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. . . . . . . . . . . . . . . . . . . . . . . . . 451 4.5. Separation from Mixed C8 Streams . . . . . . . . 459

2. Physical Properties . . . . . . . . . . . . . . . . . . . 452 5. Environmental Protection . . . . . . . . . . . . . . 459
3. Chemical Properties . . . . . . . . . . . . . . . . . . 452 6. Quality Specifications. . . . . . . . . . . . . . . . . . 459
4. Production . . . . . . . . . . . . . . . . . . . . . . . . . . 452 7. Handling, Storage, and Transportation . . . . 460
4.1. Alkylation with Non-Zeolite Lewis Acid 8. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . 453 9. Economic Aspects . . . . . . . . . . . . . . . . . . . . 460
4.2. Vapor-Phase Alkylation over Zeolites . . . . . . 455 10. Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . 461
4.3. Liquid-Phase Alkylation over Zeolites . . . . . 457 References . . . . . . . . . . . . . . . . . . . . . . . . . . 463
4.4. Mixed-Phase Zeolite-Based Process . . . . . . . 458

1. Introduction aromatic hydrocarbons with olefins in the pres-

ence of aluminum chloride catalyst was first
Ethylbenzene [100-41-4], phenylethane, practiced by BALSOHN in 1879 [1]. However,
C6H5CH2CH3, Mr 106.168, is a single-ring alky- FRIEDEL and CRAFTS pioneered much of the early
laromatic compound. It is almost exclusively research on alkylation and aluminum chloride
(>99 %) used as an intermediate for the manu- catalysis.
facture of styrene monomer [100-42-5], Several facilities built during the 1960s recov-
C6H5CHCH2, one of the most important ered ethylbenzene by fractionation of mixed
large-volume commodity chemicals. Styrene xylenes produced in refinery catalytic reforming
production, which uses ethylbenzene as a starting units. This practice has largely been discontinued
raw material, consumes ca. 50 % of the worlds due to poor economics that result from high
benzene production. Less than 1 % of the ethyl- energy and investment costs, as well as small
benzene produced is used as a paint solvent or as economies of scale in comparison to the conven-
an intermediate for the production of diethylben- tional alkylation routes.
zene and acetophenone. Ethylbenzene was first produced on a com-
Commercially, almost all ethylbenzene is pro- mercial scale in the 1930s by Dow Chemical
duced by alkylating benzene with ethylene. The in the United States and by BASF in Germany.
newest technologies utilize synthetic zeolites The ethylbenzene/styrene industry remained
installed in fixed-bed reactors to catalyze the relatively insignificant until World War II.
alkylation in the liquid phase. Another proven The tremendous demand for synthetic styrene
route uses narrower pore synthetic zeolites, also butadiene rubber (SBR) during the war
installed in fixed-bed reactors, to effect the prompted accelerated technology improve-
alkylation in the vapor phase. A considerable ments and tremendous capacity expansion. This
quantity of ethylbenzene is still produced by considerable wartime effort led to the construc-
alkylation with homogeneous aluminum chlo- tion of several large-scale factories, and styrene
ride catalyst in the liquid phase, though the recent production quickly became a significant indus-
trend in the industry has been to retrofit such try. In 1999 world annual production capacity
units with zeolite technology. The alkylation of of ethylbenzene reached almost 25
106 t.

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a10_035.pub2
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 Ethylbenzene 453

aromatic streams. Only a small number of plants In the older conventional AlCl3 process
in the world still utilize this method. (see Fig. 1) which is seldom practiced now,
three phases are present in the reactor: aromatic
liquid, ethylene gas, and a liquid catalyst com-
4.1. Alkylation with Non-Zeolite Lewis plex phase (a reddish brown material called red
Acid Catalysts oil). A mixture of catalyst complex, dry ben-
zene, and recycled polyalkylbenzenes is contin-
Liquid-phase aluminum chloride processes were uously fed to the reactor and agitated to disperse
first commercialized in the 1930s. Several com- the catalyst complex phase in the aromatic
panies developed variations of this technology, phase. Ethylene and the catalyst promoter are
including Dow Chemical, BASF, Shell Chemi- injected into the reaction mixture through spar-
cal, Monsanto/Lummus, Soci
et
e Chimiques des gers, and essentially 100 % of the ethylene is
Charbonnages, and Union Carbide/Badger. Of converted. Commercial plants typically operate
the aluminum chloride plants still in operation, at ethylene/benzene molar ratios of ca. 0.3
the majority of them utilize the Monsanto/Lum- 0.35. As this ratio is increased, more side reac-
mus technology, widely considered the most tions, such as transalkylation and isomeric
advanced of the aluminum chloride processes. rearrangement, occurr. Further alkylation of
Lummus discontinued licensing this technology ethylbenzene leads to the reversible formation
with the commercialization of their liquid-phase of lower molecular mass polyalkylbenzenes.
zeolite process around 1990. The loss in yield due to residue formation is
Alkylation of benzene with ethylene is highly minimized by recycling this material to the
exothermic (DH  114 kJ/mol); in the pres- alkylation reactor. In addition, because the
ence of aluminum chloride the reaction is very reaction occurs close to thermodynamic equi-
fast and produces almost stoichiometric yields of librium, the traditional processes use a single
ethylbenzene. In addition to AlCl3, a wide range reactor to alkylate benzene and transalkylate
of Lewis acid catalysts, including AlBr3, FeCl3, polyalkylbenzenes.
ZrCl4, and BF3, have been used. Aluminum The reaction temperature is generally limited
chloride processes generally use ethyl chloride to 130  C; a higher temperature rapidly deacti-
or hydrogen chloride as a catalyst promoter. vates the catalyst and favors formation of non-
These halide promoters reduce the amount of aromatics and polyalkylbenzenes, which are
AlCl3 required. The reaction mechanism has preferentially absorbed by the highly acidic
been studied in detail [5]. catalyst complex and form byproducts. Sufficient

