ISSN 09655441, Petroleum Chemistry, 2011, Vol. 51, No. 1, pp. 3948. Pleiades Publishing, Ltd., 2010.

Original Russian Text I.M. Gerzeliev, S.N. Khadzhiev, I.E. Sakharova, 2011, published in Neftekhimiya, 2011, Vol. 51, No. 1, pp. 4049.
39
The synthesis of ethylbenzene (EB), one of the
most important highproductionvolume petrochem
icals, is becoming increasingly more important as zeo
lite catalysts have been found to have industrial appli
cation. The high growth rate of EB production is due
to the increasing demand for products derived from it.
More than 90% of ethylene is used to produce styrene,
one of the most important chemicals, approximately
65% of which is used to produce polystyrene. The
other part is used for the manufacture of acrylonitrile
butadienestyrene and styreneacrylonitrile copoly
mers, unsaturated polyesters, and styrenebutadiene
rubber [1]. A large proportion of the global demand for
benzene is determined by the production of EB. The
dynamics of growth in EB consumption can be traced
in the following global/Russian benzene production
capacity (in millions of tons): 18.8/0.7 in 1976 [2],
25.1/0.9 in 1986, 33.5/1.0 in 1996 [3], and 41.0/1.7 in
2007 [1]. The total global EB production capacity rap
idly increases and makes about 29 million tons per
year. The annual growth of the EB market reaches 4
5%, and the global demand for EB in 2011 is forecast
to approach 35.5 million t [4]. The volume of EB/sty
rene production in Russia amounted to 186/162,
580/516, and 805/700 thousand t in 1997, 2004, and
2009, respectively. The manufacturers of EB/styrene
in Russia are OAO Nizhnekamskneftekhim
(345000/300000 t/yr), OAO Salavatnefteorgsintez
(230000/200000 t/yr), OAO Stirol (ZAO Sibur
Khimprom) (140000/120000 t/yr), and OAO Angarsk
Petrochemical Company (90000/80000 t/yr).
The majority of EB is produced via benzene alkyla
tion with ethylene in the presence of acid catalysts.
Depending on the catalyst used and the alkylation
conditions, di, tri, and tetraethylbenzenes (of which
diethylbenzenes (DEB) make 8597 wt %) in an
amount of 1 to 15 wt % of the total alkylate are formed
along with ethylbenzene. To improve the EB produc
tion efficiency, the alkylation process is combined with
transalkylation, which allows the byproduct poly
alkylbenzenes (PEB) to be converted into EB.
The earliest technologies developed since the 1930s
employed strong mineral acids or Lewis acids (e.g.,
H
2
SO
4
, HF, and BF
3
) as catalysts for the EB synthesis.
These acids are highly toxic, corrosive, and dangerous
to handle and transport [5]. In the 1950s, the Friedel
Crafts catalyst AlCl
3
found very wide application as an
EB synthesis catalyst, although its use made the pro
cess rather complicated and laborconsuming. In
addition, there were disadvantages associated with the
sensitivity of the catalyst to trace impurities in the ole
fin and corrosion of equipment [6].
In 1975, the Monsanto/Lummus technology using
AlCl
3
and consisting of alkylation and transalkylation
in the same reactor (Table 1) held a firm position in
global EB production. By 1987, eleven plants with a
total capacity of 3.1 million tons per year of EB per
annum operated on the basis of this technology,
including the largest Monsanto unit, which had an
output of 770 thousand tons per year [3].
As a possible solution to the corrosion control
problem, UOP in 1960 proposed a liquid phase pro
cess using BF
3
/Al
2
O
3
as a catalyst (Alkar process) and
Ethylbenzene Synthesis and Benzene Transalkylation
with Diethylbenzenes on Zeolite Catalysts
I. M. Gerzeliev, S. N. Khadzhiev, and I. E. Sakharova
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
email: gerzeliev@ips.ac.ru; khadzhiev@ips.ac.ru; sakharova@ips.ac.ru
Received August 27, 2010
AbstractProcesses for the manufacturing of ethylbenzene (EB), one of the most important highvolume
petrochemicals, have been surveyed. Trends concerning the use of catalysts and technologies for this purpose
have been discussed. It has been shown that the transalkylation of benzene with diethylbenzenes is an integral
part of modern EB production units. Catalysts based on beta, Y, and mordenite zeolites have been subjected
to comparative testing in the transalkylation process. Data on the correlation of the physicochemical and cat
alytic properties of the test catalysts are presented, and a rapid procedure for evaluating the catalyst stability
under laboratory conditions is described. Catalyst samples based on zeolite Y, which turned out to be the most
active in the transalkylation reaction, have been tested for a life time on a pilot unit. Data on the effect of the
process parameters on the output characteristics are presented, and basic guidelines for selection of the opti
mal process conditions are given. The numerical values of the kinetic parameters describing experimental
data for the transalkylation reaction have been determined.
DOI: 10.1134/S0965544111010038
40
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
GERZELIEV et al.
a gasphase process with H
3
PO
4
on kieselguhr. How
ever, due to partial carryover of the active component,
the corrosion problem has not been completely elimi
nated. In addition, such catalysts experience fast deac
tivation in transalkylation with PEB and their regener
ation is fraught with difficulties [7].
Solid Acid Catalysts
The first solid acid catalysts were amorphous alu
minosilicate gels, and they were used in the 1940s to
mediate a vaporphase EB manufacturing process [8].
In 1966, it was shown [9] that macroporous zeolites X
and Y (REX, HY, and REY) are more effective EB
synthesis catalysts than amorphous aluminosilicates.
In the Soviet Union at that time, the EB manufactur
ing process in the presence of synthetic zeolites was
studied intensively by Academician Kh.M. Minachev
and his group [10]. In an extended series of studies,
crystallites of many structural types were examined,
such as faujasites X and Y (including dealuminated
species), mordenite, omega, offerite, and various pen
tasils synthesized with the use of organic structure
forming agents (templates) (ZSM5, ZSM8, and
ultrasil) or without templates (TsVM).
The industrial application of a zeolite catalyst in
the production of EB was pioneered by MobilBad
ger in 1980. The process was carried out in the gas
phase on the HZSM5 catalyst having an onstream
time of 6090 days. Similar to the process conducted
on the AlCl
3
HCl complex, polyethylbenzenes were
recycled to the reactor in which they entered into tran
salkylation. Beginning from the first industrial appli
cation, more than 35 units with a total capacity of
about 8 million tons/year licensed the MobilBadger
technology [11]. In the 1990s, MobilBadger devel
oped the thirdgeneration EB manufacture process,
which by then, in contrast, used a separate transalky
lation reactor. The onstream time increased from
90 days to 1 year (Table 1) [7]. Owing to the thermody
namic factors, the process of benzene transalkylation
with DEB requires somewhat more severe conditions
as compared to alkylation, so that the spatial separa
tion of alkylation and transalkylation significantly
increased the efficiency of the process.
Some studies have shown that alkylation/tran
salkylation catalysts may be the same or different [3,
12, 13]. A survey of the patent literature over the
period from 1967 to 2010 allowed us to elucidate in
more detail the dynamics of the alkylation/transalky
lation processes on different catalysts (Fig. 1). Until
the 1990s, the synthesis of EB on zeolite catalysts
under gasphase conditions was preferred. Since that
time, the overwhelming majority of patent applica
tions were devoted to liquidphase EB manufacturing
processes. It should be noted that the most preferred
alkylation catalysts are beta, MCM22, MCM36,
and MCM49 zeolites and the transalkylation cata
lysts are beta and Y zeolites. The advantages of the liq
uidphase processes are a lower energy consumption,
as compared to the vaporphase process, due to lower
temperatures of the processes; a longer catalyst life
time; and a higher selectivity. To run such processes, it
was necessary to pass from the traditional catalytic sys
tems based on mesoporous zeolites (ZSM5, pore size
of ~5.56 ) to highperformance catalysts based on
macroporous zeolites (beta, pore size ~6.57.5 ; Y
with pores of ~79 ; mordenite with a pore size of
~6.57 ; omega; MCM22; etc.).
The first liquidphase EB production process on a
zeolite catalyst was commercialized by Lum
mus/Unocal/UOP in 1989 in Japan. The plant capac
ity for EB was 210000 t/yr [14]. Under this technology,
the alkylation and transalkylation processes occur in
separate reactors on the zeolite Y catalyst. By 1997,
three such units operated in Japan and one operated in

