Styrene

S
Guy B. Woodle
UOP LLC, Des Plaines, Illinois, U.S.A.

INTRODUCTION its unsaturated side chain and aromatic ring. For

example, styrene can be oxidized to form benzoic acid,
Styrene is one of the most important aromatic benzaldehyde, styrene oxide, and other oxygenated
monomers used for the manufacture of plastics. compounds. Styrene oxide is used in the production
Small-scale commercial production of styrene began of various cosmetics, perfumes, agricultural and
in the 1930s. Demand for styrene-based plastics has biological chemicals.
grown significantly, and in 2003 the worldwide annual
production capacity was approximately 24.5 million
metric tons.[1]
REACTION KINETICS AND
About 65% of styrene is used to produce polystyrene.
THERMODYNAMICS
Polystyrene is used in the manufacture of many
commonly used products such as toys, household and
Essentially all commercially produced styrene uses
kitchen appliances, plastic drinking cups, housings
ethylbenzene (EB) as a feedstock. Between 85% and
for computers and electronics, foam packaging, and
90% of worldwide styrene production is based on EB
insulation. Polystyrene finds such widespread use because
dehydrogenation. The remaining 10–15% of styrene
it is relatively inexpensive to produce and is easy to poly-
is obtained as a coproduct in a process to produce
merize and copolymerize, resulting in plastics with a
propylene oxide.
broad range of characteristics. In addition to poly-
styrene, styrene is used to produce acrylonitrile–butadiene–
styrene polymer, styrene–acrylonitrile polymer, and Ethylbenzene Dehydrogenation
styrene–butadiene synthetic rubber (SBR).
The development of styrene technologies was Ethylbenzene is catalytically dehydrogenated in the
mainly driven by demand for cheap synthetic rubber presence of steam according to the equation:
during and immediately after World War II. Between
5% and 10% of total styrene produced becomes a
component of synthetic rubbers, which are copolymers
CH3 CH2
of styrene and butadiene (SBR). Styrene copolymers
containing acrylonitrile are specialty materials that
are used for specific applications. Demand for styrene
for the period 2004–2009 is estimated to grow at a rate + H2
of approximately 4% per year.[1]

PHYSICAL AND CHEMICAL PROPERTIES
Styrene is a colorless aromatic liquid. It is only very
slightly soluble in water, but infinitely soluble in
alcohol and ether. Additional properties are listed in
Table 1.
Styrene is chemically reactive with the most
important reaction being its polymerization to form
polystyrene. Styrene can also copolymerize with
other monomers, such as butadiene and acrylo-
nitrile, to produce a variety of industrially important
copolymers.
In addition to polymerization, styrene can undergo
other types of reactions due to the chemical nature of
Encyclopedia of Chemical Processing DOI: 10.1081/E-ECHP-120007970
Copyright # 2006 by Taylor & Francis. All rights reserved.
The reaction is highly endothermic and conversion
is limited in extent by equilibrium. The reaction
equilibrium constant is defined as:
Keq ¼ ðPsty # Ph2Þ=Peb
where Psty is the partial pressure of styrene, Ph2 is the
partial pressure of hydrogen; and Peb is the partial
pressure of ethylbenzene.
High temperature, steam dilution, and low system
pressure produce an equilibrium more favorable to
styrene. For endothermic vapor-phase reactions, the
equilibrium constant increases with temperature and
2859
2860 Styrene

Table 1 Physical properties of styrene

Molecular weight 104.152
a
Specific gravity 0.903
Melting point, & C "30.628
Boiling point, & C 145.2
Critical temperature, & C 373
Critical pressure, atm 46.1
Vapor pressure, mm& Hg 1 5 20 10 40 60 100 200 400 760
at T & C
"7.0 18.0 30.8 44.6 59.8 69.5 82.0 101.3 122.5 145.2
a
Density is at 20& C referred to water at 4& C.
(From Perry, R.H., Green, D.W., Eds.; Perry’s Chemical Engineers Handbook, 6th Ed.; McGraw-Hill: New York, 1984; 3-60 and Miller, S.A.,
Ed.; Ethylene and Its Industrial Derivatives; 901 pp.)