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
454 Ethylbenzene Vol. 13

pressure is maintained to keep the reactants in the lated components. The bottoms product of the
liquid phase. Because the reaction mixture is second column is fed to a final column where the
highly corrosive, the alkylation reactors are lined recyclable polyalkylbenzenes are stripped from
with brick or glass. High-alloy construction nonrecyclable high molecular mass residue com-
materials are also required for the piping and pounds. The residue stream, or flux oil, consist-
handling systems. ing primarily of polycyclic aromatics, is burned
The liquid reactor effluent is cooled and dis- as fuel.
charged into a settler, where the heavy catalyst Because the alkylation mixture can tolerate
phase is decanted from the organic liquid-phase only minor amounts of water, the recycle ben-
and recycled. The organic phase is washed with zene and fresh benzene must be dried thoroughly
water and caustic to remove dissolved AlCl3 and prior to entering the reactor. Water not only
promoter. The aqueous phase from these treat- increases corrosion, but also decreases catalyst
ment steps is first neutralized and then recovered activity. Benzene dehydration is accomplished in
as a saturated aluminum chloride solution and a a separate column.
wet aluminum hydroxide sludge. The improved Monsanto process (see Fig. 2)
Removal of dissolved catalyst from the organ- has several advantages over the conventional
ic stream has long been a challenge for ethylben- AlCl3 processes. Over time many conventional
zene producers. CdF Chimie found that more AlCl3 plants have been retrofitted with this tech-
complete recovery of AlCl3 could be achieved by nology. The most important advantage is a
first contacting the organic phase with ammonia significant reduction in the amount of AlCl3
instead of sodium hydroxide [6]. catalyst used, thus lessening the problem and
Purification of the ethylbenzene product is cost of waste catalyst disposal. Monsanto found
usually accomplished in a series of three distil- that by increasing temperature and by careful
lation columns. The unconverted benzene is control of ethylene addition, the required AlCl3
recovered in the first column as an overhead concentration could be reduced to the solubility
distillate. The second column separates the limit, thereby eliminating the separate catalyst
ethylbenzene product from the heavier polyalky- complex phase [7]. Therefore, the alkylation