Table 1. Main ethylbenzene manufacturing processes
Monsanto
Lummus
1975
MobilBad
ger (second
generation)
1980
Lummus
Unocal
UOP 1989
MobilBad
ger (third
generation)
1990
CDtech EB
1994
MobilRay
theon
EBMAX
1995
Lummus
UOP
EBONE
1996
Alkylation
Temperature, C 160 390440 240270 390440
Catalyst A1C1
3
ZSM5 Y ZSM5 Y MCM22 EBZ500
Phase Liquid Vapor Liquid Vapor Liquid Liquid
Benzene/ethylene in
feedstock (mol)
2.5 7.6 7.2 7.6 4 46
Life time, years 0.25 1 1 5 3 2
EB yield, wt % 99.7 98.1 98.2 99.2 99.7 99.5 99.6
Transalkylation
Catalyst Combined with alkylation Y ZSM5 Y ZSM5 EBZ100
Phase Liquid Vapor Liquid Vapor Liquid
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
ETHYLBENZENE SYNTHESIS AND BENZENE TRANSALKYLATION 41
China. Thirteen other units with capacities ranging
from 100000 to 530000 t/yr are at various stages of
design and construction [3]. Data have recently
appeared to show that zeolite beta, which exhibits a
high activity in mediation of the liquidphase alkyla
tion process, is a more selective catalyst than zeolite Y.
Zeolite beta has also turned out to be a good catalyst
for the liquidphase transalkylation with mDEB [15].
As a result of investigations in the early 1990s,
Chevron patented a liquidphase alkylation and tran
salkylation process on zeolite beta in the United States
[16], and EniChem (Polimeri Europa) claimed a sim
ilar process in 1991 in Europe [17]. In 1994, ABB
Lummus Global, Inc., and Chemical Research &
Licensing proposed the CDTECH process for ethyl
benzene manufacturing (Table 1), which is based on
the use of a reactor/distillation column. Under this
technology, EB is withdrawn from the system after iso
lation and polyalkylbenzenes are sent to a separate
transalkylation reactor. After the commissioning in
Japan of the first industrialscale unit with a capacity
of 260000 t/yr by EB, two other units with capacities
of 140000 and 477000 t/yr were commissioned in
Argentina and Canada in 2000 [11].
Shortly after that, data on a higher selectivity of the
catalyst MCM22 as compared to ultrastable Y (USY)
or beta at similar parameters of activity in the alkyla
tion of benzene with ethylene were reported [5, 18]. In
1995, Mobil/Raytheon introduced the new EBMax
process for the manufacturing of EB on a MCM22
based catalyst at the Chiba Styrene Monomer plant in
Japan. The alkylation process was conducted in the
liquid phase, and the catalyst onstream time
exceeded 3 years. Transalkylation was conducted in
the gas phase on the catalyst ZSM5 in a separate reac
tor and, later, in the liquid phase over the TRANS4
catalyst [11].
In 1996, Lummus/UOP patented the EBOne pro
cess, in which separate alkylation and transalkylation
reactors were charged with zeolite betabased catalysts
EBZ500 and EBZ100, respectively. The process
gives highpurity ethylbenzene (99.9 wt %) with a yield
of 99.6 wt %. A high stability of catalyst operation, low
recycle rates of benzene and polyethylbenzenes, and
the simple design of the reactor made from carbon
steel ensure a relatively low cost for the process [7].
In Russia, the synthesis of EB on zeolite catalysts
under both gasphase and liquidphase conditions was
developed by the Grozny Research Institute and the
Zelinsky Institute of Organic Chemistry in the late
1980s. The process was implemented in the 1990s at
the reconstructed plant of OAO Salavatnefteorgsintez
to have a capacity of 230000 ton/year. On the basis of
international practice at the time, the gasphase mode
of the process was preferred. For a number of well
known economic reasons, the construction took
awhile to complete and the plant was not commis
sioned until 2003 [19]. The facility meets the design
parameters and has operated steadily through the
present. Further improvement of the plant suggests the
involvement of a liquidphase DEB transalkylation
unit as the first step and then transfer to the liquid
phase mode of the EB synthesis.
For this purpose, we studied the benzene transalky
lation reactions with DEB as described below. The task
of the study was to find a catalyst sample with optimal
100
90
80
70
60
50
40
1970 1969 1973 1990 1991 1993 1994 1997 1997 1999 2001 2006 2008 2010
O
u
t
p
u
t

