1- cyclohexanol cyclohexanone

Benzene is hydrogenated to cyclohexane. Cyclohexane is then oxidized to cyclohexanol, cyclohexanone, or adipic acid (qv). Adipic acid is used to produce nylon. Cyclohexane manufacture was responsible for about 14% of benzene consumption in 1988. 

Hydrocarbon Oxidation. The oxidation of hydrocarbons (qv) and hydrocarbon derivatives can be significantly altered by boron compounds. Several large-scale commercial processes, such as the oxidation of cyclohexane to a cyclohexanol—cyclohexanone mixture in nylon manufacture, are based on boron compounds (see Cylcohexanoland cyclohexanone Eibers, polyamide). A number of patents have been issued on the use of borate esters and boroxines in hydrocarbon oxidation reactions, but commercial processes apparently use boric acid as the preferred boron source. The Hterature in this field has been covered through 1967 (47). Since that time the Hterature consists of foreign patents, but no significant appHcations have been reported for borate esters. 

Estimated aimual cyclohexanone production capacities are shown in Table 3 the production is greater than 90% captive for caprolactam production (13). The aimual cyclohexanol production is only 10 thousand metric tons. These production figures do not include KA-od (cyclohexanol-cyclohexanone) production for adipic acid. Worldwide annual capacity for cyclohexanone is approximately 3.0 million metric tons, also primarily for caprolactam production. Projected new capacity for caprolactam could add 0.5 million metric tons worldwide in this decade. 

Water with aniline, benzene, benzyl alcohol, carbon disulfide, carbon tetrachloride, chloroform, cyclohexane, cyclohexanol, cyclohexanone, diethyl ether, ethyl acetate, isoamyl alcohol, methyl ethyl ketone, nitromethane, tributyl phosphate or toluene. 

Therefore, CL and die depolymerized product from which CL is regenerated contain various impurities which are present in widely fluctuating amounts depending on the reclamation processes involved. In particular, the presence of cyclohexanone, cyclohexanone oxime, octahydrophenazine, aniline, and other easily oxidized compounds affects die permanganate number. Also volatile substances such as aniline, cyclohexylamine, cyclohexanol, cyclohexanone, nitrocy-clohexanone, and aliphatic amines may also be present in the CL.22... 

The reaction product was filtered to remove catalyst and analyzed in GC equipped with an HP5 (30 m X 0.32 mm X 0.25 pm) column. The temperature program used for analysis (31 °C - 35 min - 1 °C/min - 40 °C - 10 °C/min -120 °C) ensured complete separation of the cyclohexanol, cyclohexanone, and phenol peaks. The conversion and selectivity were calculated directly from the area of each peak. 

Py-GC/MS of Laropal K80 results in a number of intense oligomeric fragments, while smaller fragments are minor pyrolysis products [71]. Cyclohexene, cyclohexanol, cyclohexanone, methyl-cyclohexanone and methylene-cyclohexanone can be attributed to secondary pyrolysis products of the monomeric units (Figure 12.7). The most intense... 

The recombination of the cyclohexyl peroxy radicals produced in one of these two reaction pathways gives rise to cyclohexanol, cyclohexanone and oxygen ( disproportionation ) ... 

Ketones play an important role in the decomposition of peroxides to form radicals in alcohols undergoing oxidation. The formed hydroxyhydroperoxide decomposes to form radicals more rapidly than hydrogen peroxide. With an increase in the ketone concentration, there is an increase in the proportion of peroxide in the form of hydroxyhydroperoxide, with the corresponding increase in the rate of formation of radicals. This was proved by the acceptor radical method in the cyclohexanol-cyclohexanone-hydrogen peroxide system [59], The equilibrium constant was found to be K — 0.10 L mol 1 (373 K), 0.11 L mol 1 (383 K), and 0.12 L mol 1 (393 K). The rate constant of free radical generation results in the formation of cyclohexylhydroxy hydroperoxide decomposition and was found to be ki = 2.2 x 104 exp(—67.8/7 7) s 1 [59]. 