can be determined according to the following The key dealkylation reactions can be described by
equation:[2] the following equations:

ln Keq ¼ 16:12 " ð15; 350=TÞ CH3

where Keq is the equilibrium constant in atmospheres

and T is the temperature in K. + H 2C CH2
The equilibrium constant has the dimension of
pressure since two moles of products are formed for
each mole of EB converted. Therefore, a higher total
pressure will shift the reaction equilibrium to the left CH3 CH3
and reduce EB conversion. Lower pressure results in
greater EB conversion without an accompanying
significant decrease in styrene selectivity.
Another method to create a positive shift in + H2 + CH4
equilibrium is the use of steam dilution to reduce the
partial pressures of EB, styrene, and hydrogen. Steam
dilution provides the same effect as a reduction in total Both methane and ethylene undergo steam reform-
pressure. ing reactions according to the following equations:
Steam dilution has several other important benefits.
First, steam supplies heat to the reacting mixture. CH4 þ H2 O ! CO þ 3H2
Consequently, the drop in temperature for a given
EB conversion is lower, allowing greater EB conver-
sions to be obtained with the same inlet temperature. C2 H4 þ 2H2 O ! 2CO þ 4H2
Second, a minimum amount of steam appears to keep
the catalyst in the required oxidation state for high The water–gas shift reaction also occurs and is
activity. The actual quantity of steam varies with the generally near equilibrium at the reaction temperature:
type of catalyst used. Third, steam is believed to
suppress the deposition of carbonaceous material on CO þ H2 O $ CO2 þ H2
the catalyst. If the carbonaceous material is allowed
to accumulate, the catalyst will become fouled and its The combination of dealkylation, steam reforming,
activity will decline to unacceptable levels. and water–gas shift side reactions should be avoided,
The reaction feed mixture undergoes certain other if possible. In addition to losing valuable EB feed by
reactions that are not equilibrium limited under typical dealkylation, the resultant net formation of carbon
operating conditions. Most important among these dioxide and hydrogen by this combination of reactions
are the dealkylation reactions that result in the inhibits the primary dehydrogenation reaction. The net
formation of benzene and ethylene or toluene and hydrogen formation gives an unfavorable shift in equi-
methane. Other reactions produce small amountsof librium, while the presence of carbon dioxide has a
a-methylstyrene and other high boiling components. negative effect on dehydrogenation catalyst activity.[3]
Styrene
Typically, there is less methane and ethylene present
in the effluent of a reactor than would be expected from
the benzene and toluene formation. Carbon monoxide
is generally about 10 mol% of the total carbon oxides.
The critical operating and design parameters for EB
dehydrogenation are discussed in the following
paragraphs.
Reaction temperature
Because the dehydrogenation reaction is endothermic,
the reaction mixture temperature decreases as the
reaction proceeds. The reaction rate slows because of
the closer approach to equilibrium and the decrease
in kinetic reaction rate with the decreasing tempera-
ture. Furthermore, the equilibrium constant is less
favorable at lower temperature. Therefore, in a normal
design, about 80% of the temperature drop occurs in
approximately the first third of the catalyst bed.
As a result, a high inlet catalyst temperature is
required. However, high temperature also increases
the rates of nonselective thermal reactions and dealky-
lation reactions, which form benzene and toluene
by-products. In particular, as temperature is increased,
the rate of benzene formation increases significantly
relative to the rate of styrene formation. This means
there is an effective upper limit to the inlet temperature
if high styrene selectivity is a required criterion. Reac-
tion temperature is generally adjusted by changing
either the steam temperature or the steam-to-oil ratio.
Catalyst quantity
The amount of catalyst relative to EB feed is an
important parameter for optimum reactor perfor-
mance. Too little catalyst will prevent a close approach
to equilibrium. If EB conversion is low, then distilla-
tion costs associated with recovery and recycle of the
unconverted EB can become significant. With too
much catalyst, the EB conversion reaches equilibrium
before the outlet of the catalyst bed, while the side
reactions continue leading to loss of selectivity.
The optimum catalyst quantity is achieved by
balancing the EB conversion level and the styrene
yield. Catalysts typically lose activity with time on-