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 Ethylbenzene 455

occurs in a single homogeneous liquid phase problems associated with aluminum chloride
instead of in the two liquid phases of earlier processes were avoided. However, even small
processes. Monsanto claimed that a separate amounts of water (< 1 g/kg) hydrolyzed the BF3
catalyst complex phase may actually prevent the catalyst.
attainment of maximum reactor yields. With a The alkylation reaction took place at high
few exceptions, the flow scheme of the Monsanto pressure (2.5 3.5 MPa) and low temperature
process is nearly the same as that of more tradi- (100 150  C). Dried benzene, ethylene, and
tional processes. The process is also capable of makeup BF3 catalyst were fed to the reactor.
operating with low-concentration ethylene feed. Typically, ethylene/benzene molar ratios be-
Typically, the alkylation temperature is main- tween 0.15 and 0.2 were used. The reactor inlet
tained at 160 180  C. This higher operating temperature was controlled by recycling a small
temperature enhances catalyst activity with the portion of the reactor effluent. Transalkylation
additional benefit that the heat of reaction can be took place in a separate reactor. Dry benzene, BF3
recovered as low-pressure steam. catalyst, and recycled polyethylbenzenes were
Whereas the traditional process accomplishes fed to the transalkylation reactor, which operated
alkylation and transalkylation in a single reactor, at higher temperature (180 230  C) than the
the homogeneous catalyst system must employ a alkylation reactor. The effluent streams from the
separate transalkylation reactor. At the lower two reactors were combined and passed to a
catalyst concentrations, the recycle of substantial benzene recovery column where benzene was
amounts of polyalkylbenzenes terminates the separated for recycle to the reactors. Boron
alkylation reaction. Therefore, only dry benzene, trifluoride and light hydrocarbons were taken
ethylene, and catalyst are fed to the alkylation overhead as a vapor stream from which the BF3
reactor. The recycle polyethylbenzene stream is was recovered for recycle. The bottoms from the
mixed with the alkylation reactor effluent prior to benzene recovery column was sent to a product
entering the transalkylation reactor. The trans- column where ethylbenzene of > 99.9 % purity
alkylation reactor is operated at much lower was taken overhead. A final column served to
temperature than the primary alkylation reactor. recover polyethylbenzenes for recycle to the
After transalkylation, the reaction products transalkylation reactor.
are washed and neutralized to remove residual The Alkar process could operate with an eth-
AlCl3. With the homogeneous process, all of the ylene feed containing as little as 8 10 mol %
catalyst remains in solution. The catalyst-free ethylene, enabling a variety of refinery and coke-
organic reaction mixture is then purified by using oven gas streams to be used. However, purifica-
the sequence described for the conventional tion of these streams was necessary to remove
AlCl3 process. As with other AlCl3 processes, components that poison the BF3 catalyst, e.g.,
the organic residue is used as fuel and the alumi- trace amounts of water, sulfur compounds, and
num chloride waste streams are usually sold or oxygenates.
sent to treatment facilities.
In 1999 about 40 % of the ethylbenzene man-
ufactured worldwide used aluminum chloride 4.2. Vapor-Phase Alkylation over
technology. Another technology based on Lewis Zeolites
acids is the so-called Alkar process. Developed
by UOP and based on boron trifluoride catalyst, The Mobil Badger vapor-phase technology
this process had modest success in the 1960s, but was developed in the 1970s around Mobils
fell from favor because of high maintenance ZSM-5 synthetic zeolite and has been available
costs resulting from the severe corrosion caused in several different designs. The original first-
by small quantities of water. In the developed generation design, commercialized by American
countries, only one Alkar plant is still in Hoechst in 1980, carried out vapor-phase alkyl-
operation. ation and transalkylation in a single reactor by
However, the process produced a high-purity recycling polyethylbenzene to the front end of
ethylbenzene product and could use dilute ethyl- the process, similar to conventional aluminum
ene feedstock. If the entry of water into the chloride technology. The newest, so-called third-
process was strictly prevented, the corrosion generation technology performs transalkylation
456 Ethylbenzene Vol. 13

in a separate lower pressure reaction step. The The alkylation reactor typically operates in the
third-generation technology offered significant range of 350 450  C and 1 3 MPa. At this
benefits in yield, purity, and capital cost, and was temperature, > 99 % of the net process heat input
widely used in the 1990s to debottleneck older and exothermic heat of reaction can be recovered
vapor-phase plants. as steam. The reaction section includes a multibed
The vapor-phase zeolite process is particular- reactor, a fired heater and heat recovery equip-
ly suited to dilute ethylene streams, particularly ment. The reactor operates with significant over-
refinery off-gas from fluid catalytic cracking all excess of benzene relative to ethylene.
(FCC) units. Until technologies using zeolites in Slow catalyst deactivation occurs as a result of
the liquid phase were commercialized in the coke formation and requires periodic regenera-
1990s, the vapor-phase zeolite process was the tion. In situ regeneration takes ca. 36 h and may
dominant technology of new plants, primarily be necessary after 18 24 months of operation,
because it avoided the aqueous waste streams depending on the operating conditions. The cat-
produced from aluminum chloride plants. Mo- alyst is less sensitive to water, sulfur, and other
bil Badger licensed a total of 31 units since poisons than the Lewis acid catalysts and zeolites
1980, and the technology is still licensed for operating in the liquid phase.
dilute-ethylene-based plants. The reactor effluent passes to the purification
The fixed-bed ZSM-5 catalyst promotes the section as a vapor. The benzene from this stream
same overall alkylation chemistry as in the other is distilled overhead in the first distillation
processes; however, ethylene molecules are column and is subsequently recycled to the
adsorbed onto the Brnsted acid sites within the reactors. The ethylbenzene product is taken as
catalyst, which activates the ethylene molecule the overhead product from the second column.
and allows bonding with benzene molecules to The bottoms product from this column is sent to
occur. Hence, the range of higher alkylated aro- the last column where the recyclable alkylben-
matic byproducts formed by the Mobil Badger zenes and polyalkylbenzenes are separated from
process is somewhat different than those of the heavy nonrecyclable residue. The low-viscosity
Friedel Crafts processes. residue stream, consisting mainly of diphenyl-
Carbon steel is the primary material of con- methane and diphenylethane, is burned as fuel.
struction; high-alloy materials and brick linings Recyclable higher alkylbenzenes and poly-
are not required. A diagram of the third-genera- alkylbenzenes are sent to the vapor-phase
tion design is shown in Figure 3. transalkylator, where they are converted in the