Copper(II) sulfate Cumene hydroperoxide Cyanides Cyclohexanol Cyclohexanone Decaborane-14 Diazomethane 1,1-Dichloroethylene Dimethylformamide Hydroxylamine, magnesium Acids (inorganic or organic) Acids, water or steam, fluorine, magnesium, nitric acid and nitrates, nitrites Oxidants Hydrogen peroxide, nitric acid Dimethyl sulfoxide, ethers, halocarbons Alkali metals, calcium sulfate Air, chlorotrifluoroethylene, ozone, perchloryl fluoride Halocarbons, inorganic and organic nitrates, bromine, chromium(VI) oxide, aluminum trimethyl, phosphorus trioxide... 

Bromine (dry gas) Bromine (liquid) Bromobenzene Butanol Butyl acetate Butylamine Butylchloride Butyric acid Calcium chloride Carbon tetrachloride Castor oil Cellosolve Cellosolve acetate Chlorine (dry gas) Chlorine water Chloroacetic acid Chlorobenzene Chloroform Chlorosulfonic acid Chromic acid Citric acid Colza oil Copper sulfate Cyclohexane Cyclohexanol Cyclohexanone... 

Chao, C.C. and Sherman, J.D. (1982) Bulk cyclohexanol/cyclohexanone separation by selective adsorption on zeolitic molecular sieves. U.S. Patent 4,283,560. 

Diphenylamine N-Methylaniline Charcoal Charcoal Anisoyl Chloride Anisoyl Chloride Cyclohexanol Cyclohexanone Cacodylic Acid... 

Cooper and Waters (13) first reported the oxidation of cyclohexane by cobalt(III) perchlorate in aqueous acetonitrile to give a mixture of cyclohexanol, cyclohexanone, and adipic acid. A more detailed study of this oxidation (74), using cobalt(III) acetate in acetic acid at 80°C, both with and without oxygen, gives products, such as cyclohexylacetate, that can only be explained if there is a direct interaction of cobalt(III) with the C—H [Pg.182]

Nitric acid is used for nitrating numerous other compounds to produce nitrates. Nitric acid is used to produce adipic acid (C6H4O10), which is used in the production of nylon (see Nylon). In this process, cyclohexane is oxidized to a cyclohexanol-cyclohexanone mixture. Cyclohexanol and cyclohexanone are then oxidized with nitric acid to adipic acid. 

CYCLOHEXANOL-CYCLOHEXANONE. Cyclohexanol is a color less, viscous liquid with a camphnraceous odor. It is used chiefly as a chemical intermediate, a stabilizer, and a homogenizer for various soap detergent emulsions, and as a solvent for lacquers and varnishes. Cyclohexanol was first prepared by the treatment of 4-iodocydohexanol with zinc dust in glacial acetic acid, and later by the catalytic hydrogenation of phenol at elevated temperatures and pressures. 

Homolytic liquid-phase processes are generally well suited to the synthesis of carboxylic acids, viz. acetic, benzoic or terephthalic acids which are resistant to further oxidation. These processes operate at high temperature (150-250°C) and generally use soluble cobalt or manganese salts as the main catalyst components. High conversions and selectivities are usually obtained with methyl-substituted aromatic hydrocarbons such as toluene and xylenes.95,96 The cobalt-catalyzed oxidation of cyclohexane by air to a cyclohexanol-cyclohexanone mixture is a very important industrial process since these products are intermediates in the manufacture of adipic acid (for nylon 6,6) and caprolactam (nylon 6). However, the conversion is limited to ca. 10% in order to prevent consecutive oxidations, with roughly 70% selectivity.97... 

Cyclohexanol + cyclohexanone Cyclohexane o2 2 160 °C, 10 bar, [Co], C = 6-10%, S = 65-75% Homogeneous, homolytic Dupont, ICI, DSM, Scientific Design (boric acid) Adipic acid (caprolactam)... 

Adipic acid is a most important petrochemical product which is mostly used for the synthesis of nylon 6.6 from its condensation with hexamethylenediamine. Cyclohexane is transformed to adipic acid in two steps (a) oxidation of cyclohexane to a cyclohexanol-cyclohexanone mixture (ol-one) via the formation of cyclohexyl hydroperoxide followed by (b) oxidation of the ol-one mixture to adipic acid by nitric acid (equation 239). 

Scheme 2.2 Oxidation of cyclohexane to a mixture cyclohexanol/cyclohexanone.

Cyclohexanol, cyclohexanone and cyclohexylhydroperoxide were identified as major oxidation products. 

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