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

Ethyl benzene (EB) is an important intermediate for
styrene synthesis. In industry, EB is mainly manufac-
tured by the alkylation of benzene with ethylene via two
methods, i.e., the gas-phase method and the liquid-
phase method. The recently developed gas-phase method
is the Mobil-Badger technology1 over the catalyst
molecular ZSM-5. The gas-phase method employs mod-
erate pressure (1.0-20.8 MPa) and high temperature
(573-773 K), which leads to higher energy consumption
and strict requirements for the apparatus. Moreover,
this method suffers from several disadvantages. For
example, more byproducts are produced, especially
toluene at about 1000-2000 ppm, which is much higher
than the levels required by the downstream processes;
the selectivity toward ethyl benzene is low, and the
deactivation of the catalyst is so serious that it requires
periodic regeneration.
The traditional liquid-phase methods are performed
over catalyst AlCl3. The Unocal-Lummus-UOP tech-
nology2 over a solid acid catalyst containing Y-zeolite
is the most developed one that can improve the defects
of the gas-phase method. The temperature is lower
(<573 K), and the selectivity of ethyl benzene is higher.
The main advantages are that the composition of
toluene in the product is only 20-40 ppm and the life
of the catalyst is longer. The catalyst can run for 1 year
under recycling diethyl benzene. However, the required
pressure is higher than 3.5 MPa.
One difficulty encountered in the alkylation of ben-
zene with ethylene is that the formed EB is more
reactive than benzene with respect to ethylene, which
leads to the production of diethyl benzenes (DEBs). The
DEBs are more reactive than EB and therefore have a
tendency to form triethyl benzene (TEB). To limit these
polyalkylation reactions, a large excess of benzene with
respect to ethylene at the entry of the alkylation reactor
* To whom correspondence should be addressed. Present
address: Max-Planck-Institute for Dynamics of Complex
Technical Systems, Sandtorstrasse 1, D-39106 Magdeburg,
Germany. Tel.: +49-391-6110387. Fax: +49-391-6110542.
E-mail: qi@mpi-magdeburg.mpg.de.
10.1021/ie0342816 CCC: $27.50 © 2004 American Chemical Society
Published on Web 06/25/2004
ratio of benzene to ethylene (B/E) is generally about
2-2.5 for processes using AlCl3, and it can even reach
8-16 for processes using zeolite in the gas-phase
reactor. In the Unocal-Lummus-UOP method, the feed
ratio is 4-10 at 2.79-6.99 MPa and 10 at 6.55 MPa.
However, the large excess of benzene will result in
higher equipment investment costs and much greater
operating costs to separate benzene from the product
and to recycle it to the reactors.
To make use of the advantages of the liquid-phase
method, several publications have reported improve-
ments of the reaction in the liquid phase3-9 and new
types of reactors.10-13 Bellussi et al.3 found a higher
activity and selectivity on β-zeolite than Y-zeolite.
Gao10,11 and Shi et al.12,13 investigated this reaction
system under supercritical conditions over Y- and
β-zeolites. They studied the mechanism of the catalyst
deactivation under different reaction conditions and
concluded that the catalyst deactivation will be serious
if the liquid molar fraction of ethylene is higher than
0.1.
A technology making use of benefits of the liquid-
phase method will be favorable if it can reduce the feed
B/E ratio and prolong the life of the catalyst. The main
point is to acquire a low liquid composition of ethylene
such that the deactivation of the catalyst can be
depressed. Reactive distillation is suitable for overcom-
ing drawbacks of the liquid-phase method because two
functions, i.e., reaction and distillation, are integrated
in one single column. Two patents have demonstrated
ideas to use enriched ethylene14 (or pure ethylene) and
dilute ethylene15 sources. For the latter, the dry feed
gas should be pretreated by desulfurization and dehy-
dration, and the feed B/E ratio is about 2.5. For the
former, the feed B/E ratio could be as low as the
stoichiometric coefficient ratio, i.e., 1:1. Some benzene
and ethylene should be withdrawn with the lights at
the overhead of the column. At such a low feed ratio,
the product quality and the catalyst life must be
examined during a long-run test. So far, there is no
sound process analysis available in the scientific litera-
ture. In particular, a detailed process study based on a
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
0)
dz
- (aAc)nLi - Ac ∑ νikrk
k)1
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
later.
