Xylenes manufacture

Otani, S., Sato, M., Kanaoka, M., Akita, S., Ogawa, D., and Tsuchiya, Y. (1977) Development of p-xylene manufacturing processes utilizing a new continuous adsorption technology. Am. Soc. Mech. Eng., Appl. Mech. Div., 1, 550-556. 

Xylene Manufacture of resins, paints, varnishes, other chemicals, general solvent for adhesives Edema... 

PARA-XYLENE MANUFACTURING CATALYTIC REACTIONS AND PROCESSES... 

Mononitro derivatives of o- and p-xylenes Dinitro derivatives of o- and p-xylene Trinitro derivatives of 0- and p-xylene Manufacture of trinitroxylene (TNX)... 

Example 13.1 Phthalic anhydride is an important intermediate for the plastics industry. Manufacture is by the controlled oxidation of o-xylene or naphthalene. The most common route uses o-xylene via the reaction... 

Figure 13.5 shows a flowsheet for the manufacture of phthalic anhydride by the oxidation of o-xylene. Air and o-xylene are heated and mixed in a Venturi, where the o-xylene vaporizes. The reaction mixture enters a tubular catalytic reactor. The heat of reaction is removed from the reactor by recirculation of molten salt. The temperature control in the reactor would be diflficult to maintain by methods other than molten salt. 

Crystallizes in colourless needles m.p. 300° (sublimes). Manufactured by the oxidation of p-xylene and used in the production of Terylene (see also polyesters). U.S. production 1980 2-05 megatonnes. 

Amm oxida tion, a vapor-phase reaction of hydrocarbon with ammonia and oxygen (air) (eq. 2), can be used to produce hydrogen cyanide (HCN), acrylonitrile, acetonitrile (as a by-product of acrylonitrile manufacture), methacrylonitrile, hen onitrile, and toluinitnles from methane, propylene, butylene, toluene, and xylenes, respectively (4). 

Coke oven light oil is a by-product of the manufacture of coke for the steel industry. When coal is subjected to high temperature carbonization, it yields 16—25 Hters /tonne of light oil that contains 3—6 vol % of mixed xylenes. 

The initial manufacture of mixed xylenes and the subsequent production of high purity PX and OX consists of a series of stages in which (/) the mixed xylenes ate initially produced (2) PX and/or OX are separated from the mixed xylenes stream and (3) the PX- (and perhaps OX-) depleted xylene stream is isomerized back to an equiUbtium mixture of xylenes and then recycled back to the separation step. These steps are discussed below. 

The EB present in recovered mixed xylenes is largely converted to xylenes or benzene. The EB used to make styrene is predominately manufactured by the alkylation of benzene with ethylene. 

Manufacture. For the commercial production of DPXN (di-/)-xylylene) (3), two principal synthetic routes have been used the direct pyrolysis of -xylene (4, X = Y = H) and the 1,6-Hofmaim elimination of ammonium (HNR3 ) from a quaternary ammonium hydroxide (4, X = H, Y = NR3 ). Most of the routes to DPX share a common strategy PX is generated at a controlled rate in a dilute medium, so that its conversion to dimer is favored over the conversion to polymer. The polymer by-product is of no value because it can neither be recycled nor processed into a commercially useful form. Its formation is minimised by careful attention to process engineering. The chemistry of the direct pyrolysis route is shown in equation 1 ... 

Raw Materials. Eor the first decade of PET manufacture, only DMT could be made sufficiently pure to produce high molecular weight PET. DMT is made by the catalytic air oxidation of -xylene to cmde TA, esterification with methanol, and purification by crystallization and distillation. After about 1965, processes to purify cmde TA by hydrogenation and crystallization became commercial (52) (see Phthalic ACID AND OTHER... 

More recently, a commercial process has been introduced for the manufacture of methyl isocyanate (MIC) which involves the dehydrogenation of /V-m ethyl form am i de [123-39-7] in the presence of palladium, platinum [7440-06-4], or mthenium [7440-18-8], at temperatures between 50—300°C (31). Aprotic solvents, such as ben2ene [71-43-2], xylenes, or toluene [108-88-3], may optionally be used. A variation of this synthesis employs stoichiometric amounts of palladium chloride [7647-10-1], PdCl2. 

