1. Historical Profile 1.

1 Introduction to Ethyl Benzene (EB): Ethyl benzene is an organic chemical compound which is an aromatic hydrocarbon (HC). Its major use is in th petrochemical industry as an intermediate compound for the production of styrene, which in turn is used for making polystyrene, a commonly used plastic material. Although often present in small amounts in crude oil, ethyl benzene is produced in bulk quantities by combining the petrochemicals benzene and ethylene in an acid-catalyzed chemical reaction. Catalytic hydrogenation of the ethyl benzene then gives hydrogen gas and styrene, which is vinyl benzene. Ethyl benzene is also an ingredient in some paints. Ethyl Benzene is used almost exclusively as intermediate in the production of styrene monomer. It is produced by liquid phase alkylations or vapour phase alkylations of benzene with ethylene. Commercial production started in the 1930s and has grown to over 23 million metric annually (MTA) 1.2 History of Ethyl Benzene: The alkylation of HC with olefins in the presence of AlCl3 catalyst was first practiced by M.Balsohn in 1879. However, Charles Friedel & James M. Crafts pioneered much of early research on alkylation & AlCl3 catalyst .Over a century later, the process that employ the classic Friedel-Crafts reaction chemistry remain a dominant source of EB. Ethyl benzene was first produced on a commercial scale in the 1930s by Dow Chemical in US and by BASF in the Federal Republic of Germany. Until 1980s , almost all ethyl benzene was manufactured with an aluminium chloride catalyst using a Freidal Crafts reaction mechanism . A few EB production units employed a different Freidal-Crafts catalyst, boron trifluoride. Small amount of EB also recovered as a by product from mixed xylenes streams using a very intensive distillation process. In 1980s ,the first commercial facility using a zeolite based process and the absence of maintenance and environmental problems associated with the Freidal-Crafts catalyst have allowed zeolite catalyst and to completely displace the order catalyst in all modern production facilities. The4first zeolite process was based on vapour phase reactor at temp. of over 4000C. In this temperature range, reaction such as isomerisation/cracking and hydrogen transfer produce a number of by products that contaminate the EB product. Efforts were made to reduce by-product formation by changing reaction condition, but it was not until the advent of liquid phase processes operating at temperatures lower than 2700C that zeolite catalysed processes were truly capable of producing high

purity EB . The first high purity zeolite based on technology developed by UOP and ABB Lummus Global , started up in the 1990. The Ethyl benzene- Styrene industry remained relatively insignificant until World War 2. The tremendous demand for synthetic SBR during world war prompted accelerated technology improvements and tremendous capacity expansion. This enormous wartime effort led to the construction of several large scale factories, turning styrene production quickly in to a giant industry. In 1965, 10% of EB production was from super fraction of on a commercial scale in the 1930s by Dow Chemical in US and by BASF in the Federal Republic of Germany. 1.3 Natural Occurrences: Ethyl benzene is a colourless, flammable liquid that smells like gasoline. It is naturally found in coal tar and petroleum and is also found in manufactured products such as inks, pesticides, and paints.

2. Applications
2.1 Current Applications: All commercial EB production is captive consumed for the manufacture of styrene monomer Styrene is used in the production of poly styrene and a wide range of other plastics. Of the other minor applications, the most significant in the paint industry as a solvent. Even smaller volumes go towards the production of acetophenone, diethyl benzene & ethyl anthraquinone. 2.2 Product Specification The product specification on EB is set to provide a satisfactory feedstock to the associated styrene unit. Objectionable impurities in the EB can be grouped in to two categories: a) Halides b) Diethylbenzene Purity Benzene Toluene O-xylene+cumene m,p-xylene Allylbenzene Diethylbenzene Total chlorides Total original sulphur Reactivity density@150 C APHA color 99.5 wt% min. 0.1-0.3% 0.1-0.3% 0.02% max 0.02% max 0.2% 20mg/kg max 1-3 mg/kg max 4 mg/kg max 0.869-0.872 15 max

Manufacturing Capacities: PRODUCER BP Chemicals, Texas City, TX Chevron, St. James, LA Cos-Mar, Carville, LA Dow, Freeport, TX Huntsman, Odessa, TX Lyondell Chemical, Channelview, TX Nova, Bayport, TX Sterling, Texas City, TX Westlake, Lake Charles, LA Total CAPACITY* 1,100 1,800 2,200 1,900 350 3,000 1,400 2,000 380 14,130

*Millions of pounds per year of Ethyl benzene (EB). In INDIA From Chemical Weekly Buyers Guide 2005- Vol.3

