OXIDATION

    Oxidation is the addition of oxygen to an organic compound or, conversely, the removal of hydrogen.  Reaction control is the major issue during oxidation reactions. Only partial oxidation is required for conversion of one organic compound into another or complete oxidation to carbon dioxide and water will ensue. The most common oxidation agent is air, but oxygen is frequently used. Chemical oxidizing agents (nitric acid, dichromates, permanganates, chromic anhydride, chlorates, and hydrogen peroxide) are also often used.

   As examples of oxidation processes, two processes are available for the manufacture of phenol, and both involve oxidation. The major process involves oxidation of cumene to cumene hydroperoxide, followed by decomposition to phenol and acetone. A small amount of phenol is also made by the oxidation of toluene to benzoic acid, followed by decomposition of the benzoic acid to phenol.  Benzoic acid is synthesized by liquid-phase toluene oxidation over a cobalt naphthenate catalyst with air as the oxidizing agent. An older process involving halogenation of toluene to benzotrichloride and its decomposition into benzoic acid is still used available.

   Maleic acid and anhydride are recovered as by-products of the oxidation of xylenes and naphthalenes to form phthalic acids, and are also made specifically by the partial oxidation of benzene over a vanadiump entoxide (V₂O₅) catalyst. This is a highly exothermic reaction, and several modifications of the basic process exist, including one using butylenes as the starting materials. Formic acid is made by the oxidation of formamide or by the liquidphase oxidation of n-butane to acetic acid. The by-product source is expected to dry up in the future, and the most promising route to replace it is through carbonylation of methanol.  Caprolactam, adipic acid, and hexamethylenediamine (HMDA) are all made from cyclohexane. Almost all high-purity cyclohexane is obtained by hydrogenating benzene, although some for solvent use is obtained by careful distillation of selected petroleum fractions.

   Several oxidative routes are available to change cyclohexane to cyclohexanone, cyclohexanol, and ultimately to adipic acid or caprolactam. If phenol is hydrogenated, cyclohexanone can be obtained directly; this will react with hydroxylamine to give cyclohexanone oxime that converts to caprolactam on acid rearrangement.

    Cyclohexane can also be converted to adipic acid, then adiponitrile, which can be converted to hexamethylenediamine.Adipic acid and hexamethylenediamine are used to form nylon 6,6. This route to hexamethylenediamine is competitive with alternative routes through butene. Acetaldehyde is manufactured by one of several possible processes: (1) the hydration of acetylene, no longer a significant process. (2) the Wacker process, in which ethylene is oxidized directly with air or 99% oxygen (Fig. 1) in the presence of a catalyst such as palladium chloride with a copper chloride promoter.

   The ethylene gas is bubbled, at atmospheric pressure, through the solution at its boiling point. The heat of reaction is removed by boiling of the water. Unreacted gas is recycled following condensation of the aldehyde and water, which are then separated by distillation, (3) passing ethyl alcohol over a copper or silver gauze catalyst gives a 25 percent conversion to acetaldehyde, with recirculation making a 90 to 95 percent yield possible, and (4) a process in which lower molecular weight paraffin hydrocarbons are oxidized noncatalytically to produce mixed compounds, among them acetaldehyde and acetic acid.

   Liquid-phase reactions in which oxidation is secured by the use of oxidizing compounds need no special apparatus in the sense of elaborate means for temperature control and heat removal. There is usually provided a kettle form of apparatus, closed to prevent the loss of volatile materials and fitted with a reflux condenser to return vaporized materials to the reac- tion zone, with suitable means for adding reactants rapidly or slowly as may be required and for removing the product, and provided with adequate jackets or coils through which heating or cooling means may be circulated as required.

   In the case of liquid-phase reactions in which oxidation is secured by means of atmospheric oxygen—for example, the oxidation of liquid hydrocarbons to fatty acids—special means must be provided to secure adequate mixing and contact of the two immiscible phases of gaseous oxidizing agent and the liquid being oxidized. Although temperature must be controlled and heat removed, the requirements are not severe, since the temperatures are generally low and the rate of heat generation controllable by regulation of the rate of air admission.

    Heat may be removed and temperature controlled by circulation of either the liquid being oxidized or a special cooling fluid through the reaction zone and then through an external heat exchanger. Mixing may be obtained by the use of special distributor inlets for the air, designed to spread the air throughout the liquid and constructed of materials capable of withstanding temperatures that may be considerably higher at these inlet ports than in the main body of the liquid. With materials that are sensitive to overoxidation and under conditions where good contact must be used partly to offset the retarding effect of necessarily low temperatures, thorough mixing may be provided by the use of mechanical stirring or frothing of the liquid.

   By their very nature, the vapor-phase oxidation processes result in the concentration of reaction heat in the catalyst zone, from which it must be removed in large quantities at high-temperature levels. Removal of heat is essential to prevent destruction of apparatus, catalyst, or raw material, and maintenance of temperature at the proper level is necessary to ensure the correct rate and degree of oxidation. With plant-scale operation and with reactions involving deep-seated oxidation, removal of heat constitutes a major problem. With limited oxidation, however, it may become necessary to supply heat even to oxidations conducted on a plant scale.  In the case of vapor-phase oxidation of aliphatic substances such as methanol and the lower molecular weight aliphatic hydrocarbons, the ratio of reacting oxygen is generally lower than in the case of the aromatic

hydrocarbons for the formation of the desired products, and for this reason heat removal is simpler. Furthermore, in the case of the hydrocarbons, the proportion of oxygen in the reaction mixture is generally low, resulting in low per-pass conversions and, in some instances, necessitating preliminary heating of the reactants to reaction temperature.

    Equipment for the oxidation of the aromatic hydrocarbons requires that the reactor design permit the maintenance of elevated temperatures, allow the removal of large quantities of heat at these elevated temperatures, and provide adequate catalyst surface to promote the reactions.