p
a
r
a
m
e
t
e
r
s
,

w
t

%
Patenting year
AlCl
3
H
3
PO
4
/
kieselguhr
vap. phase
UOP
1
2
3
1
2
3
4
AlCl
3
H
3
PO
4
/
kieselguhr
vap. phase
UOP
ZSM5
vap. phase
Mobil
ZSM5
vap. phase
Mobil
H
liq. phase
MOR
liq. phase
Dow
Chem.
ZSM5
vap. phase
Mobil
MCM49
liq. phase
Mobil
MOR
liq. phase
Dow
Chem.
Omega
liq. phase
Fina
Tech.
H
liq. phase
H
liq. phase
Mobil
ZSM5
liq. phase
Mobil
H
liq. phase
Mobil
Chem.
H/F
liq. phase
China
Petro
MCM22
liq. phase
Mobil
H
liq. phase
UOP
MCM36
mix. phase
Exxon
Mobil
H
liq. phase
Fina
Tech.
USM8
liq. phase
UOP
Chem
H/F
liq. phase
China
Petro
HY
liq. phase
UOP
HY
liq. phase
Fina
Tech.
H, HY,
MCM22
liq. phase
UOP
H/F
liq. phase
Exxon
Mobil
Fig. 1. Development of the processes of benzene alkylation with ethylene and benzene transalkylation with diethylbenzenes with
respect to the catalyst used over the time period of 1967 to 2010. Notation: (1) conversion of ethylene in the alkylation, (2) eth
ylbenzene alkylation selectivity, (3) ethylbenzene transalkylation selectivity, and (4) conversion of DEB in the transalkylation.
42
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
GERZELIEV et al.
activity, selectivity, and stability and to determine opti
mal process conditions.
EXPERIMENTAL
To study the transalkylation reaction, we synthe
sized three samples of catalysts based on zeolite beta
manufactured by AZKiOS (Angarsk Catalyst and
Organic Synthesis Plant) with beta/AHO weight ratios
of 30/70, 50/50, and 70/30 (denoted by Beta30,
Beta50, and Beta70, respectively). As benchmarks,
reference samples with beta/AHO weight ratios of
0/100 and 100/0 were used (denoted as 100% Al
2
O
3
and 100% beta, respectively).
Catalysts containing 70, 50, and 30% zeolite in the
support were prepared by mixing zeolite beta with a
cake of aluminum hydroxide (manufactured by
AZKiOS) preliminarily peptized with nitric acid at a
pH of 3. The catalyst mass was thoroughly stirred,
evaporated to a shapeable state, extruded, dried first at
room temperature and then in an oven at 120 for 5
6 h, and calcined in air with a stepwise increase in tem
perature to 540. The sample containing 100% zeo
lite beta was prepared by pelletizing and subsequent
calcining under the same conditions, grinding, and
screening for the desired fraction. The catalysts used
for comparative testing were HYBF (binderfree,
based on zeolite Y) purchased from Salavatnefte
orgsintez and the imported (Zeolyst) catalysts MOR
based on mordenite, HY based on zeolite Y, and Beta*
based on zeolite beta.
The acid properties of the catalysts were tested by
the ammonia temperatureprogrammed desorption
(TPD NH
3
) technique on a Chemisorb 2750 instru
ment. The analysis procedure included the following
steps: preconditioning the sample in a helium stream
at a temperature of 550 over 1 h, cooling to room
temperature, adsorbing ammonia (5 vol % NH
3
/N
2
)
for 30 min, and stripping the weakly bound ammonia
in a helium stream at 100. After baseline stabiliza
tion, desorption of ammonia in a helium stream was
performed (heating rate 8C/min). The flow rate of all
gases was 30 ml/min. The crystallineframework
structure and the state of zeolite OH groups were stud
ied by infrared spectroscopy with a Bruker IFS66 v/s
Fouriertransform IR spectrometer in the range of
4004000 cm
1
. To measure the spectra, all catalyst
samples were prepared as a nujol mull pressed into a
monolayer between two potassium bromide plates.
The nujol absorption bands were subtracted from the
spectrum.
The catalytic properties were tested in a laboratory
setup with a flow reactor of 10 mm in inner diameter
and 150 mm in height, taking a catalyst (fraction
0.251.0 mm) charge of 2 cm
3
. Comparative testing of
the catalysts in the laboratory setup was carried out
under predeterminedly severe conditions: a tempera
ture of 230, a pressure of 0.1 MPa, a feed weight
hourly space velocity (WHSV) of 10 h
1
, a ben
zene/DEB weight ratio in the feed of 3/1, and a feed
stock supply time of 240400 min, with sampling
every 40 min. At atmospheric pressure, an increased
feed WHSV, and a low benzene/DEB ratio in the feed
stock, the deactivation is more rapid; therefore, this
approach allows us to evaluate the comparative char
acteristics of the catalysts within quite a short period.
Longterm tests were run on a pilot plant in the con
tinuous mode in a reactor with an inner diameter of
25 mm, a height of 1300 mm, and a catalyst (fraction
1.251.6 mm) charge of 80 cm
3
.
The life time testing of the zeolite beta catalysts was
carried out under the following conditions: a temper
ature of 250, a pressure of 3.0 MPa, a feed WHSV of
2 h
1
, a 3/1 benzene/DEB weight ratio in the feed
stock; and sampling at regular 4h intervals. The life
time of the zeolite Y catalysts was examined under the
following initial conditions: a temperature of 190; a
pressure of 2.5 MPa, a feed WHSV of 1.3 h
1
, a ben
zene/DEB weight ratio in the feedstock of 5.5/1, and
sampling at 6h intervals. The feed mixture was pre
pared from highgrade benzene (GOST (State Stan
dard) 957293, a base substance content of 99.7% with
the rest made up of nheptane, methylcyclopentane,
