Article No : a10_035
Ethylbenzene
VINCENT A. WELCH, Washington Group Intl., Inc. (formerly The Badger Company),
Cambridge, Massachusetts, United States
KEVIN J. FALLON, Washington Group Intl., Inc. (formerly The Badger Company),
Cambridge, Massachusetts, United States
HEINZ-PETER GELBKE, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic
of Germany
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . . . . . . . . . . .
3. Chemical Properties . . . . . . . . . . . . . . . . . .
4. Production . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Alkylation with Non-Zeolite Lewis Acid
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Vapor-Phase Alkylation over Zeolites . . . . . .
4.3. Liquid-Phase Alkylation over Zeolites . . . . .
4.4. Mixed-Phase Zeolite-Based Process . . . . . . .
1. Introduction
Ethylbenzene [100-41-4], phenylethane,
C6H5CH2CH3, Mr 106.168, is a single-ring alky-
laromatic compound. It is almost exclusively
(>99 %) used as an intermediate for the manu-
facture of styrene monomer [100-42-5],
C6H5CHCH2, one of the most important
large-volume commodity chemicals. Styrene
production, which uses ethylbenzene as a starting
raw material, consumes ca. 50 % of the worlds
benzene production. Less than 1 % of the ethyl-
benzene produced is used as a paint solvent or as
an intermediate for the production of diethylben-
zene and acetophenone.
Commercially, almost all ethylbenzene is pro-
duced by alkylating benzene with ethylene. The
newest technologies utilize synthetic zeolites
installed in fixed-bed reactors to catalyze the
alkylation in the liquid phase. Another proven
route uses narrower pore synthetic zeolites, also
installed in fixed-bed reactors, to effect the
alkylation in the vapor phase. A considerable
quantity of ethylbenzene is still produced by
alkylation with homogeneous aluminum chlo-
ride catalyst in the liquid phase, though the recent
trend in the industry has been to retrofit such
units with zeolite technology. The alkylation of

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/14356007.a10_035.pub2
451 4.5. Separation from Mixed C8 Streams . . . . . . . . 459
452 5. Environmental Protection . . . . . . . . . . . . . . 459
452 6. Quality Specifications. . . . . . . . . . . . . . . . . . 459
452 7. Handling, Storage, and Transportation . . . . 460
8. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
453 9. Economic Aspects . . . . . . . . . . . . . . . . . . . . 460
455 10. Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . 461
457 References . . . . . . . . . . . . . . . . . . . . . . . . . . 463
458
aromatic hydrocarbons with olefins in the pres-
ence of aluminum chloride catalyst was first
practiced by BALSOHN in 1879 [1]. However,
FRIEDEL and CRAFTS pioneered much of the early
research on alkylation and aluminum chloride
catalysis.
Several facilities built during the 1960s recov-
ered ethylbenzene by fractionation of mixed
xylenes produced in refinery catalytic reforming
units. This practice has largely been discontinued
due to poor economics that result from high
energy and investment costs, as well as small
economies of scale in comparison to the conven-
tional alkylation routes.
Ethylbenzene was first produced on a com-
mercial scale in the 1930s by Dow Chemical
in the United States and by BASF in Germany.
The ethylbenzene/styrene industry remained
relatively insignificant until World War II.
The tremendous demand for synthetic styrene
butadiene rubber (SBR) during the war
prompted accelerated technology improve-
ments and tremendous capacity expansion. This
considerable wartime effort led to the construc-
tion of several large-scale factories, and styrene
production quickly became a significant indus-
try. In 1999 world annual production capacity
of ethylbenzene reached almost 25
106 t.
452 Ethylbenzene Vol. 13

Throughout the 1990s, most of the capacity A reaction of increasing commercial impor-
increase occurred in the Far Eastern countries tance is the oxidation of ethylbenzene by air to
other than Japan, where the basic petrochemical the hydroperoxide C6H5CH(OOH)CH3 [3071-
industries have undergone considerable devel- 32-7]. The reaction takes place in the liquid phase
opment and expansion. without a catalyst. However, because hydroper-
oxides are unstable, exposure to high tempera-
ture must be minimized to reduce the rate of
2. Physical Properties decomposition. The production of byproducts is
reduced if the temperature is gradually lowered
Under normal conditions, ethylbenzene is a clear, during the course of the reaction. The hydroper-
colorless liquid with a characteristic aromatic oxide is subsequently treated with propylene to
odor. Ethylbenzene is an irritant to the skin and give styrene and propylene oxide as co-products.
eyes and is moderately toxic by ingestion, inha- In 1999 about 15 % of the ethylbenzene produced
lation, and skin adsorption. Some physical prop- worldwide was used in the co-production of
erties of ethylbenzene follow [2], [3]: styrene monomer and propylene oxide.
Like toluene, ethylbenzene can be dealkylated
catalytically or thermally to benzene. Ethylben-
Density at 15  C 0.87139 g/cm3 zene also undergoes other reactions typical of
at 20  C 0.8670 g/cm3
alkylaromatic compounds [4].
at 25  C 0.86262 g/cm3
mp 94.949  C
bp at 101.3 kPa 136.2 C
Refractive index at 20  C 1.49588 4. Production
at 25  C 1.49320
Critical pressure 3609 kPa (36.09 bar)
Critical temperature 344.02  C Alkylation of benzene with ethylene is the source
Flash point (closed cup) 15  C of nearly all ethylbenzene. For several decades
Autoignition temperature 460  C most alkylation plants utilized dissolved Lewis
Flammability limit lower 1.0 %
acids, in most cases aluminum chloride, to cata-
upper 6.7 %
Latent heat fusion 86.3 J/g lyze the reaction in the liquid phase. About 40 %
vaporization 335 J/g of worldwide ethylbenzene production still
Heating value, gross 42 999 J/g utilizes variations on this method. Although the
net 40 928 J/g
aluminum chloride route generally provides
Kinematic viscosity at 37.8  C 0.6428
106 m2/S
at 98.9  C 0.390
106 m2/S competitive economics, disposal of the resulting
Surface tension 28.48 mN/m waste streams has become increasingly costly.
