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Styrene

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

INTRODUCTION Styrene is one of the most important aromatic monomers used for the manufacture of plastics. Small-scale commercial production of styrene began in the 1930s. Demand for styrene-based plastics has grown signicantly, and in 2003 the worldwide annual production capacity was approximately 24.5 million metric tons.[1] About 65% of styrene is used to produce polystyrene. Polystyrene is used in the manufacture of many commonly used products such as toys, household and kitchen appliances, plastic drinking cups, housings for computers and electronics, foam packaging, and insulation. Polystyrene nds such widespread use because it is relatively inexpensive to produce and is easy to polymerize and copolymerize, resulting in plastics with a broad range of characteristics. In addition to polystyrene, styrene is used to produce acrylonitrilebutadiene styrene polymer, styreneacrylonitrile polymer, and styrenebutadiene synthetic rubber (SBR). The development of styrene technologies was mainly driven by demand for cheap synthetic rubber during and immediately after World War II. Between 5% and 10% of total styrene produced becomes a component of synthetic rubbers, which are copolymers of styrene and butadiene (SBR). Styrene copolymers containing acrylonitrile are specialty materials that are used for specic applications. Demand for styrene for the period 20042009 is estimated to grow at a rate of approximately 4% per year.[1]

its unsaturated side chain and aromatic ring. For example, styrene can be oxidized to form benzoic acid, benzaldehyde, styrene oxide, and other oxygenated compounds. Styrene oxide is used in the production of various cosmetics, perfumes, agricultural and biological chemicals.

REACTION KINETICS AND THERMODYNAMICS Essentially all commercially produced styrene uses ethylbenzene (EB) as a feedstock. Between 85% and 90% of worldwide styrene production is based on EB dehydrogenation. The remaining 1015% of styrene is obtained as a coproduct in a process to produce propylene oxide.

Ethylbenzene Dehydrogenation Ethylbenzene is catalytically dehydrogenated in the presence of steam according to the equation:

CH3

CH2

H2

PHYSICAL AND CHEMICAL PROPERTIES Styrene is a colorless aromatic liquid. It is only very slightly soluble in water, but innitely 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 acrylonitrile, 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 dened as: Keq Psty Ph2=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
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Table 1 Physical properties of styrene Molecular weight Specic gravitya Melting point, C Boiling point,  C Critical temperature, C Critical pressure, atm Vapor pressure, mm Hg at T  C
a

104.152 0.903 30.628 145.2




373 46.1 1 7.0 5 18.0 20 30.8 10 44.6 40 59.8 60 69.5 100 82.0 200 101.3 400 122.5 760 145.2

Density is at 20 C referred to water at 4 C. (From Perry, R.H., Green, D.W., Eds.; Perrys 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 equation:[2]

according

to

the

following

The key dealkylation reactions can be described by the following equations:


CH3

ln Keq 16:12 15; 350=T where Keq is the equilibrium constant in atmospheres and T is the temperature in K. 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 and reduce EB conversion. Lower pressure results in greater EB conversion without an accompanying signicant decrease in styrene selectivity. Another method to create a positive shift in 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 pressure. Steam dilution has several other important benets. First, steam supplies heat to the reacting mixture. Consequently, the drop in temperature for a given EB conversion is lower, allowing greater EB conversions to be obtained with the same inlet temperature. Second, a minimum amount of steam appears to keep the catalyst in the required oxidation state for high activity. The actual quantity of steam varies with the type of catalyst used. Third, steam is believed to suppress the deposition of carbonaceous material on the catalyst. If the carbonaceous material is allowed to accumulate, the catalyst will become fouled and its activity will decline to unacceptable levels. The reaction feed mixture undergoes certain other reactions that are not equilibrium limited under typical operating conditions. Most important among these are the dealkylation reactions that result in the formation of benzene and ethylene or toluene and methane. Other reactions produce small amountsof a-methylstyrene and other high boiling components.