Pashim Petrochem Ltd. Amol Chemicals & Polymers Chemaroma Drug House Chemico Forum Enterprizes Ganesh Trading Co. Manish Chemicals Mikit Chemicals Om Chemi Pharma Perfect Chemicals Solvchem Tanay Corporation

3. MARKET SURVEY 3.1 Current & Projected Demand: Demand ( till 2004): 1999: 13,193 million pounds 2000: 13,444 million pounds 2004: 14,552 million pounds Growth Historical (1995 - 2000): 0.7 percent per year. Strength EB demand runs parallel to that of styrene, and styrene is a mature and stable commodity, used in many homo-polymer, copolymer and ter-polymer applications. These applications cover a wide scope in industrial, consumer and medical products. Weakness EBs major shortcoming is that it is essentially a one market segment product styrene. Moreover, as the styrene is produced with captive EB there is not much noticeable market activity. 3.2 Price & Price Variations: PRICE Historical (1995 - 2000): High, $0.25 per pound, bulk, f.o.b. Houston, TX, list ($ 0.5511 / Kg) By Friday 8 August, 2008: EB was valued at $1,554-1,570/tonne FOB NWE ($ 1.5541.570 / Kg) Price Variations: The US unit sales value of EB in $/Kg from 1960 1986: Year 1960 1965 1970 1973 Sales ( $/Kg) 0.13 0.09 0.09 0.11
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1974 1975 1978 1979 1980 1983 1986 3.3 Application wise Consumption Pattern: Application Styrene Production Paint industry as a solvent

0.37 0.20 0.24 0.35 0.50 0.51 0.480.51

Consumption ( in % ) 99 % < 1%

Production of Acetophenone, Diethylbenzene,Ethyl < 1% anthraquinone 3.4 Site Considerations: Before any site selection work begins the company should be organized for expansion planning in a way that depends on the size of the firm. A company may want to utilize a standing committee, a special project team or planning by one person. In any event the planning function must be clear cut responsibility of one individual. Site Selection Factor: 1. Markets 2. Work force 3. Unionization 4. Transportation 5. Energy 6. Business climate 7. Water and waste systems 8. Living conditions 9. Topography

The basic aim of the site selector is to choose a location that maximizes income and minimizes cost compromises usually have to be made. No site is ever perfect, and it is the mission of the site selection team to weigh the alternatives and compromises on the best choice. Plant layout: Plant layout involves developing physical equipment for a processing facility. The development must affect a balance of equipment spacing and integration of specific systems related to facility as a whole. Some of the factors to be considered for designing the plant layout are: 1. Process 2. Economics 3. Client requirements 4. Operation 5. Erection and maintenance 6. Safety 7. Environment 8. Appearance 9. Expansion In-line plant layouts are made in various arrangements which often are referred to by letter designation. Various configurations are formed based on the main artery of the process unit i.e. the pipe rack, which contains long process and the utility lines that connect distant equipment and product piping entering and leaving the plant. Space for instrument and electrical feeders is allocated in the pipe rack such that they are connected to the related equipment. This area is kept free of piping and its related supports. Generally an I shaped plot is used for small process and an H-shape plot for larger units. In developing the plant layout for a chemical plant, it is essential that the firm decisions are made early as to equipments arrangement. This eliminates changes, which cost man-hours as the job progresses through engineering and design. The distillation sections are based on a grade-level process plant layout configuration. The steam generation and power facilities are housed in a building. The basic arrangement follows the equipment spacing charts and clearance tables. Based on all above factors
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we have selected Mumbai as our plant site due to good availability of raw materials as well as for better market. The word Utilities is now generally used for the ancillary services needed in the operation of any production process. These services will normally be supplied from a central site facility; and will include: 1. Electricity. 2. Steam, for process heating. 3. Cooling water. 4. Water for general use. 5. Demineralised water. 6. Compressed air. 7. Inert-gas supplies. 8. Refrigeration. 9. Effluent disposal facilities.

A Typical Site Plan

4. Properties 4.1 Physical Properties: Under ordinary conditions, EB is a clear liquid with a characteristic aromatic odor. EB is an irritant to the skin & eyes and is ordinary toxic by ingestion and skin adsorption. The properties are as follows: IUPAC Name Other names Identifiers CAS Number RTECS Number SMILES Molecular Formula Molar Mass Appearance Density (at 150 c) Density ( at 200 c) Density ( at 250 c) M.P. B.P. ( at 101.3 K Pa) Refractive index (at 200 c) Refractive index ( at 250 c ) Critical pressure Critical temperature Flash point Auto ignition temperature Flammability limit ( lower) Flammability limit ( Upper) Latent heat ( fusion) Latent heat ( vaporization) Heating value ( gross) Heating Value ( net) Kinematic viscosity (at 37.8 0 c ) Kinematic viscosity (at 98.90 c ) Ethylbenzene Ethylbenzol, EB, Phenylethane [100-41-4] DA0700000 c1ccccc1CC C8H10 106.167 g/mol Colourless liquid 0.87139 g/cc 0.8669 g/cc 0.86262 g/cc -94.949 0 c 136.860 c 1.49588 1.49320 3609 K Pa (36.09 bar) 344.02 0 c 150 c 4600 c 1.0% 1.5% ----86.3 j/kg 335 j/kg 42999 j/kg 40928 j/kg 0.6428 * 10 -6 m2 / s 0.390 * 10 -6 m2 / s

