催化学报

催化学报 ›› 2006, Vol. 27 ›› Issue (4): 365-368.

• 研究论文 • 上一篇    

铋改性的钒磷氧化物液相催化氧化环己烷的反应机理

何笃贵1,纪红兵2,罗思睿2,袁秋兰2   

  1. 1 湘南学院化学与生命科学系, 湖南郴州 423000; 2 华南理工大学化工与能源学院, 广东广州 510640
  • 收稿日期:2006-04-25 出版日期:2006-04-25 发布日期:1984-12-26

Reaction Mechanism of Liquid-Phase Oxidation of Cyclohexane Catalyzed by Bi-Modified Vanadium-Phosphorous Oxide Catalyst

HE Dugui1, JI Hongbing2*, LUO Sirui2, YUAN Qiulan2   

  1. 1 Department of Chemistry and Life Science, Xiangnan University, Chenzhou 423000, Hunan, China; 2 School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
  • Received:2006-04-25 Online:2006-04-25 Published:1984-12-26

PDF

837

被引次数

35

摘要： 制备了铋改性的钒磷氧化物(Bi-VPO)催化剂,并将其用于液相催化氧化环己烷,研究了该反应的反应机理. 结果表明,铋改性可大大提高VPO催化剂在温和条件下对环己烷液相氧化的催化性能. 无溶剂实验和四氢呋喃作溶剂的实验证明反应过程中溶剂乙腈和H2O2之间存在相互作用; 自由基捕捉实验证明环己烷氧化过程中存在自由基反应历程; 环己醇氧化实验证明环己酮并不是来自环己醇的氧化,而是由环己烷直接氧化得到的.

关键词: 铋, 钒磷氧化物, 环己烷, 液相氧化, 反应机理

Abstract: Bi-modified vanadium-phosphorous oxide (Bi-VPO) catalysts were prepared and used in liquid-phase oxidation of cyclohexane. The results showed that Bi modification could greatly enhance the catalytic performance of Bi-VPO for the oxidation of cyclohexane under mild conditions. The experiments without any solvent and with tetrahydrofuran as a solvent indicated the existence of interaction between acetonitrile and hydrogen peroxide. The free radical trap experiment proved that a free radical process is present in the catalytic system. The oxidation experiment of cyclohexanol explained that cyclohexanone is derived directly from cyclohexane oxidation instead of cyclohexanol oxidation.

Key words: bismuth, vanadium-phosphorous oxide, cyclohexane, liquid-phase oxidation, reaction mechanism