Maleic anhydride from naphthalene

Fumaric acid may be prepared by heating maleic acid, with or without catalysts. It is also obtained as by-product in the manufacture of phthalic anhydride from naphthalene. The acid is a solid melting at 284°C. Fumaric acid is sometimes preferred to maleic anhydride as it is less corrosive, it tends to give lighter coloured products and the resins have slightly greater heat resistance. 

Extension of the Kunii-Levenspiel bubbling-bed model for first-order reactions to complex systems is of practical significance, since most of the processes conducted in fluidized-bed reactors involve such systems. Thus, the yield or selectivity to a desired product is a primary design issue which should be considered. As described in Chapter 5, reactions may occur in series or parallel, or a combination of both. Specific examples include the production of acrylonitrile from propylene, in which other nitriles may be formed, oxidation of butadiene and butene to produce maleic anhydride and other oxidation products, and the production of phthalic anhydride from naphthalene, in which phthalic anhydride may undergo further oxidation. 

The oxidation of aromatic hydrocarbons originating from coal is one of the first organic gas phase oxidation processes carried out on an industrial scale. The development of these processes was initiated by the discovery that the V2Os catalyst used for the oxidation of sulphur dioxide was also applicable to the partial oxidation of benzene to maleic anhydride and naphthalene to phthalic anhydride. Remarkably, V2Os-based catalysts are still used in these processes today as they appear superior to any other type of catalyst. 

Other catalytic reactions carried out in fluidized-bed reactors are the oxidation of naphthalene to phthalic anhydride [2, 6, 80] the ammoxidation of isobutane to mcthacrylonitrilc [2] the synthesis of maleic anhydride from the naphtha cracker C4 fraction (Mitsubishi process [81, 82]) or from n-butane (ALMA process [83], [84]) the reaction of acetylene with acetic acid to vinyl acetate [2] the oxychlorination of ethylene to 1,2-di-chloroethane [2, 6, 85, 86] the chlorination of methane [2], the reaction of phenol with methanol to cresol and 2,6-xylenol [2, 87] the reaction of methanol to gasoline... 

Phthallc anhydride from naphthalene or o-xylene 1D Maleic 4cld anhydride from benzene... 

Supported vanadla used to promote the selective oxidation of hydrocarbons. Is another example. Vanadia with or without promoters, may be supported on silica (naphthalene oxidation [38]), on tltanla o-xylene oxidation [39]) or on a-alumlna (benzene oxidation [ AO]). It was believed that supports should have open porosity (and associated lower surface area) in order to minimise over oxidation to carbon oxides. However, it was shown that reasonably high activities and selectivitles could be obtained over vanadla supported on high surface area material and it was suggested that low selectivity was, in fact, primarily associated with high acidity on the support [AI]. In agreement with this, vanadla supported on 7-alumina shoved zero selectivity for the production of maleic anhydride from benzene If this Is the case, then a high surface area support with minimal acidity would be desired,... 

A reaction related to cleavage is aromatic ring degradation. Phthalic anhydride used to be prepared from naphthalene, and maleic anhydride from benzene, with air and V2O5 catalyst, losing 2 carbon atoms as CO2. More modern processes use o-xylene and butadiene (or -butane) respectively. However, the analogous formation of quinolinic (pyridine-2,3-dicarboxylic) acid from quinoline is still practised. Hypochlorite [94], hypochlorite or chlorite/Ru catalyst [95], or simply alkaline H2O2 [96] can be used. 

Theoretical approaches to catalysis in the 1920s drew some criticism from those working at the laboratory bench. One such critic was Charles R. Downs, who had developed vapor-phase oxidation processes for making maleic acid from benzene and phthalic anhydride from naphthalene for Barrett Chemical Co. (20) ... 

During the manufacture of phthalic anhydride from naphthalene and 6>-xylene, small amounts of MA, citraconic anhydrides, and benzoic acid are coproduced.MA comprises 6% of the product.In some cases, after removal of phthalic anhydride by condensation, the exhaust gases are scrubbed with water. In many cases, the aqueous solution of maleic acid is recovered in the form of fumaric acid. Koppers in the United States recovers 10 MM lb of MA from the phthalic plant. ... 

The major aromatics (organics having at least one ring structure with six carbon atoms) manufactured include benzene, toluene, xylene, and naphthalene. Other aromatics manufactured include phenol, chlorobenzene, styrene, phthalic and maleic anhydride, nitrobenzene, and aniline. Benzene is generally recovered from cracker streams at petrochemical plants and is used for the manufacture of phenol, styrene, aniline, nitrobenzene, sulfonated detergents, pesticides such as hexachlorobenzene, cyclohexane (an important intermediate in synthetic fiber manufacture), and caprolactam, used in the manufacture of nylon. Benzene is also used as a general purpose solvent. 

