ETHYLBENZENE

Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release
ETHYLBENZENE - Ethylbenzene (Vincent A. Welch, Kevin J. Fallon)
References
Ethylbenzene
REVISED MARCH 2001
VINCENT A. WELCH, Washington Group Intl., Inc. (formerly The Badger Company), Cambridge,
Massachusetts 02142, United States
KEVIN J. FALLON, Washington Group Intl., Inc. (formerly The Badger Company), Cambridge,
Massachusetts 02142, United States
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1. Introduction
Ethylbenzene [100-41-4], phenylethane, C6H5CH2CH3, Mr 106.168, is a single-ring alkylaromatic

compound. It is almost exclusively (>99%) used as an intermediate for the manufacture of styrene
monomer [100-42-5], C6H5CH=CH2, one of the most important large-volume commodity chemicals.
Styrene production, which uses ethylbenzene as a starting raw material, consumes ca. 50% of the
world's benzene production. Less than 1% of the ethylbenzene produced is used as a paint solvent or as
an intermediate for the production of diethylbenzene and acetophenone.
Commercially, almost all ethylbenzene is produced 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 chloride catalyst in the liquid phase, though the
recent trend in the industry has been to retrofit such units with zeolite technology. The alkylation of
aromatic hydrocarbons with olefins in the presence 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 recovered 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 conventional alkylation routes.
Ethylbenzene was first produced on a commercial 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 improvements and tremendous capacity expansion. This
considerable wartime effort led to the construction of several large-scale factories, and styrene
Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release © Wiley-VCH. Weinheim. Germany.
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production quickly became a significant industry. In 1999 world annual production capacity of
ethylbenzene reached almost 25 × 106 t. Throughout the 1990s, most of the capacity increase occurred
in the Far Eastern countries other than Japan, where the basic petrochemical industries have undergone
considerable development and expansion.
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2. Physical Properties
Under normal conditions, ethylbenzene is a clear, colorless liquid with a characteristic aromatic odor.
Ethylbenzene is an irritant to the skin and eyes and is moderately toxic by ingestion, inhalation, and
skin adsorption. Some physical properties of ethylbenzene follow [2], [3]:
Density at 15 °C 0.87139 g/cm3

at 20 °C 0.8670 g/cm3
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
at 25 °C 1.49320
Critical pressure 3609 kPa (36.09 bar)
Critical temperature 344.02 °C
Flash point (closed cup) 15 °C
Autoignition temperature 460 °C
Flammability limit lower 1.0%
upper 6.7%
Latent heat fusion 86.3 J/g
vaporization 335 J/g
Heating value, gross 42 999 J/g
net 40 928 J/g
Kinematic viscosity at 37.8 °C 0.6428×10–6 m2/S
at 98.9 °C 0.390×10–6 m2/S
Surface tension 28.48 mN/m
Specific heat capacity
ideal gas, 25 °C 1169 J kg–1 K–1
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liquid, 25 °C 1752 J kg–1 K–1

