STYRENE Vol 22

STYRENE

Styrene [100-42-5] (phenylethene, vinylbenzene, phenylethylene, styrol, cinnamene), C 6 H 5 CH| |CH 2 , is the simplest and by far the most important
member of a series of aromatic monomers. Also known commercially as styrene monomer (SM), styrene is produced in large quantities for
polymerization. It is a versatile monomer extensively used for the manufacture of plastics, including crystalline polystyrene, rubber-modified impact
polystyrene, expandable polystyrene, acrylonitrilebutadienestyrene copolymer (ABS), styreneacrylonitrile resins (SAN), styrenebutadiene latex,
styrenebutadiene rubber (qv) (SBR), and unsaturated polyester resins (see ACRYLONITRILE POLYMERS; STYRENE PLASTICS).
Styrene was first isolated in the nineteenth century from the distillation of storax, a natural balsam. Although it was known to polymerize, no
commercial applications were attempted for many years because the polymers were brittle and readily cracked. The development of dehydrogenation
processes by I. G. Farben in Germany and Dow Chemical in the United States during the 1930s was the first step toward the modern styrene
technology. Several plants were built in Germany before World War II to produce styrene, primarily for making synthetic rubber. It also became a
material of strategic importance in the United States when the supply of nature rubber from South Asia was cut off from the Allied countries's
access, and large-scale plants were built. After the war the demand for styrene monomer continued to grow, but its main use has shifted from
synthetic rubber to polystyrene. Polystyrene (PS) as of ca 1996 accounts for 65% of the total styrene demand. The production of styrene in the
United States was 2.0 million metric tons in 1970, which increased to 3:2 £ 106 t in 1980 and 5:0 £ 106 t in 1995. Rapid growth has also been seen in
Western Europe and Japan and, since the 1980s in the Pacific Rim. The total worldwide production was approximately 16:5 £ 106 t in 1995 and is
projected to grow at a rate of more than 4% annually until the year 2005. Many factors contribute to its growth: it is a liquid that can be handled
easily and safely, it can be polymerized and copolymerized under a variety of conditions by common methods of plastics technology to a large
number of polymers of different properties and applications, polystyrene is easy to extrude and mold and is one of the least expensive thermoplastics
volumetrically, the raw materials benzene and ethylene are produced in very large quantities in refineries and can be supplied to styrene plants
through pipelines, and the manufacturing technologies are efficient and plants can be built on a large scale to produce styrene at low cost.
Two process routes are used commercially for the manufacture of styrene: dehydrogenation and coproduction with propylene oxide. Both
routes use ethylbenzene as the intermediate; ethylbenzene is made from benzene and ethylene. The manufacture of styrene via ethylbenzene
consumes more than 50% of the commercial benzene in the world. The great majority of the ethylbenzene and styrene plants are based on licensed
technologies which are available at rather modest licensing fees. Styrene is a commodity chemical traded in large volumes domestically and
internationally. The product specifications are largely dictated by the market. The minimum purity is usually 99.8%, which can be easily met in a
well-operated plant of modern design. Some producers choose to have their plants designed to produce high purity styrene at a small incremental
investment to gain marketing advantages and in anticipation of its future demand. Production of 99.95% styrene could become routine as a result of
recent advances in manufacturing technology.
The commodity nature of the product and the easy access to the licensed processes enable new producers, particularly in developing
countries, to enter the global styrene merchant market with little experience in styrene technology. Access to ethylene, which cannot be easily
transported by means other than pipelines, is a key factor in considering new styrene facilities. Timing, or luck, is even more important because the
supply and demand of styrene are seldom in balance and the price fluctuates broadly and rapidly as a result. Most of the time, the producers either
suffer losses (19811985, 19911993) or enjoy handsome profits (19871990, 1994mid-1995). Investments in styrene plants are known to have
been recovered in less than a year, but prosperity encourages over-investment and lean years may follow.

Properties
Styrene is a colorless liquid with an aromatic odor. Important physical properties of styrene are shown in Table 1 (1). Styrene is infinitely soluble in
acetone, carbon tetrachloride, benzene, ether, n-heptane, and ethanol. Nearly all of the commercial styrene is consumed in polymerization and
copolymerization processes. Common methods in plastics technology such as mass, suspension, solution, and emulsion polymerization can be used
to manufacture polystyrene and styrene copolymers with different physical characteristics, but processes relating to the first two methods account
for most of the styrene polymers currently (ca 1996) being manufactured (28). Polymerization generally takes place by free-radical reactions
initiated thermally or catalytically. Polymerization occurs slowly even at ambient temperatures. It can be retarded by inhibitors.

a
Table 1. Physical Properties of Styrene Monomer

Property Value
boiling point at 101.3 kPa = 1 atm, C 145.0
freezing point, C ¡30:6
flash point (fire point), C
Tag open-cup 34.4 (34.4)
Cleveland open-cup 31.4 (34.4)
autoignition temperature, C 490.0
explosive limits in air, % 1.16.1
b 1445:58
vapor pressure, kPa, Antoine equation log 10 P = 6:08201 ¡
209:43 + t± C
c 3.81
critical pressure, Pc, MPa
critical temperature, tc, C 369.0

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 STYRENE Vol 22

critical volume,Vc, cm3/g 3.55

refractive index, nD20 1.5467
at 0C 20C 60C 100C 140C
viscosity, mPa¢s(=cP) 1.040 0.763 0.470 0.326 0.243
surface tension, mN/m (= dyn=cm) 31.80 30.86 29.01 27.15 25.30
d 0.9237 0.9059 0.8702 0.8346
density, g/cm3
e 1.636 1.690 1.811 1.983 2.238
specific heat (liquid), J/(g¢K)
e 1.179
specific heat (vapor) at 25C, Cp, J/(g¢K)
e
latent heat of vaporization, Hv, J/g
at 25C 428.44
145C 354.34
heat of combustion (gas at constant pressure) at 25C, Hc, 4262.78
e
kJ/mol
e 147.36
heat of formation (liquid) at 25C, Hf, kJ/mol
heat of polymerization, 74.48
e
kJ/mol
Q value 1.0
e value ¡0:8
volumetric shrinkage upon polymeri-zation, vol % 17.0
cubical coefficient of expansion, ± C ¡1
at 20C 9:710 £ 10¡4
40C 9:902 £ 10¡4
solubility (at 25C), wt %
monomer in H2O 0.032
H2O in monomer 0.070
a
Ref. 1.
b
To convert from log10 PkPa to log10 Pmm Hg, add 0.8751 to the constant.
c
To convert MPa to psi, multiply by 145.
d
Density at 150C is 0.7900 g/cm3.
e
To convert J to cal, divide by 4.184.

Styrene undergoes many reactions of an unsaturated compound, such as addition, and of an aromatic compound, such as substitution (2,8). It
reacts with various oxidizing agents to form styrene oxide, benzaldehyde, benzoic acid, and other oxygenated compounds. It reacts with benzene on
an acidic catalyst to form diphenylethane. Further dehydrogenation of styrene to phenylacetylene is unfavorable even at the high temperature of
600C, but a concentration of about 50 ppm of phenylacetylene is usually seen in the commercial styrene product.

Ethylbenzene Manufacture
Styrene is manufactured from ethylbenzene. Ethylbenzene [100-41-4] is produced by alkylation of benzene with ethylene, except for a very small
fraction that is recovered from mixed C8 aromatics by superfractionation. Ethylbenzene and styrene units are almost always installed together with
matching capacities because nearly all of the ethylbenzene produced commercially is converted to styrene. Alkylation is exothermic and
dehydrogenation is endothermic. In a typical ethylbenzenestyrene complex, energy economy is realized by advantageously integrating the energy
flows of the two units. A plant intended to produce ethylbenzene exclusively or mostly for the merchant market is also not considered viable
because the merchant market is small and sporadic.
The reaction of benzene and ethylene takes place on acidic catalysts and
C 6 H 6 + CH2 |CH 2 *
) C 6 H 5 CH 2 CH 3
can be carried out either in the liquid orvapor phase. Benzene in excess of the stoichiometric ratio to ethylene is used. The forward reaction is highly
favored thermodynamically; the equilibrium conversion of ethylene is nearly complete. Alkylation does not stop at monoethylbenzene. Part of the
ethylbenzene is further alkylated to diethylbenzenes, triethylbenzenes, tetraethylbenzenes, etc, collectively referred to as polyethylbenzenes (PEB). A
high benzene-to-ethylene ratio in the feed mixture gives a low polyethylbenzenes-to-ethylbenzene ratio in the reaction product, but requires larger
equipment and more energy consumption to recover the additional unreacted benzene by distillation for recycle to the reactor. The quantity of
polyalkylbenzenes formed relative to ethylbenzene is also affected by the catalyst and reaction conditions. The polyethylbenzenes are recovered by
distillation and transalkylated with benzene to produce additional ethylbenzene. For example, the transalkylation of diethylbenzene proceeds as
follows:
CH3 CH2 C6 H4 CH2 CH3 + C6 H6 *
) 2 C6 H5 CH2 CH3
The transalkylation reaction is essentiallyisothermal and is reversible. A high ratio of benzene to polyethylbenzene favors the transalkylation reaction
to the right and retards the disproportionation reaction to the left. Although alkylation and transalkylation can be carried out in the same reactor, as