Surface Tension Specific heat capacity ( ideal gas, 250 C) Specific heat capacity ( liquid, 250 C) Acentric factor Critical compressibility LEL UEL

28.48 mN/m 1169 kg-1 K-1 1752 kg-1 K-1 0.311 0.264 1.2 % 6.8 %

4.2 Chemical Properties: The most important chemical reaction of EB is its dehydrogenation to Styrene. The reaction is carried out at: 1. High temprature ( 600-6700 c) 2. Usually over an iron oxide catalyst 3. Steam is used as dilutent Commercially, selectivities to styrene range from 89-96%with per rpass conversion 65-70%.

Another reaction of commercial importance is the oxidation of EB by air to hydroperoxides C6H5CH(OOH)CH3 The reaction takes place in the liquid phase , with no catalyst required. With a suitable catalyst EB can be converted to xylenes. Commercial processes for isomerizing xylenes usually involve the catalytic isomerization or dealkylation of EB. EB may be dealkylated catalytically or thermally to benzene.

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4.3 Environmental & Health Effects: Emergency Overview: Clear, colourless liquid with a characteristic, sweet, gasoline-like, aromatic odour. Flammable liquid and vapour. Liquid can accumulate static charge by flow, splashing and agitation. Vapour is heavier than air and may spread long distances. Distant ignition and flashback are possible. Liquid can float on water and may travel to distant locations and/or spread fire. Closed containers may rupture and explode in heat of fire. TOXIC. May be harmful if inhaled. Central nervous system depressant. Vapour may cause headache, nausea, dizziness, drowsiness, confusion, unconsciousness and possibly death. SKIN IRRITANT. May cause skin irritation. Aspiration hazard. Swallowing or vomiting of the liquid may result in aspiration (breathing) into the lungs. POSSIBLE CANCER HAZARD - may cause cancer, based on animal information. Potential Health effects: Effect of short Term Exposure: Inhalation: Ethylbenzene readily forms high vapour concentrations and should be considered toxic by this route of exposure. Inhalation of the vapour or mists can irritate the nose and throat and produce symptoms of central nervous system depression such as mild unsteadiness, headache, nausea, dizziness and a feeling of drunkenness at approximately 100-200 ppm. Much higher concentrations can cause more severe symptoms including unconsciousness and death. Human volunteers exposed to 85 ppm for 8 hours reported no adverse health effects. Above 100 ppm, mild unsteadiness, sleepiness and headache were reported. In another report, approximately 100 ppm (cited as 400 mg/m3) produced a slight irritating effect on the respiratory tract, occasional headaches, sleepiness, slight drowsiness after 8 hours. More pronounced irritation, frequent headaches, sleepiness and a feeling of drunkenness were observed at 200 ppm (860 mg/m3). At 1150 ppm (5000 mg/m3), irritation of nose and throat was experienced. Exposure to 1000-2000 ppm (0.1-0.2%) for 6 minutes caused irritation of the nose and throat, fatigue and increasing unsteadiness, chest constriction and dizziness in 4-6 male volunteers. Exposure to 5000 ppm (0.5%) was considered intolerable. Skin Contact: The liquid can cause moderate irritation, based on animal information. Ethylbenzene is absorbed through the skin to a small extent, but harmful effects are not expected to occur by this route of exposure.
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Eye Contact: The liquid can cause mild to moderate irritation, based on limited animal information. Volunteers reported that exposure to approximately 100 ppm was slightly irritating to the eyes. At 1000 ppm (0.1%) the vapour was very irritating to the eyes of 4-6 volunteers, producing smarting and burning, accompanied by profuse tearing. This irritation, gradually decreased until, after a minute or two, it was barely noticeable. At 2000 ppm (0.2%), the irritation was almost intolerable upon first exposure, but again became less irritating upon continued exposure, while 5000 ppm (0.5%) was considered intolerable. Ingestion: Ethylbenzene has relatively low toxicity following ingestion. As a central nervous system (CNS) depressant, it can cause nausea, vomiting, headache and dizziness. Very large amounts may cause unconsciousness and death. Ethylbenzene can cause severe lung damage or death if the liquid is accidentally breathed into the lungs (aspirated), based on physical properties. There are no reports of aspiration occurring in humans. Ingestion is not a typical route of occupational exposure.