Specific heat capacity In addition, this route is susceptible to severe
ideal gas, 25  C 1169 J kg1 K1
corrosion of equipment and piping. Since the
liquid, 25  C 1752 J kg1 K1
Acentric factor 0.3026 early 1980s, technologies using heterogeneous
Critical compressibility 0.263 zeolites, operating in the vapor phase and more
recently in the liquid phase, have been most
often selected for new grass-roots plants. More
recently, increasing environmental pressures and
3. Chemical Properties improvements in the zeolite processes have pro-
vided incentives to a number of operators of
The most important commercial reaction of eth- aluminum chloride units to retrofit with zeolite
ylbenzene is its dehydrogenation to styrene. The technology. About 106 t of capacity in several
reaction is carried out at high temperature plants were changed to zeolite technology from
(600 660  C), usually over a potassium- 1997 to 1999, and as of 2000, more conversions
promoted iron oxide catalyst. Steam is used as are in the engineering phase. It has been nearly
a diluent. Commercially, selectivities for styrene ten years since the last significant grass-roots
range from 90 to 97 mol % with per-pass con- capacity utilizing aluminum chloride technology
versions of 60 70 %. Side reactions involve came on-stream.
mainly the dealkylation of ethylbenzene to A very minor amount of ethylbenzene is
benzene and toluene. produced by superfractionation of mixed C8
Vol. 13
aromatic streams. Only a small number of plants
in the world still utilize this method.
4.1. Alkylation with Non-Zeolite Lewis
Acid Catalysts
Liquid-phase aluminum chloride processes were
first commercialized in the 1930s. Several com-
panies developed variations of this technology,
including Dow Chemical, BASF, Shell Chemi-
cal, Monsanto/Lummus, Soci
et
e Chimiques des
Charbonnages, and Union Carbide/Badger. Of
the aluminum chloride plants still in operation,
the majority of them utilize the Monsanto/Lum-
mus technology, widely considered the most
advanced of the aluminum chloride processes.
Lummus discontinued licensing this technology
with the commercialization of their liquid-phase
zeolite process around 1990.
Alkylation of benzene with ethylene is highly
exothermic (DH  114 kJ/mol); in the pres-
ence of aluminum chloride the reaction is very
fast and produces almost stoichiometric yields of
ethylbenzene. In addition to AlCl3, a wide range
of Lewis acid catalysts, including AlBr3, FeCl3,
ZrCl4, and BF3, have been used. Aluminum
chloride processes generally use ethyl chloride
or hydrogen chloride as a catalyst promoter.
These halide promoters reduce the amount of
AlCl3 required. The reaction mechanism has
been studied in detail [5].
Figure 1. Aluminum chloride process for ethylbenzene production a) Catalyst mix tank; b) Alkylation reactor; c) Settling tank;
d) Acid separator; e) Caustic separator; f) Water separator; g) Benzene recovery column; h) Benzene dehydrator column;
i) Ethylbenzene recovery column; j) Polyethylbenzene column
Ethylbenzene 453
In the older conventional AlCl3 process
(see Fig. 1) which is seldom practiced now,
three phases are present in the reactor: aromatic
liquid, ethylene gas, and a liquid catalyst com-
plex phase (a reddish brown material called red
oil). A mixture of catalyst complex, dry ben-
zene, and recycled polyalkylbenzenes is contin-
uously fed to the reactor and agitated to disperse
the catalyst complex phase in the aromatic
phase. Ethylene and the catalyst promoter are
injected into the reaction mixture through spar-
gers, and essentially 100 % of the ethylene is
converted. Commercial plants typically operate
at ethylene/benzene molar ratios of ca. 0.3
0.35. As this ratio is increased, more side reac-
tions, such as transalkylation and isomeric
rearrangement, occurr. Further alkylation of
ethylbenzene leads to the reversible formation
of lower molecular mass polyalkylbenzenes.
The loss in yield due to residue formation is
minimized by recycling this material to the
alkylation reactor. In addition, because the
reaction occurs close to thermodynamic equi-
librium, the traditional processes use a single
reactor to alkylate benzene and transalkylate
polyalkylbenzenes.
The reaction temperature is generally limited
to 130  C; a higher temperature rapidly deacti-
vates the catalyst and favors formation of non-
aromatics and polyalkylbenzenes, which are
preferentially absorbed by the highly acidic
catalyst complex and form byproducts. Sufficient
454 Ethylbenzene
pressure is maintained to keep the reactants in the
liquid phase. Because the reaction mixture is
highly corrosive, the alkylation reactors are lined
with brick or glass. High-alloy construction
materials are also required for the piping and
handling systems.
The liquid reactor effluent is cooled and dis-
charged into a settler, where the heavy catalyst
phase is decanted from the organic liquid-phase
and recycled. The organic phase is washed with
water and caustic to remove dissolved AlCl3 and
promoter. The aqueous phase from these treat-
ment steps is first neutralized and then recovered
as a saturated aluminum chloride solution and a
wet aluminum hydroxide sludge.
Removal of dissolved catalyst from the organ-
ic stream has long been a challenge for ethylben-
zene producers. CdF Chimie found that more
complete recovery of AlCl3 could be achieved by
first contacting the organic phase with ammonia
instead of sodium hydroxide [6].