methylcyclohexane, and toluene) and technicalgrade
diethylbenzene (TU (Technical Specifications) 2414
135057665752007; (base substance content of at
least 85%, including not less than 45% mDEB).
RESULTS AND DISCUSSION
Thermodynamics
Thermodynamic calculations based on the values
of the standard Gibbs energy of formation and
the thermochemical properties of DEB [20] showed
that a change in temperature from 200 to 235 has lit
tle effect on the equilibrium conversion of DEB
(Fig. 2). However, the conversion turns out to strongly
depend on the benzene/DEB mass ratio in the feed
mixture, especially in the range of 1 to 8. With a further
increase in the benzene/DEB ratio, its effect on the
DEB conversion becomes less pronounced. From the
practical point of view, in order to achieve a substantial
equilibrium conversion of DEB, it is necessary to
maintain a benzene/DEB weight ratio in the feedstock
of at least 3/1.
Physicochemical Properties of Catalysts
The NH
3
TPD data made it possible to evaluate
the acid properties of the catalysts synthesized in this
work and selected for comparison. In the order of
descending acidity, the samples are arranged as fol
lows: HY > HYBF > MOR > Beta* > Beta70, with
total concentrations of acid sites of 849.9 > 838.5 >
804.8 > 721.1 > 571.2 mol NH
3
/g, respectively. Thus,
the catalyst samples based on zeolite Y and mordenite
have a larger number of acid sites (and are closer to
G
f
0
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
ETHYLBENZENE SYNTHESIS AND BENZENE TRANSALKYLATION 43
one another in this parameter) than the zeolite beta
catalyst. From these results we can expect that the cat
alytic activity of HY, NYBS and MOR should be
higher than that of zeolite beta samples.
Published IR data for zeolites [21] show that with a
decrease in the SiOSi bond angles, the
frequency of antisymmetric SiOSi stretching
vibrations (
as SiOSi
at 11501050 cm
1
) increases
and the frequency of symmetric stretching vibrations
(
s SiOSi
at 802604 cm
1
) decreases. The spectral
characteristics according to the position of maximums
of the principal absorption bands show that the angle
value drops in the order: Beta70 > Beta* > MOR >
HYBF > HY. The SiOSi bending bands (
SiOSi
at
650450 cm
1
) behave in the same manner; namely,
there is splitting into five band in this region for the
first three catalysts in the series and there are three
bands close in value for the each of the last two sam
ples. Hence, it can be concluded that the geometries of
the SiOSi nodes in the aforementioned series of
catalysts are close to each other in the first three and
the last two samples.
Figure 3 collates the spectra of zeolites in the
region of absorption of OH bonds. There are no
bands due to the isolated zeolite OH bonds in the
region above 3700 cm
1
for any of the samples. How
ever, the Beta70, Beta*, and MOR samples exhibit
bands at 3640 cm
1
attributed to weakly associated OH
groups. This band for the HY and HYBF samples is
further shifted toward longer wavelengths, a fact that is
associated with the manifestation of association
between several closely arranged OH groups.
Catalytic Tests
The results of comparative testing of the given cat
alysts showed that the samples based on zeolite beta
have a lower activity (DEB conversion) in the tran
salkylation reaction over the mordenitecontaining
catalyst or the HY and HYBF samples (Table 2). The
MOR and Beta70 catalysts are characterized by the
highest selectivity for EB (97.0 and 92.6 wt %, respec
tively). The enhanced selectivity of the MOR and
Beta70 catalysts is explained by the structural features
of the zeolites used. Zeolite beta has a threedimen
sional pore system similar to that of Y, but without
large cavities in which byproducts with a large molec
ular size are preferably formed, a fact that leads to a
decrease in the selectivity for desired EB in the case of
zeolite Y catalysts.
The catalytic characteristics obtained correlate
well with the physicochemical properties of the sam
ples. According to the IR data, the highest intensity of
OH groups observed in the spectra belonging to the
most active zeolite Y samples and the NH
3
TPD data
indicate a greater number of acid sites in these cata
lysts as compared to zeolite beta samples. Moreover,
the number of acid sites in the mordenite sample
barely ranks below that for the zeolite Y catalyst.
Catalyst Operation Stability
Comparative testing of the catalysts showed that
the samples differ quite strongly in stability, as is man
ifested in the plot of the EB concentration versus the
catalyst onstream time (Fig. 4).
To describe this dependence, we have chosen a
exponential function represented in the general form
by the expression y =
x
(the domain of the function is
(0, + )) [22]. The partial function applicable to the
given purpose has the form: = 10
f
, where is the
EB concentration, wt %; is the factor that indicates
the initial concentration of EB, wt %; is the catalyst
onstream time, min; and f (stability factor) is the
coefficient characterizing the stability of the catalyst
over time.
100
30 28 26 24 22 20 18 16 14 12 10 8 6 4 2 0
95
90
85
80
75
70
65
60
55
50
45
40
D
E
B