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has been practiced in some processes, higher ethylbenzene yield and purity are achieved with a separate alkylator and transalkylator, operating under
different conditions optimized for the respective reactions.
A number of side reactions occur in both the alkylator and the transalkylator, including oligomerization, cracking, dehydrogenation,
isomerization, alkylation of alkanes by ethylene, alkylation of toluene by ethylene, alkylation of benzene by higher olefins, etc. The reactor effluent
can be shown by high sensitivity chromatography to contain a large number of aromatic and nonaromatic by-products, most of them in parts per
million or less. Isomerization causes formation of xylenes. Oligomerization is the first step in the formation of most of the by-products and is the
side reaction that is most harmful to the yield and quality of the product and the stability of the catalyst. Some of the oligomers boil close to
ethylbenzene and remain as nonaromatic impurities in the product. Other oligomers react further to form cumene, n-propylbenzene, butylbenzenes,
and other higher alkylbenzenes. These alkylbenzenes either become impurities in the product or are recycled with the polyethylbenzene stream to the
transalkylator. Depending on the process used, the alkylbenzenes that cannot be transalkylated to ethylbenzene are either decomposed or converted
to heavies on repeated recycle. The heavies, consisting of diphenyl compounds and heavy aromatics and nonaromatics, are rejected from the process
as residue, which is usually used as fuel. Control of side reactions and by-products is the most important consideration in the development of
catalysts and processes for ethylbenzene production.
The benzene feedstock contains C6 nonaromatics, ranging from 50 to 2000 ppm, depending on the source of supply. The C6 nonaromatics
do not directly contaminate the product because their boiling points are typically 4060C lower than that of ethylbenzene. However, part of these
nonaromatics are alkylated by ethylene in certain processes to form higher nonaromatics, which may contaminate the product. The nonaromatics
may also be cracked in the reactors, and the resulting components react with benzene to form various alkylbenzenes, such as cumene, which may
also contaminate the product. The only aromatic impurity in a significant concentration in the typical benzene feedstock is toluene, ranging from 50
to 1000 ppm. It reacts with ethylene to form ethyltoluene in the alkylator; ethyltoluene is converted back to toluene in the transalkylator. Toluene is
distilled together with ethylbenzene and becomes a product impurity that is innocuous downstream in the dehydrogenation process. However, any
ethyltoluene that is not separated from ethylbenzene contaminates the styrene product as ethyltoluene and vinyltoluene.
The ethylene feedstock used in most plants is of high purity and contains 2002000 ppm of ethane as the only significant impurity. Ethane is
inert in the reactor and is rejected from the plant in the vent gas for use as fuel. Dilute gas streams, such as treated fluid-catalytic cracking (FCC)
off-gas from refineries with ethylene concentrations as low as 10%, have also been used as the ethylene feedstock. The refinery FCC off-gas, which
is otherwise used as fuel, can be an attractive source of ethylene even with the added costs of the treatments needed to remove undesirable
impurities such as acetylene and higher olefins. Its use for ethylbenzene production, however, is limited by the quantity available. Only large
refineries are capable of delivering sufficient FCC off-gas to support an ethylbenzenestyrene plant of an economical scale.
Commercial ethylbenzene is manufactured almost exclusively for captive use to produce styrene; only a small fraction is traded. The
specifications of merchant ethylbenzene are usually negotiated between the seller and the buyer. An assay as low as 99% can be acceptable, provided
that most of the impurities are benzene, which is strictly a distillation consideration, and toluene, which is largely dependent on the benzene
feedstock. They are usually inconsequential in the dehydrogenation of ethylbenzene which makes far more benzene and toluene by side reactions.
However, they must not be excessive, because the distillation train in the styrene unit is designed to accept specified quantities of benzene and
toluene. Other possible impurities in ethylbenzene are nonaromatics in the C7C10 range and aromatics in the C8C10 range. Their nature and
quantities depend on the feedstocks, the process used, and the design and operation of the plant. The C7C10 nonaromatics originate, in some
processes, from oligomerization of ethylene and alkylation of the C6 nonaromatics contained in benzene. The C8C10 aromatics impurities include
xylenes, cumene, n-propylbenzene, ethyltoluenes, and butylbenzenes.
Diethylbenzenes are not considered by-products of the ethylbenzene process because they are recycled and transalkylated to ethylbenzene.
Nonetheless, their concentrations in the ethylbenzene product must be minimized. Diethylbenzenes are converted in the dehydrogenation reactor to
divinylbenzenes, which are exceedingly reactive, forming cross-linked polymers and causing polymer buildup in pipes, columns, and tanks. In severe
cases, a styrene plant can be forced to shut down to clean out the polymers. The diethylbenzene content in the ethylbenzene product is generally
specified to be 10 ppm maximum, largely because more accurate analytical instruments have become readily available only in recent years. The new
plants are designed to limit this content to ·1 ppm, which is not difficult to achieve by distillation because the relative volatility of ethylbenzene and
diethylbenzenes is very high. Chlorides are poisons to the dehydrogenation catalyst. This fact rarely poses a problem in the manufacturing process,
but possible contamination in storage and shipping must be prevented.
Most of the ethylbenzene plants built before 1980 are based on use of aluminum chloride catalysts. Aluminum chloride is an effective
alkylation catalyst but is corrosive; its use as the catalyst requires glass-lined, brick-lined, or Hastelloy reactors, and thus results in high capital costs
for the reactor section. The necessity of washing and neutralizing the reactor effluent to remove the spent catalyst adds to the complexity of both the
plant itself and its operation. It also creates an aqueous waste that is environmentally objectionable and becoming increasingly difficult to dispose of.
The corrosivity also increases plant downtime and maintenance cost. For these reasons, the aluminum chloride-based processes have not been used
for new plants in the 1990s. However, many older plants based on aluminum chloride are still in operation and together accounted for about 40% of
the worldwide ethylbenzene capacity as of 1995. The newer plants are based on zeolite catalysts.
Zeolite-Based Alkylation. Zeolites have the obvious advantages of being noncorrosive and environmentally benign. They have been
extensively researched as catalysts for ethylbenzene synthesis. Earlier efforts were unsuccessful because the catalysts did not have sufficient
selectivity and activity and were susceptible to rapid coke formation and deactivation.
The Mobil-Badger vapor-phase ethylbenzene process was the first zeolite-based process to achieve commercial success. It is based on a
synthetic zeolite catalyst, ZSM-5, developed and optimized by Mobil Oil Corporation for the synthesis of ethylbenzene (918) (see MOLECULAR
SIEVES). It has the desirable characteristics of high activity, low oligomerization, and low coke formation. The catalyst is regenerable by controlled
burning of the coke deposited on the catalyst. A process based on this catalyst was developed at The Badger Company (now Raytheon Engineers
& Constructors). In 1976, the Alkar unit at Cosden's Big Spring, Texas, refinery was converted to the Mobil-Badger process operating on dilute
ethylene feedstock. In early 1980, a single-train plant of one billion pounds (450,000 t) annual capacity was brought on-stream for American Hoechst
at Bayport, Texas. By the end of 1995, the Mobil-Badger process had been licensed to 35 plants with a combined capacity of nearly 10,000,000 t/yr,
including all of the new units built in the United States since 1980. Because alkylation is carried out in the vapor phase, the Mobil-Badger process can

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accept dilute ethylene, such as treated FCC off-gas, as well as polymer-grade ethylene as a feedstock. Two commercial plants based on this process
are in operation with dilute ethylene feeds (1820), by Shell (Stanlow, U.K.) and Dow (Terneuzen, the Netherlands).
Since its first commercialization, the Mobil-Badger process has undergone several important improvements. The Third Generation
Technology, which is offered currently (ca 1996), extends the catalyst cycle length between regenerations to two years and eliminates the spare
reactor in the earlier generations. It achieves a yield of greater than 99.5% and reduces the xylene, which is the only significant impurity in the
Mobil-Badger product, by more than 50%. Oligomerization is negligible in this process and the product does not contain nonaromatics. A unique
feature of this process is its ability to decompose nonaromatics to light gases and remove them in the vent gas, thus avoiding the need to purge part
of the recycled benzene to remove the nonaromatics. This process is also unique in its ability to remove higher alkylbenzenes such as cumene by
dealkylation and to recover the benzene value. A high nonaromatics content in the benzene feedstock and a high propylene content in the ethylene
feedstock have little effect on the yield and purity of the product.
A simplified flow diagram of the Mobil-Badger vapor-phase process is shown in Figure 1. Fresh and recycled benzene are vaporized and
preheated to the desired temperature and fed to a multistage fixed-bed reactor. Ethylene is distributed to the individual stages. Alkylation takes place
in the vapor phase at 350450C and the pressure that is deemed to be most economical for the individual plant, usually 0.692.76 MPa (100400
psig). Separately, the polyethylbenzene stream from the distillation section is mixed with benzene, vaporized and heated, and fed to the
transalkylator, where polyethylbenzenes react with benzene to form additional ethylbenzene. The combined reactor effluent, consisting of excess
benzene, ethylbenzene, polyethylbenzenes, and trace impurities, is distilled in the benzene column. Benzene is condensed in the overhead for recycle
to the reactors. Light hydrocarbons consisting of the ethane contained in the ethylene feed and components decomposed from the nonaromatic
contained in the fresh benzene feed are removed as vent gas for use as fuel. The bottoms from the benzene column are distilled in the ethylbenzene
column to recover the ethylbenzene product in the overhead. The bottoms stream from the ethylbenzene column is further distilled in the
polyethylbenzene column to remove a small quantity of residue, the latter being a free-flowing liquid usually used as fuel. The overhead
polyethylbenzene stream is recycled to the reactor section for transalkylation to ethylbenzene. The process heat, including the heat of reaction, is
recovered by generating steam for use in the styrene unit. The heat-exchange system, not shown in Figure 1, is designed to optimize the overall
efficiency of the ethylbenzenestyrene complex, consistent with the utility costs and constraints of the individual location.

Fig. 1. Mobil-Badger vapor-phase ethylbenzene process where PEB = polyethylbenzene .

A liquid-phase process based on an ultraselective Y (USY)-type zeolite catalyst developed by Unocal in the 1980s (21,22) and licensed by ABB
Lummus Crest was commercialized at Nippon Styrene Monomer Corporation in 1990. Three commercial plants based on this process were in
operation, all in Japan, as of mid-1995. This process is now called the Lummus-UOP process. The flow scheme of this liquid-phase process, shown
schematically in Figure 2, is similar to the Mobil-Badger vapor-phase process. The differences are primarily in the catalysts, reaction conditions,
reactor sizes, yields, and product specifications. To maximize the productivity of the catalyst in the Unocal process, the reactors operate at close to
the critical temperatures of the reaction mixtures, ie, up to 270C, and at pressures sufficient to maintain the reaction mixtures in the liquid state, ie,
approximately 3.79 MPa (550 psig). A compressor is required unless the supply pressure of ethylene is sufficient to deliver it to the reactor. Large
quantities of catalyst are required in two multistage alkylators and a transalkylator. To suppress ethylene oligomerization on the USY catalysts, water
is injected into the feed stream to moderate the catalyst activity. Because the catalyst is susceptible to poisoning by basic materials, especially nitrogen
compounds, the benzene feed is pretreated in clay guard chambers. Some of the C6 nonaromatics contained in the fresh benzene are decomposed to

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components which may react with benzene to form various alkylbenzenes, or are alkylated to higher nonaromatics which may contaminate the
product. The remaining C6 nonaromatics are removed by purging a fraction of the recycled benzene called benzene drag. The overall yield to
ethylbenzene is estimated to be 9898.5%, with the residue accounting for most of losses. The ethylbenzene produced from this process contains
low concentrations of xylene, but substantial quantities of other aromatic impurities (mainly cumene, n-propylbenzene, and ethyltoluene) and
nonaromatic impurities. Because complete dissolution of ethylene is essential to liquid-phase alkylation, this process is not suitable for low
concentration ethylene feeds, such as FCC off-gas; in order to provide sufficient liquid to dissolve the diluents (mainly ethane, methane, and
hydrogen), the benzene recycle rate would have to be raised to an uneconomical level.

Fig. 2. LummusUnocalUOP liquid-phase ethylbenzene process where PEB = polyethylbenzene .

