2.

1 MANUFACTURING PROCESSES AND SELECTION:

Many different techniques have been investigated for the manufacture of styrene monomer. Of these, the following methods have been used or seriously considered for commercial production: 1. Dehydrogenation of ethyl benzene . O!idation of ethyl benzene to ethyl benzene hydro pero!ide, which reacts with propylene o!ide, after which the alcohol is dehydrated to styrene ". O!idative conversion of ethyl benzene to phenyl ethanol via acetophenon and subsequent dehydration of alcohol #. $ide%chain chlorination of ethyl benzene followed by dechlorination &. $ide%chain chlorination of ethyl benzene, hydrolysis to the corresponding alcohols, followed by dehydration '. (yrolysis of petroleum recovery from various petroleum processes )he first two methods are only two commercially utilized routes to styrene production. Method " was practiced by *nion%+arbide +orporation but later was replaced with a dehydrogenation process. Methods # , &, involving chlorine, have generally been suffered from high cost of the raw materials and from the chlorinated contaminants in the monomer. Manufacture of styrene directly from petroleum streams is difficult and costly. )he two commercially important routes to styrene are based on ethyl benzene production by al-ylation of benzene and ethylene. .esearch programs aimed at replacing e!pensive benzene and ethylene feed stoc-s with less costly alternatives have been carried out by a number of companies. 2.1.1 Oxidation Proce : One of the most notable o!idation processes is /alcon international0s process to produce styrene from propylene o!ide. 1n this technique, ethyl benzene is o!idized to hydro pero!ide as follows: C!"#C"2C"$ % O2 C!"#C"&OO"'C"$

)he reaction ta-es place in the liquid phase with air bubbling through the liquid, and no catalyst is required. /owever, since hydro pero!ides are unstable compounds, e!posure to high temperature must be minimized to reduce the rate of decomposition. 2ewer by%products are formed from the decomposition if the reaction temperature is gradually reduced during the course of reaction, i.e., from 1"&%1'3 deg. + during the first half of reaction to 1 &%1&& deg. + during the second half. )he reaction is more selective to the production of by%product acids, when it is carried out at constant temperature than when the temperature is gradually reduced. 1n practice, the temperature is reduced by means of a series of reactors, each of which is maintained at a progressively lower temperature. )he pressure required for the reaction is not critical4 533%1&33 -(a is sufficient to maintain the reactants at liquid phase.
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.eaction is given below: C6H5CH(OOH)CH3 + CH3CH=C"2 C6H5CH(OH)CH3 + CH3CH(O)CH2

+atalysts for this reaction are compounds of metals, e.g. molybdenum, tungsten, vanadium. )he epo!idation reaction generally proceeds at 133%1"33+ in the liquid phase under self%generated pressures. )he conversion of ethyl benzene hydro pero!ide is nearly complete, and selectivity of the reaction in producing propylene o!ide is greater than 637. )he alcohol can be dehydrated to styrene or it is reduced to ethyl benzene for recycle if styrene is not desired. Montoro, a $panish 8oint venture between O!irane and 9npetrol, first commercializes the process in 1:6". )he plant had an annual capacity of 6.&;13# ton of styrene and ";13# ton of propylene o!ide. )he O!irane plant in +hannelview, )e!as, set up in 1:66 had a capacity of . &;13& ton annual production. 2.1.2. De()dro*enation o+ Et(), -en.ene: .eaction% C!"#C"2C"$ C!"#C"/C"$ % "2 % & "R '

$everal licensed process are available for the conversion of ethyl%benzene to styrene. <lthough all such processes share the catalytic dehydrogenation of ethyl benzene to styrene in the presence of steam, there are two distinct approaches to the reaction section design: the adiabatic process and the isothermal process. <s the dehydrogenation reaction is endothermic, requiring 1. '%1."" M=>-g of ethyl benzene converted at &3+, heat must be supplied. 1n the adiabatic process, steam superheated to 533%:&3 deg. + is mi!ed with preheated ethyl benzene ?9@A feed prior to e!posure to the catalyst. )he isothermal process ta-es place in (2. and reaction heat is provided by indirect heat e!change between the process fluid and a suitable heat transfer medium, e.g., flue gas ?@<$2 technologyA. 2or a given dehydrogenation catalyst, the catalyst life, the molar conversion of ethyl benzene, and the molar selectivity of ethyl benzene to styrene are affected by reactor operating pressure, molar steam to hydrocarbon ratio, reactor operating temperature and reactor liquid hourly space velocity ?B/$CA . 2or all catalysts, there is a compromise between activity, otherwise 9@ conversion, and styrene selectivity. @ecause the dehydrogenation reaction produces moles of products otherwise styrene and hydrogen, for every mole of reactant, i.e., 9@ ,the desired reaction course can be enhanced by adding steam to the reactor system to reduce the styrene partial pressure in the reactor and>or by reducing the reactor operating pressure. <s these increase conversion or other refinements and approaches equilibrium, the rate of the main reaction slows down but the rates of undesired side reactions do not. <diabatic operating pressures were generally about 1"5 -(a with molar steam to hydrocarbon ratio above 1#:1. 2or the isothermal reactor designs, it is maintained at '% 5:1. $ince the reaction is endothermic with increase in temperature, conversion also increases. /owever, an upper limit to reactor temperature, when temperature is increased above '13 deg. +, thermal crac-ing of 9@ , styrene occurs, since in isothermal process the temp maintained at &53%'13 deg. + across the catalyst bed, where in adiabatic reactor the feed mi!ture generally
5

