Cyclohexane oxidation catalyzed by manganese oxide octahedral molecular sieves—Effect of acidity of the catalyst

Abstract

Oxidation of cyclohexane is an important industrial process, its oxidation products, cyclohexanol and cyclohexanone are raw materials for adipic acid and caprolactam synthesis. Acid exchanged cryptomelane type manganese oxide octahedral molecular sieves (H-K-OMS-2) was used for liquid phase oxidation of cyclohexane with t-butyl hydroperoxide as an oxidant. The H + form of K-OMS-2 was synthesized by ion-exchange of K-OMS-2 with concentrated nitric acid. H-K-OMS-2 has been found to be an efficient catalyst for the oxidation of cyclohexane with a high conversion (∼60%). More than 90% selectivity for cyclohexanol and cyclohexanone was obtained. A turn over number (TON) of 73 was obtained in 24 h at 80 °C and if we consider only contributions of acidic manganese sites then the TON is 287. Effect of increase in number of acid sites of the K-OMS-2 was correlated with the increase in conversion. The reactions were carried out in a semi-batch reactor at 80 °C using acetonitrile as solvent. Effects of solvent, temperature, and amount of t-butyl hydroperoxide on conversion and selectivity were studied.