Styrene process facilities

DeVOx A catalytic oxidation process for destroying volatile organic compounds in effluent gases. The catalyst contains a non-noble metal and can easily be regenerated. Typical operating temperatures for 95 percent VOC conversion are 175 to 225°C for oxygenates, and 350°C for toluene. Developed in 1995 by Shell, Stork Comprimo, and CRI Catalysts. First installed in 1996 at Shell Nederland Chemie s styrene butadiene rubber facility at Pemis. 

The recovery and purification facilities in such a process are complex. One reason is that oxygenated by-products are made in the reactors. Oxygenates hinder polymerization of styrene and cause coIot instability. Elaborate purification is required to remove the oxygenates. 

The overall reactivities of these radicals in their ummolecular 5-hexenyl cyclization processes reflects those same factors which affect the reactivity of partially-fluorinated radicals in their bimolecular addition reactions with alkenes, such as styrene. Table 17 indicates this clearly, and it also reflects the general leveling effect which would be expected for the more facile unimolecular cyclization processes which have log A s about 1-2 units larger than those for the bimolecular additions. 

Commercial plants Presently, 36 operating plants incorporate the Lummus/UOP styrene Classic technology. Three operating facilities are using the SMART process technology. Many future units using the SMART process are expected to be retrofits of conventional units, since the technology is well suited for revamps. 

A modern styrene facility is currently under construction in Australia using this dilute C2H , homogeneous alkylation process. 

The commodity nature of the product and the easy access to the licensed processes enable new producers, particularly in developing coimtries, to enter the global styrene merchant market with litde experience in styrene technology. Access to ethjiene, which cannot be easily transported by means other than pipelines, is a key factor in considering new styrene facilities. Timing, or luck, is even more important because the supply and demand of styrene are seldom in balance and the price fluctuates broadly and rapidly as a result. Most of the time, the producers either suffer losses (1981—1985,1991—1993) or enjoy handsome profits (1987—1990,1994—mid-1995). Investments in styrene plants are known to have been recovered in less than a year, but prosperity encourages over-investment and lean years may foUow. 

TBHP vide supra). The autoxidation of EB is performed at 120-160 °C and 1- bar. MBA and acetophenone (ACP) are formed as by-products via the facile termination of the secondary 1-methylbenzylperoxy radicals. In order to minimize by-product formation by further oxidation of MBA and ACP, the autoxidation is carried out to only low conversions (< 12 %). This solution (ca. 10 %) of EBHP in EB is used in the epoxidation step, i.e., EB is the solvent for the latter step. A high propene/EBHP molar ratio is used and reaction conditions are similar to those of the TBHP process vide supra). The PO selectivity is reported to be 90 % at 92 % EBHP conversion [30] but in practice it may be higher. For comparison the heterogeneous Ti /SiOa catalyst in fixed-bed operation reportedly gives 93-94 % PO selectivity at 96 % EBHP conversion [11]. The products are separated by distillation and MBA is dehydrated to styrene in the vapor phase over a Ti02 catalyst. 

The radical nature of nitroxide-mediated processes also allows novel types of block copolymers to be prepared in which copolymers, not homopolymer, are employed as one of the blocks. One of the simplest examples incorporate random copolymers124 and the novelty of these structures is based on the inability to prepare random copolymers by living anionic or cationic procedures. This is in direct contrast to the facile synthesis of well-defined random copolymers by nitroxide-mediated systems. While similar in concept, random block copolymers are more like traditional block copolymers than random copolymers in that there are two discrete blocks, the main difference being one or more of these blocks is composed of a random copolymer segment. For example, homopolystyrene starting blocks can be used to initiate the copolymerization of styrene and 4-vi-nylpyridine to give a block copolymer consisting of a polystyrene block and a random copolymer of styrene and 4-vinylpyridine as the second block.166... 

All these processes suffer the drawback of producing a coproduct that needs to be sold separately tert-butyl alcohol, styrene) or recycled (cumyl alcohol). They are also multistep, and require complex facilities. 

Specifically, PVC blends with polyethylene, polypropylene, or polystyrene could offer significant potential. PVC offers rigidity combined with flammability resistance. In essence, PVC offers the promise to be the lowest cost method to flame retard these polymers. The processing temperatures for the polyolefins and polystyrene are within the critical range for PVC. In fact, addition of the polyolefins to PVC should enhance its ability to be extruded and injected molded. PVC has been utilized in blends with functional styrenics (ABS and styrene-maleic anhydride co-and terpolymers) as well as PMMA offering the key advantage of improved flame resistance. Reactive extrusion concepts applied to PVC blends with polyolefins and polystyrene appear to be a facile method for compatibilization should the proper chemical modifications be found. He et al. [1997] noted the use of solid-state chlorinated polyethylene as a compatibilizer for PVC/LLDPE blends with a significant improvement in mechanical properties. A recent treatise [Datta and Lohse,... 

Because strong Bronsted (proton) acids and Lewis acids can initiate styrene polymerization, other cationically polymerizable monomers can be added to the styrene-based copolymer list. Due to the facile occurrence of chain transfer processes of polymer chains with impurities, cationically prepared polystyrene-based polymers are low molecular weight materials. Nevertheless, low molecular weight polystyrenes still find important applications as additives, as tackifiers for pressure sensitive adhesives, and in hot melt adhesives. However, the market for low molecular weight polystyrene is small. 

Copolymerizations are powerful ways to produce polymers with speeifie properties with well defined strueture. However, they involve the costly modification of existing production facilities of polystyrenes. To satisfy small market niches, modified polystyrenes ean be obtained through grafting reactions by chemical reactions on a polymer melt in an extruder (reactive extrusion) to achieve functionalities on the polymeric chains. Thus, grafting reactions are the preferred methods to achieve functionality commercially because they are low cost alternatives to the eopolymerization processes despite low grafting efficieney. For example, polystyrenes have been grafted with brominated styrene to enhanee the flame resistance of polystyrenes, as shown in Reaction 13. 

Ethylene oxide is manufactured hy direct oxidation of ethylene, in contrast PO is only obtained in coproduct processes. The classical process, chlorination of propylene, is still used by Dow, one of the world s largest producer of polyether polyols. In contrast, all other producers use the Halcon process, based on the simultaneous production of PO and styrene monomer or t-butyl alcohol. In view of the demise of AITBE (methyl-f-butyl ether based on t-butyl alcohol) as a fuel additive, the styrene coproduct process (POSM) will remain as the economically viable route to PO. A recent example is the new (SMPO) plant of Basell at Moerdijk in the Netherlands. The largest producer of PO, the former Arco (now Lyondell), has sold its global polyol business to Bayer in 1999. Lyondell will also provide Bayer a long-term, low cost supply of PO. Recently, Dow annoimced that it also will use the POSM route to PO in a new facility. 

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