TS-1分子筛催化苯甲醛或环己酮氨肟化反应机理  

Ammoximation Reaction Mechanism of Benzaldehyde or Cyclohexanone Catalyzed by TS-1 Zeolite

作　　者：杨永佳[1] 夏长久[1] 林民[1] 朱斌[1] 彭欣欣[1] 罗一斌[1] 舒兴田[1] YANG Yongjia;XIA Changjiu;LIN Min;ZHU Bin;PENG Xinxin;LUO Yibin;SHU Xingtian(State Key Laboratory of Catalytic Materials and Reaction Engineering,Research Institute of Petroleum Processing,SINOPEC,Beijing 100083,China)

机构地区：[1]中国石化石油化工科学研究院石油化工催化材料与反应工程国家重点实验室,北京100083

出　　处：《石油学报（石油加工）》2020年第4期653-660,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点基础研究发展计划“973”项目(2006CB202500.7-22);国家青年基金项目(201808244)资助。

摘　　要：采用在线红外光谱仪对苯甲醛、环己酮氨肟化反应过程进行跟踪检测,并设计两步实验法,系统探究了TS-1/H2O2催化氧化体系中苯甲醛、环己酮氨肟化反应机理。结果表明:环己酮氨肟化反应过程不存在亚胺路径,反应主要遵循羟胺路径;苯甲醛氨肟化反应过程中,苯甲醛与氨可相互作用生成亚胺中间体,亚胺中间体可进一步被TS-1/H2O2催化氧化为苯甲醛肟;同时该过程氨可被TS-1/H2O2催化氧化为羟胺中间体(NH 2OH),苯甲醛与羟胺反应直接生成苯甲醛肟,即苯甲醛氨肟化反应过程中同时存在亚胺路径和羟胺路径。Ammoximation reaction mechanism of benzaldehyde or cyclohexanone was systematically investigated.Ammoximation of either benzaldehyde or cyclohexanone was monitored in situ by online infrared spectroscopy.Ammoximation reaction through two steps were designed to explore the reaction intermediate.It can be concluded that cyclohexanone ammoximation mainly proceeds through hydroxylamine route since there is no imine intermediate formed from cyclohexanone and NH3·H2O.However,it is found that imine intermediate can be formed by in-situ condensation of benzaldehyde with NH3·H2O during benzaldehyde ammoximation.Subsequently,benzaldehyde imine can be further catalytically oxidized to form benzaldehyde oxime by TS-1/H2O2.During the above process,hydroxylamine intermediate(NH 2OH)also can be formed by NH3·H2O oxidation by TS-1/H2O2.Then,benzaldehyde oxime can be produced by subsequent reaction between hydroxylamine and benzaldehyde.Therefore,both imine pathway and hydroxylamine pathway exist in benzaldehyde ammoximation process.

关 键 词：苯甲醛 环己酮 氨肟化 反应机理 在线红外光谱 

分 类 号：TQ215[化学工程—有机化工]