Purification of the ethylbenzene product is
usually accomplished in a series of three distil-
lation columns. The unconverted benzene is
recovered in the first column as an overhead
distillate. The second column separates the
ethylbenzene product from the heavier polyalky-
Figure 2. Homogeneous liquid-phase alkylation process for ethylbenzene production a) Benzene drying column; b) Alkylation
reactor; c) Catalyst preparation tank; d) Transalkylator; e) Flash drum; f) Vent gas scrubbing system; g) Decantor;
h) Neutralization system
Vol. 13
lated components. The bottoms product of the
second column is fed to a final column where the
recyclable polyalkylbenzenes are stripped from
nonrecyclable high molecular mass residue com-
pounds. The residue stream, or flux oil, consist-
ing primarily of polycyclic aromatics, is burned
as fuel.
Because the alkylation mixture can tolerate
only minor amounts of water, the recycle ben-
zene and fresh benzene must be dried thoroughly
prior to entering the reactor. Water not only
increases corrosion, but also decreases catalyst
activity. Benzene dehydration is accomplished in
a separate column.
The improved Monsanto process (see Fig. 2)
has several advantages over the conventional
AlCl3 processes. Over time many conventional
AlCl3 plants have been retrofitted with this tech-
nology. The most important advantage is a
significant reduction in the amount of AlCl3
catalyst used, thus lessening the problem and
cost of waste catalyst disposal. Monsanto found
that by increasing temperature and by careful
control of ethylene addition, the required AlCl3
concentration could be reduced to the solubility
limit, thereby eliminating the separate catalyst
complex phase [7]. Therefore, the alkylation
Vol. 13
occurs in a single homogeneous liquid phase
instead of in the two liquid phases of earlier
processes. Monsanto claimed that a separate
catalyst complex phase may actually prevent the
attainment of maximum reactor yields. With a
few exceptions, the flow scheme of the Monsanto
process is nearly the same as that of more tradi-
tional processes. The process is also capable of
operating with low-concentration ethylene feed.
Typically, the alkylation temperature is main-
tained at 160 180  C. This higher operating
temperature enhances catalyst activity with the
additional benefit that the heat of reaction can be
recovered as low-pressure steam.
Whereas the traditional process accomplishes
alkylation and transalkylation in a single reactor,
the homogeneous catalyst system must employ a
separate transalkylation reactor. At the lower
catalyst concentrations, the recycle of substantial
amounts of polyalkylbenzenes terminates the
alkylation reaction. Therefore, only dry benzene,
ethylene, and catalyst are fed to the alkylation
reactor. The recycle polyethylbenzene stream is
mixed with the alkylation reactor effluent prior to
entering the transalkylation reactor. The trans-
alkylation reactor is operated at much lower
temperature than the primary alkylation reactor.
After transalkylation, the reaction products
are washed and neutralized to remove residual
AlCl3. With the homogeneous process, all of the
catalyst remains in solution. The catalyst-free
organic reaction mixture is then purified by using
the sequence described for the conventional
AlCl3 process. As with other AlCl3 processes,
the organic residue is used as fuel and the alumi-
num chloride waste streams are usually sold or
sent to treatment facilities.
In 1999 about 40 % of the ethylbenzene man-
ufactured worldwide used aluminum chloride
technology. Another technology based on Lewis
acids is the so-called Alkar process. Developed
by UOP and based on boron trifluoride catalyst,
this process had modest success in the 1960s, but
fell from favor because of high maintenance
costs resulting from the severe corrosion caused
by small quantities of water. In the developed
countries, only one Alkar plant is still in
operation.
However, the process produced a high-purity
ethylbenzene product and could use dilute ethyl-
ene feedstock. If the entry of water into the
process was strictly prevented, the corrosion
Ethylbenzene 455
problems associated with aluminum chloride
processes were avoided. However, even small
amounts of water (< 1 g/kg) hydrolyzed the BF3
catalyst.
The alkylation reaction took place at high
pressure (2.5 3.5 MPa) and low temperature
(100 150  C). Dried benzene, ethylene, and
makeup BF3 catalyst were fed to the reactor.
Typically, ethylene/benzene molar ratios be-
tween 0.15 and 0.2 were used. The reactor inlet
temperature was controlled by recycling a small
portion of the reactor effluent. Transalkylation
took place in a separate reactor. Dry benzene, BF3
catalyst, and recycled polyethylbenzenes were
fed to the transalkylation reactor, which operated
at higher temperature (180 230  C) than the
alkylation reactor. The effluent streams from the
two reactors were combined and passed to a
benzene recovery column where benzene was
separated for recycle to the reactors. Boron
trifluoride and light hydrocarbons were taken
overhead as a vapor stream from which the BF3
was recovered for recycle. The bottoms from the
benzene recovery column was sent to a product
column where ethylbenzene of > 99.9 % purity
was taken overhead. A final column served to
recover polyethylbenzenes for recycle to the
transalkylation reactor.
The Alkar process could operate with an eth-
ylene feed containing as little as 8 10 mol %
ethylene, enabling a variety of refinery and coke-
oven gas streams to be used. However, purifica-
tion of these streams was necessary to remove
components that poison the BF3 catalyst, e.g.,
trace amounts of water, sulfur compounds, and
oxygenates.
4.2. Vapor-Phase Alkylation over
Zeolites
The Mobil Badger vapor-phase technology
was developed in the 1970s around Mobils
ZSM-5 synthetic zeolite and has been available
in several different designs. The original first-
generation design, commercialized by American
Hoechst in 1980, carried out vapor-phase alkyl-
ation and transalkylation in a single reactor by
recycling polyethylbenzene to the front end of
the process, similar to conventional aluminum
chloride technology. The newest, so-called third-
generation technology performs transalkylation
456 Ethylbenzene
in a separate lower pressure reaction step. The
third-generation technology offered significant
benefits in yield, purity, and capital cost, and was
widely used in the 1990s to debottleneck older
vapor-phase plants.