H 2C

CH2

CH3

CH3

H2

CH4

Both methane and ethylene undergo steam reforming reactions according to the following equations: CH4 H2 O ! CO 3H2

C2 H4 2H2 O ! 2CO 4H2 The watergas shift reaction also occurs and is generally near equilibrium at the reaction temperature: CO H2 O $ CO2 H2 The combination of dealkylation, steam reforming, and watergas shift side reactions should be avoided, if possible. In addition to losing valuable EB feed by dealkylation, the resultant net formation of carbon dioxide and hydrogen by this combination of reactions inhibits the primary dehydrogenation reaction. The net hydrogen formation gives an unfavorable shift in equilibrium, while the presence of carbon dioxide has a negative effect on dehydrogenation catalyst activity.[3]

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Typically, there is less methane and ethylene present in the efuent 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 temperature. 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 rst 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 dealkylation reactions, which form benzene and toluene by-products. In particular, as temperature is increased, the rate of benzene formation increases signicantly 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. Reaction 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 performance. Too little catalyst will prevent a close approach to equilibrium. If EB conversion is low, then distillation costs associated with recovery and recycle of the unconverted EB can become signicant. 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 onstream, 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 signicant increase in the volume of reactants due to the reaction stoichiometry. Lower pressure favors higher

equilibrium conversion to styrene. Reaction pressure is established during the plant design at the lowest practical level. Modern commercial reactors operate below atmospheric pressure. Pressures as low as 300 mm Hg or lower are common. The key side reactions 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 catalysts 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 promoters. 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 benets. 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 manufacture proprietary catalysts, which have been mainly for use in their own respective technologies.

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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 rst step is oxidation of EB to form EB hydroperoxide. 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 signicant disadvantage because the EB hydroperoxide 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 puried 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.

COMMERCIAL PRODUCTION Reactor Design One important aspect of modern day EB dehydrogenation 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 signicant subsequent conversions to a complex mixture of higher aromatics, such as anthracene and=or pyrene, as well as coke. Thermal reactions do not occur at a signicant 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 steamcommonly called primary steamto 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 conguration are key factors for controlling thermal reactions.

Fig. 1 Propylene oxidestyrene process chemistry.

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Commercial adiabatic reactors are typically of radial ow construction with the ow path moving from in to out. This radial outow geometry requires a much lower inlet volume to obtain proper distribution of the feed vapor through the catalyst bed than either an axial ow or a radial inow reactor conguration. The radial ow reactor design also provides the advantage of low pressure drop since the ow path through the catalyst is much shorter relative to an axial ow 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 centerpipe, potentially causing ow maldistribution and causing the feed vapor to enter the catalyst bed with a velocity that can result in erosion and attrition of catalyst particles. A single-stage reactor with practical limits of temperature, pressure, and steam dilution is limited to 4050% per pass conversion of EB. If the singlestage reactor efuent 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 conversions of 6075% per pass can be achieved. This process of reheating and adding catalyst stages can be repeated as frequently as economically feasible. With each additional 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

reactors are highly engineered. Designers use specialized computational uid dynamics programs to study ow characteristics throughout a reactor.

Commercial Adiabatic Dehydrogenation Processes Most commercial styrene plants are based on either the Lummus=UOP technology or the Fina=Badger technology. 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 rst 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 ow diagram is shown in Fig. 2. Fresh and recycled EB are combined with steam and fed to the dehydrogenation reaction section of the plant. The reactor efuent is condensed and separated into off-gas, process condensate, and a dehydrogenated mixture. The hydrogen rich off-gas stream is recovered through an off-gas compressor for use as a fuel gas. The process condensate is stripped of organics and either recycled for use within the styrene plant or exported. The dehydrogenated 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.

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Fig. 3 Lummus=UOP classic SM process dehydrogenation section.