stream, which has the effect of decreasing the effective
active catalyst quantity for reaction. Compensation for
aging catalyst is achieved by adjusting other operating
parameters, in particular, the reaction temperature.
Reaction pressure
Ethylbenzene dehydrogenation results in a significant
increase in the volume of reactants due to the reac-
tion stoichiometry. Lower pressure favors higher
2861
equilibrium conversion to styrene. Reaction pressure
is established during the plant design at the lowest
practical level. Modern commercial reactors operate S
below atmospheric pressure. Pressures as low as
300 mm Hg or lower are common. The key side reac-
tions are largely independent of reaction pressure;
hence, operating at lower pressures also provides
higher styrene yield.
Steam dilution or steam-to-oil ratio
The main functions of steam dilution are to act as a
diluent to reduce the hydrocarbon partial pressures,
providing heat for the endothermic dehydrogenation
reaction, and maintaining the catalyst’s active surface
in a desirable state. Increasing the steam-to-oil ratio
has the net effect of improving the EB conversion
and styrene yield. However, costs associated with
generating and superheating the dilution steam also
increase and eventually offset the reaction advantages.
Catalyst type and properties
Ethylbenzene dehydrogenation is generally catalyzed
by a potassium-promoted iron oxide catalyst. The
most widely used catalysts are composed of iron oxide,
potassium carbonate, and various metal oxide promo-
ters. Examples of metal oxide promoters include
chromium oxide, cerium oxide, molybdenum oxide,
and vanadium oxide.[4] The potassium component
substantially increases catalyst activity relative to an
unpromoted iron oxide catalyst. Potassium has been
shown to provide other benefits. In particular, it
reduces the formation of carbonaceous deposits on
the catalyst surface, which prolongs catalyst life.
Properties such as catalyst size and shape also
impact performance. In theory, smaller sized catalyst
will increase reaction rates by providing more available
catalyst surface area than larger sized catalyst. Small
catalyst particles, however, have a disadvantage in that
they result in greater pressure drop through a reactor
and higher overall reaction pressures. To address this,
catalyst developers have used specialized shapes, such
as ribbed extrudates, to gain the advantage of
increased surface area without incurring the penalty
of increased pressure drop and reaction pressure.
The Sud-Chemie Group and Criterion Catalysts are
the major catalyst developers and manufacturers for
the styrene industry. Both companies offer a wide
range of catalysts to suit individual processing needs.
Ethylbenzene conversion, styrene selectivity, catalyst
activity, and catalyst stability can be optimized by
selecting the best catalyst or a combination of catalysts
for a particular application. Dow and BASF manufac-
ture proprietary catalysts, which have been mainly for
use in their own respective technologies.
2862
Propylene Oxide with Styrene Co-production
In the late 1960s, a method was discovered to produce
propylene oxide by the epoxidation of propylene using
organic hydroperoxides as the epoxidizing agent.[5]
During the epoxidation reaction, the hydroperoxide
is essentially converted to the corresponding alcohol,
which in turn can be dehydrated to a more desirable
coproduct. Styrene is coproduced in the form of this
process that uses EB hydroperoxide as the epoxidizing
agent. The chemistry of this process can be broken
down into three main reactions as shown in Fig. 1.
The first step is oxidation of EB to form EB hydro-
peroxide. The oxidation is carried out in the liquid
phase with a target EB conversion of approximately
13%.[6] Although higher conversions are attractive
from an EB recovery and recycle standpoint, there is
a significant disadvantage because the EB hydroperox-
ide selectivity declines sharply. The second step is
epoxidation of propylene to form propylene oxide
product and 1-phenylethanol. In the last step, the
1-phenylethanol is dehydrated to styrene and water.
The dehydrated reaction mixture is typically stripped
of light components and rerun in a styrene column to
remove heavy by-products, resulting in a purified
styrene product.
The design and operation of a propylene oxide=
styrene process plant is complicated and includes
numerous pieces of equipment. As a result, the total
investment cost for a commercial-scale plant is about
four times that of an EB dehydrogenation plant to
produce the same quantity of styrene product.
Styrene
COMMERCIAL PRODUCTION
Reactor Design
One important aspect of modern day EB dehydro-
genation reactor design is managing the operating