c
o
n
v
e
r
s
i
o
n
,

w
t

%
Benzene/DEB mass ratio
Fig. 2. Dependence of the equilibrium conversion of
diethylbenzenes on the benzene/diethylbenzene weight
ratio in the feedstock in the temperature range of
200235C.
0.5
0.4
0.3
0.2
0.1
0
0.1
3100 3700 3500 3300
0.7
3900
Wavenumber, cm
1
0.6
A
b
s
o
r
b
a
n
c
e
,

a
r
b
.

u
n
i
t
s
1
2
3
4
5
Fig. 3. Comparison of the spectra of the catalysts (1)
Beta70, (2) HYBF, (3) HY, (4) Beta*, and (5) MOR in the
region of OH stretching vibrations.
44
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
GERZELIEV et al.
Taking the logarithm of this expression results in
the linear relationship between and the on
stream time = + f, from which the power
index f can readily be obtained as f = ( )/.
Thus, equations were found for the test samples in
which the first term shows the initial EB concentration
and the power index f(f 10
5
) characterizes the cat
alyst stability with time (the socalled stability fac
tor):
y(Beta70) = 13.9 10
8.1
; (HYBF) = 22.2 10
92.7
;
(Beta*) = 19.2 10
72.1
; (HY) = 29.3 10
131.1
;
y(MOR) = 16.9 10
44.8
.
y log
y log a log
y log a log
In the general exponential function ( = a