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 Ethylbenzene 457

presence of excess benzene over zeolite cata- the first plant being operated by Nippon SM in
lyst. Because the transalkylator has lower pres- Oita, Japan under license from ABB Lummus
sure but higher temperature relative to the Global and Unocal (UOP later became ABBs
alkylator, higher alkylbenzenes are dealkylated partner when they acquired Unocals zeolite
while diethylbenzene is transalkylated to ethyl- business). This process has utilized ultrastable
benzene. The ability to dealkylate higher alkyl- zeolite Y or more recently zeolite beta. Another
benzenes, known to be residue precursors, liquid-phase EB process, EBMax, became avail-
serves to decrease overall residue production. able from Mobil Badger and is based on a
The older first- and second-generation pro- Mobil MCM-22 catalyst and first operated at
cesses were similar, the major difference being Chiba Styrene Monomer Corp., also in Japan.
that the recycle polyethylbenzene stream was A total of twelve all-liquid-phase zeolite plants
recycled to the alkylation reactor. For that reason were operating at the end of 1999. Although there
the process had inferior performance relative to are differences between the two available liquid-
the third-generation design. phase technologies, the latest versions of both
Though most often used with polymer-grade lead to lower investment cost and better product
ethylene, this process is adaptable to dilute quality than was possible with previously avail-
ethylene feedstocks. The process has operated able technologies using polymer-grade ethylene.
on a mixed C2 stream provided from a debot- The vapor-phase technology is now typically
tlenecked distillation train from a naphtha licensed by Mobil/Badger for dilute-ethylene
cracker. Additionally, and perhaps of more applications.
interest due to low feedstock cost, is the adapt- These liquid phase processes all utilize wid-
ability to dilute ethylene steams produced from er pore zeolites than ZSM-5, which is necessary
FCC off-gas. Two world-scale Mobil Badger to overcome the diffusional limitations of
units operate with FCC off-gas, one since 1991 the liquid-phase mechanism. Both licensors
and one since 1998 [8]. usually recommend off-site regeneration of
catalyst because of long catalyst cycle times.
Off-site regeneration results in less on-site
4.3. Liquid-Phase Alkylation over equipment being required and hence in reduced
Zeolites investment.
The flowsheets of the two technologies are
All-liquid phase processes using zeolite catalysts quite similar (Figs. 4 and 5). Ethylene is injected
began to appear in commercial operation in 1990, into a fixed bed alkylation reactor with multiple

Figure 4. Lummus/UOP ethylbenzene process [9] a) Alkylation reactor; b) Transalkylation reactor; c) Benzene column;
d) Ethylbenzene column; e) Polyethylbenzene column
458 Ethylbenzene Vol. 13

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 4.4. Mixed-Phase Zeolite-Based

temperatures vary from process to process, but Process
they must be kept below the critical temperature
of benzene (289  C). Pressures must be high A mixed-phase ethylbenzene process is offered
enough to keep the light gases in solution and for license by CDTech, a partnership between
are on the order of 4 MPa. Excess benzene is ABB Lummus Global and Chemical Research
distilled overhead from the effluent and is and Licensing, Co. [10], [11] The first unit started
recycled to alkylation. The benzene column in 1994, and as of 1999, three plants were oper-
bottoms enter the ethylbenzene product col- ating. The main distinction of this process is the
umn, from which the ethylbenzene is distilled alkylation reactor, which contains bales of zeo-
overhead. The bottoms of the ethylbenzene lite catalyst in a reactive-distillation column.
column are fed to the polyethylbenzene col- Ethylene gas and benzene liquid are fed to the
umn, which separates higher alkylbenzenes and reactive-distillation column. Because of its abili-
polyethylbenzenes from the residue. This over- ty to handle the ethylene feed in the vapor phase,
head stream is fed to the liquid-phase transalk- the process has been applied to dilute ethylene
ylation reactor, where it is combined with streams produced from steam cracker distillation
excess benzene from the benzene column dis- trains. It has also been applied to polymer grade
tillate. Effluent from the transalkylator is ethylene. A flow scheme is shown in Figure 6.
returned to the distillation train. An alkylator and benzene stripper operate togeth-
Besides benzene, major impurities in the eth- er as a distillation column. The overhead benzene
ylbenzene product can include nonaromatics and unconverted ethylene are in turn fed to a
(naphthenes), toluene, and higher alkylbenzenes. finishing reactor, which also utilizes zeolite.
Depending on the operating conditions and tech- Bottoms from the benzene stripper are fraction-
nology, these components can originate from ated into ethylbenzene product in the overhead
the feed benzene or be generated in the reactor. product column, and then transalkylatable poly-
There is a wide variation in distillation column ethylbenzenes are distilled from the residue.
operating conditions, particularly in revamped The polyethylbenzenes are sent to a liquid-phase
facilities. There is also a wide variation in excess transalkylation reactor in the presence of excess
benzene from plant to plant. These details are benzene, and the transalkylation effluent is
held confidentially by the licensors. returned to the fractionation train.
Vol. 13 Ethylbenzene 459