A two-phase process developed by CDTech in the 1980s (22,23) and licensed also by ABB Lummus Crest is claimed to be applicable to dilute
ethylene feed as well as polymer-grade ethylene feed. The alkylation reaction is carried out in a catalytic distillation column with the liquid and vapor
in countercurrent flow. The catalyst is packaged into bales, which are usually fiber glass containers having a cylindrical shape. The bales are arranged
in the column to provide separate paths for the liquid to move downward by gravity and for the vapor to move upward by pressure. The complexity
of the reactor and the use of baled catalyst, which does not flow freely, complicate the loading, unloading, and regeneration of the catalyst. The
mechanical design of this column is an adaptation of CDTech's process for the etherification of methanol and isobutene to methyl tert-butyl ether
(MTBE). In the MTBE application, catalytic distillation permits partial separation of the reactants and product, thus shifting the etherification
reaction toward formation of MTBE, which is otherwise limited by thermodynamic equilibrium. The heat of reaction is removed by evaporation of
some reactants in the column. This feature is beneficial to etherification, which is thermodynamically more favorable at a lower temperature.
However, these benefits of catalytic distillation do not apply to the alkylation reaction. The alkylation of benzene is virtually irreversible, the
conversion of ethylene being over 99.9999% in thermodynamic equilibrium. The sole purpose of using a catalytic distillation column for alkylation is
to suppress oligomerization of ethylene on the catalyst. Oligomerization is a higher order reaction than alkylation with respect to the ethylene
concentration. A high benzene-to-ethylene ratio would give a low ethylene concentration in the reaction mixture and restrain oligomerization, but it
carries an economic penalty in the recovery and recycle of benzene. Catalytic distillation offers an alternative way to reduce the local ethylene
concentration. The segregation of ethylene in the vapor phase and aromatics in the liquid phase creates mass-transfer barriers to hinder the transport
of ethylene to the catalyst, which is in contact with the liquid, thus retarding oligomerization of ethylene. The mass-transfer barriers, however, also
retard the conversion of ethylene to ethylbenzene, thus requiring a large catalyst volume and a complex reactor system to avoid a high ethylene loss.
In addition to the alkylator, a finishing reactor of the conventional packed bed design is required to complete the conversion of ethylene. Although
removal of the heat of reaction by evaporation in principle permits injection of the entire ethylene feed to a single catalytic bed, in practice the
catalyst is divided into several beds to allow multiple injections of ethylene to further reduce the local ethylene concentration. The countercurrent
flow of liquid and vapor results in a condition wherein the highest concentrations of ethylene and alkylated benzenes meet at the bottom layer of the
catalyst. It favors the formation of polyethylbenzenes and adds duty to the transalkylation system. A distillation column is still required to recover the
unreacted benzene in the alkylator and transalkylator effluents. One design option is to place the alkylator on top of the benzene column. This
option, however, makes the loading and unloading of the baled catalyst even more difficult. A commercial plant based on this technology was
reported to have been commissioned at Mitsubishi Chemical in Japan in late 1994.
A vapor-phase process primarily for FCC off-gas feeds was developed by Sinopec Technology Company based on a zeolite catalyst of the

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Pentasil type (24,25). It relies on frequent regeneration of the catalyst to minimize pretreatment of the FCC off-gas and allows the impurities in the
feed gas to react with benzene to form by-products. Consequently, the product yield and purity are low. Joint licensing by ABB Lummus Crest and
Sinopec was announced in 1994.
All of the processes described above require more benzene recycle than the aluminum chloride-based processes. Retrofitting an existing
aluminum chloride-based plant to a zeolite-based plant requires not only replacement of the reaction section but also additional investment in the
distillation train. Several producers have chosen to replace their old plants during the 1980s and early 1990s with new ones based on the
Mobil-Badger process, at expanded capacities.
More recently, a new alkylation technology named EBMax was developed by Mobil Oil Corporation and Raytheon Engineers & Constructors
and commercialized in Japan in late 1995 at Chiba Styrene Monomer Company, in a unit originally based on the Lummus-UOP liquid-phase process.
The EBMax technology is based on a new Mobil zeolite catalyst called MCM-22. MCM-22 overcomes the oligomerization problem that plagues
other liquid-phase alkylation processes. Because the catalyst is highly active for alkylation but inactive for oligomerization and cracking, it permits
operation at low benzene-to-ethylene ratios, while achieving the highest yield and product purity among the ethylbenzene processes (26).
Aluminum Chloride-Based Alkylation. The earlier alkylation processes were variations of the Friedel-Craft reaction on an
aluminum chloride catalyst complex in a liquid-phase reactor (27), including those developed by Dow Chemical, BASF, Monsanto, and Union
Carbide in cooperation with Badger. The Union Carbide-Badger process was the one most widely used during the 1960s and 1970s, with 20 plants
built worldwide.
An improved aluminum chloride-based process was developed by Monsanto (28) in the 1970s. Using a presynthesized aluminum chloride
complex and operating the reactor at higher temperature and pressure, the catalyst inventory is reduced to below its solubility in the reaction
mixture. The reactants and the catalyst complex are mixed in the reactor to form a homogeneous liquid. The transalkylation of polyethylbenzenes is
carried out separately. These improvements result in a higher yield. The higher reactor temperature permits recovery of the heat of reaction as useful
steam. The reduced inventory of the catalyst, however, also reduces its capacity to resist deactivation by water and other poisons. A simplified flow
diagram of the homogeneous alkylation process is shown in Figure 3. Alkylation and transalkylation are carried out either in two separate reactors or
in a single vessel with two compartments. The catalyst complex is synthesized separately. It enters into an upflow alkylator together with benzene
that has been dried in a dehydration column. Ethylene is sparged into the liquid in the reactor. The reaction progresses as the liquid moves upward,
and the reaction mixture circulates through a heat exchanger where the exothermic heat of reaction is recovered as low pressure steam. The effluent
from the alkylator is mixed with the polyethylbenzene (PEB) stream recovered in the distillation section. This mixture passes through the
transalkylator where part of the polyethylbenzenes react with benzene to form additional ethylbenzene. In a plant operating in the steady state, the
polyethylbenzenes made in the alkylator are offset by the polyethylbenzenes converted in the transalkylator, so that the recycle rate remains constant.
The effluent from the transalkylator is flashed to remove the light components which then go to the vent gas. The liquid is cooled, water-washed,
and neutralized with caustic solution to remove the aluminum catalyst. The washed organic phase is separated into four fractions in a series of three
distillation columns. The first column recovers unreacted benzene for recycle to the reactor; the second recovers and purifies the ethylbenzene
product; and the third separates the polyethylbenzene stream from the residue for recycle to the reactor section.

Fig. 3. Monsanto ethylbenzene process. Courtesy of Hydrocarbon Processing.

Other Technologies. Ethylbenzene can be recovered from mixed C8 aromatics by superfractionation. This technology was first
practiced by Cosden Oil & Chemical Company in 1957 (Big Spring, Texas), based on a design developed jointly with The Badger Company. Several
superfractionation plants were built in the United States, Europe, and Japan around 1960. This route is no longer competitive, for several reasons.
The quantity that can be recovered is limited by the supply of mixed C8 aromatics and by the low ethylbenzene content (ca 20%). High capital and
energy costs resulting from the small boiling-point difference of 1.8C between ethylbenzene and para-xylene and low product purity are some other
factors. A process for recovery of ethylbenzene from C8 aromatic streams by selective adsorption called EBEX was developed by UOP in the 1970s.
The Alkar process (2931), developed by UOP and commercialized in 1960 at Cosden, uses boron trifluoride on alumina support as the
catalyst. It has been used for polymer-grade as well as dilute ethylene feeds. This process produces a high purity product, but the high corrosivity of
the fluoride and the susceptibility of the catalyst to poisoning have prevented it from gaining widespread acceptance. The last plant based on this

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 STYRENE Vol 22

process was built by Shell at Moerdijk, the Netherlands, in 1979. It was decommissioned and replaced in 1992 by a new plant based on the
Mobil-Badger process. Another process for ethylbenzene production developed by UOP based on a solid phosphoric acid catalyst (32) was
commercialized at El Paso Natural Gas Company's (Odessa, Texas) plant in the 1960s using a dilute ethylene feed. The conversion of ethylene and
the selectivity to ethylbenzene are low. This technology is similar to UOP's SPA process, which was widely used for the production of cumene, but it
did not meet with the same degree of success.
Production of ethylbenzene from butadiene has been investigated by many researchers. It consists of two steps: cyclodimerization of
1,3-butadiene to 4-vinylcyclohexene and dehydrogenation of the vinylcyclohexene to ethylbenzene.

Styrene Manufacture
Styrene manufacture by dehydrogenation of ethylbenzene is simple in concept and has the virtue of being a single-product technology, an important
consideration for a product of such enormous volume. This route is used for nearly 90% of the worldwide styrene production. The rest is obtained
from the coproduction of propylene oxide (PO) and styrene (SM). The POSM route is complex and capital-intensive in comparison to
dehydrogenation of ethylbenzene, but it still can be very attractive. However, its use is limited by the mismatch between the demands for styrene and
propylene oxides (qv). The global demand for propylene oxide is only 2/10 of that of styrene by weight, while the ratio of propylene oxide to styrene
from the POSM route is more than 4:10. The propylene oxide from POSM must also compete with that obtained from other routes.
Consequently, the propylene oxide market dictates the POSM capacity that can be profitably installed, and the larger-volume styrene is thus
reduced to the status of a by-product. As such, this styrene can be priced elastically and profitably at the same time. The POSM operators are thus
the envy of the styrene industry when propylene oxide is in demand. However, the styrene production in the POSM plant cannot be increased
alone to take advantage of a rising styrene market, and viewed in this light their position becomes less enviable. The POSM processes, unlike some
of the dehydrogenation processes, are not available for licensing.
Dehydrogenation. The dehydrogenation of ethylbenzene to styrene takes
C6 H5 CH2 CH3 *
) C6 H5 CH|CH2 + H2
place on a promoted iron oxidepotassiumoxide catalyst in a fixed-bed reactor at the 550680C temperature range in the presence of steam. The
reaction is limited by thermodynamic equilibrium. Low pressure favors the forward reaction, as is to be expected from the stoichiometric relation
that one mole of reactant dissociates into two moles of products. Earlier dehydrogenation reactors were designed for operation above atmospheric
pressure, at about 138 kPa (20 psia), so that a compressor would not be required to remove hydrogen from the condensed reactor effluent. Since the
1970s, vacuum design has become standard because the benefits of high conversion and selectivity achievable and low dilution steam required at low
pressure outweigh the cost of the compressor. Pressures of 41 kPa (6 psia) or lower at the reactor outlet have been designed. Dehydrogenation is an
endothermic reaction. The reaction rate is highly temperature-dependent. High temperature favors dehydrogenation both kinetically and
thermodynamically but also increases by-products from side reactions and decreases the styrene selectivity.
The main by-products in the dehydrogenation reactor are toluene and benzene. The formation of toluene accounts for the biggest yield loss,
ie, approximately 2% of the styrene produced when a high selectivity catalyst is used. Toluene is formed mostly from styrene by catalytic reactions
such as the following:
C6 H5 CH|CH2 + 2 H2 ! C6 H5 CH3 + CH4

