(PRODUCTION OF CYCLOHEXANE)

The hydrogenation of benzene produces cyclohexane. Many catalyst systems, such as Ni/alumina and Ni/Pd, are used for the reaction. General reaction conditions are 160220C and 2530 atmospheres. Higher temperatures and pressures may also be used with sulfided catalysts:

Older methods use a liquid phase process (Figure 10-11). New gas phase processes operate at higher temperatures with noble metal catalysts. Using high temperatures accelerates the reaction (faster rate). The hydrogenation of benzene to cyclohexane is characterized by a highly exothermic reaction and a significant decrease in the product volume Equilibrium conditions are therefore strongly affected by temperature and pressure.

Cyclohexane is a colorless liquid, insoluble in water but soluble in hydrocarbon solvents, alcohol, and acetone. As a cyclic paraffin, it can be easily dehydrogenated to benzene. The dehydrogenation of cyclohexane and its derivatives (present in naphthas) to aromatic hydrocarbons is an important reaction in the catalytic reforming process. Essentially, all cyclohexane is oxidized either to a cyclohexanone -cyclohexanol mixture used for making caprolactam or to adipic acid. These are monomers for making nylon 6 and nylon 6/6.

A white crystalline dicarboxylic acid, C6H11O4, that is derived from oxidation of various fats, slightly soluble in water and soluble in alcohol and acetone, and used especially in the manufacture of nylon and polyurethane foams.

a) The main use of adipic acid is as monomer for the production of nylon by a polycondensation reaction with hexamethylene diamine forming 6,6nylon. b) Monomer for production of Polyurethane c) Reactant to form plasticizers and lubricant components d) Food Ingredient as a flavorant and gelling aid.

Oxidation of Cyclohexane (Cyclohexanone-Cyclohexanol and Adipic Acid)

Cyclohexane is oxidized in a liquid-phase process to a mixture of cyclohexanone and cyclohexanol (KA oil). The reaction conditions are 95120C at approximately 10 atmospheres in the presence of a cobalt acetate and orthoboric acid catalyst system. About 95% yield can be obtained:

KA oil is used to produce caprolactam, the monomer for nylon 6. Caprolactam is also produced from toluene through the intermediate formation of cyclohexane carboxylic acid. Cyclohexane is also a precursor for adipic acid. Oxidizing cyclohexane in the liquid-phase at lower temperatures and for longer residence times (than for KA oil) with a cobalt acetate catalyst produces adipic acid:

Adipic acid and its esters are used to make nylon 6/6.

Historically, adipic acid was prepared from various fats using oxidation. Current commercial adipic acid is produced from cyclohexane by two oxidation steps. Cyclohexane + O2 cyclohexanol and cyclohexanone + byproducts Cyclohexanol/cyclohexanone + nitric acid + air adipic acid + nitrous oxide (The mixture of cyclohexanol and cyclohexanone produced from cyclohexane is commercially called "KA oil", the abbreviation of "Ketone-Alcohol oil".)

Other patented processes include those using phenol as feedstock. For example, phenol can be hydrogenated to KA oil, which is further processed to give adipic acid. Utilizing principles of green chemistry, a new method of synthesis has been developed, which involves oxidizing cyclohexene with hydrogen peroxide via a tungsten catalyst and a phase transfer catalyst to produce adipic acid. The waste product is water.

Process emissions from the production of adipic acid vary depending upon the technologies and level of emissions controls employed by a facility. Adipic acid production also generates emissions of non-methane volatile organic compounds (NMVOC), carbon monoxide (CO), and nitrogen oxides (NOx).

Nylon 66 (Polyhexamethyleneadipate)

Polyamides are the second largest group of synthetic fibers after polyesters. However, they were the first synthetic fibers that appeared in the market in 1940. This was the result of the work of W. H. Carothers in USA who developed nylon 66. At about the same time nylon 6 was also developed in Germany by I. G. Farben. Both of these nylons still dominate the market for polyamides. However, due to patent restrictions and raw materials considerations, nylon 66 is most extensively produced in USA and nylon 6 is most extensively produced in Europe.

Numbers that follow the word nylon denote the number of carbons present within a repeating unit and whether one or two monomers are being used in polymer formation. For nylons using a single monomer such as nylon 6 or nylon 12, the numbers 6 and 12 denote the number of carbons in caprolactam and laurolactam, respectively.

