Of o-xylene

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. 

The addition of sulphuric acid increased the rate of nitration of benzene, and under the influence of this additive the rate became proportional to the first powers of the concentrations of aromatic, acetyl nitrate and sulphuric acid. Sulphuric acid markedly catalysed the zeroth-order nitration and acetoxylation of o-xylene without affecting the kinetic form of the reaction. ... 

In the nitration and acetoxylation of o-xylene the addition of acetic acid increased the rate in proportion to its concentration, the presence of 3-0 mol 1" accelerating the rate by a factor of 30. In the presence of a substantial concentration (2-2 mol 1 ) of acetic acid the rate of reaction obeyed the following kinetic expression... 

More information has appeared concerning the nature of the side reactions, such as acetoxylation, which occur when certain methylated aromatic hydrocarbons are treated with mixtures prepared from nitric acid and acetic anhydride. Blackstock, Fischer, Richards, Vaughan and Wright have provided excellent evidence in support of a suggested ( 5.3.5) addition-elimination route towards 3,4-dimethylphenyl acetate in the reaction of o-xylene. Two intermediates were isolated, both of which gave rise to 3,4-dimethylphenyl acetate in aqueous acidic media and when subjected to vapour phase chromatography. One was positively identified, by ultraviolet, infra-red, n.m.r., and mass spectrometric studies, as the compound (l). The other was less stable and less well identified, but could be (ll). 

The higher price of the petroleum product results from its higher quaUty, ie, higher purity, lower sulfur content, etc. The price of cmde coal-tar naphthalene is primarily associated with that of o-xylene, its chief competitor as phthaUc anhydride feedstock. 

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 first of the benzene polycarboxyUc acids to become a commercial product was phthabc acid, mosdy in the form of the anhydride. The anhydride is obtained by the catalytic vapor-phase air oxidation of o-xylene or naphthalene. The lUPAC name of phthabc anhydride is 1,3-isobenzofurandione... 

Naphthalene (qv) from coal tar continued to be the feedstock of choice ia both the United States and Germany until the late 1950s, when a shortage of naphthalene coupled with the availabihty of xylenes from a burgeoning petrochemical industry forced many companies to use o-xylene [95-47-6] (8). Air oxidation of 90% pure o-xylene to phthaUc anhydride was commercialized ia 1946 (9,10). An advantage of o-xylene is the theoretical yield to phthaUc anhydride of 1.395 kg/kg. With naphthalene, two of the ten carbon atoms are lost to carbon oxide formation and at most a 1.157-kg/kg yield is possible. Although both are suitable feedstocks, o-xylene is overwhelmingly favored. Coal-tar naphthalene is used ia some cases, eg, where it is readily available from coke operations ia steel mills (see Steel). Naphthalene can be produced by hydrodealkylation of substituted naphthalenes from refinery operations (8), but no refinery-produced napthalene is used as feedstock. Alkyl naphthalenes can be converted directiy to phthaUc anhydride, but at low yields (11,12). 

Vapor-phase catalytic oxidation of dutene is a mote direct route to the dianhydtide. Hbls in Europe apparently uses this route, which eliminates the need for a separate dehydration step and for handling of any oxidants or solvents. Continuous operation is faciHtated, corrosion is minimized, and product recovery is simplified. The vapor-phase oxidation of dutene is similar to that of o-xylene to phthaHc anhydtide, and phthaHc anhydtide units can be... 

Another sulfur dioxide appHcation in oil refining is as a selective extraction solvent in the Edeleanu process (323), wherein aromatic components are extracted from a kerosene stream by sulfur dioxide, leaving a purified stream of saturated aHphatic hydrocarbons which are relatively insoluble in sulfur dioxide. Sulfur dioxide acts as a cocatalyst or catalyst modifier in certain processes for oxidation of o-xylene or naphthalene to phthaHc anhydride (324,325). 