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 (40 CFR 63, Subparts F, G, H). Producers can
comply by installing collection devices on pro-
Less than 1 % of worldwide ethylbenzene pro- cess vents, improved seals on pumps and valves,
duction is recovered from mixed xylene and floating roof tanks.
streams, usually in conjunction with xylene Alkylation plants that use aluminum chloride
production from reformate. Although adsorp- technology produce an aqueous waste stream
tion processes have been developed, most nota- from the reactor effluent wash section. In the
bly the EBEX process of UOP, ethylbenzene mid-1970s, plants produced a wet aluminum
production from these sources has been mainly hydroxide sludge which was deposited in a land-
performed by distillation. Because of the diffi- fill (Class 1). More modern plants recover a
culty of the separation, the process is generally concentrated aluminum chloride solution that
termed superfractionation. It was first undertak- has found use in municipal water treatment or
en by Cosden Oil & Chemical Company in industrial floc applications. However, where
1957, using technology jointly developed with demand from such applications does not exist,
the Badger Company. The separation generally disposal can present a problem. Sometimes
requires three distillation columns in series, hazardous-waste incineration is required.
each having over 100 stages. Several units were Studies have shown ethylbenzene to be toxic
built during the 1960s in the United States, to aquatic life in relatively low concentration
Europe, and Japan. However, the increased cost (10 100 mg/kg). Therefore, runoff from spills,
of energy and high capital cost has made this fire control, etc. should be diked to prevent it
route noncompetitive. from entering streams or water supplies.

5. Environmental Protection 6. Quality Specifications

In the United States ethylbenzene plants must The product specification on ethylbenzene is set
conform to the requirements of U.S. EPA to provide a satisfactory feedstock to the associ-
National Emission Standard Organic Air Pollutants ated styrene unit. Objectionable impurities in the
from the Synthetic Organic Chemical Industry ethylbenzene can be grouped into two categories:
460 Ethylbenzene Vol. 13

