Catalyst-free and solvent-free oxidation of cycloalkanes(C5-C8) with molecular oxygen:Determination of autoxidation temperature and product distribution  

作　　者：Haimin Shen Yan Wang Jinhui Deng Long Zhang Yuanbin She 

机构地区：[1]State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology

出　　处：《Chinese Journal of Chemical Engineering》2018年第5期1064-1070,共7页中国化学工程学报（英文版）

基　　金：Supported by the National Natural Science Foundation of China(Grant No.21476270,21306176,21776259,21276006);Scientific Research Launching Foundation of Zhejiang University of Technology(Grant No.G2817101103)

摘　　要：Autoxidation of cycloalkanes （C5-C8） with molecular oxygen under catalyst-free and solvent-free conditions was conducted systematically for the first time, focusing on the autoxidation temperature and product distribution. The autoxidation of cyclopentane, cyclohexane, cycloheptane and cyclooctane occurs at 120 ℃, 130 ℃, 120 ℃, and 105 ℃ respectively, with obvious oxidized products formation. At 140 ℃, 145 ℃, 130 ℃ and 125 ℃, acceptable yields of the oxidized products could be obtained for them, and the oxidized product distributions were investigated in detail. The autoxidation of cycloalkanes follows the pseudo-first-order kinetic model and the apparent activation energies （Ea） for the autoxidation of cyclopentane and cyclohexane are 159.76 kJ. tool-1 and 86.75 kJ. mol-1 respectively. This study can act as an important reference in screen of suitable reaction temperature and comparison of the performance of various catalysts in the catalytic oxidation of cycloalkanes in the attempt to enhance the oxidized product selectivity.Autoxidation of cycloalkanes(C5–C8) with molecular oxygen under catalyst-free and solvent-free conditions was conducted systematically for the first time, focusing on the autoxidation temperature and product distribution. The autoxidation of cyclopentane, cyclohexane, cycloheptane and cyclooctane occurs at 120 ℃,130 ℃, 120 ℃, and 105 ℃ respectively, with obvious oxidized products formation. At 140 ℃, 145 ℃, 130 ℃ and 125 ℃, acceptable yields of the oxidized products could be obtained for them, and the oxidized product distributions were investigated in detail. The autoxidation of cycloalkanes follows the pseudo-first-order kinetic model and the apparent activation energies(E_a) for the autoxidation of cyclopentane and cyclohexane are 159.76 kJ·mol^(-1) and 86.75 kJ·mol^(-1) respectively. This study can act as an important reference in screen of suitable reaction temperature and comparison of the performance of various catalysts in the catalytic oxidation of cycloalkanes in the attempt to enhance the oxidized product selectivity.

关 键 词：CYCLOALKANE Oxidation Autoxidation temperature Product distribution 

分 类 号：TQ203.5[化学工程—有机化工]