C6 H5 CH|CH2 ! C6 H5 CH3 + C
The formation of benzeneaccounts for a yield loss of up to 1% of the styrene produced, mostly the result of thermal decomposition of ethylbenzene
and styrene. Other by-products include carbon dioxide, methane, ethylene, phenylacetylene, -methylstyrene, allylbenzene, vinyltoluenes, xylenes,
cumene, n-propylbenzene, ethyltoluenes, butylbenzenes, and heavy aromatics. Although they are rather insignificant in terms of the related yield
losses, these compounds can affect the cost of purification and the quality of the styrene product. The alkylbenzene and alkenylbenzene by-products
are formed by free-radical and catalytic reactions from ethylbenzene and styrene. With the exception of phenylacetylene, these compounds may also
originate from impurities in the ethylbenzene feedstock. Phenylacetylene is formed from dehydrogenation of styrene thermally and catalytically. It is
largely temperature-dependent but is also affected by catalyst formulation. Its concentration relative to styrene increases typically from 50 ppm at the
start-of-run of a high selectivity catalyst to over 100 ppm at the end-of-run as the temperature is raised to compensate for the declining activity of
the catalyst. Phenylacetylene is undesirable in certain styrene uses, such as SBR, because of its propensity to cross-link with styrene and to terminate
free-radical reactions during polymerization. If necessary, it can be reduced to parts per million in the styrene product by hydrogenation on a noble
metal catalyst under mild conditions. Technologies such as Fina-Badger's PAR technology are available for this treatment. Among the aromatic
by-products, -methylstyrene has the highest concentration in crude styrene. It is partially separated from styrene by distillation and removed in the
residue stream.
A small fraction of the hydrocarbons decompose and deposit on the catalyst as carbon. Although the effect is minute in terms of yield losses,
this carbon can still significantly reduce the activity of the catalyst. The carbon is formed from cracking of alkyl groups on the aromatic ring and of
nonaromatics present in certain ethylbenzene feedstocks. It can be removed by the water gas reaction, which is catalyzed by potassium compounds
in the catalyst. Steam, which is
C + 2 H2 O ! CO2 + 2 H2
co-fedwith ethylbenzene to the reactor, serves three purposes: as an energy carrier, it supplies the endothermic heat of reaction; as a diluent, it shifts
the equilibrium toward the formation of styrene; and as a reactant in the water gas reaction, it retards and limits carbon deposition on the catalyst.
However, as important as steam is in the dehydrogenation reactor, its use must be minimized for economic reasons. The steam-to-hydrocarbon
ratio, or SHR, is an important consideration in the selection of catalysts and processes.
Dehydrogenation catalysts usually contain 4090% Fe2O3, 530% K2O, and promoters such as chromium, cerium, molybdenum, calcium,

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 STYRENE Vol 22

and magnesium oxides. Criterion Catalysts (partnership company of Shell and American Cyanamid) and the Sud-Chemie Group (including
Sud-Chemie in Germany, United Catalysts in the United States, and Nissen Girdler in Japan) are the principal catalyst developers and manufacturers
for the styrene industry. Dow and BASF manufacture proprietary catalysts, primarily for captive use. During the 1970s, Shell-105 catalyst, called
C-105 as of ca 1996 and marketed by Criterion, was widely used because of its high activity and high chemical and mechanical stability (34), despite a
modest selectivity in the 8993% range. As raw material costs for styrene production increased rapidly during the 1970s, the need for development
of high selectivity catalysts became urgent. The earlier catalysts of this type suffer from poor mechanical integrity and low activity. The high
selectivity catalysts generally require higher reaction temperature to effect the same ethylbenzene conversion. The higher temperature imposes
additional demands on the equipment metallurgy, and increases the formation of phenylacetylene. During the 1980s, the mechanical integrity of the
high selectivity catalyst was greatly improved. The catalyst manufacturers have also had considerable success in increasing the activity while
preserving the selectivity. Criterion (34) offers a series of high selectivity catalysts, including C-025A, C-045, VersiCat, and IronCat. The Sud-Chemie
Group (35) offers the G-64, G-84, and Styromax series of catalysts.
An important property of the dehydrogenation catalyst is its steam stability, which refers to the ability of the catalyst to sustain the desired
ethylbenzene conversion under a given set of operating conditions, ie, pressure, temperature, and especially steam-to-hydrocarbon ratio (SHR).
Steam instability is characterized by accelerated decrease in the ethylbenzene conversion as a result of rapid carbon deposition on the catalyst when
the SHR is too low. Most catalysts require a minimum SHR in the 810 range. Since the steam-to-hydrocarbon ratio has a large impact on the energy
efficiency of a styrene plant, the search for a high selectivity catalyst that is stable at a low ratio has been a topic of intensive research efforts. A
recently developed catalyst has been shown to be stable at a SHR of 7 or lower while retaining a high selectivity in pilot-plant operations.
The quantity of catalyst used for a given plant capacity is related to the liquid hourly space velocity (LHSV), ie, the volume of liquid
hydrocarbon feed per hour per volume of catalyst. To determine the optimal LHSV for a given design, several factors are considered: ethylene
conversion, styrene selectivity, temperature, pressure, pressure drop, SHR, and catalyst life and cost. In most cases, the LHSV is in the range of
0.40.5 h/L. It corresponds to a large quantity of catalyst, approximately 120 m3 or 120160 t depending on the density of the catalyst, for a plant of
300,000 t/yr capacity.
All of the dehydrogenation catalysts deteriorate, or age, in use, causing the ethylbenzene conversion to decrease with time. This phenomenon
is intrinsic in the catalytic reaction, though the aging rate may also be affected by poisons and impurities in the feed. The iron oxidepotassium oxide
catalyst is susceptible to poisoning by chlorides, but this is a rare occurrence in commercial plants, particularly when the ethylbenzene feedstock
comes from a zeolite-based process. In most cases catalyst aging is caused by carbon deposition on the catalyst, chemical decomposition of the
active ingredient in the catalyst, and mechanical disintegration of catalyst particles. In commercial practice, the reaction temperature is increased to
compensate for the decrease in the activity of the catalyst and to maintain the desired conversion. This procedure continues until the temperature
reaches the limit allowed by the mechanical design of the reactor system or when the styrene selectively is deemed too low to be economical. The
useful lives of dehydrogenation catalysts vary from one to four years, and in most cases 1824 months, depending on the nature of the catalyst, the
design and operation of the reactor system, and the quality of the feedstock. Catalyst is a significant cost in the production of styrene owing to the
large quantity required. There is considerable incentive to extend the useful life of the catalyst. Even more important than savings in catalyst cost is
the reduction in downtime and increase in production that result from an extended catalyst life. Carbon deposition can be reversed to a large degree
by steaming the catalyst, but the effect is only short-term; frequent steaming is not deemed to be economical. Steaming is ineffective for extending
catalyst life because it does not prevent chemical decomposition of the catalyst. A method of preventing decomposition and disintegration of the
dehydrogenation catalysts called Catalyst Stabilization Technology (CST) was invented in 1995 at Weymouth Laboratory of Raytheon Engineers and
Constructors (36).
Dehydrogenation is carried out either isothermally or adiabatically. In principle, isothermal dehydrogenation has the duel advantage of
avoiding a very high temperature at the reactor inlet and maintaining a sufficiently high temperature at the reactor outlet. In practice, these
advantages are negated by formidable heat-transfer problems. First, to facilitate heat transfer from an external source to provide the reaction heat,
expensive tubular reactors are used. Second, the reaction temperature exceeds the stable temperatures of the molten salts commonly used as
heat-transfer media in tubular reactors. Flue gas is used, but its heat capacity and heat-transfer rate are low, requiring a large number of tubes and
multiple reactor trains for large plants. Isothermal processes are practiced by BASF in Europe and Asahi in Japan. An isothermal reactor system that
uses a molten salt mixture of sodium, lithium, and potassium carbonates as the heating medium has been offered for licensing by Lurgi, Montedison,
and Denggendarfer. A demonstration unit was built in 1985 by Montedison at Montova, Italy. High conversion and selectivity are claimed but no
commercial units have been built.
In an adiabatic reactor, the endothermic heat of reaction is supplied by the preheated steam that is mixed with ethylbenzene upstream of the
reactor. As the reaction progresses, the temperature decreases. To obtain a high conversion of ethylbenzene to styrene, usually two, and occasionally
three, reactors are used in series with a reheater between the reactors to raise the temperature of the reaction mixture. The reactors are fixed bed in
design with the catalyst confined between two concentric screens in each reactor, which is cylindrical and vertical. The reaction mixture flows radially
from the inner screen through the catalyst and outside screen. The radial design provides a large flow area and minimizes the pressure drop through
the catalyst in an economical way. Large plants with a single train capable of producing more than 500,000 t/yr of styrene are in operation.
Other than the reactor system, the distillation column that separates the unconverted ethylbenzene from the crude styrene is the most
important and expensive equipment in a styrene plant. It is expensive because the relative volatility between ethylbenzene and styrene is small,
requiring a large number of distillation stages and a high reflux ratio. Its design must also take into consideration that styrene polymerizes in the
liquid phase even at the ambient temperature and the rate of polymerization increases rapidly with the temperature and the concentration. In
addition to reducing the styrene yield, polymerization could cause operating difficulties. Therefore, the distillation is carried out at a high vacuum to
keep the temperature low, and inhibitors are used to retard polymerization. Many efforts have been made to minimize the pressure drop in the
distillation column, and thus to reduce the temperatures in the stripping section and in the reboiler. The Linde sieve tray (37), developed in the
1960s, succeeded in reducing the pressure drop, decreasing the liquid holdup, and increasing the tray efficiency. Another significant advancement in
the styrene distillation technology was introduced in the 1980s by the development of structural packings (38). This results in further reduction of
pressure drop and increases of separation efficiency and throughput. Structural packings are offered by several equipment manufacturers, including
Glitch, Koch, Norton, and Sultzer.

