石油学报(石油加工) ›› 2020, Vol. 36 ›› Issue (4): 653-660.doi: 10.3969/j.issn.1001-8719.2020.04.001

• 研究报告 •    下一篇

TS-1分子筛催化苯甲醛或环己酮氨肟化反应机理

杨永佳, 夏长久, 林民, 朱斌, 彭欣欣, 罗一斌, 舒兴田   

  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
  • 收稿日期:2019-05-21 修回日期:2020-02-06 出版日期:2020-07-25 发布日期:2020-09-23
  • 通讯作者: 林民,男,教授级高级工程师,博士,从事烃类选择性氧化催化剂和工艺方面的研究,Tel: 010-82368801, E-mail:linmin.ripp@sinopec.com;夏长久,男,高级工程师,博士,从事杂原子分子筛与催化氧化方面的研究;Tel:82368801, E-mail:xiachangjiu.ripp@sinopec.com E-mail:15652720101@163.com
  • 作者简介:杨永佳,男,博士,从事催化氧化新反应基础研究
  • 基金资助:
    国家重点基础研究发展计划“973”项目(2006CB202500.7-22)和国家青年基金项目(201808244)资助

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

YANG Yongjia, XIA Changjiu, LIN Min, ZHU Bin, PENG Xinxin, LUO Yibin, SHU Xingtian   

  1.  State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
  • Received:2019-05-21 Revised:2020-02-06 Online:2020-07-25 Published:2020-09-23
  • Supported by:
     

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(NH2OH),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。

关键词: 苯甲醛, 环己酮, 氨肟化, 反应机理, 在线红外光谱

Abstract: 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 (NH2OH) 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.

Key words: benzaldehyde, cyclohexanone, ammoximation, reaction mechanism, online infrared spectroscopy

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