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 (9-xylene [95-47-6] in Eigure 8 is recovered by a two-stage distillation. Eirst it is separated (or spHt) from / -xylene [108-38-3] and the other Cg aromatics in a superfractionating column, the xylene spHtter, (Unit H). The bottoms, a mixture of o-xylene and Cg aromatics, is redistilled (or remn) in Unit I to recover o-xylene of 96-H% purity. 

In another example, Ti02 can be deposited on a siHca support body in order to obtain a stable high surface titania. This is necessary because Ti02 sinters badly on heating in the bulk oxide and loses surface area. The Ti02 Si02 combination is useful as a catalyst for the oxidation of o-xylene to phthaHc anhydride. 

Dich1oromethy1)-2-(trichioromethy1)henzene [2741-57-3] the end product of exhaustive side-chain chlorination of o-xylene (80) is an iatermediate ia the manufacture of phthalaldehydic acid [119-67-5]. 

Cataljdic reactions performed in fluid beds are not too numerous. Among these are the oxidation of o-xylene to phthalic anhydride, the Deacon process for oxidizing HCl to CI2, producing acrylonitrile from propylene and ammonia in an oxidation, and the ethylene dichloride process. In the petroleum industry, cataljdic cracking and catalyst regeneration is done in fluid beds as well as some hydroforming reactions. 

The prime function of the saturated acid is to space out the double bonds and thus reduce the density of cross-linking. Phthalic anhydride is most commonly used for this purpose because it provides an inflexible link and maintains the rigidity in the cured resin. It has been used in increasing proportions during the past decade since its low price enables cheaper resins to be made. The most detrimental effect of this is to reduce the heat resistance of the laminates but this is frequently unimportant. It is usually produced by catalytic oxidation of o-xylene but sometimes naphthalene and is a crystalline solid melting at 131°C. 

In 1997, the U.S. produced approximately 7.8 billion pounds of p-xylene and only one billion pounds of o-xylene. ... 

Currently, phthalic anhydride is mainly produced through catalyzed oxidation of o-xylene. A variety of metal oxides are used as catalysts. A typical one is V2O5 -1- Ti02/Sb203. Approximate conditions for the vapor-phase oxidation are 375-435°C and 0.7 atmosphere. The yield of phthalic anhydride is about 85% ... 

Liquid-phase oxidation of o-xylene also works at approximately 150°C. Cobalt or manganese acetate in acetic acid medium serves as a catalyst. 

In 1932, A. A. Levine and A. G. Cole studied the ozonolysis of o-xylene and isolated three products glyoxal, 2,3-butanedione, and pyruvaldehvde ... 

In what ratio would you expect the three products to be formed if o-xylene is a resonance hybrid of two structures The actual ratio found was 3 parts glyoxal, 1 part 2,3-butanedione, and 2 parts pyruvaldehyde. What conclusions can you draw about the structure of o-xylene ... 

Besides the technical method starting from naphthalene, phthalic acid and its substituted derivatives can be prepared by oxidation of o-xylene to phthalic acid with potassium permanganate. This compound can be subsequently transformed via an anhydride, imide, and amide to a derivative of phthalonitrile, which is the more convenient starting material for several coordination compounds. The synthesis of the ferf-butyl-substituted dicarbonitrile, which is a very common starting material for highly soluble phthalocyanines, is shown below.97,105... 

The reaction scheme is rather complex also in the case of the oxidation of o-xylene (41a, 87a), of the oxidative dehydrogenation of n-butenes over bismuth-molybdenum catalyst (87b), or of ethylbenzene on aluminum oxide catalysts (87c), in the hydrogenolysis of glucose (87d) over Ni-kieselguhr or of n-butane on a nickel on silica catalyst (87e), and in the hydrogenation of succinimide in isopropyl alcohol on Ni-Al2Oa catalyst (87f) or of acetophenone on Rh-Al203 catalyst (87g). Decomposition of n-and sec-butyl acetates on synthetic zeolites accompanied by the isomerization of the formed butenes has also been the subject of a kinetic study (87h). 