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To minimize yield losses and to prevent equipment fouling by polymer formation, which may lead to a reduced production rate and plant
shutdown, polymerization inhibitors are used in the distillation train, product storage, and more recently in vent gas compressors. Inhibitor usage is a
significant cost in the production of styrene. Sulfur was used extensively as polymerization inhibitor until the mid-1970s. It is effective but the
residue leaving the distillation train is contaminated with sulfur and is not environmentally acceptable as fuel. New inhibitors, mostly
nitrogen-containing organic compounds such as dinitrophenol and dinitrocresol, have been developed to replace sulfur. They are more expensive
and some are highly toxic, but it is acceptable to use the residue containing inhibitors of this type as fuel. The styrene product also needs inhibitor to
retard polymerization in storage and shipping. The most commonly used inhibitor for this service is 4-tert-butylcatechol [98-29-3] (TBC), which is
colorless, usually in 1015 ppm concentration. The term inhibitor is used in the styrene industry often indiscriminately to denote substances ranging
from true inhibitor to retarder. True inhibitors prevent the initiation of polymerization by reacting rapidly with free radicals; retarders reduce the rate
of polymerization. New inhibitor systems that are claimed to be capable of dramatically reducing polymer formation have been developed by
Uniroyal Chemical under the trade name SFR, by Betz Process Chemicals under the trade name STYREX, and by Ciba-Geigy.
The qualities of the styrene product and toluene by-product depend primarily on three factors: the impurities in the ethylbenzene feedstock,
the catalyst used, and the design and operation of the dehydrogenation and distillation units. Other than benzene and toluene, the presence of which
is usually inconsequential, possible impurities in ethylbenzene are C7C10 nonaromatics and C8C10 aromatics. Parts of the nonaromatics are cracked
and dehydrogenated. The C7 and some of the C8 nonaromatics remain in the toluene stream as alkane and alkene impurities and decrease its
by-product value. These impurities are also reported to be the likely cause of color problems in the toluene by-product (39). The remaining
nonaromatics remain in the styrene product. Among the C8 aromatics, m- and p-xylene can be recycled to extinction; o-xylene remains in the styrene
product. The C9C10 aromatics include cumene, n-propylbenzene, ethyltoluenes, butylbenzenes, etc. They pass through the dehydrogenation reactor
partly unchanged and partly converted to their corresponding dehydrogenated compounds. For example, cumene is partially converted to
-methylstyrene. Part of these aromatic and dehydrogenated compounds remain in the styrene product.
The development of the high selectivity catalyst is the most important advancement in the styrene manufacturing technology during the
quarter century prior to the mid-1990s. Other important improvements include better design of the reactor system to assure uniform composition,
temperature, and distribution of the reaction mixture, to minimize thermal reactions, and to prevent localized catalyst aging; low reactor pressure to
enhance styrene selectivity and catalyst stability; efficient heat exchange systems to reduce the energy cost; structural packings to reduce the pressure
drops in distillation columns; polymerization inhibitors that are more effective and less environmentally objectionable; use of high purity
ethylbenzene feedstock to increase the purity of the styrene product; and improved design of the recovery and purification system to minimize
polymer formation and styrene loss to the residue.
A modern adiabatic dehydrogenation unit with two reactors and an interreactor reheater, operating with a high selectivity catalyst and at a
pressure of 41 kPa (6 psia) at the second reactor outlet, can give a styrene selectivity as high as 97% at an ethylbenzene conversion of 6070%. The
choice of a desired conversion is a matter of economic optimization. A low conversion gives a high selectivity but increases energy consumption; a
high conversion decreases the energy cost but increases the raw material cost.
Most of the styrene plants in operation or under construction in the world as of ca 1996 are based on one of two adiabatic processes: the
Fina-Badger process licensed by Badger Technology Division of Raytheon Engineers & Constructors and the Monsanto process licensed by ABB
Lummus Crest. Dow Chemical, a primary styrene producer, uses its own adiabatic process. These processes are similar to one another in principle,
but differ in details. In selecting a process, the licensee usually considers the capital cost, yield, product quality, energy efficiency, inhibitor
consumption, plant reliability, operating flexibility, and other factors that are of significance to the project. The details are important. For example,
operating reliability and flexibility have proved to be crucial to the profitability of a plant because the supply and demand of styrene are seldom in
balance. From 1980 to the mid-1990s its price has fluctuated by as much as a factor of three or more within one or two years, whereas the raw
material and energy costs have remained relatively stable.
Figure 4 illustrates a typical dehydrogenation unit. Fresh and recycled ethylbenzene are combined and mixed with steam, then heat-exchanged
with the reactor effluent. The vapor mixture of ethylbenzene and steam is raised to the desired reaction temperature by mixing with more steam that
has been superheated to 800C or higher in a fired heater. This mixture is fed to the reactors, two or three stages in series with interstage reheaters.
The reactor effluent goes through heat exchangers to preheat the ethylbenzenesteam feed mixture and to generate steam for use in the distillation
train. The condensed reactor effluent is separated in the settling drum into vent gas (mostly hydrogen), process water, and organic phase. The vent
gas is removed by a compressor for use as fuel or for hydrogen recovery. The process water is stripped of organics and reused. The organic phase
with polymerization inhibitor added is pumped to the distillation train. In an optional energy recovery scheme offered in conjunction with the
Fina-Badger process, after the high level energy in the reactor effluent is recovered, the latent heat is recovered by using the condensing reactor
effluent to vaporize a ethylbenzenewater azeotrope, which is then compressed and used as the reactor feed. This option is highly energy efficient
but requires an incremental investment. It has been used in the Far East.

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Fig. 4. Manufacture of styrene by adiabatic dehydrogenation of ethylbenzene: A, steam superheater; B, reactor section; C, feedeffluent exchanger;
D, condenser; and E, settling drum. Courtesy of The Badger Company, Inc.

Figure 5 illustrates a typical distillation train in a styrene plant. Benzene and toluene by-products are recovered in the overhead of the
benzenetoluene column. The bottoms from the benzenetoluene column are distilled in the ethylbenzene recycle column, where the separation of
ethylbenzene and styrene is effected. The ethylbenzene, containing up to 3% styrene, is taken overhead and recycled to the dehydrogenation section.
The bottoms, which contain styrene, by-products heavier than styrene, polymers, inhibitor, and up to 1000 ppm ethylbenzene, are pumped to the
styrene finishing column. The overhead product from this column is purified styrene. The bottoms are further processed in a residue-finishing
system to recover additional styrene from the residue, which consists of heavy by-products, polymers, and inhibitor. The residue is used as fuel. The
residue-finishing system can be a flash evaporator or a small distillation column. This distillation sequence is used in the Fina-Badger process and the
Dow process.
In the Monsanto process (now called Lummus-UOP Classic process, as distinct from the SMART process to be described later),
ethylbenzene, together with benzene and toluene, is separated from styrene in the first column. The overhead condensate from this column then
goes to the benzenetoluene column and is redistilled to recover the benzenetoluene fraction in the overhead and ethylbenzene in the bottoms. It
has been argued that energy is wasted in this scheme by distilling the benzenetoluene fraction twice, once together with ethylbenzene and once
away from ethylbenzene. Actually, this extra energy consumption, which can be computed, is small. It has also been argued that less polymer is
formed in having the styrene bypass the benzenetoluene column. Actually, any possible reduction of polymerization resulting from this
arrangement, which has never been substantiated, is insignificant because polymerization of the styrene in solution with ethylbenzene through a
small benzenetoluene column is negligible in comparison with polymerization of the high concentration styrene in the much larger
ethylbenzenestyrene distillation column. Moreover, the higher vapor and liquid loadings required by having to distill benzene and toluene together
with ethylbenzene may slightly increase styrene polymerization. In any case, these effects are insignificantly small and every process owner continues
to use its own design very likely for historical reasons. An optional scheme to utilize the latent heat of the ethylbenzene vapor in the column
overhead to vaporize an ethylbenzenewater azeotrope for use as reactor feed is offered in conjunction with the Monsanto process. This scheme
recovers less energy than the Fina-Badger scheme but does not require a compressor. However, the condensing temperature of the ethylbenzene
vapor must be raised by having the ethylbenzenestyrene column operate at higher temperatures. The inhibitor usage and polymer formation
increase substantially because the rate of polymerization increases rapidly with the temperature. Consequently, the quantity and viscosity of the
residue are high. A wipe-film evaporator is then used downstream of the styrene finishing column to minimize yield losses. This scheme has also
been used in the Far East. It has been reported that the increased polymerization has caused difficult operating problems and reduced operating
flexibility. The economics of the optional energy recovery schemes are marginal at best in most situations insofar as the energy savings are negated
by the incremental investment, extra inhibitor usage and yield losses, and reduced operating flexibility. Neither of them is used by the producers in
the United States.

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Fig. 5. Purification of styrene in the dehydrogenation reactor effluent in the FinaBadger styrene process: A, benzenetoluene column; B,
ethylbenzene recycle column; C, styrene finishing column; and D, residue finishing. Courtesy of The Badger Company, Inc.

The benzenetoluene fraction is further fractionated in a small column, not shown in Figure 5, to recover benzene for recycle to the
alkylation unit and toluene for sale. This toluene can be converted to benzene by hydrodealkylation but the high selectivity catalyst has reduced the
formation of toluene in the dehydrogenation reactor to the point where the cost of installing a hydrodealkylation unit is difficult to justify even in a
large styrene plant.
POSM Coproduction. The coproduction of propylene oxide and styrene (4049) includes three reaction steps: (1) oxidation of
ethylbenzene to ethylbenzene hydroperoxide, (2) epoxidation of ethylbenzene hydroperoxide with propylene to form -phenylethanol and
propylene oxide, and (3) dehydration of -phenylethanol to styrene.
C6 H5 CH2 CH3 + O2 ! C6 H5 CH(CH3 )OOH

C6 H5 CH(CH3 )OH ! C6 H5 CH|CH2 + H2 O

The oxidation step is similar to the oxidation of cumene to cumene hydroperoxide that was developed earlier and is widely used in the
production of phenol and acetone. It is carried out with air bubbling through the liquid reaction mixture in a series of reactors with decreasing
temperatures from 150 to 130C, approximately. The epoxidation of ethylbenzene hydroperoxide to -phenylethanol and propylene oxide is the key
development in the process. It is carried out in the liquid phase at 100130C and catalyzed by a soluble molybdenum naphthenate catalyst, also in a
series of reactors with interreactor coolers. The dehydration of -phenylethanol to styrene takes place over an acidic catalyst at about 225C. A
commercial plant (50,51) was commissioned in Spain in 1973 by Halcon International in a joint venture with Enpetrol based on these reactions, in a
process that became known as the Oxirane process, owned by Oxirane Corporation, a joint venture of ARCO and Halcon International. Oxirane
Corporation merged into ARCO in 1980 and this process is now generally known as the ARCO process. It is used by ARCO at its Channelview,
Texas, plant and in Japan and Korea in joint ventures with local companies. A similar process was developed by Shell (5255) and commercialized in
1979 at its Moerdijk plant in the Netherlands. The Shell process uses a heterogeneous catalyst of titanium oxide on silica support in the epoxidation
step. Another plant by Shell is under construction in Singapore (ca 1996).
The recovery and purification facilities in these processes are also complex. One reason is that oxygenated by-products are made in the
reactors. Oxygenates, particularly aldehydes, are known to hinder polymerization of styrene and to cause color instability. Elaborate purification is
required to remove the oxygenates. The styrene assay becomes very high as a result, but its quality as a monomer relative to the styrene produced by
the dehydrogenation technology has been a matter of differing opinion among polymer producers.
Other Technologies. As important as dehydrogenation of ethylbenzene is in the production of styrene, it suffers from two theoretical
disadvantages: it is endothermic and is limited by thermodynamic equilibrium. The endothermicity requires heat input at high temperature, which is
difficult. The thermodynamic limitation necessitates the separation of the unreacted ethylbenzene from styrene, which are close-boiling compounds.
The obvious solution is to effect the reaction oxidatively:
1
C6 H5 CH2 CH3 + =2 O2 ! C6 H5 CH|CH2 + H2 O

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 STYRENE Vol 22

Oxidative dehydrogenation is exothermic and is irreversible for all practical purposes. It could greatly reduce the cost of styrene production. The
theoretical elegance and the potential benefit of the concept are so seductive that it has been a topic of extensive research and development since the
1940s not only in the petrochemical industry but also in universities. Molecular oxygen as well as various oxygen carriers, such as sulfur trioxide and
ferric oxide, have been used as oxidants in fixed-bed and fluid-bed reactors. These research efforts have not resulted in commercial processes mainly
because the selectivity to styrene is too low, in comparison with the dehydrogenation technology, to be economical.
A similar but somewhat less ambitious approach is to carry out dehydrogenation of ethylbenzene and oxidation of the hydrogen product
alternately in separate reactors containing different catalysts:
Dehydrogenation C6 H5 CH2 CH3 *
) C6 H5 CH|CH2 + H2

