst to Ethylbenzene by in-situ
respectively, kJ/mol
IR. J. Mol. Catal. A Chem. 2002, 179, 253.
K ) chemical equilibrium constant (8) Chu, P.; Landis, M. E.; Le, Q. N. Production of Ethyl
Ki ) distribution coefficient of species i Benzene. U.S. Patent 5,334,795, 1994.
ki ) mass transfer coefficient of species i in the vapor (9) Wang, Y. H. Kinetics Study on the Liquid-Phase Alkylation
phase, m/s of Benzene with Ethylene over Y-Zeolite. Master’s Thesis, East
L, V ) flow rates for the liquid and vapor phases, China University of Science and Technology, Shanghai, China,
respectively, mol/s 1991.
ni ) molar flux of species i, mol/m2‚s (10) Gao, Y. Study on the Suppercritical Reaction of Alkylation
NC ) number of components of Benzene with Ethylene. Ph.D. Dissertation, East China Uni-
versity of Science and Technology, Shanghai, China, 1994.
NR ) number of reactions
(11) Gao, Y.; Yuan W. K. Coking Mechanism of Zeolite for
P ) pressure, MPa Supercritical Fluid Alkylation of Benzene. Process Tech. Proc.
r ) reaction rate, mol/s‚m3 1996, 12, 151.
rf ) molar flow rate ratio of the reflux to the benzene feed, (12) Shi, Y. F.; Gao, Y.; Dai, Y. C.; Yuan, W. K. Kinetic for
mol/mol Benzene and Ethylene Reaction in Near-Critical Regions. Chem.
T ) temperature, K Eng. Sci. 2001, 56, 1403.
x, y ) molar compositions in the liquid and vapor phases, (13) Shi, Y. F.; Gao, Y.; Yuan, W. K. Some Characterization of
respectively β-Zeolite for Alkylation of Benzene in Near Critical Regions. Catal.
z ) column coordinate, m Today 2002, 74, 91.
(14) Zhang, J. R.; Li, D. F.; Fu, J. Q.; Cao, G. Process and
vi,k ) stoichiometric coefficients of species i in reaction k
Apparatus for Preparation of Ethylbenzene by Alkylation of
Superscripts and Subscripts Benzene with Dilute Ethylene Contained in Dry Gas by Catalytic
Distillation. U.S. Patent 6,504,071 B2, 2003.
F, f ) feed (15) Smith, L. A.; Arganbright, A.; Hearn, D. Process for the
I ) vapor-liquid interface Preparation of Ethyl Benzene. U.S. Patent 5,476,978, 1995.
i ) species i (16) Zhang, R. S.; Zhang, J. T.; Song, H. Y. High Effective
j ) stage j Packing for Distillation. CN Patent 92,222,666.0, 1992.
k ) reaction k
Received for review December 1, 2003
L, V ) liquid and vapor phases, respectively
Revised manuscript received March 26, 2004
Abbreviations Accepted May 20, 2004
DEB ) diethyl benzene IE0342816