introduced at ''3%'13 deg. +. Decreasing the residence time in the adiabatic process reduces the potential selectivity over isothermal process. <s for B/$C, molar conversion of 9@ is an inverse function of this parameter since higher velocities mean lower residence time. )his in turn reduces molar conversion. 2or adiabatic reactors designed B/$Cs of 3.#%3.' m">hr 9@ per cubic meter of catalyst. Dithin this range, a '3%637 molar conversion of 9@ and a :3%:&7 molar selectivity of 9@ to styrene can be achieved with commercially available dehydrogenation. 1t is believed that similar results are obtained with the isothermal process. )he main difference between the isothermal and adiabatic processes is in the way the endothermic reaction heat is supplied. 1n principle, the isothermal reactor is designed li-e a shell and tube heat e!changer: a fi!ed bed dehydrogenation catalyst and reactant gas is on the tube side, and a suitable heat transfer medium is on the shell side. )he diameter of the self% contained reactor tubes are 13% 3 cm and the lengths are .#%".6 m. <ll commercial catalysts are formulated around an iron o!ide base inherent to this ferric compound is the reduction to lower o!ides at the dehydrogenation reaction temperature. )he most widely used additives are chromic o!ide as the stabilizer and potassium o!ide as the co-e retardants. )hus, the catalyst is self% regenerative, thereby allowing such residues to build up to an equilibrium level. One difference between licensed adiabatic technologies is in the configuration of the dehydrogenation reactor, e.g., instead of a radialEflow reactor, a fi!ed%bed a!ial reactor may be employed. <nother difference in technologies is in the reactor feed heat e!changer section. 1nstead of only steam passing through a fired heater, all of the 9@ and vaporization>dilution is combined with the mi!ture is raised to the reaction temp in a fired heater. <lthough similar in concept, the process involves heating the steam and 9@ in separate coils of a fired heater. <s temperatures well above 5&3 deg. + may be encountered with both processes, the potential for thermal crac-ing of 9@ is increased. )herefore, the residence time in heater should be minimized. 2.1.$. Ot(er Tec(no,o*ie 9thylbenzene can be recovered from mi!ed +5 aromatics by super fractionation. )his technology was first practiced by +osden Oil , +hemical +ompany in 1:&6 ?@ig $pring, )e!asA, based on a design developed 8ointly with )he @adger +ompany. $everal super fractionation plants were built in the *nited $tates, 9urope, and =apan around 1:'3. )he quantity that can be recovered is limited by the supply of mi!ed +5 aromatics and by the low ethylbenzene content ?ca 37A. /igh capital and energy costs resulting from the small boiling% point difference of 1.5 deg. + between ethylbenzene and para%!ylene and low product purity are some other factors. < process for recovery of ethylbenzene from +5 aromatic streams by selective adsorption called 9@9F was developed by *O( in the 1:63s. (roduction of ethylbenzene from butadiene has been investigated by many researchers. 1t consists of two steps: cyclodimerization of 1,"%butadiene to #% vinylcyclohe!ene and dehydrogenation of the vinylcyclohe!ene to ethylbenzene.
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2.2. PURIFICATION
)o obtain the desired product, crude styrene effluent from the reaction section must be fractionated and undesirable by%products are removed. )o minimize the polymerization of vinyl aromatic compounds, low temp vacuum distillation of the crude styrene is necessary. 2urther reduction in polymerization is obtained by employing inhibitors. 1nhibitors were used as e!tensively polymerization reductant. )he main non sulfur inhibitors are nitrogen%substituted aromatics, e.g., nitro%phenols. )he most commonly used commercial inhibitor for this service #% tert%butylcetahol. )he entire purification section is composed of three vacuum fractionators in series. 1n the first column benzene, toluene impurities are been separated from the crude styrene. )he ne!t column is 9@ recycle column, where unreacted 9@ is recovered and fed bacto the reactor. )he separation of 9@ from styrene is difficult because they have a very close boiling point. /igh efficiency, low%pressure distillation column are used. /owever, e!tensive effort is being made to commercialize the use of pac-ing for this purpose. $uch approach offers significant reduction in pressure drop. )he bottom stream from the 9@ recycle stream is been fed to the final styrene purification column. )he feed stream to the final purification column contains 9@ at a concentration of 1333 ppm. /igh purity product of styrene is obtained as the distillate and send to storage.