Liquid-phase oxidation of hydrocarbon

N. M. Emanuel, E. T. Denisov, and Z. K. Maizus, Liquid Phase Oxidation of Hydrocarbons, Plenum Press, New York, 1967. 

Autooxidation. Liquid-phase oxidation of hydrocarbons, alcohols, and aldehydes by oxygen produces chemiluminescence in quantum yields of 10 to 10 ° ein/mol (128—130). Although the efficiency is low, the chemiluminescent reaction is important because it provides an easy tool for study of the kinetics and properties of autooxidation reactions including industrially important processes (128,131). The light is derived from combination of peroxyl radicals (132), which are primarily responsible for the propagation and termination of the autooxidation chain reaction. The chemiluminescent termination step for secondary peroxy radicals is as follows ... 

Catalysis by Transition Metal Ions and Complexes in Liquid-Phase Oxidation of Hydrocarbons and Aldehydes by Dioxygen... 

Oxidation of organic compounds by dioxygen is a phenomenon of exceptional importance in nature, technology, and life. The liquid-phase oxidation of hydrocarbons forms the basis of several efficient technological synthetic processes such as the production of phenol via cumene oxidation, cyclohexanone from cyclohexane, styrene oxide from ethylbenzene, etc. The intensive development of oxidative petrochemical processes was observed in 1950-1970. Free radicals participate in the oxidation of organic compounds. Oxidation occurs very often as a chain reaction. Hydroperoxides are formed as intermediates and accelerate oxidation. The chemistry of the liquid-phase oxidation of organic compounds is closely interwoven with free radical chemistry, chemistry of peroxides, kinetics of chain reactions, and polymer chemistry. 

Chain Mechanism of Liquid-Phase Oxidation of Hydrocarbons... 

CL accompanies many reactions of the liquid-phase oxidation of hydrocarbons, ketones, and other compounds. It was discovered in 1959 for liquid-phase ethylbenzene oxidation [219,220]. This phenomenon was intensively studied in the 1960s and 1970s, providing foundation for several methods of study of oxidation, decay of initiators, and kinetics of antioxidant action [12,17,221], Later this technique was effectively used to study the mechanism of solid polymer oxidation (see Chapter 13). 

GF Fedorova. The Study of Chemiluminescence in Liquid-Phase Oxidation of Hydrocarbons. Thesis Dissertation, Institute of Chemical Physics, Moscow, 1979, pp 1-30 [in Russian]. 

ACID CATALYSIS IN LIQUID-PHASE OXIDATION OF HYDROCARBONS AND ALCOHOLS... 

Anthracene and 2,6-dinitrophenol terminate chains in oxidizing PP reacting with alkyl as well as with peroxyl radicals [50]. It is important to note that the last two inhibitors retard the liquid phase oxidation of hydrocarbons and aldehydes only by the reaction with peroxyl... 

Metals and metal oxides, as a rule, accelerate the liquid-phase oxidation of hydrocarbons. This acceleration is produced by the initiation of free radicals via catalytic decomposition of hydroperoxides or catalysis of the reaction of RH with dioxygen (see Chapter 10). In addition to the catalytic action, a solid powder of different compounds gives evidence of the inhibiting action [1-3]. Here are a few examples. The following metals in the form of a powder retard the autoxidation of a hydrocarbon mixture (fuel T-6, at T= 398 K) Mg, Mo, Ni, Nb V, W, and Zn [4,5]. The retarding action of the following compounds was described in the literature. 

Formation of products containing less than four carbon atoms is not related to the catalytic activity of the metal on the decomposition of hydroperoxides. Hence, the liquid-phase oxidation of hydrocarbons involves heterogeneous catalytic reactions of isomerization and decomposition of peroxide radicals, proceeding on the reactor surface. 

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