For nylons using two monomers such as nylon 610, the first number, 6, indicates the number of carbons in the hexamethylene diamine and the other number, 10, is for the second monomer sebacic acid. Polyamides are produced by the reaction between a dicarboxylic acid and a diamine (e.g., nylon 66), ring openings of a lactam, (e.g., nylon 6) or by the polymerization of w-amino acids (e.g., nylon 11).

Nylon 66 is produced by the reaction of hexamethylenediamine and adipic acid. This produces hexamethylenediammonium adipate salt. The product is a dilute salt solution concentrated to approximately 60% and charged with acetic acid to a reactor where water is continuously removed. The presence of a small amount of acetic acid limits the degree of polymerization to the desired level:

The temperature is then increased to 270300C and the pressure to approximately 16 atmospheres, which favors the formation of the polymer. The pressure is finally reduced to atmospheric to permit further water removal. After a total of three hours, nylon 66 is extruded under nitrogen pressure.

Nylons are generally characterized by relatively high melting points due to the presence of the amide linkage. They are also highly crystalline, and the degree of crystallinity depends upon factors such as the polymer structure and the distance between the amide linkages. An increase in polymer crystallinity increases its tensile strength, abrasion resistance, and modulus of elasticity. Hydrogen bonding in polyamides is fairly strong and has a pronounced effect on the physical properties of the polymer such as the crystallinity, melting point, and water absorption.

Nylons, however, are to some extent subject to deterioration by light. This has been explained on the basis of chain breaking and crosslinking. Nylons are liable to attack by mineral acids but are resistant to alkalies. They are difficult to ignite and are selfextinguishing. In general, most nylons have remarkably similar properties, and the preference of using one nylon over the other is usually dictated by economic considerations except for specialized uses.

Nylons have a variety of uses ranging from tire cord to carpet to hosiery. The most important application is cord followed by apparel. Nylon staple and filaments are extensively used in the carpet industry. Nylon fiber is also used for a variety of other articles such as seat belts, monofilament finishes, and knitwear. Because of its high tenacity and elasticity, it is a valuable fiber for ropes, parachutes, and underwear.

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 + TiO2/Sb2O3. Approximate conditions for the vapor-phase oxidation are 375435C and 0.7 atmosphere. The yield of phthalic anhydride is about 85%:

Liquid-phase oxidation of o-xylene also works at approximately 150C. Cobalt or manganese acetate in acetic acid medium serves as a catalyst. The major by-products of this process are maleic anhydride, benzoic acid, and citraconic anhydride (methylmaleic anhydride). Maleic anhydride could be recovered economically.

Phthalic anhydrides main use is for producing plasticizers by reactions with C4C10 alcohols. The most important polyvinyl chloride plasticizer is formed by the reaction of 2-ethylhexanol (produced via butyraldehyde) and phthalic anhydride. Phthalic anhydride is also used to make polyester and alkyd resins. It is a precursor for phthalonitrile by an ammoxidation route used to produce phthalamide and phathilimide.

Phthalic anhydride release to the atmosphere could result from its manufacture and use in many products and its use in the manufacture of other commercial materials, polyester resins, and alkyd resins, phthaleins, phthalates, benzoic acid, sythetic indigo, artifical resins (glyptal), synthetic fibers, dyes, pigments, pharmaceuticals, insecticides and chlorinated products.

It is released from industrial plants which produce phthalic anhydride by oxidation of xylenes and naphthalene; from the incineration of industrial refuse and water sludges and slurries from plastic products and other manufacturing processes; phthalic anhydride has been detected in leachate from municipal and separate industrial wastes containing plastics.

If phthalic anhydride is released to soil, it will not be expected to sorb to the soil. It is expected to hydrolyze in moist soils. If it is released to water it will not be expected to bioconcentrate in aquatic organisms, sorb to sediments, or to evaporate. Hydrolysis will be a major fate process based on an estimated half-life of 1.5 minutes. If it is released to the atmosphere it may be susceptible to direct photolysis.

The estimated vapor-phase half-life in the atmosphere is about 32 days as a result of ring addition of photochemically produced hydroxyl radicals. Exposure to phthalic anhydride result mainly from occupational exposure involving the inhalation of contaminated air.