) used to
describe the dependence, which yields a straight line
in the xy coordinates, the factor f is 0. Therefore, the
lower the value of this factor is, the closer the plot is to
a straight line and the higher the catalyst stability is
over time. Thus, using this catalyst stability assessment
procedure, we have shown that the sample Beta70 with
the lowest value of stability factor f has the best char
acteristics, thereby bringing the plot of the EB con
centration versus time close to the straight line. The
foreign HY catalyst based on zeolite Y exhibits the
least stability. The factor f for this sample is 16 times
that for the catalyst Beta70.
Life Time Tests
For longterm testing of catalysts in time, a pilot
unit capable of continuous operation has been
designed. The most stable (in time) catalyst Beta70
and two samples HY and HYBF having the highest
activity were selected for further study, mostly based
on the results of laboratory tests. The catalyst Beta70
was tested under more severe conditions to reduce the
time required to obtain characteristic data on its stable
operation. The Beta70 testing results showed that the
initial EB concentration of 21.5 wt % (initial DEB
conversion of 65 wt %) gradually decreases during the
first 60 h on stream (Fig. 5a), reaching a plateau to
have EB concentrations of 18.2 and 17.7 wt % and
DEB conversion degrees of 48.6 and 45.8 wt % over
the regions of 70120 and 120160 h, respectively. It
should be noted that, beginning from 140 h until the
end of the experimental run, the concentration of EB
remained almost unchanged, and the catalyst seemed
Table 2. Results of experiments on the transalkylation of benzene with DEB on zeolite catalysts at a temperature of 230C, a
SV of 10 h
1
, B/DEB weight ratio of 3/1, and a reaction time of 240 min
No. Catalyst
Average concentration, wt % Average output parameters, wt %
EB DEB isomers TriEB isomers
X
(DEB)
S
(EB)

(EB)
Catalysts synthesized on the basis of zeolite beta
1 100% Al
2
O
3
0.07 22.9 0.02 0.4 8.6 0.3
2 Beta30 9.2 14.7 0.7 36.1 88.5 32.3
3 Beta50 12.4 13.5 0.8 41.3 90.5 37.0
4 Beta70 13.3 12.4 0.9 43.3 92.6 38.8
5 100% Beta 15.8 10.7 1.1 53.5 92.8 45.9
Reference catalysts
6 Beta* 13.6 14.5 1.3 34.9 90.3 38.6
7 MOR 13.6 11.5 0.3 46.4 97.0 39.9
8 HY 16.0 11.6 1.5 47.9 88.3 45.5
9 HYBC 14.4 11.4 1.4 47.1 89.8 42.2
X (DEB) is the DEB conversion, S(EB) is the selectivity (relative concentration of EB in the reaction products), and (EB) is the percentage
yield of EB in terms of the DEB in the feedstock.
6
400 0 50 100 150 200 250 300 350
8
10
12
14
16
18
20
22
24
26
28
30
Time on stream, min
E
B

c
o
n
c
e
n
t
r
a
t
i
o
n
,

w
t

%

1
2
2
3
4
5
1
Fig. 4. Dependence of the ethylbenzene (EB) concentra
tion on the time on stream for the test catalysts samples
catalysts (1) Beta70, (2) HYBF, (3) HY, (4) Beta*, and (5)
MOR.
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
ETHYLBENZENE SYNTHESIS AND BENZENE TRANSALKYLATION 45
to reach the steady operation level with its characteris
tic activity under the given conditions.
In the case of the HYBF catalyst (Fig. 5b), the
average EB concentration, which is an indicator of the
initial catalyst activity, was 21.9 wt % over the first
150 h of testing at a DEB conversion of 86.9 wt %.
Between 150 and 426 h, the EB concentration gradu
ally declined to 19.3 wt %; after that the reactor tem
perature was elevated by 10 as compared to the ini
tial temperature, which led to stabilization of the EB
concentration in the reaction products at a level of
20.9 wt % and a DEB conversion of 84.0 wt %. The
results of the testing of the HY catalyst in a pilot plant
showed that the sample exhibits a high initial activity:
over the first 40 h on stream, the average concentration
of EB was 23.3 wt % (Fig. 5b) and the DEB conversion
was 87.4 wt %. During the process, the temperature
was elevated in a stepwise manner from 190 to 200
by 55 h and to = 205 by 417 h on stream to main
tain an EB concentration at the level of 22.5 wt %.
Comparing the data obtained on the HY catalyst
with the results of HYBF catalyst testing in the pilot
plant (under similar conditions of the process), we can
state that over time on stream ranging from 10 to
600 h, the former exhibits a somewhat higher activity
(according to the DEB conversion and the EB con
centration in the product) with equal selectivity for EB
and close yields of EB formed per gram of catalyst
(Table 3).
The Beta70 sample is a hightemperature catalyst
and, as has been already noted, it was tested under
conditions other than those used for testing the zeolite
Y samples. Thus, not all output parameters obtained
on these catalysts are comparable under identical test
ing conditions. One of the objective parameters of
comparison is the yield of EB per gram of catalyst; this
quantity for the catalyst Beta70 is 1.5 times that for HY
or HYBF. Thus, the catalyst Beta70 can be selected as
one of the most effective in the transalkylation reac
tion providing that the of process parameters are prop
erly selected.
After testing the catalysts HY and HYBF, they
were analyzed for the amount of builtup irreversibly
adsorbed deposits by the differential thermal (Ther
mogravimetry TGA/DSC1 instrument) and elemental
analysis (EA1108 Elemental Analyzer) techniques.
The results showed that these two methods give close
values for the amount of coke, wherein its amount
was higher on the HY than on the HYBF sample
(Table 3). From these data, it can be concluded that
the HY catalyst sample probably has specific structural
features that allow it to retain a high activity over a long
period of time despite the large amount of irreversibly
adsorbed deposits.
19
Time on stream, h
600 500 400 300 200 100 0
18
20
21
22
23
24
25
E
B