1
Oxidation H 2 + =2 O 2 ! H 2 O
The oxidation reactor replaces the reheater in the adiabatic dehydrogenation technology. The oxidation of hydrogen not only reheats the
reaction mixture from a dehydrogenation reactor but also shifts the reaction equilibrium, thus allowing a higher conversion of ethylbenzene in the
following dehydrogenation reactor. An ethylbenzene conversion of greater than 80% is claimed to be obtainable with three dehydrogenation
reactors and two oxidation reactors. Such an oxidative reheat technology using a palladium catalyst in the oxidation reactor was developed by UOP
(56) and implemented in a demonstration-scale unit at Mitsubishi Chemical in Japan. It was offered for licensing as a new styrene process in the
mid-1980s under the trade name of StyroPlus. It has not attained commercial acceptance, probably because of the high cost of the palladium catalyst
and the necessity of diluting the oxygen with steam prior to its injection into the reaction mixture. There are also concerns about the safety of the
oxygen mixing step, potential damage to the dehydrogenation catalyst by oxygen, and the possibility of contaminating the styrene product with
oxygenates. It is now called oxidative reheat technology and offered as a way of increasing existing plant capacity. It is also called SMART (styrene
monomer advanced reactor technology) in combination with the Monsanto dehydrogenation process licensed by ABB Lummus Crest (5558).
A three-step process involving the oxidation of acetophenone, hydrogenation of the ketone to -phenylethanol, and dehydration of the
alcohol to styrene was practiced commercially by Union Carbide (59) until the early 1960s. Other technologies considered during the infancy of the
styrene industry include side-chain chlorination of ethylbenzene followed by dehydrochlorination or followed by hydrolysis and dehydration.
Technologies for producing styrene from alternative raw materials have also been seriously investigated. Toluene is priced lower than benzene
historically and its use as a starting raw material in lieu of benzene received much attention during the 1970s. Side-chain alkylation of toluene with
methanol or formaldehyde was studied by Monsanto and others (60,61). Monsanto and others (6264) also undertook programs to develop
oxidative coupling of toluene to stilbene, followed by disproportionation of stilbene with ethylene to form styrene:
2 C6 H5 CH3 + O2 ! C6 H5 CH|CHC6 H5 + 2 H2 O

C6 H5 CH|CHC6 H5 + CH2 |CH2 ! 2 C6 H5 CH|CH2

This route uses toluene in lieu of benzene and cutsthe ethylene consumption in half in comparison with the commercial alkylationdehydrogenation
technology via ethylbenzene. It affords a potential cost savings of 20% in raw materials. It would also avoid the costly separation of ethylbenzene
and styrene. In actuality, however, these toluene-based technologies suffer from low yields which negate the potential advantages. They were not
brought to the commercial stage, and the research programs were discontinued in the early 1980s. A technology for cracking diphenylethane to
styrene and benzene originally developed by Nippon Petrochemicals is reported to have been used to reclaim the diphenylethane contained in the
residue from a ethylbenzene plant based on the Unocal alkylation process. Recovery of styrene from various petroleum streams, such as pyrolysis
gasoline, has been considered but is deemed uneconomical.
Production of styrene from butadiene has also been extensively investigated. Recently, Dow announced licensing a process involving
cyclodimerization of 1,3-butadiene to 4-vinylcyclohexene, followed by oxidative dehydrogenation of the vinylcyclohexene to styrene (65,66). The
cyclodimerization step takes place in
2 C4 H6 ! C6 H9 CH|CH2

the liquid phase at about 100C and 2.76 MPa (400psig) over a copperzeolite catalyst. The vinylcyclohexene is converted to styrene by oxidative
dehydrogenation with molecular oxygen diluted with steam in the vapor phase at about 400C
C6 H9 CH|CH2 + O2 ! C6 H5 CH|CH2 + 2 H2 O

and 138 kPa (20 psig) on a mixed metal oxidecatalyst. A three-step process from butadiene to styrene has also been extensively investigated (6769).
The first step also involves cyclodimerization of butadiene to vinylcyclohexene, using an iron dinitrosyl chloridezinc catalyst complex which is very
active and selective. The reaction is carried out in tetrahydrofuran solvent at about 75C and 0.52 MPa (75 psig). The second step involves
dehydrogenation of vinylcyclohexene to ethylbenzene in the vapor phase at 400C and 0.69 MPa (100 psig) or
C6 H9 CH|CH2 ! C6 H5 CH2 CH3 + H2
higher pressure on a noblemetal catalyst. The third step is the conventional dehydrogenation of ethylbenzene to styrene. Recent interest in the
butadiene route is prompted by the projection of a worldwide surplus of butadiene as a by-product of ethylene plants. The potential of this route is
limited by the supply of butadiene as a low priced by-product in a quantity sufficient to support a styrene plant of an economical size. This limitation
can be readily seen from the fact that a world-scale naphtha cracker that produces 450,000 t/yr of ethylene generates only enough by-product
butadiene to support a styrene plant of 50,000 t/yr capacity. In contrast, it requires only 84,000 t/yr of ethylene to support a world-scale styrene
plant of 300,000 t/yr capacity. Nevertheless, it is conceivable that the butadiene from a big naphtha cracker can be economically converted to
ethylbenzene, which would then be used to supplement the ethylbenzene from alkylation for the production of styrene on an economical scale.

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 STYRENE Vol 22

Economic Aspects
Capacity. The producers of styrene in the United States and their capacities (6971), together with the technologies used, are listed in
Table 2. It is a mature industry and the capacity in the United States is not expected to increase rapidly. The annual capacity of 5:3 £ 106 t already
substantially exceeds the domestic demand. Approximately 20% of U.S. production is exported. The U.S. styrene producers benefit from the huge
ethylene capacity and the relatively low energy cost present in the Gulf Coast.

Table 2. U.S. Styrene Producers and Capacities, 1995

Technologies
Company (location) Capacity, 103 Ethylbenzene Styrene
t/yr
Amoco (Texas City, Tex.) 364 AlCl3 dehydro
ARCO (Channelview, Tex.) 511 Monsanto AlCl3 ARCO PO/SM
636 Mobil-Badger ZSM-5 ARCO PO/SM
Chevron (St. James, La.) 682 Mobil-Badger ZSM-5 Fina-Badger dehydro
Cos-Mar (Carville, La.) 864 Mobil-Badger ZSM-5 Fina-Badger dehydro
Dow (Freeport, Tex.) 636 Dow AlCl3 Dow dehydro
Huntsman (Bayport, Tex.) 568 Mobil-Badger ZSM-5 Fina-Badger dehydro
Rexene (Odessa, Tex.) 145 UOP Alkar UOP dehydro
Sterling (Texas City, Tex.) 727 Monsanto AlCl3 Monsanto dehydro
Westlake (Lake Charles, La.) 159 Mobil-Badger ZSM-5 Fina-Badger dehydro
Total 5292

Worldwide styrene capacity, approximately 18 £ 106 t=yr , is shown by geographic region in Table 3. Styrene is also a mature industry in
Western Europe and Japan. In the other areas of Pacific Rim, particularly in Korea, the capacity has been increasing rapidly since the early 1980s. A
large number of new construction projects are in progress or in planning in Korea, Taiwan, South Asia, China, and India. The styrene capacity in the
Asia/Pacific region, including Japan, is expected to surpass that in North America by 1998.

Table 3. Worldwide Styrene Capacity, 1995

Regions Capacity, 103 t/yr

North America 6,200
South America 400
Western Europe 4,200
Eastern Europe 1,200
Asia/Pacific 5,500
Middle East/Africa 600
Total 18,100

Supply and Demand. Styrene is traded in large volumes internationally. Its supply and demand must therefore be viewed in a global
perspective. The supply, demand, and net trade by geographic region in 1995 are estimated in Table 4. The worldwide production in 1995 was
estimated to be approximately 17 £ 106 t. The demand is expected to grow at 2.5% per year in the United States and at a somewhat lesser rate in
Western Europe and Japan. The demand in the rest of the Asia/Pacific region is expected to grow at a high rate, up to 10% per year. There was a
huge shortage of styrene production in the Asia/Pacific region in the decade from 19851995. It is expected to continue into the early part of the
twenty-first century in spite of the rapid capacity expansion. This regional supply/demand imbalance is presently covered mostly by imports from
North America. North America and, increasingly, the Middle East will thus continue to be the exporters. Worldwide, the demand of styrene is
expected to grow at an average rate of 4.5% annually until the year 2005.

Table 4. Worldwide Styrene Supply and Demand, 1995

Regions Production, 103 t/yr Demand, 103 t/yr Net trade, 103 t/yr
North America 5,900 4,900 1,000
South America 400 600 (200)
Western Europe 4,000 4,000
Eastern Europe 1,100 1,300 (200)
Asia/Pacific 5,300 6,300 (1,000)
Middle East/Africa 600 200 400
Total 17,300

Price. Styrene is a global commodity chemical. Its price is fairly uniform worldwide, except for short-term fluctuations on the regional

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 STYRENE Vol 22

spot market. However, the price of styrene has been highly cyclic. During the worldwide recession in the early 1980s, it went below $450/metric ton,
which was less than the cost of production. With the economic recovery in the mid-1980s, it increased rapidly, reaching $1500/t or higher on the
spot market in the Far East in 1988. The 19871989 period was extraordinarily profitable years for styrene producers. Many new plants were
constructed and excessive production capacity followed. The price then dropped to about $500/t during 19911993 period. It again surged in early
1994, reaching $1350/t on the spot market during the second quarter of 1995, but then plunged to $500/t within a few months. As of September
1996, contract prices were ca $660/t but spot prices were still under $550/t.

Specifications and Analysis

Styrene specifications are largely dictated by the market. There is no formal agreement in the industry. Specifications for a typical
polymerization-grade styrene product are shown in Table 5. The typical assay increased from 99.6% to 99.8% during the 1980s. As of 1996, an assay
of 99.8% is still generally accepted. Newer plants in the United States are designed for 99.90% purity and in some cases as high as 99.95%. Some
producers choose to have their plants designed to produce high purity styrene at a small incremental investment to gain marketing advantages and in
anticipation of its future demand.

Table 5. Specifications for Typical Polymerization-Grade Styrene Monomer Product

Parameter Specification
a Test method
purity 99.80
b chromatography
hydrocarbon impurities 2000 chromatography
color 10
c ASTM D1209
polymer 10 ASTM D2121
aldehydes (as benzaldehyde) 50 ASTM D2119
peroxides (as hydrogen peroxide) 30 ASTM D2340
d ASTM D2120
TBC (inhibitor) 1050
chlorides (as chlorine) 1 ASTM D4929
sulfur 1 ASTM D2747
a
Value shown is in ppm by wt max, unless otherwise specified.
b
Wt % min.
c
PtCo scale, max.
d
4-tert-Butylcatechol.

