First industrial-scale biomimetic oxidation of hydrocarbon with air over metalloporphyrins as cytochrome P-450 monooxygenase model and its mechanistic studies

A novel industrial-scale trial for cyclohexane oxidation with air over metalloporphyrins as cytochrome P-450 monooxygenase model was reported. Upon addition of extremely low concentrations (1-5 ppm) of simple cobalt porphyrin to the commercial cyclohexane oxidation system, and decrease of the reaction temperature and pressure about 20 degrees C and 0.4 MPa respectively, the conversion rate of the cyclohexane oxidation increased from 4.8% to 7.1%, the yield of cyclohexanone raised from 77% to 87%, and a 70,000-ton cyclohexanone equipment set yielded an output of 125,000 tons cyclohexanone. Furthermore, a novel biological-chemical-cycle coupling mechanism was proposed to rationalize the aerobic oxidations of hydrocarbons catalyzed by the metalloporphyrins.