The vapor-phase zeolite process is particular-
ly suited to dilute ethylene streams, particularly
refinery off-gas from fluid catalytic cracking
(FCC) units. Until technologies using zeolites in
the liquid phase were commercialized in the
1990s, the vapor-phase zeolite process was the
dominant technology of new plants, primarily
because it avoided the aqueous waste streams
produced from aluminum chloride plants. Mo-
bil Badger licensed a total of 31 units since
1980, and the technology is still licensed for
dilute-ethylene-based plants.
The fixed-bed ZSM-5 catalyst promotes the
same overall alkylation chemistry as in the other
processes; however, ethylene molecules are
adsorbed onto the Brnsted acid sites within the
catalyst, which activates the ethylene molecule
and allows bonding with benzene molecules to
occur. Hence, the range of higher alkylated aro-
matic byproducts formed by the Mobil Badger
process is somewhat different than those of the
Friedel Crafts processes.
Carbon steel is the primary material of con-
struction; high-alloy materials and brick linings
are not required. A diagram of the third-genera-
tion design is shown in Figure 3.
Figure 3. Third-generation Mobil Badger ethylbenzene process a)Reactor-feed heater; b) Alkylation reactor; c) Benzene
recovery column; d) Ethylbenzene recovery column; e) Polyethylenebenzene recovery column; f) Secondary reactor;
g) Stabilizer
Vol. 13
The alkylation reactor typically operates in the
range of 350 450  C and 1 3 MPa. At this
temperature, > 99 % of the net process heat input
and exothermic heat of reaction can be recovered
as steam. The reaction section includes a multibed
reactor, a fired heater and heat recovery equip-
ment. The reactor operates with significant over-
all excess of benzene relative to ethylene.
Slow catalyst deactivation occurs as a result of
coke formation and requires periodic regenera-
tion. In situ regeneration takes ca. 36 h and may
be necessary after 18 24 months of operation,
depending on the operating conditions. The cat-
alyst is less sensitive to water, sulfur, and other
poisons than the Lewis acid catalysts and zeolites
operating in the liquid phase.
The reactor effluent passes to the purification
section as a vapor. The benzene from this stream
is distilled overhead in the first distillation
column and is subsequently recycled to the
reactors. The ethylbenzene product is taken as
the overhead product from the second column.
The bottoms product from this column is sent to
the last column where the recyclable alkylben-
zenes and polyalkylbenzenes are separated from
heavy nonrecyclable residue. The low-viscosity
residue stream, consisting mainly of diphenyl-
methane and diphenylethane, is burned as fuel.
Recyclable higher alkylbenzenes and poly-
alkylbenzenes are sent to the vapor-phase
transalkylator, where they are converted in the
Vol. 13
presence of excess benzene over zeolite cata-
lyst. Because the transalkylator has lower pres-
sure but higher temperature relative to the
alkylator, higher alkylbenzenes are dealkylated
while diethylbenzene is transalkylated to ethyl-
benzene. The ability to dealkylate higher alkyl-
benzenes, known to be residue precursors,
serves to decrease overall residue production.
The older first- and second-generation pro-
cesses were similar, the major difference being
that the recycle polyethylbenzene stream was
recycled to the alkylation reactor. For that reason
the process had inferior performance relative to
the third-generation design.
Though most often used with polymer-grade
ethylene, this process is adaptable to dilute
ethylene feedstocks. The process has operated
on a mixed C2 stream provided from a debot-
tlenecked distillation train from a naphtha
cracker. Additionally, and perhaps of more
interest due to low feedstock cost, is the adapt-
ability to dilute ethylene steams produced from
FCC off-gas. Two world-scale Mobil Badger
units operate with FCC off-gas, one since 1991
and one since 1998 [8].
4.3. Liquid-Phase Alkylation over
Zeolites
All-liquid phase processes using zeolite catalysts
began to appear in commercial operation in 1990,
Figure 4. Lummus/UOP ethylbenzene process [9] a) Alkylation reactor; b) Transalkylation reactor; c) Benzene column;
d) Ethylbenzene column; e) Polyethylbenzene column
Ethylbenzene 457
the first plant being operated by Nippon SM in
Oita, Japan under license from ABB Lummus
Global and Unocal (UOP later became ABBs
partner when they acquired Unocals zeolite
business). This process has utilized ultrastable
zeolite Y or more recently zeolite beta. Another
liquid-phase EB process, EBMax, became avail-
able from Mobil Badger and is based on a
Mobil MCM-22 catalyst and first operated at
Chiba Styrene Monomer Corp., also in Japan.
A total of twelve all-liquid-phase zeolite plants
were operating at the end of 1999. Although there
are differences between the two available liquid-
phase technologies, the latest versions of both
lead to lower investment cost and better product
quality than was possible with previously avail-
able technologies using polymer-grade ethylene.
The vapor-phase technology is now typically
licensed by Mobil/Badger for dilute-ethylene
applications.
These liquid phase processes all utilize wid-
er pore zeolites than ZSM-5, which is necessary
to overcome the diffusional limitations of
the liquid-phase mechanism. Both licensors
usually recommend off-site regeneration of
catalyst because of long catalyst cycle times.
Off-site regeneration results in less on-site
equipment being required and hence in reduced
investment.