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
equation
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) ∑
i)1
xi ) 1, ∑
i)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
NC NR
dL dV
0)
dz
-
dz
- Ac ∑ ∑ νikrk
i)1k)1
(9)

The energy balances in the liquid and vapor phases are

d(Lh)
0) - (aAc)eL (10)
dz
d(VH)
0)- + (aAc)eV (11)
dz
At the vapor-liquid interface, e ) eL ) eV. The overall
energy balance is
d(Lh) d(VH)
0) - (12)
dz dz
To solve the model equations, the Newton-Raphson
method is used. The initial values of variables (including
the possible feeds) at the upper boundary of each stage
are given and then are intergrated to the lower bound-
ary. The residuals between the new calculated and the
former-step values at each boundary are used to gener-
ate the new values. The calculation continues until the
residuals are smaller than the given accuracy.
The vapor-liquid equilibrium is calculated using the
Benedict-Webb-Rubin-Starling (BWRS) model. The
parameters for the BWRS model and for enthalpy are
taken from Aspen. The mass transfer coefficients are
taken from the in-house report on the applied packing16
kVi ) biV 0.7 (13)
where the parameters bi are 0.0003 for ethylene and
0.000 01 for benzene, ethyl benzene, and diethyl ben-
zene.
By using the above model, the experimental packed
reactive distillation column (Figure 5; for details see the
Experiment section) is simulated at steady state. The
corresponding configurations and operating conditions
are listed in Table 1. From Figure 2a, one can infer an
Figure 2. Composition and temperature profiles of components
in the liquid phase. P ) 1.8 MPa, B/E ) 3.9, rf ) 10.
important message about the compositions in the liquid
phase. The liquid molar fraction of ethylene is very low
(about 0.0003-0.001) in the reactive section except for
the upper part (about 0.01), which illustrates the
conjunct effect of chemical reaction and distillation in
the reactive distillation column. Because of the large
difference of boiling points between ethylene and the
other components (>250 K at 1.8 MPa), ethylene has
very strong potential to concentrate in the reactive
section. However, the fast reaction of ethylene with
benzene consumes much of the ethylene as it is being
concentrated along the reactive zone toward the top of
column. Moreover, because benzene is lighter than the
alkylated benzenes (difference of boiling points > 75 K
at 1.8 MPa), the latter will be continuously removed
toward the bottom of the column during the course of
the reaction through the simultaneous distillation. As
a result, the liquid phase in the reactive zone contains
mainly benzene (molar fraction of about 0.9), and the
local ratio of benzene to ethylene is higher than 50,
which is much higher than the feed ratio. Consequently,
the further consecutive polyalkylation and transalkyl-
ation reactions can be greatly depressed such that the
concentrations of the polyalkylated benzenes can be
maintained at a very low level, which is favorable not
only for a high selectivity toward the desired product
but also for suppressing the deactivation of the catalyst.
In addition, by reactive distillation, the heat released
by the reaction is continuously removed by liquid-phase
evaporation during the reaction process, which results
in a much better temperature profile of the reactor for
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
B/E
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
section.
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

Table 4. Experimental Results: Product Compositiona
B/E composition in bottom (mol %)
(mol/mol) B EB IPB MPB DEB
1.7 47.34 48.88 0.006 0.020 3.08
2.1 54.98 43.24 - 0.005 1.52
3.9 75.98 22.61 - 0.003 1.25
5.7 82.99 16.37 - 0.002 0.58
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,
φ-type stainless Cannon packing (φ ) 3 mm, height )
400 mm) is installed.
Benzene (supplied by Shanghai Feida Chemicals and
purified before application to guarantee a purity higher
than 99.95 wt %) is pumped into the column at the top
of the catalyst part after being preheated. Ethylene
(supplied by Shanghai Institute of Chemical Technology
with a purity higher than 99.95 wt %) is introduced at
the bottom of the reactive section. Both the gas and the
liquid flow rates are measured through mass flow
gauges (Brooks 5950 TR). Two in-house-manufactured
ring-type distributors are applied for good distribution
of the feeds in the catalytic packing.