c
o
n
c
e
n
t
r
a
t
i
o
n
,

w
t

%

19
Time on stream, h
160 120 100 60 40 0
17
20
21
22
23
E
B

c
o
n
c
e
n
t
r
a
t
i
o
n
,

w
t

%

140 80 20
18
T = 190C
T = 200C
T = 205C
T = 210C
T = 200C
1
2
() (b)
Fig. 5. Dependence of the ethylbenzene concentration on the time on stream over (a) the catalyst Beta70 and (b) the catalysts (1)
HY and (2) HYBF.
Table 3. Comparative figures for the HY and HYBF catalysts
Sample T, C
w,
h
1
B/DEB
wt
Average
concentration, wt %
Average parameters, wt %
Amount of coke,
% C + H
EB DEB

TriEB
X
(DEB)
S
(EB)

(EB)
X
(B)
g EB/(g
cat h)
TGA
CHN
analysis
HYBF 200210 1.3 5.5 20.6 2.6 0.07 83.0 97.1 84.6 9.7 0.30 9.31 8.22
HY 190205 1.3 5.5 22.8 2.1 0.06 86.4 97.1 93.9 11.6 0.34 12.03 11.30
Beta70 250 2 3 18.5 11.9 0.2 49.7 94.7 48.6 9.0 0.47
T is the temperature, w is the space velocity, B/DEB is the benzene/DEB ratio in the feedstock. X (DEB) is the DEB conversion, S(EB) is the
selectivity (relative concentration of EB in the reaction products), (EB) is the percentage yield of EB in terms of the DEB in the feedstock,
X (B) is the conversion of benzene, and (g EB/g cat h) is yield of EBs in per 1 g/h.
46
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
GERZELIEV et al.
Process Parameters
Additional studies were conducted on the HY cat
alyst in three temperature regimes (205, 215, and
225) while varying the feed WHSV over the range of
1.312.5 h
1
( = 2.5 MPa). The results showed that
increasing the process temperature (Fig. 6a) increases
the DEB conversion, and growth of this indicator is
most pronounced at high feed WHSV. The maximum
conversion of DEB was reached at a feed WHSV of
1.3 h
1
and a temperature of 225, and its value was
88.4 wt % (equilibrium conversion of DEB 95 wt %
under these conditions).
It is interesting to elucidate the effect of change in
the process parameters on the formation of byprod
ucts in the reaction, in particular, toluene, (T) and,
especially, triethylbenzenes (TEB), since their amount
should be taken into account in the choice of the opti
mal conditions of the process. The formation of tolu
ene is apparently due to the cracking of ethylbenzene.
From the data in Fig. 6b, it is seen that the concentra
tion of toluene in the reaction product decrease in a
regular manner as the temperature of the process
decreases and the feed space velocity increases.
Triethylbenzenes are formed when two DEB mole
cules interact in the disproportionation reaction. The
temperature dependence of the TEB concentration in
the reaction product with the varying feed WHSV
(from 1.3 to 12.5 h
1
) can be seen from Fig. 6b. As the
temperature of the process decreases and the feed
space velocity increases from 1.3 to 7.5 h
1
, the TEB
concentration in the reaction products increases.
Conversely, at a WHSV of 12.5 h
1
, the amount of
TEB decreases with the decreasing temperature, a fact
that seems to indicate a change in its formation route.
A comparison of the data on the dependence of the
DEB conversion and the TEB concentration on the
temperature and the WHSV (from 1.3 to 7.5 h
1
)
shows that these dependences are opposite in nature
(Figs. 6a, 6b). This suggests that the TEB formation
reaction is suppressed (owing to lower concentrations
of DEB in the reaction mixture) as a result of a high
DEB conversion at low feed space velocities and high
temperatures, thereby leading to a decrease in the
TEB content in the reaction products.
Thus, the transalkylation process over catalysts
based on zeolite Y, in particular, over the HY sample,
can be conducted at a temperature of 190 to reach a
high conversion of DEB, while the decline in activity
with time can be counterbalanced by gradual elevation
of temperature to 230240 at a pressure of 2.5
3.0 MPa.
A criterion for the choice of an optimal feed space
velocity is the conversion of DEB. In the case of
incomplete DEB conversion, the breakthrough
should be isolated at the rectification stage and be
recycled to the transalkylation reactor. A DEB conver
sion of about 85 wt % in this context is acceptable for
industrialscale technology. This criterion is met for
the WHSV in the range of 1.32.0 h
1
. The ben
zene/DEB weight ratio in the feedstock should not be
below 3/1; in particular, an optimal ratio may be at the
level of 56/1. A further increase in this parameter will
increase the load on the separation system.
Kinetic Parameters
The results obtained by varying the parameters of
the process on the HY catalyst were treated for obtain
ing the kinetic data for the benzene transalkylation
reaction with DEB. The experimental data obtained at
temperatures 478508K, pressures of 2.53.0 MPa,
and a initial benzene/DEB mass ratio of 5.5 were used
in the calculation.
It is accepted that the reaction B + DEB 2EB
follows the firstorder law in DEB over the range of the
cantact time of 0 to 288 s examined ( = 1/w, s, where
w is the feed WHSV); i.e., the DEB conversion rate is
expressed by the relationship r =dx/d(1/W) = k(1 x),
where is the DEB conversion and k is the reaction
rate constant, in s
1
. The experimental data are accu
rately described by this equation (Fig. 7a). The values
of the rate constant k 10
3
found from the plot of
ln1/(1 x) versus 1/w (Fig. 7a) for temperatures 478,
488, 498, and 508 K are equal 1.03, 1.84, 2.33, and
3.30 s
1
, respectively. The apparent activation energy
90
80
70
60
40
30
20
12.5 7.5 3.0 2.0 1.6 1.3
50
205C
225C
215C
WHSV, h
1
D
E
B