The main equipment in the dehydrogenation reaction 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 dehydrogenator. 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 rst 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 rst stage dehydrogenator. Superheated main steam is mixed with the EB and the primary steam immediately before entering the rst stage dehydrogenator. The reactor is designed to provide a uniform reaction mixture while minimizing residence time in the centerpipe to avoid thermal reactions. The reactor efuent is cooled in a series of three waste heat exchangers before nal cooling and condensing. The rst stage of waste heat recovery is used to superheat the EB and the primary steam. Subsequent stages are used to generate steam at different pressures. Typically intermediate pressure steam and low pressure steam are generated, which are directed for use elsewhere in the styrene plant or larger EBstyrene complex. Hydrogen and light hydrocarbons removed from the condensed reactor efuent are compressed and used as fuel gas in the steam superheater. The process steam from the reactor efuent stream is condensed and separated by gravity from the liquid hydrocarbon components. The condensate is stripped of hydrocarbons and revaporized for use as process steam. The distillation section of a Lummus=UOP Classic SM plant consists of four distillation columns. The rst

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 formation.[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 dehydrogenation 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 puried 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 EBwater 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

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Fig. 4 Lummus=UOP smart SM process dehydrogenation section.

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 rst zone, hydrogen is selectively oxidized across a noble metalcontaining catalyst. The direct combustion of hydrogen reheats the reaction mixture, which is directly fed into the second zone where the standard EB dehydrogenation reaction occurs. In addition to providing the full reheating requirement, another benet of this technology is it shifts the reaction equilibrium in a favorable direction by removing the hydrogen byproduct. This shift in equilibrium allows for higher EB conversion without a corresponding decrease in styrene yield.

The Lummus=UOP Smart SM technology was rst commercialized in 1995 at Mitsubishi Chemical in Kashima, Japan. The Mitsubishi Chemical plant was designed with a dehydrogenation section containing two combination oxidationdehydrogenation 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 ammability envelope at all times.

Fina/Badger Styrene Process The Fina=Badger styrene process has evolved through many generations. The most recent design uses a ow diagram as shown in Fig. 5. Recycled and fresh EB

Fig. 5 Fina=Badger styrene process.

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Fig. 6 Fina=Badger styrene process dehydrogenation section.

are mixed with steam and fed to the primary and the secondary dehydrogenation reactors. The reactor efuent is condensed and separated into vent gas, condensate, 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 efuent is fed to the distillation section of the plant, which consists of three distillation columns. The main types of equipment in the dehydrogenation section of the plant are the steam superheater, the primary and secondary dehydrogenation reactors, and a series of feed=efuent exchangers (Fig. 6). High pressure steam is also generated by the recovery of heat from the reactor efuent 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 reactors are designed to provide low pressure drop and uniform ow distribution. The reactor efuent 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 temperature and polymer formation. The rst column in the sequence splits the benzene and toluene byproducts from the unconverted EB and styrene product. The benzene and toluene mixture is typically sent to an integrated EB plant where it is further fractionated. In this case, the benzene by-product is ultimately consumed in the EB unit and the toluene becomes a by-product stream from the EB plant.

The EB recycle column separates the unconverted EB for recycle to the dehydrogenation reactors. Recent EB recovery columns use high efciency packing to obtain minimum pressure drop through the column. This allows the column bottoms temperature to be maintained below 100 C. This is an important aspect of the design as styrene polymerization becomes signicant at temperatures higher than approximately 100 C. The EB recovery column bottoms stream is fed to a nishing column where the styrene is puried by the removal of any heavy residue. Tertiary-butyl catechol is injected into the overhead of the nishing 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 dehydrogenation.[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 specic constraints in the conventional dehydrogenation system to be overcome, in particular designing for low steam-to-oil ratios. A low steam-tooil ratio is desirable because of the substantial energy savings associated with superheating less steam. However, 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 combustion and convective heat transfer process.