those that are detrimental to the operation of the DOT Material Transportation Bureau. Other
styrene unit and those that affect the purity of the countries have regulations and safety practices
styrene product. Impurities in product ethylben- similar to those of the United States.
zene that pose an operating problem in the con- Foam, carbon dioxide, dry chemical, halon,
ventional dehydrogenative styrene process are and water (fog pattern) extinguishing media are
used in fighting ethylbenzene fires.
1. Halides, which deactivate the dehydrogena- Adequate ventilation is necessary in handling
tion catalyst and contribute to downstream and storage areas. The use of NIOSH-approved
equipment corrosion. Usually these are chlor- respirators is recommended at high concentra-
ides originating from an AlCl3 alkylation tion. Skin contact should be avoided. Chemical
section or fluorides from an Alkar unit. gloves and safety glasses should be worn if
2. Diethylbenzenes, which are dehydrogenated contact is possible.
to divinylbenzenes in the styrene reactor sec- Exposure of ethylbenzene to heat, ignition
tion. The divinylbenzenes form insoluble sources, and strong oxidizing agents should be
cross-linked polymers in the downstream pro- avoided.
cess equipment. A limit of less than 10 ppm of
diethylbenzenes in the ethylbenzene product
is usually imposed. 8. Uses
Ethylbenzene contaminants that can affect Essentially all commercial ethylbenzene produc-
styrene purity are components having a boiling tion is captively consumed for the manufacture of
range between ethylbenzene and styrene. These styrene monomer or in the co-production of
include xylenes, propylbenzenes, and ethylto- styrene monomer with propylene oxide. Styrene
luenes. The levels of cumene, n-propylbenzene, is used in the production of polystyrene and a
ethyltoluenes, and xylenes in the ethylbenzene is wide variety of other plastics (! Styrene).
controlled to meet the required styrene purity Of the minor uses, the most significant is in the
specification. paint industry as a solvent, which accounts for
A typical sales specification for a United < 1 % of production capacity. Even smaller
States manufacturer is a follows: volumes go toward the production of acetophe-
none, diethylbenzene, and ethylanthraquinone.
Purity 99.5 wt % min.
Benzene 0.05 0.3 wt %
Toluene 0.1 0.3 wt % 9. Economic Aspects
Xylenes 0.2 wt % max.
Nonaromatics 0.05 wt % max. Ethylbenzene production is linked directly to the
Propylbenzenes 0.02 wt % max.
Diethylbenzenes 10 mg/kg max.
styrene monomer market. A total of 99 % of the
Total chlorides as Cl 1 3 mg/kg max. ethylbenzene produced worldwide is used to
Total organic sulfur 4 mg/kg max. make styrene monomer. Through the 1960s and
Relative density at 15  C 0.869 0.872 into the early 1970s annual growth rates for
APHA Color 15 max.
styrene and ethylbenzene averaged 10 %. During
this period sustained growth was powered by
the expanding polystyrene market. Subsequent
7. Handling, Storage, and growth since the early 1970s has been erratic,
Transportation with the price of styrene going through four to
five year cycles, and several new ethylbenzene/
Ethylbenzene is a flammable liquid. It is stored styrene plants were built each time the price
and transported in steel containers and is subject started to rise. Since the mid-1980s the average
to the control of the appropriate regulatory agen- growth in ethylbenzene capacity worldwide has
cies. The U.S. DOT identification number is UNI been about 4 5 % per year, somewhat higher
175 and the reportable quantity is 454 kg. Details than the growth of the overall economy. As late
on regulations concerning the transport of ethyl- as the mid 1980s most Far Eastern ethylbenzene/
benzene can be found in the CFR or from the 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 Vol. 13

The low toxicity of ethylbenzene observed slight fetotoxicity. In an investigation with preg-
after a single exposure was also seen in repeated nant rabbits no fetal effects occurred in animals
dosing studies, in which significant toxicity in continuously exposed to ethylbenzene (24 h/d) at
experimental animals was produced only at rela- approximately 110 ppm. Exposure to approxi-
tively high doses. For example, when rats and mately 230 ppm was toxic to the dams, with an
mice were exposed by inhalation over three indication of fetotoxicity. In contrast, no clear
months no toxicity was observed in rats at effects were noted in pregnant rabbits and their
100 ppm and in mice at 500 ppm. Some in- offspring at 1000 ppm with a daily exposure of
creases in lung, kidney, and liver weights were 7 h/d.
measured starting at 250 ppm in rats and In vitro investigations examining the geno-
750 ppm in mice, but no histopathological toxic potential of ethylbenzene have produced
changes were apparent in any of the tissues. conflicting results. While studies in bacteria and
When rats and mice were exposed to ethylben- yeast were negative, some studies with mamma-
zene by inhalation for two years (the major part of lian cells in culture have produced some weakly
their natural life), no effects were observed in positive data. In contrast, in vivo investigations
both species at 75 ppm. Some slight changes in drosophila and in mice [micronucleus test, test
were found at 250 ppm, but even at 750 ppm for unscheduled DNA synthesis (UDS)] were
there were no effects on overall survival in mice negative. In summary, while there may be some
and female rats. Only male rats in the 750 ppm weak potential for ethylbenzene to interact with
exposure group showed a reduced survival as the DNA of isolated cells in vitro, the consistent
compared to untreated controls. The reduction in lack of a response in various in vivo test systems
survival was attributed to a rat-specific nephro- indicates that ethylbenzene is not a mutagenic
toxicity that can not be extrapolated to humans. hazard. A limited in vitro mutagenicity database
While exposure to ethylbenzene at 750 ppm for also is available for most of the metabolites of
two years had little effect on survival, it did ethylbenzene (see below): 1-phenylethanol,
produce an increase in hepatic and pulmonary acetophenone, w-hydroxyacetophenone, phe-
tumors in mice and an increase in the incidence of nyl glyoxylic acid, mandelic acid, benzoic acid,
renal tumours in male rats (see below). hippuric acid, and 2-, 3-, and 4-ethylphenol.
Various toxicological investigations have Again, although there are some conflicting
considered the potential reproductive toxicity results the overall weight of evidence is that
of ethylbenzene. In the three-month inhalation these metabolites do not exhibit a clear geno-
study described above no effects were found on toxic potential.
the reproductive tissues of rats and mice at A two-year inhalation carcinogenicity study
exposures up to 1000 ppm. has been carried out in rats and mice with
Other studies in which pregnant mice, rats, or exposures to ethylbenzene at 0, 250, and
rabbits were exposed to ethylbenzene have pro- 750 ppm. Treatment at 750 ppm produced an
duced divergent results. For example, increases increased incidence of kidney tumors in male
in fetal malformations have been reported when rats, an increased incidence of lung tumors in
pregnant mice were exposed to 113 ppm ethyl- male mice, and an increase in the incidence of
benzene. The study did not find any other effects liver tumors in female mice. At 250 ppm in-
indicating fetotoxicity, but insufficient informa- creased tumor rates were not observed. By com-
tion was supplied by the investigators to enable parison an oral two-year study with rats and mice
an in-depth evaluation. Rats exposed continu- in which the animals were exposed 250 or
ously (24 h/d) up to 540 ppm showed slight 500 mg/kg/d1 of mixed xylenes (containing
maternal toxicity accompanied by fetotoxicity 17% ethylbenzene) showed no exposure-related
with some retardations and variations of fetal tumor response.
development. At the same concentrations, but As ethylbenzene does not interact with genet-
with exposures lasting only 6 h/d, no adverse ic material in vivo, various studies were carried
findings were noted on the dams and offspring. In out to investigate the mode of action responsible
another study in which pregnant rats were for the excess tumor formation seen in the
exposed to 1000 ppm ethylbenzene for 6 two-year inhalation study. In rats ethylben-
7 h/d, maternal toxicity was associated with zene-induced nephrotoxicity has been shown to
Vol. 13 Ethylbenzene 463