Effects of Long-Term (Chronic) Exposure: Nervous System: A number of human population studies involving painters and other occupational groups exposed to a wide range of solvents, including ethylbenzene, have led to some investigators to conclude that long-term exposure to solvents may cause permanent effects on the central nervous system (CNS). The signs and symptoms are ill-defined and include headaches, memory loss, fatigue and altered emotional reactivity. This syndrome is commonly known as Organic Solvent Syndrome. There are no specific studies that implicate ethylbenzene as a causal agent, although it is present in many of the paints and other solvent-containing products. The available studies tend to have a number of deficiencies including concurrent exposure to many different chemicals, and lack of exposure data. In a limited study, most workers exposed to up to 11.5 ppm (cited as 0.05 mg/L) complained of headaches, irritability and of tiring rapidly. Functional nervous system disturbances were found in some workers employed for over 7 years.

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Skin: Repeated or prolonged contact may cause dry, red, chapped skin (dermatitis). Skin Sensitization: No allergic skin reaction was observed among 25 volunteers exposed to 10% ethylbenzene in petrolatum. Hearing: Studies in rats have shown that simultaneous exposure to ethyl benzene and noise increases the potential for hearing damage above that for noise exposure alone. Guinea pigs do not appear to be sensitive to these effects.(54,55) The relevance of these observations to human exposures is not known.

4.4 Handling, Storage & Transportation: EB is a flammable liquid. It is stored & transported in steel containers. The US DOT identification number is UN 1175. Foam, Carbon dioxide, dry chemical, halon & water ( fog pattern) are used in fighting EB fires. The use of NIOSH approved respirators is recommended at high concentration. Skin contact should be avoided.

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5. Manufacturing Processes: Currently, the primary source of ethyl benzene is the alkylation of benzene with ethylene. The only other source, the super fractionation of mixed C8 aromatic streams, supplies only a small portion of the ethyl benzene produced. Two distinct types of ethyl benzene alkylation processes are currently used commercially: liquid- phase alkylation and vapor-phase alkylation. 5.1 Liquid Phase Alkylation: Liquid phase aluminum chloride processes have been the dominant source of ethylbenzene since the 1930s. Several companies have developed variations of this technology. Processes currently in use include those of Dow chemical, BASF, shell chemical, Monsanto, societe chimique des cahrbonnages, and union carbide/ badger. The Monsanto process is currently the most modern commercially licensed aluminum chloride alkylation technology. Alkylation of benzene with in the presence of an aluminum chloride catalyst complex is exothermic (H-114 kJ/mol); the reaction is very fast and produces almost stoichiometric yields of ethy lbenzene. In addition to AlCl3, a wide range of Lewis acid catalysts, including AlBr3, FeCl3, and BF3, have been used. Aluminum chloride processes generally use ethyl chloride or hydrogen chloride as a catalyst promoter. These halide promoters reduce the amount of AlCl3 required. The reaction mechanism has been studied in detail Alkylation: In the conventional AlCl3 process (see Fig 1), three phases are present in the reactor. Aromatic liquid, ethylene gas, and a liquid catalyst complex phase (a reddish brown material called red oil). A mixture of catalyst complex, dry benzene, and recycled polyalkyl benzenes is continuously fed to the reactor and agitated to disperse the catalyst complex phase in the aromatic phase. Ethylene and the catalyst promoter are injected into the reaction mixture through spargers, and essentially 100% of the ethylene is converted. Low ethylene: Benzene ratios are used to give optimum overall yield of ethylbenzene. Commercial plants typically operate at ethylene: because molar ratios of ca.0.3-0.35. As the ratio is increased, more side reactions, such as transalkylation and isomeric rearrangement, occur. Further alkylation of ethylbenzene leads to the reversible formation of lower molecular mass polyalkylbenzenes. The loss in net yield due to residue is minimized by recycling this material to the alkylation reactor. In addition, because the reaction occurs close to thermodynamic equilibrium, the traditional processes use a single reactor to alkylate benzene and transalkylate polyalkylbenzenes.