It is worth noting that the difference of the boiling
temperature between ethylene and other components
is very large, e.g., 183.5 K at the normal atmosphere
and 251.2 K at the investigated pressure compared with
benzene. Therefore, very slight change of the ethylene
composition in the liquid phase will leads to an obvious
variation of the boiling point of the liquid mixture. In
this work, the concentration of ethylene inside the
column is not measured because of its strong evapora-
tion and the high system pressure. Instead, the com-
positions, especially ethylene, in the liquid phase are
estimated by simulation compared with the measured
temperature. For this purpose, several thermocouples
are installed at important positions of the column (T1-
T7 in Figure 5).
The column, including the condenser and reboiler, is
covered with heat-insulating material. Before the reac-
tion experiments, the overall heat effectiveness of the
column (i.e., the ratio of the heat-exchange duty of the
condenser to that of the reboiler) is measured, which is
about 0.84 at the investigated conditions. During the
experiment, the flow rate of the cooling agent for the
condenser is determined to maintain the molar flow rate
ratio rf at about 10. The system pressure is measured
and controlled through a pressure controller with the
aid of an electric heater wrapping the reboiler.
The samples of bottom product are analyzed by gas
chromatograph and mass spectrograph GC-MS (Turbo-
Mass, PE). Because diethyl benzene and triethyl ben-
zene can be transalkylated to ethyl benzene,15 EB, DEB,
and TEB together are taken as the desired product. The
selectivity is defined as
xEB + xDEB + xTEB
β) (14)
1 - xB
In the experiments, the feasibility of prolonging the
catalyst life and product quality at different feed B/E
ratios is studied. The extent of catalyst deactivation is
characterized by the content of carbon in the catalyst.
The experiments are carried out at different feed
ratios of benzene to ethylene (B/E ) 5.7 f 3.9 f 2.1 f
1.7) and at a constant pressure of 1.8 MPa. Before the
Ind. Eng. Chem. Res., Vol. 43, No. 15, 2004 4109
DMEB TEB 4EB EBP TMA selectivity (%)
0.034 0.412 0.203 0.011 0.017 99.5
0.009 0.163 0.062 0.010 0.003 99.8
- 0.105 0.045 0.009 - 99.8
- 0.046 0.009 0.009 - 99.9
reaction experiment, nitrogen is first introduced to
exhaust the air inside the column. Then, 800 cm3 of
benzene is pumped into the column. During the heating
to reach the given system pressure, the inert gas
(nitrogen) is expelled by adjusting the valve over the
condenser. After the system reaches steady state for 2
h, benzene is fed into the column at the specified flow
rate and ethylene is regulated to the column at an
amplitude of 0.8 cm3/s until the assigned flow rate is
reached. The product is vented from the reboiler and is
cooled. No any distillate is withdrawn.
The experiments are operated continuously with a
total time of 408 h. During the whole experiment, the
flow rate of benzene is fixed at 1.55 × 10-3 mol/s, and
the flow rate of ethylene is regulated correspondingly.
For each of the first three runs (B/E ) 5.7, 3.9, 2.1), it
takes about 8-12 h to reach a steady state. After
operating at steady state for 12 h, the flow rate of
ethylene is regulated for the next run. For the last run
(i.e., B/E ) 1.7), the operating time is 330 h.
Experimental results and discussions
Experimental Results. By using GC-MS, the ex-
perimental products are analyzed, and the structures
of the compounds are determined. Before the installa-
tion of the catalyst into the packing, a preliminary
experiment is carried out by introducing benzene and
ethylene into the column. No product can be detected.
For B/E ) 1.7-5.7 and P ) 1.8 MPa, the experimental
results are shown in Table 4. Ethylene is fully con-
verted, and the selectivity toward EB, DEB, and TEB
is higher than 99.5%. The principal alkylated benzene
product is EB. In addition, there are other polyalkylated
products including DEB, TEB, tetraethyl benzene, and
3-ethyl diphenyl. At lower feed B/E ratios, the composi-
tion of byproducts increases, and even more byproducts
are produced. For example, at B/E ) 1.7, dimethyl ethyl
benzene, isopropyl benzene, and the multi-ring sub-
stance R,R,γ-trimethyl anthracene are found, the latter
two of which are not detected at B/E ) 2.1. In other
words, when the feed B/E ratio is too low, more high-
boiling alkylated benzene compounds are formed, which
is harmful to the catalyst. It is worth noting that the
byproducts toluene and xylene, normally produced in
other reactors, cannot be detected in this work.