c
o
n
v
e
r
s
i
o
n
,

w
t

%
0.18
0.15
0.13
0.10
0.05
0.03
0
12.5 7.5 3.0 2.0 1.6 1.3
0.08
1 205C
1 225C
1 215C
WHSV, h
1
C
o
n
c
e
n
t
r
a
t
i
o
n
,

w
t

%

2 215C
2 225C
2 205C
()
(b)
Fig. 6. Dependence of (a) the conversion of diethylbenzenes (DEB) and (b) the concentration of (1) toluene (T) and (2) trieth
ylbenzenes (TEB) of the feed space velocity at temperatures of 205, 215, and 225C.
PETROLEUM CHEMISTRY Vol. 51 No. 1 2011
ETHYLBENZENE SYNTHESIS AND BENZENE TRANSALKYLATION 47
calculated from the Arrhenius plot lnk = lnk
0
E/RT
(k
0
is the preexponential factor; R is the gas constant
(8.3144 J/mol K); and T is the temperature, K) is
78 kJ/mol (Fig. 7b).
This value of the activation energy is commensura
ble with the values reported previously for the tran
salkylation reaction of aromatic hydrocarbons [15, 23,
24]. For example, the activation energy of benzene
transalkylation with mDEB on the zeolite beta cata
lyst [15] varies in the range of 75104.6 kJ/mol at tem
peratures of 483543 K. The activation energy for the
transalkylation of mxylene using a series of catalysts
based on dealuminated HY in the temperature range
of 513593 K is 95.5119.4 kJ/mol [23]. According to
published data [24], the activation energy of benzene
transalkylation with diisopropylbenzene on SAPO5
at 478548 K is 130.2 kJ/mol.
Thus, analysis of the published academicresearch
and patent data shows that the largest global compa
nies have passed from the vapor to the liquidphase
mode of the EB manufacture process. The implemen
tation of the benzene alkylation reaction with ethylene
and transalkylation reaction with DEB in separate
reactors significantly improves the efficiency of the
process. Different catalysts can be used for the tran
salkylation of benzene with DEB, depending on the
goal; the samples synthesized on the basis of zeolite Y
exhibit a higher initial activity in the reaction, but they
rank below the mordenite catalyst and the zeolite
betabased samples in time stability in yield, and the
latter catalysts, in turn, are characterized by a lower
activity. If the requirements are limited by a high selec
tivity for EB, it is necessary to apply mordenite and
zeolite beta catalysts. The results of the tests show that
the catalysts HY and HYBF exhibit a fairly high and
stable activity over time, and these samples can be used
for the industrial process of benzene transalkylation
with DEB.
ACKNOWLEDGMENTS
The authors are indebted to OAO Salavatnefte
orgsintez and the Zeolyst company for kindly present
ing the catalyst samples.
The IR spectra of the catalysts were recorded and
interpreted by Prof. G.N. Bondarenko, the character
istics of coked catalysts were measured by G.A. Shan
dryuk and E.B. Krutko, and the zeolite betabased
catalysts were synthesized by N.S. Khashagulgova
and staff members of the Topchiev Institute of Petro
chemical Synthesis, whose assistance is greatly
acknowledged.
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6.5
6.0
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5.0
1.0
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0 300 250 200 150 100 50
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