The advance (ca 1996) in alkylation technology enables the production of ultrahigh purity ethylbenzene at a low cost. With this ethylbenzene
as the intermediate, a dehydrogenation unit of the present design will be able to produce styrene of 99.95% purity routinely. It may prompt a new
standard in the styrene industry.
Methods for the analysis of styrene monomer are also shown in Table 5. The freezing point measurement was the standard method for the
determination of styrene assay until the 1970s, but it has been largely replaced by gas chromatography. Modern gas chromatography gives a great
amount of detail on the impurities and is accurate to parts per million or lower; styrene assay is determined by difference. However, certain
impurities and properties are not amenable to chromatographic analysis. Color is measured spectrophotometrically and registered on the APHA or
the platinumcobalt scale. The TBC (4-tert-butylcatechol, the inhibitor) is extracted with aqueous sodium hydroxide and the resulting reddish
quinone is measured photometrically. The polymer content is precipitated by addition of methanol to the monomer and the resulting mixture is
measured with a turbidity meter. Other possible impurities, such as chlorides, sulfur, aldehydes (expressed as benzaldehyde), and peroxides
(expressed as hydrogen peroxide) are measured by the methods commonly used in the chemical industry, also listed in Table 5.

Health and Safety Factors

Styrene is mildly toxic, flammable, and can be made to polymerize violently under certain conditions. However, handled according to proper
procedures, it is a relatively safe organic chemical. Styrene vapor has an odor threshold of 50150 ppm (72,73).
Styrene is listed in the U.S. Toxic Substance Control Act (TSCA) Inventory of Chemicals. It is not confirmed as a carcinogen but is
considered a suspect carcinogen. The recommended exposure limits are OSHA PEL 50 ppm, ACGIH TLV 50 ppm. For higher concentrations,
NIOSH/MSHA-approved respiratory protection devices should be used. For skin protection, use of protective garments and gloves of Viton,
Nitrile, or PVA construction should be made. The acute effects of overexposure to styrene are shown in Table 6 (74).

a
Table 6. Acute Effects of Overexposure to Styrene

Area affected Effect

eye slight to moderate irritation
skin slight irritation; repeated exposure may produce severe irritation including blistering
inhalation may cause headache, nausea, dizziness, muscle weakness; produces central nervous system depression; irritates nose,
throat, and lungs
ingestion may cause nausea, headache, dizziness, muscle weakness; produces central nervous system depression, and diarrhea;

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 STYRENE Vol 22

may be aspirated into lungs if swallowed, resulting in pulmonary edema and chemical pneumonitis
a
Ref. 74.

Styrene liquid is inflammable and has sufficient vapor pressure at slightly elevated temperatures to form explosive mixtures with air, as shown
in Figure 6. Uninhibited styrene polymerizes slowly at room temperature, and the polymerization rate increases with the temperature. Styrene
polymerization is exothermic and this can cause the reaction to run awry. Polymerization can be inhibited by the presence of 10 ppm or more of
TBC. Oxygen is necessary for effective action of the inhibitor (75). It is recommended that air be added periodically to the storage vessels, which are
blanketed with an inert gas. Properly inhibited and attended, styrene can be stored for an extended period of time. In climates where the average
daily temperature in excess of 27C is common, refrigeration of bulk storage is recommended (76). Copper and copper alloys should not be used in
the handling or storage of styrene, because copper can dissolve in styrene to cause discoloration and interferes with polymerization.

Fig. 6. Approximate explosive limits of styrene monomer vapor in equilibrium with liquid styrene in air, where £ represents the explosive region. To
convert kPa to mm Hg, multiply by 7.5. Courtesy of the Dow Chemical Company.

Uses
Commercial styrene is used almost entirely for the manufacture of polymers. Polystyrene accounts for 64% of the worldwide demand for styrene.
The rest is for manufacture of copolymers: ABS, 9%; SB latex, 7%; UPR, 5%; SBR, 4%; others, 11%.
Polystyrene (PS). Common applications include packaging, food containers, and disposable tableware; toys; furniture, appliances,
television cabinets, and sports goods; and audio and video cassettes. For some of these applications, PS is modified by blending or graft
polymerization with SBR to form impact polystyrene, which is less sensitive to breakage. Expandable polystyrene is widely used in construction for
thermal insulation.
AcrylonitrileButadieneStyrene Copolymer (ABS). Uses for ABS are in sewer pipes, vehicle parts, appliance parts, business
machine casings, sports goods, luggage, and toys.
StyreneButadiene Latex. SB latex is used in coatings, carpet backing, paper adhesives, cement additives, and latex paint.
StyreneButadiene Rubber (SBR). This elastomer is used primarily in tires, vehicle parts, and electrical components.
Unsaturated Polyester Resins (UPR). The principal uses are in putty, coatings, and adhesives. Glass-reinforced UPR is used for
marine, construction, and vehicle materials, as well as for electrical parts.

Derivatives
A large number of compounds related to styrene have been reported in the literature. Those having the vinyl group CH 2| |CH| attached to the
aromatic ring are referred to as styrenic monomers. Several of them have been used for manufacturing small-volume specialty polymers. The
specialty styrenic monomers that are manufactured in commercial quantities are vinyltoluene, para-methylstyrene, -methylstyrene, and
divinylbenzene. In addition, 4-tert-butylstyrene [1746-23-2] (TBS) is a specialty monomer that is superior to vinyltoluene and para-methylstyrene in
many applications. It is manufactured by Amoco in a complex process and its use has been limited by its high price. Deltech is market-testing a TBS
monomer that is produced in a much simpler process that can substantially reduce its price and widen its use. Other styrenic monomers produced in
small quantities include chlorostyrene and vinylbenzene chloride.
With the exception of -methylstyrene, which is a by-product of the phenol acetone process, these specialty monomers are more difficult
and expensive to manufacture than styrene. Their more complex molecular structures give rise to the formation of more types and greater quantities
of by-products in chemical reactions, and the yields are low in comparison with styrene synthesis. As a result, the recovery and purification facilities
are more complex. The high boiling points of these monomers require that distillation be carried out at high temperatures, which would cause high
yield losses to polymerization, or at low pressures, which would increase the investment and operating costs. These difficulties, together with the lack

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 STYRENE Vol 22

of economy in large-scale production, keep the cost of these monomers high and limit their uses.
Vinyltoluene. This is a specialty monomer with properties similar to those of styrene (77). It was originally developed to compete with
styrene when benzene was in short supply after World War II. It is more difficult to manufacture than styrene. With the development of new
technologies for producing benzene from petroleum, notably catalytic reforming and naphtha cracking, styrene retained its lead position and became
a large-volume monomer. Vinyltoluene [25013-15-4] has continued to be produced for special applications. Its copolymers are more heat-resistant
than the corresponding styrene copolymers. The increased solubility in aliphatic solvents and the faster reaction rates resulting from the added
methyl group make vinyltoluene better suited than styrene as a specialty monomer for paint, varnish, and polyester applications.
Vinyltoluene (VT) is a mixture of meta- and para-vinyltoluenes, typically in the ratio of 60:40. This isomer ratio results from the ratio of the
corresponding ethyltoluenes in thermodynamic equilibrium. Physical properties and chemical analysis of a typical vinyltoluene product are shown in
Tables 7 and 8, respectively. Vinyltoluene monomer is produced by Dow Chemical Company and Fina Oil & Chemical Company. The worldwide
consumption is estimated to be approximately 100,000 t/yr.

a
Table 7. Physical Properties of a 60:40 Mixture of m- and p-Vinyltoluene

Property Value
molecular weight 118.17
refractive index, n20D 1.5422
viscosity at 20C, mPa¢s(=cP) 0.837
surface tension at 20C, mN/m (=dyn=cm) 31.66
density at 20C, g/cm3 0.8973
boiling point at 101.3 kPa (=1 atm), C 172
freezing point, C ¡77
flash point (Cleveland open-cup), C 60
fire point (Cleveland open-cup), C 68.3
autoignition temperature, C 575
explosive limits, % in air 1.96.1
b
vapor pressure, kPa
at 20C 0.15
60C 1.76
160C 74.66
c 4.19
critical pressure, Pc, MPa
critical temperature, tc, C 382
critical volume, Vc, mL/g 3.33
critical density, dc, g/mL 0.30
d 1.2284
specific heat of vapor, Cp, at 25C, J/(g¢K)
d
latent heat of vaporization, Hv, J/g
at 25C 426.10
boiling point 349.24
d 4816.54
heat of combustion (Hc), kJ/mol , gas at constant pressure at 25C
d 115.48
heat of formation (Hf), kJ/mol , liquid at 25C
d +66:9 § 0:2
heat of polymerization, kJ/mol
Q value 0.95
e value ¡0:89
shrinkage upon polymerization, vol % 12.6
cubical coefficient of expansion at 20C 9:361 £ 10¡4
solubility, wt % in H2O at 25C 0.0089
H2O in monomer at 25C 0.47
e
solvent compatibility
a
Ref. 1.
b
To convert kPa to mm Hg, multiply by 7.5.
c
To convert MPa to psi, multiply by 145.
d
To convert J to cal, divide by 4.184.
e
Infinitely soluble in acetone, carbon tetrachloride, benzene, diethyl ether, n-heptane, and ethanol.

a
Table 8. Chemical Analysis of Commercial Vinyltoluene

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 STYRENE Vol 22

Assay ppm
b

purity 99.6
c

polymer none
phenylacetylene 58
aldehydes as CHO 10
peroxides as H2O2 5
chlorides as Cl 5
TBC 12
m-vinyltoluene 60
c

p-vinyltoluene 40
c

a
Ref. 1.
b
Unless otherwise indicated.
c
Percent.

Ethyltoluene is manufactured by aluminum chloride-catalyzed alkylation similar to that used for ethylbenzene production. All three isomers
are formed. A typical analysis of the reactor effluent is shown in Table 9. After the unconverted toluene and light by-products are removed, the
mixture of ethyltoluene isomers and polyethyltoluenes is fractionated to recover the meta and para isomers (bp 161.3 and 162.0C, respectively) as
the overhead product, which typically contains 0.2% or less ortho isomer (bp 165.1C). This isomer separation is difficult but essential because
o-ethyltoluene undergoes ring closure to form indan and indene in the subsequent dehydrogenation process. These compounds are even more
difficult to remove from vinyltoluene, and their presence in the monomer results in inferior polymers. The o-ethyltoluene and polyethyltoluenes are
recovered and recycled to the reactor for isomerization and transalkylation to produce more ethyltoluenes. Fina uses a zeolite-catalyzed vapor-phase
alkylation process to produce ethyltoluenes.

