钒络合物及其负载型催化剂的烃类催化氧化机理  

Catalytic Oxidation Mechanism of Hydrocarbons Using Vanadium Picolinic Complexes Catalyst and Its Zeolite-encapsulated Catalyst

作　　者：周颖霏[1] 柏子龙[1] 陈绍洲[1] 

机构地区：[1]华东理工大学石油加工研究所,上海200237

出　　处：《华东理工大学学报（自然科学版）》2003年第2期138-143,共6页Journal of East China University of Science and Technology

基　　金：国家自然科学基金资助项目(2976019);教育部"高等学校骨干教师资助计划"资助项目。

摘　　要：制备了钒络合物催化剂及其分子筛负载型催化剂,并对1-辛烯、环己烷、甲苯、正己烷和正庚烷的均相及非均相催化氧化反应进行了研究。实验结果表明,非均相催化剂不但具备与均相催化剂相似的催化氧化性能,还对伯醇和对位产物有较好的择形选择性。本研究还考察了乙腈、二氯甲烷等溶剂对烃类均相及非均相催化氧化反应的溶剂效应,提出并验证了钒络合物催化剂作用下烃类催化氧化反应的自由基反应机理。Zeoliteencapsulated vanadium(Ⅳ) picolinic complexes catalyst and corresponding homogeneous catalyst VO(pic)2·H2O are prepared. The catalysts are used in the oxidation of 1octene, cyclohexane, toluene, nhexane and nheptane. The results suggest that the 'shipinabottle' catalyst retains the same catalytic activity as homogeneous catalyst VO(pic)2·H2O and exhibits good shape selectivity as compared to the unencapsulated complexes. The effect of solvents, including acetonitrile, dichloromethane and hexane, on alkanes catalytic oxidation are investigated. A free radical mechanism of hydrocarbons catalytic oxidation is suggested and proved by adding a free radical trap.

关 键 词：烃类 催化氧化反应 自由基反应机理 钒络合物催化剂 分子筛负载型催化剂 石油化工 

分 类 号：TE624.9[石油与天然气工程—油气加工工程]