The flowsheets of the two technologies are
quite similar (Figs. 4 and 5). Ethylene is injected
into a fixed bed alkylation reactor with multiple
458 Ethylbenzene
Figure 5. Mobil Badger EBMax process a) Alkylation reactor; b) Transalkylation reactor; c) Benzene column; d) Vent-gas
column; e) Ethylbenzene column; f) Polyethylbenzene column
stages in the presence of excess benzene. Reactor
temperatures vary from process to process, but
they must be kept below the critical temperature
of benzene (289  C). Pressures must be high
enough to keep the light gases in solution and
are on the order of 4 MPa. Excess benzene is
distilled overhead from the effluent and is
recycled to alkylation. The benzene column
bottoms enter the ethylbenzene product col-
umn, from which the ethylbenzene is distilled
overhead. The bottoms of the ethylbenzene
column are fed to the polyethylbenzene col-
umn, which separates higher alkylbenzenes and
polyethylbenzenes from the residue. This over-
head stream is fed to the liquid-phase transalk-
ylation reactor, where it is combined with
excess benzene from the benzene column dis-
tillate. Effluent from the transalkylator is
returned to the distillation train.
Besides benzene, major impurities in the eth-
ylbenzene product can include nonaromatics
(naphthenes), toluene, and higher alkylbenzenes.
Depending on the operating conditions and tech-
nology, these components can originate from
the feed benzene or be generated in the reactor.
There is a wide variation in distillation column
operating conditions, particularly in revamped
facilities. There is also a wide variation in excess
benzene from plant to plant. These details are
held confidentially by the licensors.
Vol. 13
4.4. Mixed-Phase Zeolite-Based
Process
A mixed-phase ethylbenzene process is offered
for license by CDTech, a partnership between
ABB Lummus Global and Chemical Research
and Licensing, Co. [10], [11] The first unit started
in 1994, and as of 1999, three plants were oper-
ating. The main distinction of this process is the
alkylation reactor, which contains bales of zeo-
lite catalyst in a reactive-distillation column.
Ethylene gas and benzene liquid are fed to the
reactive-distillation column. Because of its abili-
ty to handle the ethylene feed in the vapor phase,
the process has been applied to dilute ethylene
streams produced from steam cracker distillation
trains. It has also been applied to polymer grade
ethylene. A flow scheme is shown in Figure 6.
An alkylator and benzene stripper operate togeth-
er as a distillation column. The overhead benzene
and unconverted ethylene are in turn fed to a
finishing reactor, which also utilizes zeolite.
Bottoms from the benzene stripper are fraction-
ated into ethylbenzene product in the overhead
product column, and then transalkylatable poly-
ethylbenzenes are distilled from the residue.
The polyethylbenzenes are sent to a liquid-phase
transalkylation reactor in the presence of excess
benzene, and the transalkylation effluent is
returned to the fractionation train.
Vol. 13
Figure 6. CDTech ethylbenzene process a) Finishing reactor; b) Transalkylator; c) Alkylator; d) Benzene stripper;
e) Ethylbenzene column; f) Polyethylbenzene column BFW boiler feed water, PEB polyethylbenzene
4.5. Separation from Mixed C8 Streams
Less than 1 % of worldwide ethylbenzene pro-
duction is recovered from mixed xylene
streams, usually in conjunction with xylene
production from reformate. Although adsorp-
tion processes have been developed, most nota-
bly the EBEX process of UOP, ethylbenzene
production from these sources has been mainly
performed by distillation. Because of the diffi-
culty of the separation, the process is generally
termed superfractionation. It was first undertak-
en by Cosden Oil & Chemical Company in
1957, using technology jointly developed with
the Badger Company. The separation generally
requires three distillation columns in series,
each having over 100 stages. Several units were
built during the 1960s in the United States,
Europe, and Japan. However, the increased cost
of energy and high capital cost has made this
route noncompetitive.
5. Environmental Protection
In the United States ethylbenzene plants must
conform to the requirements of U.S. EPA
National Emission Standard Organic Air Pollutants
from the Synthetic Organic Chemical Industry
Ethylbenzene 459
(40 CFR 63, Subparts F, G, H). Producers can
comply by installing collection devices on pro-
cess vents, improved seals on pumps and valves,
and floating roof tanks.
Alkylation plants that use aluminum chloride
technology produce an aqueous waste stream
from the reactor effluent wash section. In the
mid-1970s, plants produced a wet aluminum
hydroxide sludge which was deposited in a land-
fill (Class 1). More modern plants recover a
concentrated aluminum chloride solution that
has found use in municipal water treatment or
industrial floc applications. However, where
demand from such applications does not exist,
disposal can present a problem. Sometimes
hazardous-waste incineration is required.
Studies have shown ethylbenzene to be toxic
to aquatic life in relatively low concentration
(10 100 mg/kg). Therefore, runoff from spills,
fire control, etc. should be diked to prevent it
from entering streams or water supplies.
6. Quality Specifications
The product specification on ethylbenzene is set
to provide a satisfactory feedstock to the associ-
ated styrene unit. Objectionable impurities in the
ethylbenzene can be grouped into two categories:
460 Ethylbenzene
those that are detrimental to the operation of the
styrene unit and those that affect the purity of the
styrene product. Impurities in product ethylben-
zene that pose an operating problem in the con-
ventional dehydrogenative styrene process are
1. Halides, which deactivate the dehydrogena-
tion catalyst and contribute to downstream
equipment corrosion. Usually these are chlor-
ides originating from an AlCl3 alkylation
section or fluorides from an Alkar unit.
2. Diethylbenzenes, which are dehydrogenated
to divinylbenzenes in the styrene reactor sec-
tion. The divinylbenzenes form insoluble
cross-linked polymers in the downstream pro-
cess equipment. A limit of less than 10 ppm of
diethylbenzenes in the ethylbenzene product
is usually imposed.