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The reaction temperature is generally limited to 1300C; a higher temperature rapidly deactivates the catalyst and favors formation of non aromatics and polyalkyllbenzenes, which are preferential absorbed by the highly acidic catalyst complex, resulting in byproduct formation. Sufficient pressure is maintained to keep the reactants in the liquid phase. High alloy materials of construction are also required for the piping and handling systems. The liquid reactor effluent is cooled and discharged into a settler, where the heavy catalyst phase is decanted from the organic liquid phase and recycled. The organic phase is washed with water and caustic to remove dissolved AlCl3 and promoter. The aqueous phase from these treatment steps in first neutralized and then recovered as a saturated aluminum chloride solution and wet aluminum hydroxide sludge. Removal of dissolved catalyst from the catalyst from the organic stream has long been a problem for ethylbenzene producers. Recently CdF chime found that more complete recovery of AlCl3 could be achieved by first contacting the organic phase with ammonia instead of sodium hydroxide. Separation: Purification of the ethyl benzene product is usually accomplished in a series of three distillation columns. The unreacted benzene is recovered by the first columns as an overhead distillate. The second column separates the ethyl benzene product from the heavier polyalkylated components. The bottoms product of the second column is fed to a final column, where the recyclable polyalkylbenzenes are stripped from non recyclable high molecular mass residue compounds. The residue or flux oil, consisting primarily of polycyclic aromatics, is burned as fuel. Because the alkylation mixture can tolerate only minor amounts of water, the recycled benzene and fresh benzene must be dried thoroughly prior to entering the reactor. Water not only increases corrosion, but also decreases catalyst activity. Benzene dehydration is accomplished in a separate column. The improved Monsanto process has distinct advantages compared to conventional AlCl3 processes. The most of these is a significant reduction in the AlCl3 catalyst use, thus lessening the problem of waste catalyst disposal. Monsanto found that by an increase in temperature and by careful control of ethylene addition, the required AlCl3 concentration could be reduced to the solubility limit, thereby eliminating the separate catalyst complex phase. Therefore, alkylation occurs in a single homogeneous liquid phase instead of the two liquid phases is earlier processes. Monsanto claims that a separate catalyst complex phase may actually prevent the attainment of maximum reactor yields. With a few exceptions, the flow scheme of the Monsanto process is nearly the same as that of more traditional processes. The process is also capable of operating with low- concentration ethylene feed. The process is also capable of operating with low concentration ethylene feed. Typically, the alkylation
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temperature is maintained at 160-1800C. This higher operating temperature enhances catalyst activity, with the additional benefit that the heat of reaction can be recovered as low- pressure steam. Whereas the traditional process accomplishes alkylation and transalkylation in a single reactor, the homogenous catalyst system must employ a separate transalkylation reactor. At lower catalyst concentrations, the recycle of substantial amounts of polyalkylbenzenes terminates the alkylation reaction. Therefore, only dry benzene, ethylene, and catalyst are fed to the alkylation reactor. The recycle polyethylbenzene stream is mixed with the alkylation reactor effluent prior to entering the transalkylation reactor. The transalkylation reactor is operated at much lower temperature than the primary alkylation reactor. After transalkylation, the reaction products are washed and neutralized to remove residual AlCl3. With the homogenous process, all of the catalyst remains in solution. The catalyst-free organic reaction mixture is then purified using the sequence described previously for the conventional AlCl3 process. As with other AlCl3 process, the organic residue is used as fuel and the aluminium chloride waste streams are usually sold, or sent to treatment facilities. 5.2 Vapor Phase Alkylation: Vapor-phase alkylation has been practiced since the early 1940s, but at that time processes were unable to compete with liquid-phase aluminum chloride based technology. The alkar process developed by UOP, based on boron trifluoride catalyst, had modest success in the 1960s, but fell from favor because of high maintenance costs resulting from the severe corrosion caused by small quantities of water. Nevertheless, some ethylbenzene units continue to use this process. The Mobil badger ethylbenzene process represents the latest and most successful vapor phase technology to be introduced. The process was developed in the 1970s around Mobils versatile ZSM-5 synthetic zeolite catalyst. Earlier attempts at using zeolite or molecular sieves for benzene alkylation had suffered from rapid catalyst deactivation because of coke formation and poor transalkylation capabilities. The Mobil catalyst combines superior resistance to coke formation with high catalytic activity for both alkylation and transalkylation by American Hoechst Corp. at their 408x10-3/t/a Bayport, Texas plant. Currently nine commercial plants have been licensed, representing ca. 3x10106 t/a of production capacity. ALKAR PROCESS: This process produces a high purity ethylbenzene product and can use dilute ethylene feed stock. If the entry of water into the process is strictly prevented, the corrosion problems associated with aluminum chloride processors are avoided. However, even small amounts of water (<1mg/kg) hy6drolze the BF, catalyst. The alkyation reaction
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takes place at high pressure (2.5-3.5 Mpa; 25-35 bar) and low temperature (1001500C). Dehydrated benzene, ethylene, and make up BF3, catalysts are fed to the reactor. Typically, ethylene; benzene molar ratios between 0.15 and 0.2 are used. The reactor inlet temperature is controlled by recycling a small portion of the reactor effluent. Transalkylation takes place in a separate reactor. Dry benzene, BF3 catalyst, and recycled polyethlybenzene are fed to the transalkylation reactor. The effluent streams from the two reactors are combined and passed to a benzene recovery column, where benzene is separated for recycle to the reactors. Boron trifluoride and light hydrocarbons are taken over head as a vapour stream from which the BF3, is recovered for recycle. The bottom for the benzene recovery column is sent to a product column, where ethyl benzene of > 99.9% purity is taken overhead. A final column serves to recover polyethylbenzenes for recycle to the transalkylation reactor. The alkar process can operate with ethylene feed containing as low as 8-10 mol% ethylene, enabling a variety of refinery and coke-oven gas streams to be used. However, purification of these streams is necessary to remove components that poison the BF3 catalyst, e.g., trace amounts of water sulfur compound, and oxygenates. Mobil-Badger Process: The fixed bed ZSM-5 catalyst promotes the same overall alkylation chemistry as those used in the other processes; however, the reaction mechanism is different. Ethylene molecules are adsorbed onto the Bronsted acid sites within the catalyst, which activates the ethylene molecule and allows bonding with benzene molecules to occur. Hence, the range of higher alkylated aromatic byproducts formed by the Mobil Badger process is somewhat different than that for the Friedel Crafts processes. These components do not affect the ethyl benzene product purity and are recycled to the reactor for transalkylation or dealkylation. The Mobil-Badger heterogeneous catalyst system offers several advantages when compared to the other commercially available processes. The most important are that it is noncorrosive and non-polluting. The catalyst is essentially silica alumina, which is environmentally inert. Because no aqueous waste streams are produced by the process, the equipment for waste treatment and for catalyst recovery is eliminated. In addition, carbon steel is the primary material of construction, high-alloy materials and brick linings are not required. The reactor typically operates at 400-4500C and 2-3 MPa (20-30 bars). At this temperature >99% of the net process heat input and exothermic heat of reaction can be recovered as steam.