conditions to minimize thermal reactions. The major
by-product from the thermal reaction of EB to styrene
is benzene with significant subsequent conversions to a
complex mixture of higher aromatics, such as anthra-
cene and=or pyrene, as well as coke. Thermal reactions
do not occur at a significant level below about 600% C,
but become a considerable factor affecting overall yield
when temperatures rise above 655% C.
One technique to reduce thermal reactions is to
delay heating the EB to the reaction inlet temperature
until the last possible moment before being exposed to
the catalyst. The method involves superheating EB
vapor, along with a portion of the dilution steam, to
a temperature below approximately 580% C. The EB is
vaporized with a certain amount of steam—commonly
called primary steam—to suppress coking. The EB
primary steam is combined with the major part of
the dilution steam immediately prior to entering the
dehydrogenation catalyst bed. The major portion of
the dilution steam is generally referred to as main
steam. The main steam is superheated to a temperature
such that, when it is mixed with the EB and the
primary steam, the total combined feed mixture
reaches the desired catalyst inlet temperature.
Reactor design and catalyst bed configuration
are key factors for controlling thermal reactions.
Fig. 1 Propylene oxide–styrene process
chemistry.
Styrene
Commercial adiabatic reactors are typically of radial
flow construction with the flow path moving from in
to out. This radial outflow geometry requires a much
lower inlet volume to obtain proper distribution of
the feed vapor through the catalyst bed than either
an axial flow or a radial inflow reactor configuration.
The radial flow reactor design also provides the advan-
tage of low pressure drop since the flow path through
the catalyst is much shorter relative to an axial flow
reactor. To minimize thermal reactions, the reactor
centerpipe diameter should be as small as possible to
minimize residence time at the highest temperature
throughout the reactor. However, too small a diameter
will produce a high pressure drop through the center-
pipe, potentially causing flow maldistribution and
causing the feed vapor to enter the catalyst bed with
a velocity that can result in erosion and attrition of cat-
alyst particles.
A single-stage reactor with practical limits of
temperature, pressure, and steam dilution is limited
to 40–50% per pass conversion of EB. If the single-
stage reactor effluent is reheated, the reaction mixture
moves away from equilibrium allowing for higher EB
conversion. When the reheated reaction mixture is
fed to a second stage of catalyst, then total EB conver-
sions of 60–75% per pass can be achieved. This process
of reheating and adding catalyst stages can be repeated
as frequently as economically feasible. With each addi-
tional reaction stage, however, a progressively smaller
incremental EB conversion is achieved, generally with
a corresponding decrease in styrene selectivity.
To obtain high EB conversions, typically two or
three reactors are used in series with some type of
reheating between the reactors to raise the temperature
of the reaction mixture. Modern day commercial
2863
reactors are highly engineered. Designers use specia-
lized computational fluid dynamics programs to study
flow characteristics throughout a reactor. S
Commercial Adiabatic Dehydrogenation
Processes
Most commercial styrene plants are based on either the
Lummus=UOP technology or the Fina=Badger technol-
ogy. Dow Chemical is a major styrene producer and uses
its own technology. These technologies are generally
similar, but there are key differences in the details.
Lummus/UOP Classic SMTM Process
The first commercial plant based on the Lummus=
Monsanto technology, which later became the Lummus=
UOP technology, was commissioned in 1972. Since that
time, more than 50 projects have been licensed with more
than 40 plants in commercial operation as of 2004.
A typical Lummus=UOP Classic SM process flow
diagram is shown in Fig. 2. Fresh and recycled EB
are combined with steam and fed to the dehydrogena-
tion reaction section of the plant. The reactor effluent
is condensed and separated into off-gas, process
condensate, and a dehydrogenated mixture. The hydro-
gen rich off-gas stream is recovered through an off-gas
compressor for use as a fuel gas. The process conden-
sate is stripped of organics and either recycled for use
within the styrene plant or exported. The dehydro-
genated mixture, consisting mainly of unconverted
EB, styrene product, benzene, and toluene, is fed to
the distillation section of the plant.
Fig. 2 Lummus=UOP classic SM
process.
2864