exacerbate chronic progressive nephropathy oc- The German MAK Commission formerly had
curring in aging animals, which in association assigned a MAK value of 100 ppm. In 2001,
with sustained cell proliferation finally results in taking account of the carcinogenicity data,
an increase in the background level of kidney ethylbenzene was classified as a carcinogenic
tumors [19]. Similarly, ethylbenzene at 750 ppm substance into category 3A. In the MAK process
caused an increase in cell proliferation in the lung carcinogenic chemicals are assigned to category
and liver of mice, and again this proliferative 3A if the criteria for classification in category
stimulus may result in excess tumor formation 4 or 5 are fulfilled but the database is insufficient
[20]. Further mechanistic analysis is necessary to for the establishment of a MAK or BAT value.
determine whether the observed cell replication For carcinogens of category 4 or 5 no significant
identified in mice is likely to occur in humans contribution to human cancer risk is to be
and, if so, what exposure level is relevant for expected . . . provided the MAK and BAT
establishing a health-based industrial workplace values are observed. In other words, there is in
limit. The lack of such data was the basis for the principle an exposure level without an increased
decision of the German MAK Commission to carcinogenic risk, but the data available currently
suspend its former workplace exposure limit of do not allow such a specific workplace exposure
100 ppm. limit to be assigned. The MAK value for ethyl-
Ethylbenzene is readily absorbed after inha- benzene has therefore been suspended while the
lative, oral, and dermal exposure. Metabolism Commission awaits the results of further mecha-
proceeds mainly by oxidation of the side chain nistic investigations to establish an occupational
and to a minor extent by aromatic-ring hydroxy- exposure limit (see above) [17].
lation with less than 5% being excreted in urine In 2002 ACGIH recommended a TLV-TWA
as 2- and 4-ethylphenol. Side-chain oxidation of 100 ppm and a TLV-STEL of 125 ppm. While
mainly leads to 1-phenylethanol, one of the such exposure limits relate to inhalative uptake
major urinary excretion products in rats. Further only, the ACGIH has also defined a biological
oxidative metabolism results in the production exposure index (BEI) for mandelic acid in urine
of mandelic acid, phenyl glyoxylic acid, and of 1.5 g/g creatinine [22]. As mandelic acid is a
benzoic acid. A second side-chain oxidative major urinary excretion product after exposure to
process producing 2-phenylethanol and ulti- ethylbenzene, the advantage of a BEI is that
mately leading to phenyl acetic acid is a minor uptake by all exposure routes can be integrated.
pathway. In humans mandelic acid and phenyl With regard to the carcinogenic effect, ethylben-
glyoxylic acid are the major urinary metabo- zene was assigned to group A3: confirmed
lites, accounting for approximately 80% of the animal carcinogen with unknown relevance to
absorbed ethylbenzene. humans [18].
Several regulatory and scientific commissions
have evaluated ethylbenzene and the most
important results are summarized below. References
In the EU ethylbenzene is classified and
labeled with: 1 R. H. Boundy, R. F. Boyer (eds.): Styrene, Its Polymers,
Copolymers, and Derivatives, Reinhold Publ. Co.,
. F and the risk phrase 11 highly New York 1952, p. 16.
flammable 2 American Petroleum Institute (ed.): Technical Data
. Xn and the risk phrase R 20 harmful by Book Petroleum Refining, 12th Revision Package to
inhalation 5th ed., vol. 1, American Petroleum Institute, Washing-
ton, D.C. 1997, pp. 178, 179, 1112, 1113.
3 American Petroleum Institute (ed.): Technical Data
An IARC evaluation of ethylbenzene carried out Book Petroleum Refining, metric ed., American Petro-
in 2000 concluded that while there was sufficient leum Institute, Washington, D.C. 1981, pp. 156, 157.
evidence for carcinogenicity in experimental 4 Beilstein 5, 776 786.
animals there was inadequate evidence for cancer 5 G. A. Olah (ed.): Friedel Crafts and Related Reactions,
in exposed humans. On this basis it was classified vol. 2, Wiley-Interscience, New York 1964, Part 1.
as possibly carcinogenic to humans (Group 6 CdF Chimie, US 4 117 023, 1978 (P. J. Gillet,
2B) [21]. G. Henrich).
464 Ethylbenzene Vol. 13