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The reaction section includes two parallel multi-bed reactors, a fired heater, and heat recovery equipment. The high-activity catalyst allows transalkylation and alkylation to occur simultaneously in a single reactor. Because the catalyst slowly deactivates as a result of coke formation and requires periodic regeneration, two reactors are included to allow uninterrupted production: one is on stream while the other is regenerated. Regeneration takes ca. 36h and is necessary after 6-8 weeks of operation. The catalyst is less sensitive to water, sulfur, and other poisons than the Lewis acid catalysts. The reactor effluent passes to the purification section as a hot vapor. This steam is used as the heat source for the first distillation column, which recovers the bulk of the unreacted benzene for recycle to the reactor. The remaining benzene is recovered from a second distillation column. The ethybenzene product is taken as the overhead product from the third column. The bottoms product from this column is sent to the last column, where the recyclable alkylbenzenes and polyalkylbenzenes are separated from heavy nonrecyclable residue. The low-viscosity residue stream, consisting mainly of diphenylmethane and diphenylethane, is burned as fuel. The Mobil-Badger process also can use dispute ethylene feedstocks. In semi commercial applications, the process has operated on streams containing as little as 15 mol% ethylene. 5.3 New Developments: Dow Chemical and Snamprogetti are developing a process for making ethyl benzene/styrene from ethane and benzene. The process combines the dehydrogenation of ethane and ethyl benzene in one unit and integrates the processes for preparing ethylene, ethyl benzene and styrene. This process is claimed to have lower costs than the conventional route to styrene, largely stemming from the low cost of ethane in relation to ethylene. A pilot plant has been operating since 2002 and commercialisation could be possible by the end of the decade. 5.4 Comparison between Processes: Although both the alkylation process i.e. liquid phase & vapor phase are of equal use commercially. Yet there are some differences: 1. In vapour phase alkylation, the reactors operates at higher temperatures(4004500 c) which causes catalytic deactivation by fouling as a result catalyst required periodic regeneration. 2. In vapour phase alkylation process two reactors will be required so that processing and regeneration can proceed alternatively without interrupting production. 3. All the ethylene feedstock is reacted completely in the liquid benzene, thus eliminating off gas recovery equipment.
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4. Ethyl benzene yield is 99.7% in liquid phase alkylation process while in vapour phase alkylation it is around 98%. 5. Zeolite as a catalyst can be used in any of the processes. 6. Up to 99.95wt% product purity in the with no xylene formation, in liquid phase alkylation process.