Acentric factor 0.3026
Critical compressibility 0.263
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3. Chemical Properties
The most important commercial reaction of ethylbenzene is its dehydrogenation to styrene. The
reaction is carried out at high temperature (600–660 °C), usually over a potassium-promoted iron
oxide catalyst. Steam is used as a diluent. Commercially, selectivities for styrene range from 90 to 97
mol% with per-pass conversions of 60–70%. Side reactions involve mainly the dealkylation of
ethylbenzene to benzene and toluene.
A reaction of increasing commercial importance is the oxidation of ethylbenzene by air to the
hydroperoxide C6H5CH(OOH)CH3 [3071-32-7]. The reaction takes place in the liquid phase without a
catalyst. However, because hydroperoxides are unstable, exposure to high temperature must be
minimized to reduce the rate of decomposition. The production of byproducts is reduced if the
temperature is gradually lowered during the course of the reaction. The hydroperoxide is subsequently
treated with propylene to give styrene and propylene oxide as co-products. In 1999 about 15% of the
ethylbenzene produced worldwide was used in the co-production of styrene monomer and propylene
oxide.
Like toluene, ethylbenzene can be dealkylated catalytically or thermally to benzene. Ethylbenzene also
undergoes other reactions typical of alkylaromatic compounds [4].
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4. Production
Alkylation of benzene with ethylene is the source of nearly all ethylbenzene. For several decades most
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alkylation plants utilized dissolved Lewis acids, in most cases aluminum chloride, to catalyze the
reaction in the liquid phase. About 40% of worldwide ethylbenzene production still utilizes variations
on this method. Although the aluminum chloride route generally provides competitive economics,
disposal of the resulting waste streams has become increasingly costly. In addition, this route is
susceptible to severe corrosion of equipment and piping. Since the early 1980s, technologies using
heterogeneous 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
improvements in the zeolite processes have provided incentives to a number of operators of aluminum
chloride units to retrofit with zeolite technology. About 106 t of capacity in several plants were changed
to zeolite technology from 1997 to 1999, and as of 2000, more conversions are in the engineering
phase. It has been nearly ten years since the last significant grass-roots capacity utilizing aluminum
chloride technology came on-stream.
A very minor amount of ethylbenzene is produced by superfractionation of mixed C8 aromatic streams.
Only a small number of plants in the world still utilize this method.
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4.1. Alkylation with Non-Zeolite Lewis Acid Catalysts
Liquid-phase aluminum chloride processes were first commercialized in the 1930s. Several companies
developed variations of this technology, including Dow Chemical, BASF, Shell Chemical,
Monsanto/Lummus, Socíeté Chimiques des Charbonnages, and Union Carbide/Badger. Of the
aluminum chloride plants still in operation, the majority of them utilize the Monsanto/Lummus
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 (∆H = – 114 kJ/mol); in the presence 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].
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 complex phase (a reddish
brown material called red oil). A mixture of catalyst complex, dry benzene, and recycled
polyalkylbenzenes is continuously 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
spargers, 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 reactions, 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
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formation is minimized by recycling this material to the alkylation reactor. In addition, because the
reaction occurs close to thermodynamic equilibrium, 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 deactivates the
catalyst and favors formation of nonaromatics and polyalkylbenzenes, which are preferentially
absorbed by the highly acidic catalyst complex and form byproducts. Sufficient 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 discharged 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 treatment 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 organic stream has long been a challenge for ethylbenzene
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 distillation
columns. The unconverted benzene is recovered in the first column as an overhead distillate. The
second column separates the ethylbenzene product from the heavier polyalkylated 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 compounds. The residue stream, or flux
oil, consisting primarily of polycyclic aromatics, is burned as fuel.
Because the alkylation mixture can tolerate only minor amounts of water, the recycle benzene 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 technology. 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 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 traditional processes. The process is also capable of operating with low-concentration
ethylene feed. Typically, the alkylation temperature is maintained 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 transalkylation 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
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other AlCl3 processes, the organic residue is used as fuel and the aluminum chloride waste streams are
usually sold or sent to treatment facilities.
In 1999 about 40% of the ethylbenzene manufactured 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 ethylene
feedstock. If the entry of water into the process was strictly prevented, the corrosion 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 between 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 ethylene feed containing as little as 8–10 mol% ethylene,
enabling a variety of refinery and coke-oven gas streams to be used. However, purification of these
streams was necessary to remove components that poison the BF3 catalyst, e.g., trace amounts of water,
sulfur compounds, and oxygenates.
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4.2. Vapor-Phase Alkylation over Zeolites
The Mobil–Badger vapor-phase technology was developed in the 1970s around Mobil's 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 alkylation 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 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 particularly suited to dilute ethylene streams, particularly refinery
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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. Mobil–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 Brønsted acid sites within the catalyst, which
activates the ethylene molecule and allows bonding with benzene molecules to occur. Hence, the range
of higher alkylated aromatic byproducts formed by the Mobil–Badger process is somewhat different
than those of the Friedel–Crafts processes.
Carbon steel is the primary material of construction; high-alloy materials and brick linings are not
required. A diagram of the third-generation design is shown in Figure (3).
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 equipment.
The reactor operates with significant overall excess of benzene relative to ethylene.
Slow catalyst deactivation occurs as a result of coke formation and requires periodic regeneration. In
situ regeneration takes ca. 36 h and may be necessary after 18–24 months of operation, depending on
the operating conditions. The catalyst 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 alkylbenzenes and polyalkylbenzenes
are separated from heavy nonrecyclable residue. The low-viscosity residue stream, consisting mainly of