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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 benet of a favorable shift in equilibrium. Other Processes Propylene oxide/styrene process Aside from EB dehydrogenation, the only other commercial-scale production of styrene is through a propylene oxide=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 signicant 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 rst step of the process involves the cyclodimerization 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 dehydrogenation of the 4-vinylcyclohexene to produce styrene. Dow has led the research effort in this area and has

identied catalyst formulations that provide more than 90% conversion of 4-vinylcyclohexene with approximately 92% selectivity to styrene.[11] Storage Preventing polymerization is the key to successful styrene storage. Special handling and storage procedures are required to maintain the styrene product quality and to avoid a potentially dangerous situation involving uncontrolled polymerization. During storage, styrene polymerization is prevented by maintaining low temperature and using an appropriate 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 critical to preserving product quality. Styrene storage facilities 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 temperature 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 xed 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 UNIT Produce Styrene Raw materials Ethylene Benzene By-product credits Toluene Light ends Net feedstock costs Utilities Fixed cost Total cost of production
Basis: North America, 2003

Quantity UNIT/MT 1.0000 0.2912 0.7898 0.0401 0.0401

Price $/UNIT 751 629 453 378 289

Cost $/MT 751.0 183.2 357.8 (15.1) (11.6) 514.2 95.0 35 644.2

MT MT MT MT MT

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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 componentsone dictated by the stoichiometry and the other caused by

Table 3 Styrene economics for propylene oxide-styrene process UNIT Product Styrene Raw materials Ethylene Benzene Propylene Oxygen By-product credits Light ends Propylene oxide Tars Net feedstock costs Utilities Fixed cost Total cost of production
Basis: North America, 2003

Quantity UNIT/MT 1.0000 0.3135 0.8194 0.3541 0.2529 0.1000 0.4500 0.0400

Price $/UNIT 751 629 453 465 43 289 1227 257

Cost $/MT 751.0 197.2 371.2 164.6 10.9 (28.9) (552.1) (10.3) 152.6 65.0 95 312.6

MT MT MT MT MT MT MT MT

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yield losses occurring as a result of the process technology. If the unalterable stoichiometric raw material consumption 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 incremental cost of production and the utilities and xed costs become dominant. Recent catalyst and process design improvements have reduced the variable costs of styrene production, while ever-increasing complexity and more stringent regulations have greatly increased the xed costs. Other recent trends, such as larger plant capacities and globalization of the styrene market, have also resulted in higher xed costs.[13] The result of the shift of focus from variable to xed costs is that plants are being designed for larger capacities. For example in 2003, typical new styrene plants in the Asia Pacic 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 xed 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 growing inuence 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 propylene oxide coproduct, the total cost of styrene production 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.

efforts are aimed at further improvements in existing technologies and identication of new technologies for styrene production opportunities.

REFERENCES 1. Lidback, A. StyreneThis is Not a Drill, 2004 World Petrochemical Conference, Chemical Marketing Associates, Inc.: Houston: TX, March 2325, 2004. 2. Carra, S.; Forni, L. Kinetics of catalytic dehydrogenation of ethylbenzene to styrene. Ind Eng Chem Process Des. Dev. 1965, 4 (3), 281285. 3. Matsui, J.; Sodesawa, T.; Nozaki, F. Inuence of carbon dioxide addition upon decay of activity of a potassium-promoted iron oxide catalyst for dehydrogenation of ethylbenzene. Appl. Catal. 1991, 67, 179188. 4. Hirano, T. Roles of potassium in potassium-promoted iron oxide catalyst for dehydrogenation of ethylbenzene. Appl. Catal. 1986, 26, 6579. 5. Kollar, J. Epoxidation Process. US Patent 3,351,635, November 7, 1967. 6. Chem Systems, Propylene Oxide 97=987, 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 2226, 2001. 8. Sardina, H. Dehydrogenation Process for Production of Styrene from Ethylbenzene Comprising Low Temperature Heat Recovery and Modication of the EthylbenzeneStyrene 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 ameless distributed combustion. In AIChE 2003 Spring Meeting Proceedings; AIChE Spring National Meeting. Houston: TX, April 2226, 2001. 11. Chem Systems PERP Report, Styrene from Butadiene, 93S3, Tarrytown, New York, 1995. 12. Technical Bulletin on Safe Handling & Storage of Styrene Monomer http:==www.sterlingchemicals. com=SCI=WEBSITE=scihome.nsf=(WebContentByDocID)=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.

CONCLUSIONS Since the rst 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 comparable 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

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