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6. Selected Process: We have selected liquid phase alkylation process for ethyl benzene production, now we will discuss process under the followings: Introduction to process: Efforts were made to reduce by-product formation by changing reaction condition but it was not until the advent of liquid phase at temperature lower than 2700 c that zeolite catalyzed processes were truly capable of producing. The first high purity zeolite based EB plant , based on technology developed by UOP & ABB Lummus Global started up in 1990. Technology Supplier: UOP & ABB Lummus Global Current Status: Currently 16 plants are using this technology. Raw Materials: Ethylene & Benzene Product quality achievable: 99.95wt% pure EB can be produced. Catalyst: Zeolite Material of construction: Carbon Steel Process Effluents: Inert component of ethylene feed which will appear as benzene column vent. 6.1 Process Chyemistry: EB made by the alkylation of benzene with ethylene in the presence of zeolite catalyst. Successive alkylation also occurs to minor extent, producing diethylbenzens, collectively termed polyethylene benzene (PEB) Benzene + Ethylene EB (Ethyl benzene) EB + Ethylene DEB (Di- ethyl benzene) Process Description: Benzene alkylated with the ethylene to yield a mixture of alkylated benzenes. This mixture is distilled to recover product EB, and higher ethylated benzenes (PEB). The liquid phase alkylation reactor consists of multi[le beds of zeolite catalyst operating adiabatically. Process conditions are selected to keep the aromatic reaction mixture in the liquid phase. Excess benzene is used, and ethylene is injected before each bed.
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Multiple ethylene injection points improve selectively and enhance catalyst stability. In the alkylation reactor, ethylene reacts completely, leaving only the inert constituents of the feed, such as ethane. These inters pass through the reactor and are from the plant at a convenient point. The alkylation effluents are fed to the benzene column, where benzene is taken as the over head product for recycle to the reactor. The benzene column bottoms feed the ethyl benzene column. Here EB is taken as the overhead product. The reboiler of the distillation columns may used hot oil, high-pressure steam, or direct firing. Overhead vapors are condensed in waste heat boilers, generating valuable steam useful in a downstream SM or propylene oxide/styrene monomer plant. The EB unit has considerable flexibility to mmet a verify of local site conditions in an efficient manner. If no stream export is required, the net heat import can be reduced considerably

6.3 Plant Capacity: The Ethyl benzene plant capacity is 1000MTPY(109 kg per year) based on:

er capacities of other Ethyl benzene operating plants (or projected plan

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7.Mass & Energy Balances 7.1 Process information: 1. Stream (1) Benzene is pure 2. Stream (2) ethylene contains 7 mole % ethane as impurity. Ethane dose not react but moves in the process as inerts and vent in the light column. 3. Stream (3) B: E ratio is adjusted to control reaction selectivity , 8:1. 4. Reactor (R-1) the limiting reactant achivees 100% conversion. 5. Stream (8) composition is; Inerts 45% mole Benzene - 55% mole 6. Efficiency of T 1 is such that 99.9% of benzene that is fed is in the overhead. 7. Stream(11) Ethyl benzene = 99.9% wt Benzene= 0.1% wt 8. All the EB fed in to the EB column (T2) is in overhead.

7.2 Mass balance Calculations: The plant capacity for ethyl benzene plant = 1000 MTPA For which we are suppose to produce the product as follows:The product ethyl benzene which we will produce will contain:1190 mol/hr ethyl benzene and 1.6 mol/hr benzene Since we are using liquid phase alkylation process for ethyl benzene production, for which yield and conversion are as follows: Yield=99.7%

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Conversion=100% (w.r.t ethylene) Now consider PFD for ethyl benzene plant Stream (11) Ethyl benzene=1190 mol/hr Benzene = 1.6 mol/hr Now we are coming to the reaction part, here we have reactor:-

Now we know that:Yield = [{(moles of product produced)*(stochiomertric coefficient)} /(moles of reactant converted)]/100 =99.7/100=1190/moles of reactant converted Moles of reactant converted (ethylene)= 1193.5 mol/hr Now the reactions in the reactor are:C6H6 + C2H4 benzene ethylene C6H5-C2H5 Ethyl benzene