7 Monsanto, US 3 848 012, 1974 (F. Applegath, L. E. 18 ACGIH (ed.): Documentation of the Threshold Limit
DuPree, Jr. A. C. MacFarlane, J. D. Robinson). Values for Chemical Substances, 7th ed., Cincinatti 2002.
8 K. J. Fallon, H. K. H. Wang, C. R. Venkat, UK Refinery 19 G. C. Hard, Toxicol. Sci. 69 (2002) 30 41.
Demonstrates Ethylbenzene Process, Oil & Gas Jour- 20 W. T. Stott, K. A. Johnson, R. Bahnemann, S. J. Day, R. J.
nal, April 17, 1995. McGuirk, Toxicol. Sci. 71 (2003) 53 66.
9 Hydrocarbon Process. 76 (1997) no. 3 126. 21 International Agency for Research on Cancer, IARC
10 Hydrocarbon Process. 78 (1999) no. 3 110. Monographs on the Evaluation of Carcinogenic Risk to
11 CDTech, Ethylbenzene Technology, Highest Yield Using Humans, Vol. 77, 2000, p. 227.
Zeolite Based Catalyst, ABB Lummus Global, May 1997. 22 ACGIH (ed.): Documentation of the Biological Exposure
12 J. Surdyk, K. L. Ring, Ethylbenzene in Chemical Indices, 7th ed., Cincinatti 2001.
Economics Handbook, SRI International, Menlo Park,
CA 1999.
13 R. J. Lewis, Sr., Saxs Dangerous Properties of Indus- Further Reading
trial Materials, 10th ed., John Wiley & Sons, New York,
1999. W. J. Cannella: Xylenes and Ethylbenzene, Kirk Othmer
14 ACGIH (ed.): Threshold Limit Values (TLV) and Bio- Encyclopedia of Chemical Technology, 5th edition,
logical Exposure Indices, ACGIH, Cincinnati, Ohio John Wiley & Sons, Hoboken, NJ, online DOI:
1997. 10.1002/0471238961.2425120503011414.a01.pub2.
15 DFG (ed.): MAK- und BAT-Werte-Liste, VCH, Wein- J. Cejka, A. Corma, S. Zones (eds.): Zeolites and Catalysis,
heim, Germany 1995. Wiley-VCH, Weinheim 2010.
16 F. W. Mackison, R. S. Stricoff, L. J. Partridge (eds.): G. P. Chiusoli, P. M. Maitlis (eds.): Metal-Catalysis in
NIOSH/OSHA Occupational Health Guidelines for Industrial Organic Processes, Royal Society of Chemis-
Chemical Hazards, U.S. Dept. of Health & Human Ser- try, Cambridge, UK 2006.
vices (National Institute for Occupational Safety & S. Kulprathipanja (ed.): Zeolites in Industrial Separation and
Health) Publication no. 81 123, Washington, D.C., Catalysis, Wiley-VCH, Weinheim 2010.
Jan. 1981. S. T. Oyama (ed.): Mechanisms in Homogeneous and
17 H. Greim (ed.): Gesundheitssch adliche Arbeitsstoffe; Heterogeneous Epoxidation Catalysis, Elsevier, Amster-
Toxikologisch-arbeitsmedizinische Begr undungen von dam 2008.
MAK-Werten (Maximale Arbeitsplatzkonzentrationen), J. Schellenberg (ed.): Syndiotactic Polystyrene, Wiley,
Wiley-VCH, Weinheim, Germany 2001. Hoboken, NJ 2010.