Progress In Catalysed Oxidation Of Cyclohexene

Oxidation of cyclohexene gives various products such as cyclohexenyl hydroperoxide cyclohexenol, cyclohexeneone, and cyclohexene oxid etc. The products are important industrially materials. The aspects in oxygen supply are organic peracid, tert-butyl hydroperoxide, hydrogen peroxide and molecular oxygen. However, using organic peracid and tert-butyl hydroperoxide as oxidant source demands highly for the equipments and cause environmental pollution in separation process. All of the characters mentioned above don’t suit to the demand of industrial production and green chemicals. Using molecular oxygen as oxidant source, the reaction is hard to controlled and with various products. Due to the cheap raw material and mild reaction condition, hydrogen peroxide is recognized as environmental friendly. Most reaction in oxidation of cyclohexene be catalyzed by Heteropoly acid(salt), Metals(Mo、V、Nb、Ru etc.) supported mesoporous silicate materials and metalloporphyrin or Metal phthalocyanine, they show significantly higher catalytic activity, however, synthesis of these catalysis is difficut and complicated, and needs strong conditions. Hence, it is along way to search the cheap and easily available catalysis. In this paper the research is based on phenol hydroxylation and benzene hydroxylation, oxidation of cyclohexene is investigated by using iron based catalyst, reaction conditions are optimized and reaction mechanism is discussed. The main contents are the following:1. Oxidation of cyclohexene can be catalyzed by spinel type iron oxide (MgFe2O4), FexOy catalyst is characterized by XRD、TG-DTA and FT-IR. Effects of reaction catalyst amount, the molar ration of H2O2to cyclohexene, catalyst roasting temperature temperature and solvent volume are investigated. The results showed that under the condition:cyclohexene0.01mol, H2O21.5ml (the molar ration of H2O2to cyclohexene is 1.5:1), MgFe2O40.04g, acetone volume8.0ml, reaction temperature60℃and reaction timel2h, the conversion of cyclohexene reaches to34.3%, the selectivity to2-cyclohexene-1-one is57.3%.2. Oxidation of cyclohexene can be catalyzed by Fe3+as catalyst and catechol as cocatalyst, result is showed. Effects of reaction time, temperature, the molar ration of H2O2to cyclohexene and solvent volume are investigated. The results showed that, Fe3++catechol has catalytic activity on oxidation of cyclohexene. Under the condition: cyclohexene0.01mol, H2O20.015mol, Fe(NO3)3·9H2O0.08g, n(Fe3+):n(catechol)=50:1, acetone volume8.0ml, reaction temperature60℃, the conversion of cyclohexene reaches to40.2%, the selectivity to2-cyclohexene-l-one is36.7%.3. Using Sodium metavanadate as catalyst, Effects of reaction time, temperature, he molar ration of H2O2to cyclohexene and solvent volume are investigated. Results showed that, Sodium metavanadate has good catalytic activity on oxidation of cyclohexene, the main product is2-cyclohexene-l-one. Under the condition:H2O20.01mol, NaVO30.024g, HCl(0.036g/ml)acetone volume8.0ml, reaction temperature30℃, the conversion of cyclohexene reaches to16.7%, the selectivity to2-cyclohexene-l-one is86.0%.