The main equipment in the dehydrogenation reac-
tion section of a Lummus=UOP Classic SM plant
includes a steam superheater, two dehydrogenation
reactors, a series of waste heat exchangers, and an
off-gas compressor (Fig. 3). The equipment is designed
to minimize pressure drop from the dehydrogenation
reactors inlet to the off-gas compressor.
The main steam is superheated and used to reheat
the reaction mixture for the second stage dehydrogena-
tor. The reaction mixture is reheated in a specially
designed interchanger located inside the second stage
dehydrogenator vessel shell. The cooled steam exiting
the interchanger is reheated in the steam superheater
prior to being fed to the first stage dehydrogenator.
The superheated steam can range from 700% C to as
high as approximately 850% C to achieve the desired
inlet temperature for the first stage dehydrogenator.
Superheated main steam is mixed with the EB and the
primary steam immediately before entering the first stage
dehydrogenator. The reactor is designed to provide a uni-
form reaction mixture while minimizing residence time in
the centerpipe to avoid thermal reactions. The reactor
effluent is cooled in a series of three waste heat exchan-
gers before final cooling and condensing.
The first stage of waste heat recovery is used to super-
heat the EB and the primary steam. Subsequent stages
are used to generate steam at different pressures. Typi-
cally intermediate pressure steam and low pressure
steam are generated, which are directed for use else-
where in the styrene plant or larger EB–styrene complex.
Hydrogen and light hydrocarbons removed from
the condensed reactor effluent are compressed and
used as fuel gas in the steam superheater. The process
steam from the reactor effluent stream is condensed
and separated by gravity from the liquid hydrocarbon
components. The condensate is stripped of hydrocar-
bons and revaporized for use as process steam.
The distillation section of a Lummus=UOP Classic
SM plant consists of four distillation columns. The first
Styrene
Fig. 3 Lummus=UOP classic SM process
dehydrogenation section.
column in the sequence splits the EB and the lighter
components from styrene. The EB=styrene monomer
(EB=SM) splitter is operated under vacuum and uses
structured packing, such as Sulzer Mellapak Plus
packing, to minimize temperature and polymer forma-
tion.[7] Polymerization inhibitors are injected into the
splitter to restrict polymer formation, in particular into
the bottom section of the column.
The overhead product from the EB=SM splitter is
fed to an EB recovery column. The EB recovery
column net bottoms’ stream is recycled to the dehydro-
genation section. Benzene and toluene by-products in
the recovery column overhead stream are separated
in a benzene=toluene splitter. Oftentimes, the benzene
recovered in this scheme is recycled as feed to the
upstream EB plant.
The EB=SM splitter bottoms’ stream is fed to the
SM column where the styrene is purified by removal
of any heavy residual tars. Tertiary-butyl catechol
(TBC) is injected into the overhead of the SM column,
and the column is operated under vacuum to minimize
polymer formation.
A unique feature of the Lummus=UOP Classic SM
process is the noncompressive azeotropic heat recovery
option.[8] In this option, the EB=SM splitter overhead
vapor is used to boil an EB–water azeotrope mixture,
which is then fed to the dehydrogenation reactors.
The condensation of the splitter overhead vapor
produces approximately 500 kcal=kg styrene. This
energy savings potential makes the azeotropic heat
recovery option economically attractive, in particular,
in regions with moderate to high steam costs.
Lummus/UOP Smart SMTM Process
The Lummus=UOP Smart SM process is based on an
oxidative reheat technology invented by UOP.[9]
Although this technology can be used in the design of
Styrene
a grassroots plant, it is most commonly used in a revamp
of an existing plant to increase styrene production by as
much as 60% with minimal capital investment cost.
The Lummus=UOP Smart SM technology uses
a specially designed reactor that contains two
concentric catalyst zones. A cross-sectional view of
the concentric oxidation and dehydrogenation
catalyst beds is also shown in Fig. 4. In the first zone,
hydrogen is selectively oxidized across a noble metal-
containing catalyst. The direct combustion of hydro-
gen reheats the reaction mixture, which is directly fed
into the second zone where the standard EB dehydro-
genation reaction occurs. In addition to providing the
full reheating requirement, another benefit of this
technology is it shifts the reaction equilibrium in a
favorable direction by removing the hydrogen by-
product. This shift in equilibrium allows for higher