Finally, a few miscellaneous compounds which were identified in the Delaware River and which have not been previously reported as water contaminants will be discussed Chloro (trifluoromethyl) aniline and chloro (trifluoromethyl) nitrobenzene (no. 55 and 56) were identified in the water, they had maximum concentrations at river mile 78. Both compounds represent common sub-structures in various pesticide and dye molecules, and several of the companies located along the river have patents using these compounds (30-32j. It is possible that these compounds are actually present in the river water as such, but it is also possible that they are formed in the GC injection port by pyrolytic degradation of larger pesticide or dye molecules (see above). All three binaphthyl-sulfone isomers (no. 92) were identified in the river water near Philadelphia. Product literature for one of the companies in the area indicates production of condensed sulfonated polymers derived from naphthalene sulfonic acid and maleic anhydride. It seems likely that the binaphthylsulfones are formed as by-products during preparation of this commercial product. 

The manufacturing method of making phthalic anhydride has been changing rapidly similar to the switchover in making maleic anhydride. In 1983 28% of phthalic anhydride came from naphthalene, 72% from o-... 

Compressed air and o-xylene or naphthalene vapor are mixed in an approximately 20 1 ratio and oxidized at 400°C. The product phthalic anhydride is recovered by condensation and purified by vacuum distillation. Maleic anhydride, a byproduct in both oxidations may be recovered from the waste gases in the form of maleic acid after water scrubbing. 

Phthalic anhydride is the most important product in the oxidation of o-xylene, which has become competitive with naphthalene as a feedstock for the industrial production of this component. This process is carried out at 350— 400°C and the industrial catalysts consist of doped V2Os or V2Os—Ti02 mixtures, pure or supported. Maximum yields of 70—75 mol. % (95—105 wt. %) are reported. Carbon oxides are the main by-products, besides minor amounts of tolualdehyde and maleic anhydride. Tolualde-hyde is the main product at low conversion and an essential intermediate in the phthalic anhydride formation, while maleic anhydride is mainly formed as a side-product directly from o-xlyene. 

The manufacture of phthalic anhydride (E.P., 249,973) from naphthalene, and maleic anhydride (U.S.P., 1,515,299) from benzene, is carried out by oxidation with air or oxygen in presence of V205 as catalyst. 

Heterogeneous oxidative processes operate at high temperatures (250-450 6C) and are useful for the synthesis of acrolein and acrylic acid from propylene over bismuth molybdate catalysts, the synthesis of maleic and phthalic anhydrides from the oxidation of benzene (or C4 compounds) and naphthalene (or o-xylene) respectively over vanadium oxide,101 arid the synthesis of ethylene oxide from ethylene over silver catalysts.102... 

There is no easy and/or effective method for the preparation of 1,2,3,4-tetrasubstituted naphthalenes starting from a simple naphthalene derivative and based on classical substitution methodology. A clever new route, based on the now common concept of "tandem" reactions, is illustrated as follows. Heating of the sulfoxide 1 with acetic anhydride at 120°C in the presence of maleic anhydride gave an adduct 2, C20H16O4S, in 87% yield as a mixture of diastereomers. Reaction of the adduct 2 with PTSA in THF at 25°C gave the naphthalene derivative 3 in quantitative yield. Use of methyl propiolate in place of maleic anhydride did not result in isolation of an adduct the product was the tetralone 4 (51%). 

Polyacrylamide Polyoxyethylene nonyl phenol ether Polyvinyl sulfonic acid Sulfonated benzene sodium salt Naphthalene sulfonic acid Tallow soap Isobutylene Maleic anhydride Sodium humate (extracted from brown coal) Butyric acid lauryl ethylene diamine salt ... 

In going from benzene to pentacene the largest sum of the free valence of a pair of atoms in a para position increases as does the ease of the diene synthesis in this series. It is well known that maleic anhydride hardly reacts with benzene or naphthalene. A reaction takes place with anthracene and even more readily with naphthacene and pentacene.12... 

This source of maleic anhydride accounts for less than 2 per cent of world production, bur about 10 per cent of output in Western Europe. The manufacture of phthalic anhydride by the oxidation of naphthalene or o-xylene is accompanied by the production of 5 to 6 per cent maleic anhydride, which can be recovered in the plant wastes. These can be concentrated until they contain 15 to 20 per cent maleic anhydride and about 5 per cent of other acids (phthalic, benzoic, ritracomc). UCB has developed a process it employs in its Ostend phthalic anhydride plant, from which 3000 t/year of maleic anhydride are extracted. 

After acyl halides, acid anhydrides are the most reactive carboxylic acid derivatives. Although anhydrides can be prepared by reaction of carboxylic acids with acyl chlorides as was shown in Table 19.1, the three most commonly used anhydrides are industrial chemicals and are prepared by specialized methods. Phthalic anhydride and maleic anhydride, for example, are prepared from naphthalene and butane, respectively. 

Diels-Alder addition of maleic anhydride to androsta-14,16-diene is shown from the crystal structure to have occurred by P-attack. Likewise, diffraction data have been employed to support the view that the Diels-Alder addition of substituted 1,3-dienes to hexakis(trifluoromethyl)benzvalene occurs by exo-attack. Structure (23) has been assigned to a naphthalene-diphenylacetylene photo-adduct. ... 

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