diphenylmethane and diphenylethane, is burned as fuel.
Recyclable higher alkylbenzenes and polyalkylbenzenes are sent to the vapor-phase transalkylator,
where they are converted in the presence of excess benzene over zeolite catalyst. Because the
transalkylator has lower pressure but higher temperature relative to the alkylator, higher alkylbenzenes
are dealkylated while diethylbenzene is transalkylated to ethylbenzene. The ability to dealkylate higher
alkylbenzenes, known to be residue precursors, serves to decrease overall residue production.
The older first- and second-generation processes 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 debottlenecked distillation
train from a naphtha cracker. Additionally, and perhaps of more interest due to low feedstock cost, is
the adaptability 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].
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4.3. Liquid-Phase Alkylation over Zeolites
All-liquid phase processes using zeolite catalysts began to appear in commercial operation in 1990, the
first plant being operated by Nippon SM in Oita, Japan under license from ABB Lummus Global and
Unocal (UOP later became ABB's partner when they acquired Unocal's zeolite business). This process
has utilized ultrastable zeolite Y or more recently zeolite beta. Another liquid-phase EB process,
EBMax, became available 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 available 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 wider 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 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 column, from which the ethylbenzene is
distilled overhead. The bottoms of the ethylbenzene column are fed to the polyethylbenzene column,
which separates higher alkylbenzenes and polyethylbenzenes from the residue. This overhead stream is
fed to the liquid-phase transalkylation reactor, where it is combined with excess benzene from the
benzene column distillate. Effluent from the transalkylator is returned to the distillation train.
Besides benzene, major impurities in the ethylbenzene product can include nonaromatics (naphthenes),
toluene, and higher alkylbenzenes. Depending on the operating conditions and technology, 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.
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4.4. Mixed-Phase Zeolite-Based Process
A mixed-phase ethylbenzene process is offered for license by CDTech, a partnership between ABB
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Lummus Global and Chemical Research and Licensing, Co. [10], [11] The first unit started in 1994,
and as of 1999, three plants were operating. The main distinction of this process is the alkylation
reactor, which contains bales of zeolite catalyst in a reactive-distillation column. Ethylene gas and
benzene liquid are fed to the reactive-distillation column. Because of its ability 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 together 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 fractionated into ethylbenzene product in the overhead product
column, and then transalkylatable polyethylbenzenes 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.
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4.5. Separation from Mixed C8 Streams
Less than 1% of worldwide ethylbenzene production is recovered from mixed xylene streams, usually
in conjunction with xylene production from reformate. Although adsorption processes have been
developed, most notably the EBEX process of UOP, ethylbenzene production from these sources has
been mainly performed by distillation. Because of the difficulty of the separation, the process is
generally termed superfractionation. It was first undertaken 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.
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5. Environmental Protection
In the United States ethylbenzene plants must conform to the requirements of U.S. EPA National
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Emission Standard Organic Air Pollutants from the Synthetic Organic Chemical Industry (40 CFR 63,
Subparts F, G, H). Producers can comply by installing collection devices on process 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 landfill (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.
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6. Quality Specifications
The product specification on ethylbenzene is set to provide a satisfactory feedstock to the associated
styrene unit. Objectionable impurities in the ethylbenzene can be grouped into two categories: those
that are detrimental to the operation of the styrene unit and those that affect the purity of the styrene
product. Impurities in product ethylbenzene that pose an operating problem in the conventional
dehydrogenative styrene process are
1) Halides, which deactivate the dehydrogenation catalyst and contribute to downstream equipment
corrosion. Usually these are chlorides originating from an AlCl3 alkylation section or fluorides
from an Alkar unit.
2) Diethylbenzenes, which are dehydrogenated to divinylbenzenes in the styrene reactor section. The
divinylbenzenes form insoluble cross-linked polymers in the downstream process 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 ethyltoluenes. 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.
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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.
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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 agencies. The U.S. DOT identification number is UNI 175 and the
reportable quantity is 454 kg. Details on regulations concerning the transport of ethylbenzene can be
found in the CFR or from the 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 concentration. 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.
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8. Uses
Essentially all commercial ethylbenzene production is captively consumed for the manufacture of
styrene monomer or in the co-production of styrene monomer with propylene oxide. Styrene is used in
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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 acetophenone, diethylbenzene,
and ethylanthraquinone.
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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 Far Eastern economies outside of Japan
imported large quantities from the West, particularly the United States and Canada. This pattern
changed in the late 1980s as capacity was added in Asia, most notably Korea, which today holds about
10% of the world's ethylbenzene capacity. Other Far Eastern countries installing significant new
capacity have included Singapore, Thailand, and Taiwan. Over the next five years the expansion is
likely to occur in mainland China, as multinational companies form joint ventures with local concerns
to build world-scale plants. Today each region of the world is becoming relatively self-sufficient in
ethylbenzene/styrene.
About 15% of ethylbenzene is consumed in co-production of styrene and propylene oxide. These
plants offer an economic advantage because of the value of the propylene oxide co-product, which has
remained high in part because co-production technology has not been widely available. This situation is
beginning to change, and today several producers are operating these plants in the Netherlands, Spain,
Japan, Singapore, Korea and the United States. Lower prices for propylene oxide resulting from greater
supply could slow the use of ethylbenzene in such plants, which have perhaps three to four times the
investment cost of an ethylbenzene dehydrogenation facility.
The 1999 worldwide capacity (in 103 t/a) by region is as follows:
North America 7700