EB conversion without a corresponding decrease in
styrene yield.
2865
Fig. 4 Lummus=UOP smart SM process
dehydrogenation section.
The Lummus=UOP Smart SM technology was first
commercialized in 1995 at Mitsubishi Chemical in
Kashima, Japan. The Mitsubishi Chemical plant was
designed with a dehydrogenation section containing
two combination oxidation–dehydrogenation reactors
as shown in Fig. 4.
The temperature rise in the oxidation zone is
proportional to the amount of oxygen reacted across
the catalyst bed. The oxygen is diluted in steam and
the oxygen=steam mixture is well mixed to ensure the
reaction mixture remains outside the flammability
envelope at all times.
Fina/Badger Styrene Process
The Fina=Badger styrene process has evolved through
many generations. The most recent design uses a flow
diagram as shown in Fig. 5. Recycled and fresh EB
Fig. 5 Fina=Badger styrene pro-
cess.
2866
are mixed with steam and fed to the primary and the
secondary dehydrogenation reactors. The reactor efflu-
ent is condensed and separated into vent gas, conden-
sate, and hydrocarbon. The vent gas, the majority of
which is hydrogen, is used as fuel gas. The condensate
is stripped and used as feed water for steam generation.
The hydrocarbon portion of the reactor effluent is fed
to the distillation section of the plant, which consists of
three distillation columns.
The main types of equipment in the dehydrogena-
tion section of the plant are the steam superheater,
the primary and secondary dehydrogenation reactors,
and a series of feed=effluent exchangers (Fig. 6). High
pressure steam is also generated by the recovery of heat
from the reactor effluent stream.
The major portion of steam is superheated and
used to reheat the reaction mixture for the secondary
dehydrogenation reactor. As the cooled steam exits
the reheater it is superheated again in the steam
superheater, prior to being fed to the primary
dehydrogenation reactor. The dehydrogenation reac-
tors are designed to provide low pressure drop and
uniform flow distribution. The reactor effluent is
cooled in a series of three heat exchangers that heat
the EB and steam feed to the reactors and generate
steam.
The Fina=Badger distillation section consists of
three distillation columns. All the columns are
designed to operate under vacuum to minimize tem-
perature and polymer formation. The first column
in the sequence splits the benzene and toluene by-
products from the unconverted EB and styrene pro-
duct. The benzene and toluene mixture is typically sent
to an integrated EB plant where it is further fractio-
nated. In this case, the benzene by-product is ulti-
mately consumed in the EB unit and the toluene
becomes a by-product stream from the EB plant.
Styrene
Fig. 6 Fina=Badger styrene process dehydro-
genation section.
The EB recycle column separates the unconverted EB
for recycle to the dehydrogenation reactors. Recent EB
recovery columns use high efficiency packing to obtain
minimum pressure drop through the column. This
allows the column bottoms’ temperature to be main-
tained below 100% C. This is an important aspect of the
design as styrene polymerization becomes significant at
temperatures higher than approximately 100% C.
The EB recovery column bottoms’ stream is fed to a
finishing column where the styrene is purified by the
removal of any heavy residue. Tertiary-butyl catechol
is injected into the overhead of the finishing column
to prevent polymerization. Tertiary-butyl catechol is
widely used to prevent styrene polymerization during
storage.
In 1997, Fina=Badger joined with Shell Technology
Ventures, a subsidiary of Shell Oil Company, to develop
a reheating technology called Flameless Distributed
Combustion (FDC) for application in EB dehydrogena-
tion.[10] Flameless Distributed Combustion technology is
patented by Shell Oil Company and was originally used
as a heat injector for enhanced recovery of hydrocarbons
from subterranean formations.
Flameless Distributed Combustion technology
enables specific constraints in the conventional dehy-
drogenation system to be overcome, in particular
designing for low steam-to-oil ratios. A low steam-to-
oil ratio is desirable because of the substantial energy
savings associated with superheating less steam. How-
ever, a practical lower steam-to-oil ratio limit exists
due to the metallurgy of the steam superheater, steam
transfer lines, and interstage reheater. Flameless
Distributed Combustion allows for operation at molar
steam-to-oil ratios less than 7 : 1 without a costly
metallurgy upgrade. This is accomplished by heating
the reaction mixture more directly through a combus-
tion and convective heat transfer process.
Styrene 2867