Fig. 17. Changes in fluorescent background on changing the excitation wavelength. Raman spectra of o-xylene using different exciting lines (a) Ar+ 488 nm (b) Kr+ 647.1 nm (c) Ar+ 514.5 nm (d) Kr+ 568.2 nm. Fluorescent background was substantially reduced in spectrum (b). (Courtesy Spex Industries, Inc.)...

Was prepd by passing 15% ozone thru a soln of o-xylene in acetic anhydr-ether, cooled to about... 

Subsequently, rate coefficients were determined for the zinc chloride-catalysed bromination of benzene, toluene, i-propyl-benzene, r-butylbenzene, xylenes, p-di-f-butylbenzene, mesitylene, 1,2,4-trimethyl-, sym-triethyl-, sym-tri-f-butyl-, 1,2,3,5-and 1,2,4,5-tetramethyl- and pentamethylbenzenes, all at 25.4 °C and in acetic acid, and it was shown that the reaction was inhibited by HBr.ZnCl2 which accumulates during the bromination and was considered to cause the first step of the reaction (formation of ArHBr2) to reverse320. The second-order coefficients for bromination of o-xylene at 25.0 °C were shown to be inversely dependent upon the hydrogen bromide concentration and the reversal of equilibrium (155)... 

Either Friedel-Crafts disconnection will do, but o-toluic acid (27) is available from the oxidation of o-xylene so that route is preferred as no separation of o, p-isomers is involved. 

The prepared MAC adsorbents were tested for benzene, toluene, 0-, m-, p-xylene, methanol, ethanol, iso-propanol, and MEK. The modified content of all MACs was 5wt% with respect to AC. The specific surface areas and amounts of VOC adsorbed of MACs prepared in this study are shown in Table 1. The amounts of VOC adsorbed on 5wt%-MAC with acids and alkali show a similar tendency. However, the amount of VOC adsorbed on 5wt%-PA/AC was relatively large in spite of the decrease of specific surface area excepting in case of o-xylene, m-xylene, and MEK. This suggests that the adsorption of relatively large molecules such as 0-xylene, m-xylene, and MEK was suppressed, while that of small molecules was enhanced. It can be therefore speculated that the phosphoric acid narrowed the micropores but changed the chemical nature of surface to adsorb the organic materials strongly. 

The variation of amount of VOC adsorbed and the variation of BET surface area with modified contents were shown in Fig. 1. The optimum modified content was lwt% for benzene, toluene, p-xylene, methanol, ethanol and iso-propanol, but the amount of o-xylene, m-xylene, and MEK adsorbed were decreased with increasing modified contents. Interestingly, the amount of benzene, p-xylene, and ethanol adsorbed on lwt%-PA/AC was 1.5 to 2 times that on purified AC. The BET surface area of lwt%-PA/AC (1109m /g) took the maximum value. 

Toluene/o-xylene monooxygenase in P. stutzeri strain 0X1 carried ont snccessive monooxygenation of o-xylene (Bertoni et al. 1998), and the tolnene-4-monooxygenase of Pseudomonas mendocina KRl and tolnene-3-monooxygenase of Ralstonia pickettii PKOl can hydroxylate benzene, tolnene, and o-xylene (Tao et al. 2004 Vardar and Wood 2004). 

Kim D, J-C Chae, GJ Zylstra, Y-S Kim, MH Nam, YM Kim, E Kim (2004) Identification of a novel dioxygenase involved in metabolism of o-xylene, toluene, and ethylbenzene by Rhodococcus sp. strain DK17. Appl Environ Microbiol 70 7086-7092. 

Evans PJ, DT Mang, LY Young (1991b) Degradation of toluene and m-xylene and transformation of o-xylene by denitrifying enrichment cultures. Appl Environ Microbiol 57 450-454. 

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