South America 330
Western Europe 5900
Eastern Europe 1300
Korea/Taiwan/China 3800
Page: 12
Japan 3500
Middle East and Africa 680
Southeast Asia/Australia 500
Total 24700
Similar to the direct link of ethylbenzene production to that of styrene, ethylbenzene production cost is
tied to feedstock cost. Modern processes all have raw material yields > 98–99%. Integration of the
ethylbenzene and styrene processes enables efficient energy recovery of heat from the exothermic
alkylation reaction. With 90–99% energy recovery of the heat of reaction plus the heat input to the
process, production costs are directly related to benzene and ethylene feedstock prices. The U.S. unit
sales values of ethylbenzene in $/kg from 1960 to 1997 follow [12]:
1960 0.13 1980 0.51

1965 0.09 1983 0.50
1970 0.09 1987 0.46
1973 0.11 1989 0.55
1974 0.37 1990 0.62
1975 0.20 1993 0.33
1978 0.24 1995 0.55
1979 0.35 1997 0.42
Price increases in 1974 and 1980 reflect the radical change in oil prices experienced during these
periods. Price increases in 1989/1990 and 1995 were indicative of the cyclic tightness in supply of
ethylbenzene and styrene.
Continued ...
 Title page
 Previous
References
10. Toxicology and Occupational Health
Ethylbenzene is a moderately toxic compound that is also an irritant to the skin, eyes, and upper
respiratory tract. Systemic absorption can cause depression of the central nervous system, with narcosis
at very high concentrations.
Current knowledge of the toxic effects puts this compound in a category quite separate from related
compounds, such as benzene, and therefore processing requirements are not nearly as stringent.
However, it is sufficiently hazardous to warrant extreme vigilance in its handling and proper medical
treatment in the event of exposure.
Direct contact with liquid ethylbenzene causes irritation to the skin and mucous membranes. This may
be followed by erythema and inflammation of the skin unless treated immediately. Skin rash may
Page: 13
develop after prolonged or repeated exposure.