Xylene Isomeri tion. The objective of C-8-aromatics processing is the conversion of the usual four-component feedstream (ethylbenzene and the three xylenes) into an isomerically pure xylene. Although the bulk of current demand is for xylene isomer for polyester fiber manufacture, significant markets for the other isomers exist. The primary problem is separation of the 8—40% ethylbenzene that is present in the usual feedstocks, a task that is compHcated by the closeness of the boiling points of ethylbenzene and -xylene. In addition, the equiUbrium concentrations of the xylenes present in the isomer separation train raffinate have to be reestabUshed to maximize the yield of the desired isomer. 

The U.S. naphthalene consumption by markets for 1992 is Hsted in Table 9. The production of phthaHc anhydride by vapor-phase catalytic oxidation has been the main use for naphthalene. Although its use has declined in favor of o-xylene, naphthalene is expected to maintain its present share of this market, ie, ca 18%. Both petroleum naphthalene and coal-tar naphthalene can be used for phthaHc anhydride manufacture. U.S. phthaHc anhydride capacity was 465 X lOM in 1992 (38). 

The solubiHty of phosphoms in water is about 3 ppm. However, process water used in phosphoms manufacture or handling often catties larger amounts of phosphoms as particulates or small droplets, depending on the water temperature. Phosphoms-contaminated water is commonly called phossy water. Phosphoms has low solubiHty in most common solvents, but is quite soluble in carbon disulfide and some other special solvents. The solubiHty in CS2 and benzene was formerly used in phosphoms analyses, but toxicity and increasing waste disposal costs have led to mote use of toluene and xylene, and mote tecentiy to the use of nonchemical turbidity measurements. 

Manufacture and Processing. Isophthahc acid is synthesized commercially by the Hquid-phase oxidation of / -xylene [108-38-3]. The chemistry of the oxidation is almost identical to that of -xylene oxidation to terephthahc acid, and production facihties can be used interchangeably for these two dicarboxyhc acids. However, because isophthahc acid is more soluble than terephthahc acid in reaction solvents as can be seen by comparing data in Tables 16 and 25, crystallization equipment is more important in isophthahc acid facihties. 

The diacid components for the manufacture of poly(y -phenyleneisophthalamide) and poly(p-phenyleneterephthalamide) are produced by one of two processes. In the first, the diacid chlorides are produced by the oxidation of / -xylene [108-38-3] or -xylene [106-42-3] followed by the reaction of the diacids with phosgene [75-44-5]. In the second, process m- or -xylene reacts with chlorine initiated by ultraviolet light to form the m- or Nhexachloroxylene. This then reacts with the respective aromatic dicarboxyUc acid to form the diacid chloride. 

Xylenes. The main appHcation of xylene isomers, primarily p- and 0-xylenes, is in the manufacture of plasticizers and polyester fibers and resins. Demands for xylene isomers and other aromatics such as benzene have steadily been increasing over the last two decades. The major source of xylenes is the catalytic reforming of naphtha and the pyrolysis of naphtha and gas oils. A significant amount of toluene and Cg aromatics, which have lower petrochemical value, is also produced by these processes. More valuable p- or 0-xylene isomers can be manufactured from these low value aromatics in a process complex consisting of transalkylation, eg, the Tatoray process and Mobil s toluene disproportionation (M lDP) and selective toluene disproportionation (MSTDP) processes isomerization, eg, the UOP Isomar process (88) and Mobil s high temperature isomerization (MHTI), low pressure isomerization (MLPI), and vapor-phase isomerization (MVPI) processes (89) and xylene isomer separation, eg, the UOP Parex process (90). 

Naphthalene. Until the 1960s, the principal outlet for naphthalene was the production of phthaHc anhydride however, more recently, o-xylene has replaced naphthalene as the preferred feedstock (see Phthalic acids). Nevertheless, of the 201,000 t produced in 1994 in Japan, 73.2% was used for phthaHc anhydride production. The rest was consumed in dye stuffs manufacture and a wide variety of other uses. Naphthalene is also used to produce phthaHc anhydride in the United Kingdom, Belgium, and the C2ech RepubHc, and can be used by Koppers in the United States in time of o-xylene shortages. In Europe, the traditional uses for naphthalene have been for the manufacture of P-naphthol and for dye stuff intermediates (see Dyes and dye... 

The feedstock is usually extracted toluene, but some reformers are operated under sufftciendy severe conditions or with selected feedstocks to provide toluene pure enough to be fed directiy to the dealkylation unit without extraction. In addition to toluene, xylenes can also be fed to a dealkylation unit to produce benzene. Table 20 Hsts the producers and their capacities for manufacture of benzene by hydrodealkylation of toluene. Additional information on hydrodealkylation is available in References 50 and 52. 

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