Ethylbenzene contaminants that can affect
styrene purity are components having a boiling
range between ethylbenzene and styrene. These
include xylenes, propylbenzenes, and ethylto-
luenes. The levels of cumene, n-propylbenzene,
ethyltoluenes, and xylenes in the ethylbenzene is
controlled to meet the required styrene purity
specification.
A typical sales specification for a United
States manufacturer is a follows:
Purity 99.5 wt % min.
Benzene 0.05 0.3 wt %
Toluene 0.1 0.3 wt %
Xylenes 0.2 wt % max.
Nonaromatics 0.05 wt % max.
Propylbenzenes 0.02 wt % max.
Diethylbenzenes 10 mg/kg max.
Total chlorides as Cl 1 3 mg/kg max.
Total organic sulfur 4 mg/kg max.
Relative density at 15  C 0.869 0.872
APHA Color 15 max.
7. Handling, Storage, and
Transportation
Ethylbenzene is a flammable liquid. It is stored
and transported in steel containers and is subject
to the control of the appropriate regulatory agen-
cies. The U.S. DOT identification number is UNI
175 and the reportable quantity is 454 kg. Details
on regulations concerning the transport of ethyl-
benzene can be found in the CFR or from the
Vol. 13
DOT Material Transportation Bureau. Other
countries have regulations and safety practices
similar to those of the United States.
Foam, carbon dioxide, dry chemical, halon,
and water (fog pattern) extinguishing media are
used in fighting ethylbenzene fires.
Adequate ventilation is necessary in handling
and storage areas. The use of NIOSH-approved
respirators is recommended at high concentra-
tion. Skin contact should be avoided. Chemical
gloves and safety glasses should be worn if
contact is possible.
Exposure of ethylbenzene to heat, ignition
sources, and strong oxidizing agents should be
avoided.
8. Uses
Essentially all commercial ethylbenzene produc-
tion is captively consumed for the manufacture of
styrene monomer or in the co-production of
styrene monomer with propylene oxide. Styrene
is used in the production of polystyrene and a
wide variety of other plastics (! Styrene).
Of the minor uses, the most significant is in the
paint industry as a solvent, which accounts for
< 1 % of production capacity. Even smaller
volumes go toward the production of acetophe-
none, diethylbenzene, and ethylanthraquinone.
9. Economic Aspects
Ethylbenzene production is linked directly to the
styrene monomer market. A total of 99 % of the
ethylbenzene produced worldwide is used to
make styrene monomer. Through the 1960s and
into the early 1970s annual growth rates for
styrene and ethylbenzene averaged 10 %. During
this period sustained growth was powered by
the expanding polystyrene market. Subsequent
growth since the early 1970s has been erratic,
with the price of styrene going through four to
five year cycles, and several new ethylbenzene/
styrene plants were built each time the price
started to rise. Since the mid-1980s the average
growth in ethylbenzene capacity worldwide has
been about 4 5 % per year, somewhat higher
than the growth of the overall economy. As late
as the mid 1980s most Far Eastern ethylbenzene/
styrene was produced in Japan, and the emerging
Vol. 13 Ethylbenzene 461

Far Eastern economies outside of Japan imported ethylene feedstock prices. The U.S. unit sales
large quantities from the West, particularly the values of ethylbenzene in $/kg from 1960 to 1997
United States and Canada. This pattern changed follow [12]:
in the late 1980s as capacity was added in Asia,
most notably Korea, which today holds about
1960 0.13 1980 0.51
10 % of the worlds ethylbenzene capacity. Other 1965 0.09 1983 0.50
Far Eastern countries installing significant new 1970 0.09 1987 0.46
capacity have included Singapore, Thailand, and 1973 0.11 1989 0.55
Taiwan. Over the next five years the expansion is 1974 0.37 1990 0.62
1975 0.20 1993 0.33
likely to occur in mainland China, as multina- 1978 0.24 1995 0.55
tional companies form joint ventures with local 1979 0.35 1997 0.42
concerns to build world-scale plants. Today each
region of the world is becoming relatively self-
sufficient in ethylbenzene/styrene. Price increases in 1974 and 1980 reflect the
About 15 % of ethylbenzene is consumed in radical change in oil prices experienced during
co-production of styrene and propylene oxide. these periods. Price increases in 1989/1990 and
These plants offer an economic advantage 1995 were indicative of the cyclic tightness in
because of the value of the propylene oxide supply of ethylbenzene and styrene.
co-product, which has remained high in part
because co-production technology has not been
widely available. This situation is beginning to 10. Toxicology
change, and today several producers are operat-
ing these plants in the Netherlands, Spain, Japan, The toxicology of ethylbenzene has been
Singapore, Korea and the United States. Lower reviewed regularly in toxicological textbooks
prices for propylene oxide resulting from greater and by various scientific organizations. The most
supply could slow the use of ethylbenzene in such recent reviews, specifically relating to the expo-
plants, which have perhaps three to four times the sure at the work place, are those of the German
investment cost of an ethylbenzene dehydroge- MAK-commission [17] and of the US TLV-
nation facility. Committee [18] which the reader is referred to
The 1999 worldwide capacity (in 103 t/a) by for further details.
region is as follows: The acute toxicity in experimental animals is
low; oral LD50 values in rats range from 3.5 to
4.7 g/kg body weight (b.w.). A 24-h dermal
North America 7700 LD50 value of approximately 15 g/kg b.w. has
South America 330
Western Europe 5900 been reported. The acute inhalative toxicity also
Eastern Europe 1300 is low. An 8-h exposure in experimental rats
Korea/Taiwan/China 3800 produced irritation of the respiratory tract start-
Japan 3500 ing at approximately 1000 ppm, and higher
Middle East and Africa 680
Southeast Asia/Australia 500 concentrations induced unsteadiness, stag-
Total 24 700 gering gait, and finally unconsciousness and
death at 5000 ppm. Human volunteers exposed
for 7.5 h at 25 ppm reported irritation of the
Similar to the direct link of ethylbenzene mucous membranes, which was much more
production to that of styrene, ethylbenzene pro- pronounced at 100 ppm.