Flameless Distributed Combustion technology,
unlike the Lummus=UOP Smart SM technology, does
not directly combust hydrogen from the reaction
mixture; hence it does not obtain the benefit of a favor-
able shift in equilibrium.
identified catalyst formulations that provide more
than 90% conversion of 4-vinylcyclohexene with
approximately 92% selectivity to styrene.[11] S
Storage

Other Processes Preventing polymerization is the key to successful styr-

Propylene oxide/styrene process
Aside from EB dehydrogenation, the only other commer-
cial-scale production of styrene is through a propylene oxi-
de=styrene process that produces roughly 15% of
worldwide styrene. This technology was developed as an
alternative to the chlorohydrin method for producing
propylene oxide.
Styrene from Butadiene
Because the conventional EB dehydrogenation
technologies are relatively mature, there is little room
for significant additional reduction in production
costs. This situation has motivated a lot of research
toward using alternative, lower cost feedstocks for styrene
production. One area that has been examined involves
a two-step process to convert butadiene to styrene.
The first step of the process involves the cyclo-
dimerization of butadiene to 4-vinylcyclohexene. The
reaction is exothermic and can be catalyzed by either a
copper-containing zeolite catalyst or an iron dinitrosyl
chloride catalyst complex. Although both vapor-phase
and liquid-phase processes have been studied, it
appears that liquid-phase reactions are preferred
because they achieve higher butadiene conversion
levels. The second step is oxidative dehydroge-
nation of the 4-vinylcyclohexene to produce styrene.
Dow has led the research effort in this area and has
ene storage. Special handling and storage procedures
are required to maintain the styrene product quality
and to avoid a potentially dangerous situation invol-
ving uncontrolled polymerization.
During storage, styrene polymerization is prevented
by maintaining low temperature and using an appropri-
ate polymerization inhibitor. The industry standard
styrene storage inhibitor is TBC and is typically used
at concentrations between 10 ppm and 15 ppm. To be
effective, TBC requires dissolved oxygen to be present in
concentrations roughly equal to the TBC concentration.
In addition to adding TBC inhibitor, maintaining
the styrene at the lowest practical temperature is criti-
cal to preserving product quality. Styrene storage facil-
ities are generally maintained at temperatures below
about 20! C, which allows for storage times of around
10 weeks. Even a 5! C increase in the storage tempera-
ture to 25! C can reduce the storage time to less than 4
weeks.[12] Tertiary-butyl catechol is added occasionally
during storage to maintain the concentration in the
desired range.
ECONOMICS
The cost of styrene production can be broken down
into three main components: raw materials, utilities,
and the fixed cost associated with the plant.
The utilities cost includes fuel, electricity, steam,
cooling water, catalyst, and chemical costs required to

Table 2 Styrene economics for conventional EB dehydrogenation process

Quantity Price Cost
UNIT UNIT/MT $/UNIT $/MT
Produce
Styrene MT 1.0000 751 751.0
Raw materials
Ethylene MT 0.2912 629 183.2
Benzene MT 0.7898 453 357.8
By-product credits
Toluene MT 0.0401 378 (15.1)
Light ends MT 0.0401 289 (11.6)
Net feedstock costs 514.2
Utilities 95.0
Fixed cost 35
Total cost of production 644.2
Basis: North America, 2003
2868 Styrene

Fig. 7 Distribution of styrene production

cost components.

operate the plant. The major cost components for
styrene production using conventional adiabatic
dehydrogenation process are listed in Table 2. The major
cost of production is for the ethylene and benzene raw
materials, which account for approximately 80% of the
total cost of production. The benzene cost is the largest
cost component; hence, the economics of styrene
production are highly dependent on benzene price.
The raw materials cost has two components—one
dictated by the stoichiometry and the other caused by