Acute exposure to vapor concentrations of up to 0.1% in air causes noticeable irritation to the eyes;
increasing the concentration to 0.2% produces extreme irritation of the eyes and lachrymation, in
addition to irritation of the nose and throat followed by dizziness and constriction of the chest.
Exposures of up to 1% are sufficient to cause death (through respiratory failure) in guinea pigs [13].
Although many of the effects of acute exposure are documented, no specific data on the symptoms of
chronic exposure are available.
Chronic poisoning can result through inhalation, ingestion, and by rapid absorption through the skin.
The LD50 is sufficiently high (3.5 g/kg) for ingestion to be of no practical concern [13], but TLV-
TWAs of 100 ppm (435 mg/m3), established by the ACIGH, dictate strict monitoring of vapor
emissions [14]. The short-term exposure limit (TWA-STEL) for vapors is only slightly higher at 125
ppm (543 mg/m3). The MAK value for ethylbenzene is 100 mL/m3 (440 mg/m3) [15].
Ethylbenzene that enters the blood, by inhalation or absorption through the skin, is readily metabolized.
It is excreted mainly as mandelic acid and phenylglyoxylic acid in the urine [16].
There are no reports of ethylbenzene being carcinogenic; both the ACGIH and the DFG exclude it from
their list of identified carcinogens. Similarly, no specific kidney, liver, respiratory, or skin diseases
have been found to be associated with ethylbenzene [14]. In terms of other long-term illnesses,
reference has been made to possible teratogenic effects in the fetus [13].
Continued ...
 Title page
 Previous
11. References
 [1] R. H. Boundy, R. F. Boyer (eds.): Styrene, Its Polymers, Copolymers, and Derivatives,
Reinhold Publ. Co., New York 1952, p. 16.
 [2] American Petroleum Institute (ed.): Technical Data Book – Petroleum Refining, 12th Revision
Package to 5th ed., vol. 1, American Petroleum Institute, Washington, D.C., 1997, pp. 1-78, 1-
79, 1-112, 1-113.
 [3] American Petroleum Institute (ed.): Technical Data Book – Petroleum Refining, metric ed., ,
American Petroleum Institute, Washington, D.C., 1981, pp. 1-56, 1-57.
 [4] Beilstein 5, 776–786.
 [5] G. A. Olah (ed.): Friedel–Crafts and Related Reactions, vol. 2, Wiley-Interscience, New York
1964, Part 1.
 [6] CdF Chimie, US 4 117 023, 1978 (P. J. Gillet, G. Henrich).
 [7] Monsanto, US 3 848 012, 1974 (F. Applegath, L. E. DuPree Jr., A. C. MacFarlane, J. D.
Robinson).
 [8] K. J. Fallon, H. K. H. Wang, C. R. Venkat, "UK Refinery Demonstrates Ethylbenzene
Process",Oil & Gas Journal, April 17, 1995.
 [9] Hydrocarbon Process.76 (1997) no. 3126.
 [10] Hydrocarbon Process.78 (1999) no. 3110.
Page: 14
 [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., Sax's Dangerous Properties of Industrial Materials, 10th ed., John Wiley &
Sons, New York, 1999.
 [14] ACGIH (ed.): Threshold Limit Values (TLV) and Biological Exposure Indices, ACGIH,
Cincinnati, Ohio, 1997.
 [15] DFG (ed.): MAK- und BAT-Werte-Liste, VCH, Weinheim 1995.
 [16] F. W. Mackison, R. S. Stricoff, L. J. Partridge (eds.): "NIOSH/OSHA Occupational Health
Guidelines for Chemical Hazards," U.S. Dept. of Health & Human Services (National Institute
for Occupational Safety & Health) Publication no. 81–123, Washington, D.C., Jan. 1981.
 first occurrence in article
Ethylbenzene - 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
Page: 15
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
Page: 16
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
Page: 17
Lummus/UOP ethylbenzene process [9]

a) Alkylation reactor; b) Transalkylation reactor; c) Benzene column; d) Ethylbenzene column; e)
Polyethylbenzene column
Mobil–Badger EBMax process

a) Alkylation reactor; b) Transalkylation reactor; c) Benzene column; d) Vent-gas column; e)
Ethylbenzene column; f) Polyethylbenzene column
Page: 18
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
Page: 19

ETHYLBENZENE

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ETHYLBENZENE

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Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2002 Electronic Release

ETHYLBENZENE - Ethylbenzene (Vincent A. Welch, Kevin J. Fallon)

Ethylbenzene [100-41-4], phenylethane, C6H5CH2CH3, Mr 106.168, is a single-ring alkylaromatic

Density at 15 °C 0.87139 g/cm3

liquid, 25 °C 1752 J kg–1 K–1

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

4.5. Separation from Mixed C8 Streams

Purity 99.5 wt% min.

Propylbenzenes 0.02 wt% max.

7. Handling, Storage, and Transportation

the production of polystyrene and a wide variety of other plastics (→ Styrene).

North America 7700

1960 0.13 1980 0.51

10. Toxicology and Occupational Health

develop after prolonged or repeated exposure.

 first occurrence in article

Aluminum chloride process for ethylbenzene production

 first occurrence in article

Homogeneous liquid-phase alkylation process for ethylbenzene production

 first occurrence in article

Third-generation Mobil–Badger ethylbenzene process

 first occurrence in article

Lummus/UOP ethylbenzene process [9]

 first occurrence in article

Mobil–Badger EBMax process

 first occurrence in article

CDTech ethylbenzene process

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