Liquid-phase oxidation of cyclohexane. Elementary steps in the developed process, reactivity, catalysis, and problems of conversion and selectivity

Journal Article · Mon Oct 15 04:00:00 EDT 2018 · Russian Chemical Bulletin

DOI:https://doi.org/10.1007/S11172-018-2288-Z· OSTI ID:22943446

Voronina, S. G.; Borkina, G. G. ^[1]

---

1. Institute of Chemical and Oil-Gas Technologies, Kuzbass State Technical University named after T. F. Gorbachev (Russian Federation)

The literature data concerning features of the kinetics and mechanisms of elementary steps of liquid-phase oxidation of cyclohexane and its oxygen derivatives are considered and analyzed. A comparison of rates of intermolecular and intramolecular reactions of cyclohexylperoxyl radicals under the industrial conditions indicated a necessity to take into account intramolecular interactions. The occurrence of cross recombination of hydroperoxyl and α-hydroxyperoxyl radicals without chain termination in the course of cyclohexanol and 2-hydroxycyclohexanol oxidation was proved. A significance of degenerate branching reactions involving cyclohexyl hydroperoxide in the industrial process of cyclohexane oxidation at 423 K was evaluated. The influence of the electron-withdrawing functional groups on the reactivity of carbon–hydrogen bonds of organic compounds in the reactions with electrophilic peroxyl radicals was studied. The low conversion of a substrate in the industrial process are mainly caused by the radicalchain oxidation of cyclohexanone leading only to by-products. The catalysts of cyclohexane oxidation, viz., compounds of variable valence metals, affect the reaction rate and ratio of the yields of the target products (cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone) but exert no effect on their relative reactivity. The use of the catalytic additives increasing the yield of cyclohexanone in the step of cyclohexane oxidation in the production of caprolactam is revealed to be inexpedient.

• OSTI ID: 22943446
• Journal Information: Russian Chemical Bulletin, Journal Name: Russian Chemical Bulletin Journal Issue: 10 Vol. 67; ISSN RCBUEY; ISSN 1066-5285
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
BRANCHING RATIO
CARBON
CATALYSTS
CYCLOHEXANE
CYCLOHEXANOL
CYCLOHEXANONE
HYDROGEN
LIQUIDS
METALS
OXIDATION
OXYGEN
PEROXY RADICALS
REACTION KINETICS