duction cost is tied to feedstock cost. Modern Repeated dermal applications of undiluted
processes all have raw material yields > 98 ethylbenzene led to erythema, edema, and super-
99 %. Integration of the ethylbenzene and styrene ficial necrosis. Such effects are also expected
processes enables efficient energy recovery of to occur in humans due to defatting of the skin
heat from the exothermic alkylation reaction. after repeated exposures. Instillation of undiluted
With 90 99 % energy recovery of the heat of material into the eyes of rabbits produced a slight
reaction plus the heat input to the process, pro- irritation of the conjunctival membranes but
duction costs are directly related to benzene and without corneal injury.
462 Ethylbenzene
The low toxicity of ethylbenzene observed
after a single exposure was also seen in repeated
dosing studies, in which significant toxicity in
experimental animals was produced only at rela-
tively high doses. For example, when rats and
mice were exposed by inhalation over three
months no toxicity was observed in rats at
100 ppm and in mice at 500 ppm. Some in-
creases in lung, kidney, and liver weights were
measured starting at 250 ppm in rats and
750 ppm in mice, but no histopathological
changes were apparent in any of the tissues.
When rats and mice were exposed to ethylben-
zene by inhalation for two years (the major part of
their natural life), no effects were observed in
both species at 75 ppm. Some slight changes
were found at 250 ppm, but even at 750 ppm
there were no effects on overall survival in mice
and female rats. Only male rats in the 750 ppm
exposure group showed a reduced survival as
compared to untreated controls. The reduction in
survival was attributed to a rat-specific nephro-
toxicity that can not be extrapolated to humans.
While exposure to ethylbenzene at 750 ppm for
two years had little effect on survival, it did
produce an increase in hepatic and pulmonary
tumors in mice and an increase in the incidence of
renal tumours in male rats (see below).
Various toxicological investigations have
considered the potential reproductive toxicity
of ethylbenzene. In the three-month inhalation
study described above no effects were found on
the reproductive tissues of rats and mice at
exposures up to 1000 ppm.
Other studies in which pregnant mice, rats, or
rabbits were exposed to ethylbenzene have pro-
duced divergent results. For example, increases
in fetal malformations have been reported when
pregnant mice were exposed to 113 ppm ethyl-
benzene. The study did not find any other effects
indicating fetotoxicity, but insufficient informa-
tion was supplied by the investigators to enable
an in-depth evaluation. Rats exposed continu-
ously (24 h/d) up to 540 ppm showed slight
maternal toxicity accompanied by fetotoxicity
with some retardations and variations of fetal
development. At the same concentrations, but
with exposures lasting only 6 h/d, no adverse
findings were noted on the dams and offspring. In
another study in which pregnant rats were
exposed to 1000 ppm ethylbenzene for 6
7 h/d, maternal toxicity was associated with
Vol. 13
slight fetotoxicity. In an investigation with preg-
nant rabbits no fetal effects occurred in animals
continuously exposed to ethylbenzene (24 h/d) at
approximately 110 ppm. Exposure to approxi-
mately 230 ppm was toxic to the dams, with an
indication of fetotoxicity. In contrast, no clear
effects were noted in pregnant rabbits and their
offspring at 1000 ppm with a daily exposure of
7 h/d.
In vitro investigations examining the geno-
toxic potential of ethylbenzene have produced
conflicting results. While studies in bacteria and
yeast were negative, some studies with mamma-
lian cells in culture have produced some weakly
positive data. In contrast, in vivo investigations
in drosophila and in mice [micronucleus test, test
for unscheduled DNA synthesis (UDS)] were
negative. In summary, while there may be some
weak potential for ethylbenzene to interact with
the DNA of isolated cells in vitro, the consistent
lack of a response in various in vivo test systems
indicates that ethylbenzene is not a mutagenic
hazard. A limited in vitro mutagenicity database
also is available for most of the metabolites of
ethylbenzene (see below): 1-phenylethanol,
acetophenone, w-hydroxyacetophenone, phe-
nyl glyoxylic acid, mandelic acid, benzoic acid,
hippuric acid, and 2-, 3-, and 4-ethylphenol.
Again, although there are some conflicting
results the overall weight of evidence is that
these metabolites do not exhibit a clear geno-
toxic potential.
A two-year inhalation carcinogenicity study
has been carried out in rats and mice with
exposures to ethylbenzene at 0, 250, and
750 ppm. Treatment at 750 ppm produced an
increased incidence of kidney tumors in male
rats, an increased incidence of lung tumors in
male mice, and an increase in the incidence of
liver tumors in female mice. At 250 ppm in-
creased tumor rates were not observed. By com-
parison an oral two-year study with rats and mice
in which the animals were exposed 250 or
500 mg/kg/d1 of mixed xylenes (containing
17% ethylbenzene) showed no exposure-related
tumor response.
As ethylbenzene does not interact with genet-
ic material in vivo, various studies were carried
out to investigate the mode of action responsible
for the excess tumor formation seen in the
two-year inhalation study. In rats ethylben-
zene-induced nephrotoxicity has been shown to
Vol. 13
exacerbate chronic progressive nephropathy oc-
curring in aging animals, which in association
with sustained cell proliferation finally results in
an increase in the background level of kidney
tumors [19]. Similarly, ethylbenzene at 750 ppm
caused an increase in cell proliferation in the lung
and liver of mice, and again this proliferative
stimulus may result in excess tumor formation
[20]. Further mechanistic analysis is necessary to
determine whether the observed cell replication
identified in mice is likely to occur in humans
and, if so, what exposure level is relevant for
establishing a health-based industrial workplace
limit. The lack of such data was the basis for the
decision of the German MAK Commission to
suspend its former workplace exposure limit of
100 ppm.
