Styrene process, economics

The PO/styrene process is one of those coproduct operations where the economics get muddled easily. When styrene is in short supply and high-priced, PO from these plants look good. When PO is in long supply and low-priced, styrene from these plants looks anemic. The product managers of both products are rarely in the same mood. 

The epoxidation of propylene to propylene oxide is a high-volume process, using about 10% of the propylene produced in the world via one of two processes [127]. The oldest technology is called the chlorohydrin process and uses propylene, chlorine and water as its feedstocks. Due to the environmental costs of chlorine and the development of the more-efficient direct epoxidation over Ti02/Si02 catalysts, new plants all use the hydroperoxide route. The disadvantage here is the co-production of stoichiometric amounts of styrene or butyl alcohol, which means that the process economics are dependent on finding markets not only for the product of interest, but also for the co-product The hydroperoxide route has been practiced commercially since 1979 to co-produce propylene oxide and styrene [128], so when TS-1 was developed, epoxidation was looked at extensively [129]. 

Process Economics Program Report SRI International. Menlo Park, CA, Isocyanates IE, Propylene Oxide 2E, Vinyl Chloride 5D, Terephthalic Acid and Dimethyl Terephthalate 9E, Phenol 22C, Xylene Separation 25C, BTX, Aromatics 30A, o-Xylene 34 A, m-Xylene 25 A, p-Xylene 93-3-4, Ethylbenzene/Styrene 33C, Phthalic Anhydride 34B, Glycerine and Intermediates 58, Aniline and Derivatives 76C, Bisphenol A and Phosgene 81, C1 Chlorinated Hydrocarbons 126, Chlorinated Solvent 48, Chlorofluorocarbon Alternatives 201, Reforming for BTX 129, Aromatics Processes 182 A, Propylene Oxide Derivatives 198, Acetaldehyde 24 A2, 91-1-3, Acetic Acid 37 B, Acetylene 16A, Adipic Acid 3 B, Ammonia 44 A, Caprolactam 7 C, Carbon Disulfide 171 A, Cumene 92-3-4, 22 B, 219, MDA 1 D, Ethanol 53 A, 85-2-4, Ethylene Dichloride/Vinyl Chloride 5 C, Formaldehyde 23 A, Hexamethylenediamine (HMDA) 31 B, Hydrogen Cyanide 76-3-4, Maleic Anhydride 46 C, Methane (Natural Gas) 191, Synthesis Gas 146, 148, 191 A, Methanol 148, 43 B, 93-2-2, Methyl Methacrylate 11 D, Nylon 6-41 B, Nylon 6,6-54 B, Ethylene/Propylene 29 A, Urea 56 A, Vinyl Acetate 15 A. 

Table 3 Styrene economics for propylene oxide-styrene process...

Develop a plant design for a world-scale 1 MMM Ib/yr styrene process using the new Dow technology, and determine the overall economics. 

A comparison of the chlorohydrin process with the PO/tert-butyl alcohol or PO/ styrene process is difficult and depends on the integration of the raw products and the byproducts within the production site and on the product portfolio of the producing companies. Thus, a chlorohydrin PO process can be operated most economically, if it is... 

A third source of initiator for emulsion polymerisation is hydroxyl radicals created by y-radiation of water. A review of radiation-induced emulsion polymerisation detailed efforts to use y-radiation to produce styrene, acrylonitrile, methyl methacrylate, and other similar polymers (60). The economics of y-radiation processes are claimed to compare favorably with conventional techniques although worldwide iadustrial appHcation of y-radiation processes has yet to occur. Use of y-radiation has been made for laboratory study because radical generation can be turned on and off quickly and at various rates (61). 

Determine the optimal steam ratio (kg steain/kg ethylbenzene) that should be used in the styrene reactor in order to maximize the economic potential of the process. 

Numerous enantioselective transfer hydrogenation processes have now been developed and operated at commercial scale to give consistent, high-quality products, economically. These include variously substituted aryl alcohols, styrene oxides and alicyclic and aliphatic amines. Those discussed in the public domain include (S)-3-trifluoromethylphenylethanol [48], (f )-3,5-bistrifluorophenylethanol [64], 3-nitrophenylethanol [92], (S)-4-fluorophenylethanol [lc], (f )-l-tetralol [lc], and (T)-l-methylnaphthylamine [lc]. 

Specifically, propylene oxide has reacted directly with maleic and phthalic anhydrides to produce unsaturated polyesters under these milder conditions (15, 16). This would certainly be a major first step toward simplifying the process and lowering the cost. Incidentally, use of propylene oxide in place of propylene glycol would also result in an additional saving of 1 cent per pound in total raw material cost as well (6). After polyesterification, the separate steps of cooling, dilution with styrene, catalysis, impregnation, gelation, and cure are a distinct operational and economic liability. 

Many different vinyl monomers (9) have been used to make wood-polymers during the past ten years, but methyl methacrylate (MMA) appears to be the preferred monomer for both the catalyst-heat and radiation processes. In fact, MMA is the only monomer that can be economically polymerized with gamma radiation. On the other hand, all types of liquid vinyl monomers can be polymerized with Vazo or peroxide catalysts. In many countries styrene and styrene-MMA mixtures are used with the Vazo or peroxide catalysts. 

Vinyl chloride monomer (VCM) is one of the leading chemicals used mainly for manufacturing polyvinyl chloride (PVC). The PVC worldwide production capacity in 2005 was of about 35 million tons per year, with an annual growth of about 3%, placed after polyolefines but before styrene polymers. In the 1990s the largest plant in the USA had a capacity of about 635 ktons [1], but today there are several plants over one million tons. At this scale even incremental improvements in technology have a significant economic impact. Computer simulation, process optimization and advanced computer-control techniques play a determinant role. 

The economics of any manufacturing process improves if the co-product or side product has a market. 90% of the world production of phenol is through the cumene hydroperoxide route because of the economic advantage of the coproduct acetone. Oxirane technology for the production of propylene oxide from ethyl benzene leads to a co-product styrene and from isobutane leads to a co-product /-butyl alcohol. 

SB copolymers are produced via anionic polymerization by sequential addition of styrene and 1,3-butadiene monomers. These clear, tough plastics are easily processed with conditions and equipment similar to those used for HIPS. Various amounts of GPPS are usually mixed with the SB copolymers during sheet extrusion to maximize rigidity and economics in the thermoformed parts. Typical applications include drinkware, medical packaging, lids, containers, and blister packages. 

Processing with the styrene monomer requires that precautions have to be taken to ensure the proper removal and handling of this toxic material. Legal limits in the workplace have been set up by regulations. Other monomers used include diallyl phthlate (DAP), para-methylstyrene (PMS), vinyl acetate (VA), vinyl toluene (VT), adding paraffin wax, and styrene suppressant additive. Suppliers and fabricators continue to target in the reduction of styrene monomer quickly, effectively, and economically. A wide variation in properties can be obtained by changes in polyester formulation. 

The styrene is a high-purity product, suitable for polymerization, at a very attractive cost compared with conventional styrene production routes. If desired, the mixed xylenes can also be extracted from the pygas, upgrading their value as chemical feedstock. The process is economically attractive for typical pygas and supplemental feeds, which contain 15,000 tpy or more styrene. 

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