Deactivation of the Catalyst. One of most impor-
tant features of the alkylation of benzene with ethylene
is the deactivation of the catalyst, which leads to
practical problems in industry. After running for 408 h
in reactive distillation, the apparent color of most
catalyst (80%, at the lower part of the reactive section)
changes slightly compared to that of fresh catalyst. Only
a minor part (20%, upper part of the reactive section)
shows some color change. As studied by Gao,10 the
extent of catalyst deactivation for this reaction system
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
Carbon Content10
carbon content catalyst
(wt %) activity
5.60 0.99
9.63 0.91
10.43 0.83
Table 6. Element Analysis of Carbon in Catalyst
C As mentioned in the Introduction, the main problem
reaction conditionsa (wt %) ref
fresh catalyst 0.00
under benzene at 523.15 K and 6.5 MPa for 8 h 1.29
this work, about 80% catalyst for 408 h 1.77
this work, about 20% catalyst for 408 h 5.63
supercritical reaction for 60 h 6.81
liquid reaction for 14 h 10.37
under ethylene at 523.15 K and 6.5 MPa for 10 min 14.40
vapor reaction for 5 h 15.90
a The catalysts for all experiments are the same.
Figure 6. Carbon content of the catalyst along the catalyst bed.
inside the catalyst. The relationship between the cata-
lyst activity and the carbon content is given in Table 5.
The catalyst samples at different positions are analyzed
and compared with other kinds of reaction process, as
shown in Table 6. The profile of carbon content in the
reactive section is illustrated in Figure 6.
As can be seen from Table 6, the activity of the
catalyst is not particularly sensitive to benzene (carbon
content of 1.29 wt % at pure benzene for 8 h) but is very
sensitive to ethylene (carbon content of 14.40 wt % at
pure ethylene for only 10 min). Compared to other
reaction processes, the extent of the catalyst deactiva-
tion in reactive distillation is slight. For most of the
catalyst, after 408 h, the carbon content is only slightly
higher than the case under pure benzene. For the most
deactivated catalyst in this work, the mean carbon
content is only 5.63 wt % and the activity is about 99
wt %, which are much better than the results obtained
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.
Discussion. From the above experimental and simu-
lation results, the technology of reactive distillation
provides several benefits for the alkylation of benzene
with ethylene. First, the feasible feed ratio of benzene
to ethylene is lower than that required by the liquid-
phase-based reactor (normally 4-10), and ethylene is
fully converted. The benefit from this low feed B/E ratio
can reduce the subsequent separation and recovery
problems and can provide great savings in investment
and operating costs.
Second, because the boiling points of xylene and ethyl
benzene are close (2.16-8.22 K of normal boiling points),
they are difficult to separate to obtain high-purity ethyl
benzene through traditional distillation. In the reactive
distillation process, xylene and toluene are not pro-
duced, which can improve the product quality and
simplify the downstream separation processes.
in the alkylation of benzene with ethylene in the liquid
phase is the serious deactivation of the catalyst, the
10 mechanism of which was presented by Gao.10 Because
of the high liquid composition of ethylene, coke is formed
10
by the polymerization of ethylene to high-boiling com-
10 ponents (so-called precoking) and by the alkylation of
10 ethyl benzene to polyalkylated benzene, further leading
10 to a multi-ring substance. The former dominates the
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
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
the alkylated products are the higher-boiling compo-
nents, they can be continuously removed from the
reactive zone as soon as they are formed. The high local
B/E ratio and low composition of alkylated benzenes in
the reactive zone can significantly slow the formation
of coke and hence prolong the life of the catalyst. The
important advantage of reactive distillation is that the
composition profiles in the liquid phase are not strongly
dependent on the feed ratio. Therefore, the feed B/E
ratio could be relatively lower. However, one should
realize that at too low of a feed B/E ratio, e.g., close to
the stoichiometric coefficient ratio of 1:1, the liquid
composition of ethylene will increase dramatically. As
a result, more byproducts will be formed, and the
deactivation of the catalyst will become serious. Taking
into account the deactivation of the catalyst and product
quality, the recommended feed B/E ratio is about 1.5-
2.0.
Conclusions
The alkylation of benzene with ethylene in a packed
reactive distillation column is carried out by the aid of
mathematical simulations. The influence of the molar
feed ratio of benzene to ethylene is investigated. The
deactivation of the catalyst is analyzed and compared
to that observed in other reaction processes.
The experiments demonstrate the feasibility of alkyl-
ation of benzene with ethylene in reactive distillation
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
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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