Ethylbenzene is readily absorbed after inha-
lative, oral, and dermal exposure. Metabolism
proceeds mainly by oxidation of the side chain
and to a minor extent by aromatic-ring hydroxy-
lation with less than 5% being excreted in urine
as 2- and 4-ethylphenol. Side-chain oxidation
mainly leads to 1-phenylethanol, one of the
major urinary excretion products in rats. Further
oxidative metabolism results in the production
of mandelic acid, phenyl glyoxylic acid, and
benzoic acid. A second side-chain oxidative
process producing 2-phenylethanol and ulti-
mately leading to phenyl acetic acid is a minor
pathway. In humans mandelic acid and phenyl
glyoxylic acid are the major urinary metabo-
lites, accounting for approximately 80% of the
absorbed ethylbenzene.
Several regulatory and scientific commissions
have evaluated ethylbenzene and the most
important results are summarized below.
In the EU ethylbenzene is classified and
labeled with:
. F and the risk phrase 11 highly
flammable
. Xn and the risk phrase R 20 harmful by
inhalation
An IARC evaluation of ethylbenzene carried out
in 2000 concluded that while there was sufficient
evidence for carcinogenicity in experimental
animals there was inadequate evidence for cancer
in exposed humans. On this basis it was classified
as possibly carcinogenic to humans (Group
2B) [21].
Ethylbenzene 463
The German MAK Commission formerly had
assigned a MAK value of 100 ppm. In 2001,
taking account of the carcinogenicity data,
ethylbenzene was classified as a carcinogenic
substance into category 3A. In the MAK process
carcinogenic chemicals are assigned to category
3A if the criteria for classification in category
4 or 5 are fulfilled but the database is insufficient
for the establishment of a MAK or BAT value.
For carcinogens of category 4 or 5 no significant
contribution to human cancer risk is to be
expected . . . provided the MAK and BAT
values are observed. In other words, there is in
principle an exposure level without an increased
carcinogenic risk, but the data available currently
do not allow such a specific workplace exposure
limit to be assigned. The MAK value for ethyl-
benzene has therefore been suspended while the
Commission awaits the results of further mecha-
nistic investigations to establish an occupational
exposure limit (see above) [17].
In 2002 ACGIH recommended a TLV-TWA
of 100 ppm and a TLV-STEL of 125 ppm. While
such exposure limits relate to inhalative uptake
only, the ACGIH has also defined a biological
exposure index (BEI) for mandelic acid in urine
of 1.5 g/g creatinine [22]. As mandelic acid is a
major urinary excretion product after exposure to
ethylbenzene, the advantage of a BEI is that
uptake by all exposure routes can be integrated.
With regard to the carcinogenic effect, ethylben-
zene was assigned to group A3: confirmed
animal carcinogen with unknown relevance to
humans [18].
References
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2 American Petroleum Institute (ed.): Technical Data
Book Petroleum Refining, 12th Revision Package to
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3 American Petroleum Institute (ed.): Technical Data
Book Petroleum Refining, metric ed., American Petro-
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6 CdF Chimie, US 4 117 023, 1978 (P. J. Gillet,
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464 Ethylbenzene
7 Monsanto, US 3 848 012, 1974 (F. Applegath, L. E.
DuPree, Jr. A. C. MacFarlane, J. D. Robinson).
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10 Hydrocarbon Process. 78 (1999) no. 3 110.
11 CDTech, Ethylbenzene Technology, Highest Yield Using
Zeolite Based Catalyst, ABB Lummus Global, May 1997.
12 J. Surdyk, K. L. Ring, Ethylbenzene in Chemical
Economics Handbook, SRI International, Menlo Park,
CA 1999.
13 R. J. Lewis, Sr., Saxs Dangerous Properties of Indus-
trial Materials, 10th ed., John Wiley & Sons, New York,
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15 DFG (ed.): MAK- und BAT-Werte-Liste, VCH, Wein-
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16 F. W. Mackison, R. S. Stricoff, L. J. Partridge (eds.):
NIOSH/OSHA Occupational Health Guidelines for
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Wiley-VCH, Weinheim, Germany 2001.
Vol. 13
18 ACGIH (ed.): Documentation of the Threshold Limit
Values for Chemical Substances, 7th ed., Cincinatti 2002.
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Monographs on the Evaluation of Carcinogenic Risk to
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Further Reading
W. J. Cannella: Xylenes and Ethylbenzene, Kirk Othmer
Encyclopedia of Chemical Technology, 5th edition,
John Wiley & Sons, Hoboken, NJ, online DOI:
10.1002/0471238961.2425120503011414.a01.pub2.
J. Cejka, A. Corma, S. Zones (eds.): Zeolites and Catalysis,
Wiley-VCH, Weinheim 2010.
G. P. Chiusoli, P. M. Maitlis (eds.): Metal-Catalysis in
Industrial Organic Processes, Royal Society of Chemis-
try, Cambridge, UK 2006.
S. Kulprathipanja (ed.): Zeolites in Industrial Separation and
Catalysis, Wiley-VCH, Weinheim 2010.
S. T. Oyama (ed.): Mechanisms in Homogeneous and
Heterogeneous Epoxidation Catalysis, Elsevier, Amster-
dam 2008.
J. Schellenberg (ed.): Syndiotactic Polystyrene, Wiley,
Hoboken, NJ 2010.