C6H5-C2H5 + C2H4 C6H4-(C2H5)2 Ethyl benzene ethylene Diethyl benzene

here, For 1 mole of Ethyl benzene = 1 mole of ethylene needed

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and For 1 mole of diethyl benzene = 2 moles of ethylene needed. Now after reactor 1190 mol of ethyl benzene produced So ethylene consumed is = 1190 mol Thus rest ethylene is = 1193.5 - 1190 = 3.5 mol of ethylene Since conversion is 100% It means that all ethylene had converted in to ethyl benzene and rest ethylene converted in to diethyl benzene. Now 2 moles of ethylene will produce = 1 moles of diethyl benzene So, 3.5 mol will produce = 3.5/2 = 1.75 mol/hr of diethyl benzene (DEB) Now, to minimize the production of DEB we have chosen high B : E ratio i.e. 8:1 Thus total benzene requirement is = 8 *1193.5 = 9548 mol/hr Since Ethylene is not pure it is having only 93mole % ethylene Thus total ethylene stream (ethylene+ ethane) requirement is:=1193.5/0.93 = 1283.3 mol/hr Inert = 1283.3 1193.5 = 89.8 moles/ hr After reactor will also have un-reacted benzene which will be :=Benzene fed benzene consumed = 9548-1193.5-1.75 = 8356.25 mol /hr (unreacted)

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Now consider reactor-1 (R-1) again:Inputs: Benzene = 9548 mol Ethylene = 1193.5 mol Inert = 89.8 mol Outputs: Ethyl benzene = 1190 mol Benzene = 8356.25 mol Inert = 89.8 mol Diethyl benzene = 1.75 mol

Stream:-(6) Ethyl benzene = 1190 mol/hr Benzene = 8356.25 mol/hr Inert = 89.8 mol/hr Diethyl benzene = 1.75 mol/hr

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Thus Consider Flash Column: Stream -6

Material Balances of Benzene Column

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Now consider Ethyl benzene (EB) column: Stream no :(10) Stream 10 will contain: EB= 1188.8 mol/hr DEB= 1.75 mol/hr Benzene= 2.352 mol/hr

Now as we already know that stream (11) will be: Stream (11): EB = 1188.7 mol/hr Benzene= 2.352 mol/hr Stream (12): DEB = 1.75 mol/hr

EB = 0.123 mol/hr

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Mass balance at a Glance: For Reactor Input : Stream: Component Ethylene (E) Benzene (B) Inert (I) Total Kg/hr 33.418 744.744 2.694 780.856 mol//hr 1193.5 9548 89.8

Output:

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Stream:

Component Ethyl Benzene (EB) Di-ethyl Benzene (DEB) Benzene (B) Inert (I) Total

Kg/hr 126.140 .234 651.788 2.694 780.856

mol//hr 1190 1.75 8356. 25 89.8

For Flash Column: Input: Stream: 6 Component Ethyl Benzene (EB) Di-ethyl Benzene (DEB) Benzene (B) Inert (I) Total Kg/hr 126.140 .234 651.788 2.694 780.856 mol//hr 1190 1.75 8356.25 89.8

Output: Stream: 7 Component Inert (I) Benzene (B) Ethylbenzene (EB) Total Kg/hr 1.234 4.608 0.106 5.948 mol//hr 41.151 59.074 1 101.225

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& Stream: 8 Component Ethyl Benzene (EB) Di-ethyl Benzene (DEB) Benzene (B) Inerts (I) Total Kg/hr 126.304 .234 647.179 1.460 mol//hr 1189 1.75 8297.176 48.649

For Benzene Column: Input:Stream: 8 Component Ethyl Benzene (EB) Di-ethyl Benzene (DEB) Benzene (B) Inerts (I) Total Kg/hr 126.304 .234 647.179 1.460 775.178 mol//hr 1189 1.75 8297.176 48.649

Output: Stream: 9 Component Benzene (B) Ethyl Benzene (EB) Di-ethyl Benzene (DEB) Inerts (I) Total Kg/hr 647 0.0525 0 1.460 648.51 mol//hr 8294.824 0.5 0 48.649

Stream: 10 Component Ethyl Benzene (EB) Di-ethyl Benzene (DEB) Benzene (B) Total Kg/hr 126.013 .234 0.184 126.43
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mol//hr 1188.8 1.75 2.352

For Ethyl Benzene Column: Input:

Component Ethyl Benzene (EB) Di-ethyl Benzene (DEB) Benzene (B) Total

Kg/hr 126.013 .234 0.184 126.43

mol//hr 1188.8 1.75 2.352

Output: Stream : 11 Component Ethyl Benzene (EB) Benzene (B) Total Kg/hr 126.002 0.184 126.186 mol//hr 1188.7 2.352

& Stream: 12 Component Di-ethyl Benzene (DEB) Ethyl Benzene (EB) Total Kg/hr .234 .013 0.248 mol//hr 1.75 0.123

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