Table 9. Composition of Unrefined Product Obtained in the Manufacture of Ethyltoluene

Compound Wt %
benzene and lights 0.2
toluene 48.3
ethylbenzene and xylenes 1.2
p-ethyltoluene 11.9
m-ethyltoluene 19.3
o-ethyltoluene 3.8
polyethyltoluenes and other by-products 14.4
tar 0.9

The dehydrogenation of the mixture of m- and p-ethyltoluenes is similar to that of ethylbenzene, but more dilution steam is required to
prevent rapid coking on the catalyst. The recovery and purification of vinyltoluene monomer is considerably more difficult than for styrene owing to
the high boiling point and high rate of thermal polymerization of the former and the complexity of the reactor effluent, which contains a large
number of by-products. Pressures as low as 2.7 kPa (20 mm Hg) are used to keep distillation temperatures low even in the presence of
polymerization inhibitor. The finished vinyltoluene monomer typically has an assay of 99.6%.
para-Methylstyrene. PMS is the para isomer of vinyltoluene in high purity. It is probably the only compound that has the potential to
compete against styrene in the large commodity market as a styrenic monomer. p-Methylstyrene [627-97-9] has an apparent raw material cost
advantage over styrene, and the characteristics of its polymers and copolymers are superior to those of the corresponding styrene polymers and
copolymers in some important aspects. PMS is made by alkylation of toluene with ethylene to p-ethyltoluene, followed by dehydrogenation of
p-ethyltoluene. Stoichiometrically, it takes 78 t of toluene and 24 t of ethylene to make 100 t of PMS, whereas it takes 75 t of benzene and 25 t of
ethylene to make 100 t of styrene. Toluene is priced lower than benzene by weight, and ethylene is more expensive than both. The use of toluene in
lieu of benzene and the lower ethylene requirement together give PMS a potential savings of 1020%. It has an additional cost advantage of 4% as a
monomer resulting from poly-PMS having a lower density than polystyrene, as polymers are usually sold (and used) by volume rather than by
weight.
The most difficult problem in manufacturing PMS is in the synthesis of the p-ethyltoluene precursor in high purity. A conventional alkylation
process makes all three isomers, and isolation of the para isomer from this mixture by distillation or any other technique would be prohibitively
expensive. The manufacture of PMS as a large-volume monomer became feasible with the development by Mobil of a ZSM-5 catalyst which is
selective to the para isomer in alkylation (78). It attracted much attention in the styrene industry in the early 1980s. PMS was billed as "high-tech
styrene" and forecasts were made of its gradually replacing styrene as the dominant styrenic monomer. This did not happen for several reasons.
Aside from the isomer selectivity, the production of PMS is more difficult than that of styrene with higher investment, lower yield, and higher energy
consumption in both the alkylation and dehydrogenation steps. In reality, the production cost advantage is far less than the apparent raw material
cost savings. Moreover, the markets for both the monomer and its polymers must be developed on a large scale for it to compete on the basis of
both quality and price. This requires a large investment, which would involve considerable risk in view of the well-established position of styrene
monomer in the plastics industry. It was deemed to be too risky, and the expectation of PMS becoming a large-volume monomer faded. It is now
manufactured by Deltech as a specialty monomer at Baton Rouge, Louisiana. The typical product contains 97% p-vinyltoluene, 3% m-vinyltoluene,
and 0.2% o-vinyltoluene.

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Divinylbenzene. This is a specialty monomer used primarily to make cross-linked polystyrene resins. Pure divinylbenzene (DVB)
monomer is highly reactive polymerically and is impractical to produce and store. Commercial DVB monomer (7679) is generally manufactured
and supplied as mixtures of m- and p-divinylbenzenes and ethylvinylbenzenes. DVB products are designated by commercial grades in accordance
with the divinylbenzene content. Physical properties of DVB-22 and DVB-55 are shown in Table 10. Typical analyses of DVB-22 and DVB-55 are
shown in Table 11. Divinylbenzene [1321-74-0] is readily polymerized to give brittle insoluble polymers even at ambient temperatures. The product
is heavily inhibited with TBC and sulfur to minimize polymerization and oxidation.

a
Table 10. Physical Properties of Two Divinylbenzene Mixtures

Value
Property DVB-22
b
DVB-55
b

molecular weight 130.08 130.18

refractive index, n25D 1.5326 1.5585
viscosity at 25C, mPa¢s(=cP) 0.883 1.007
surface tension at 25C, mN/m (=dyn=cm) 30.55 32.10
density at 20C, g/cm3 0.8979 0.9126
boiling point, C 180
c
195
c

freezing point, C ¡45

flash point (Cleveland open-cup), C 57 74
fire point (Cleveland open-cup), C 57 74
explosive limits, % in air 1.16.2 ¸1:1
d
e c c
critical pressure, Pc, MPa 2.45 2.45
critical temperature, tc, C 348
c
369
c

f 320.49 350.62
latent heat of vaporization, Hv, at boiling point, J/g
solubility at 25C, % in H2O 0.0065 0.0052
H2O in monomer at 25C 0.051 0.054
g
solvent compatibility
a
Ref. 1.
b
Dow Chemical Co.'s designations for 22 and 55% divinylbenzene, respectively.
c
Calculated.
d
Could not be measured at 130C.
e
To convert MPa to psi, multiply by 145.
f
To convert J to cal, divide by 4.184.
g
Both types are infinitely soluble in acetone, carbon tetrachloride, benzene, and ethanol.

a
Table 11. Chemical Analysis of Two Divinylbenzene Mixtures

Value
Assay DVB-22 DVB-55
polymer, ppm 100 100
aldehydes as CHO, ppm 40 40
peroxides as H2O2, ppm 5 5
sulfur as S, ppm 20 230
TBC, ppm 1000 1000
b 83.3 149.4
total unsaturation
divinylbenzene, %
meta 17.1 36.4
para 8.2 18.6
total 25.3 55.0
ethylvinyltoluene, %
meta 23.1 25.0
para 10.0 13.0
a
Ref. 1.
b
As ethylvinylbenzene.

Small quantities of DVB copolymerized with styrene yield polymers which have the appearance of polystyrene but possess higher heat

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 STYRENE Vol 22

distortion temperatures, greater hardness, and slightly better impact and tensile strengths. The increased resistance to thermal distortion allows the
plastics to be machined more easily and to have broader use in electrical insulation applications. Beads of styrenedivinylbenzene resins made by
suspension polymerization are used as the basis of ion-exchange resins. (The ionic sites are formed afterward by substitution on the aromatic rings.)
The cross-links resulting from divinylbenzene help stabilize the bead structure and minimize swelling. The largest use of DVB is in ion-exchange
resins for domestic and industrial water softening. Ion-exchange resins are also used as solid acid catalysts for certain reactions, such as
esterification.
Divinylbenzene is manufactured by dehydrogenation of diethylbenzene, which is an internal product in the alkylation plant for ethylbenzene
production. This internal product is normally transalkylated to produce more ethylbenzene. A stream of the diethylbenzene can be diverted for
divinylbenzene production. The technology for dehydrogenation of diethylbenzene is similar to that for dehydrogenation of ethylbenzene. The
presence of two ethyl groups on the aromatic ring, however, greatly increases the number of possible products and by-products. Light by-products
include benzene, toluene, xylene, ethylbenzene, styrene, ethyltoluene, and vinyltoluene. Meta- and para-diethylbenzenes are converted to their
corresponding ethylvinylbenzenes and divinylbenzenes. The unconverted diethylbenzenes and part of the ethylvinylbenzenes are removed together
with the light by-products and, after further fractionation, recycled to the reactor. ortho-Ethylbenzene [135-01-3] is dehydrogenated and cyclized to
naphthalene, which is removed together with other heavy by-products as the residue from the product, which is a mixture of divinylbenzenes and
ethylvinylbenzenes. This last distillation is carried out at a very low pressure of 1.332 kPa (1015 mm Hg) absolute and in the presence of inhibitors
to keep the temperature low and to prevent polymerization. Further isolation of the product components is neither necessary nor desirable. For
most commercial applications, divinylbenzene is used in low concentrations as a cross-linking agent. Ethylvinylbenzene itself is a monomer much
like vinyltoluene and is easily incorporated into polymers of styrene.
-Methylstyrene. This compound is not a styrenic monomer in the strict sense. The methyl substitution on the side chain, rather than
the aromatic ring, moderates its reactivity in polymerization. It is used as a specialty monomer in ABS resins, coatings, polyester resins, and hot-melt
adhesives. As a copolymer in ABS and polystyrene, it increases the heat-distortion resistance of the product. In coatings and resins, it moderates
reaction rates and improves clarity. Physical properties of -methylstyrene [98-83-9] are shown in Table 12.

a
Table 12. Physical Properties of -Methylstyrene

Property Value
molecular weight 118.18
refractive index, n20D 1.53864
viscosity at 20C, mPa¢s(=cP) 0.940
surface tension at 20C, mN/m (= dyn=cm) 32.40
density at 20C, g/cm3 0.9106
boiling point, C 165
freezing point, C ¡23:2
flash point (Cleveland open-cup), C 57.8
fire point (Cleveland open-cup), C 57.8
explosive limits, % in air 0.73.4
b
vapor pressure, kPa
at 20C 0.253
60C 2.400
100C 13.066
160C 88.660
c 4.36
critical pressure, Pc, MPa
critical temperature, tc, C 384
critical volume, Vc, mL/g 3.26
critical density, dc, g/mL 0.29
d
specific heat of liquid, J/(g¢K)
at 40C 2.0460
100C 2.1757
d 1.2357
specific heat of vapor at 25C, J/(g¢K)
d
latent heat of vaporization, Hv, J/g
at 25C 404.55
boiling point 326.35
d 4863.73
heat of combustion, Hc, gas at constant pressure at 25C, kJ/mol
d 112.97
heat of formation, Hf, liquid at 25C, kJ/mol

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 STYRENE Vol 22

d 39.75
heat of polymerization, kJ/mol
Q value 0.76
e value ¡1:17
cubical coefficient of expansion at 20C 9:774 £ 10¡4
solubility in H2O at 25C 0.056
H2O in monomer at 25C 0.010
e
solvent compatibility
a
Ref. 1.
b
To convert kPa to mm Hg, multiply by 7.5.
c
To convert MPa to psi, multiply by 145.
d
To convert J to cal, divide by 4.184.
e
Infinitely soluble in acetone, carbon tetrachloride, benzene, diethyl ether, n-heptane, and ethanol.

Production of -methylstyrene (AMS) from cumene by dehydrogenation was practiced commercially by Dow until 1977. It is now produced
as a by-product in the production of phenol and acetone from cumene. Cumene is manufactured by alkylation of benzene with propylene. In the
phenolacetone process, cumene is oxidized in the liquid phase thermally to cumene hydroperoxide. The hydroperoxide is split into phenol and
acetone by a cleavage reaction catalyzed by sulfur dioxide. Up to 2% of the cumene is converted to -methylstyrene. Phenol and acetone are
large-volume chemicals and the supply of the by-product -methylstyrene is well in excess of its demand. Producers are forced to hydrogenate it
back to cumene for recycle to the phenolacetone plant. Estimated plant capacities of the U.S. producers of -methylstyrene are listed in Table 13
(80).

Table 13. U.S. -Methylstyrene Producers and Capacities, 1995

Company Location Capacity, t/yr

AlliedSignal Frankford, Pa. 25,000
Aristech Haverhill, Ohio 17,300
JLM Chemicals Blue Island, Ill. 2,300
Georgia-Gulf Pasadena, Tex. 3,200
Plaquemine, La. 6,800
Texaco El Dorado, Kans. 1,400
Total 56,000

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 STYRENE Vol 22

Shiou-Shan Chen
Raytheon Engineers & Constructors

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 22