Table 3 Styrene economics for propylene oxide-styrene process

Quantity Price Cost
UNIT UNIT/MT $/UNIT $/MT
Product
Styrene MT 1.0000 751 751.0
Raw materials
Ethylene MT 0.3135 629 197.2
Benzene MT 0.8194 453 371.2
Propylene MT 0.3541 465 164.6
Oxygen MT 0.2529 43 10.9
By-product credits
Light ends MT 0.1000 289 (28.9)
Propylene oxide MT 0.4500 1227 (552.1)
Tars MT 0.0400 257 (10.3)
Net feedstock costs 152.6
Utilities 65.0
Fixed cost 95
Total cost of production 312.6
Basis: North America, 2003
Styrene
yield losses occurring as a result of the process technol-
ogy. If the unalterable stoichiometric raw material con-
sumption is removed from the cost of production, the
resultant distribution of cost components appears very
different, as shown in Fig. 7. From this perspective, the
raw materials’ cost is only about 15% of the incremen-
tal cost of production and the utilities and fixed costs
become dominant. Recent catalyst and process design
improvements have reduced the variable costs of styr-
ene production, while ever-increasing complexity and
more stringent regulations have greatly increased the
fixed costs. Other recent trends, such as larger plant
capacities and globalization of the styrene market, have
also resulted in higher fixed costs.[13]
The result of the shift of focus from variable to fixed
costs is that plants are being designed for larger capa-
cities. For example in 2003, typical new styrene plants
in the Asia Pacific Region produced an average of 350
KMTA styrene per year, nearly double the capacity of
typical plants started up just 5 years earlier. The drive
to reduce fixed costs has led to numerous revamps of
existing plants to substantially increase capacity. In
many cases, capacity expansions on the order of 50%
are being implemented.
The propylene oxide=styrene process, the only other
commercial process for production of styrene, is a grow-
ing influence on the overall styrene market economics.
When viewed from the perspective that styrene is the
primary product and propylene oxide is a by-product,
the economics of this process appear encouraging (Table
3). Depending on the credit value assigned to the propy-
lene oxide coproduct, the total cost of styrene produc-
tion can be approximately 50% of conventional EB
dehydrogenation technology. Approximately 33% of
the styrene capacity added between 1998 and 2003 was
produced using propylene oxide=styrene technology.
More recently, the trend appears to be reversing and
propylene oxide=styrene processes are accounting for
less of newly installed capacity. Although propylene
oxide=styrene plants are built to produce propylene
oxide, there is a profound impact on the styrene market
supply=demand balance.
CONCLUSIONS
Since the first commercial-scale production in the
1930s, styrene, mainly through its derivatives, has
become an integral part of life. Most people come in
contact with numerous styrene-based products
throughout the course of a normal day. Demand for
styrene is expected to continue growing at a rate com-
parable to the gross domestic product growth rate.
The chemical processing technologies that have been
developed are sophisticated, producing styrene to meet
the demand at low cost. Research and development
2869
efforts are aimed at further improvements in existing
technologies and identification of new technologies
for styrene production opportunities. S
REFERENCES
1. Lidback, A. Styrene—This is Not a Drill, 2004
World Petrochemical Conference, Chemical
Marketing Associates, Inc.: Houston: TX, March
23–25, 2004.
2. Carra, S.; Forni, L. Kinetics of catalytic dehydro-
genation of ethylbenzene to styrene. Ind Eng
Chem Process Des. Dev. 1965, 4 (3), 281–285.
3. Matsui, J.; Sodesawa, T.; Nozaki, F. Influence of
carbon dioxide addition upon decay of activity of
a potassium-promoted iron oxide catalyst for
dehydrogenation of ethylbenzene. Appl. Catal.
1991, 67, 179–188.
4. Hirano, T. Roles of potassium in potassium-pro-
moted iron oxide catalyst for dehydrogenation of
ethylbenzene. Appl. Catal. 1986, 26, 65–79.
5. Kollar, J. Epoxidation Process. US Patent
3,351,635, November 7, 1967.
6. Chem Systems, Propylene Oxide 97=98–7,
Tarrytown, New York, 1998.
7. Mullen, P. Enhancements in EB=SM technology.
In AIChE 2003 Spring Meeting Proceedings;
AIChE Spring National Meeting. Houston: TX,
April 22–26, 2001.
8. Sardina, H. Dehydrogenation Process for
Production of Styrene from Ethylbenzene Com-
prising Low Temperature Heat Recovery and
Modification of the Ethylbenzene–Styrene Feed
therewith. US Patent 4,628,136, December 9, 1986.
9. Imai, T. Dehydrogenation of Dehydrogenatable
Hydrocarbons. US Patent 4,435,607, March 6,
1984.
10. Welch, V. Advanced styrene dehydrogenation
with flameless distributed combustion. In AIChE
2003 Spring Meeting Proceedings; AIChE Spring
National Meeting. Houston: TX, April 22–26,
2001.
11. Chem Systems PERP Report, Styrene from Buta-
diene, 93S3, Tarrytown, New York, 1995.
12. Technical Bulletin on Safe Handling & Storage of
Styrene Monomer http:==www.sterlingchemicals.
com=SCI=WEBSITE=scihome.nsf=(WebContent-
ByDocID)=0AF6F53F1881D0AA8626CD90082
E36A?OpenDocument.
13. Ram, S. EB-SM splitter energy recovery options.
In Styrene Conference General Session, Styrene
Conference, Prague, Czech Republic, June 22–
25, 2003; ABB Lummus Global, Sud-Chemie
AG, and UOP LLC, 2003.