化工进展 ›› 2020, Vol. 39 ›› Issue (10): 4147-4154.DOI: 10.16085/j.issn.1000-6613.2019-2032

• 精细化工 • 上一篇    下一篇

酮肟水解反应及其羟胺产品分离的研究进展

刘家琪1(), 刘连永1, 王双瑜1, 李志会1, 张艳华1, 丁晓墅1, 张东升1,2,3(), 赵新强1,2,3, 王延吉1,2,3()   

  1. 1.河北工业大学化工学院,绿色化工与高效节能河北省重点实验室,天津 300130
    2.天津市本质安全化工 技术重点实验室,天津 300130
    3.河北省绿色化学工业产业技术研究院,河北 黄骅 061100
  • 出版日期:2020-10-05 发布日期:2020-10-09
  • 通讯作者: 张东升,王延吉
  • 作者简介:刘家琪(1993—),男,硕士研究生,研究方向为绿色反应工程与工艺。E-mail:liujiaqi_7777777@163.com
  • 基金资助:
    国家自然科学基金(21878069);河北省自然科学基金(B2016202335)

Research progress of ketoxime hydrolysis reaction and its hydroxylamine product separation

Jiaqi LIU1(), Lianyong LIU1, Shuangyu WANG1, Zhihui LI1, Yanhua ZHANG1, Xiaoshu DING1, Dongsheng ZHANG1,2,3(), Xinqiang ZHAO1,2,3, Yanji WANG1,2,3()   

  1. 1.Key Laboratory of Green Chemical Technology and High Efficient Energy Saving of Hebei Province, Hebei University of Technology, Tianjin 300130, China
    2.Tianjin Key Laboratory of Chemical Process Safety, Tianjin 300130, China
    3.Hebei Industrial Technology Research Institute of Green Chemical Industry, Huanghua 061100, Hebei, China
  • Online:2020-10-05 Published:2020-10-09
  • Contact: Dongsheng ZHANG,Yanji WANG

摘要:

羟胺(盐)是一种重要的化工原料。传统的羟胺制备方法,如拉西法、催化还原(HPO)法等,存在污染环境、工艺流程冗杂、设备腐蚀严重、原料原子利用率低等不足。基于绿色化学理念和羟胺合成的研究现状,本文以酮肟水解制备羟胺反应为重点,从水解反应的原料、催化剂、反应产物及其分离方式等角度,阐述了酮肟水解法制备羟胺产品的研究进展;并同时针对酮肟水解反应提出了质子化酮肟的反应机理,讨论了反应蒸馏(精馏、萃取)-耦合、聚二甲基硅氧烷薄(PDMS)膜原位分离法等新型反应、分离技术在酮肟水解中的最新应用。在此基础上,指出借助反应萃取-耦合等新型反应、分离技术,开发温和条件下清洁高效的催化酮肟水解一步合成羟胺及其盐的工艺过程,或将成为今后研究的热点。

关键词: 羟胺, 一步合成, 酮肟, 水解, 催化剂, 反应精馏, 蒸馏

Abstract:

Hydroxylamine and its salts are important raw materials in chemical industry. Traditional methods for preparing hydroxylamine such as the Rashing and HPO methods, suffer from some drawbacks like environmental pollution, complicated process flow, serious equipment corrosion, and low utilization of raw material atoms. Based on the concept of green chemistry and current research status of hydroxylamine synthesis, the preparation of hydroxylamine products by hydrolysis of ketoxime was introduced from the perspectives of raw materials, catalysts, products and product separation methods of hydrolysis reaction. Moreover, a protonated ketoxime reaction mechanism was proposed for the ketoxime hydrolysis reaction. The latest applications of reaction distillation (rectification, extraction) coupling and in situ PDMS membrane separation in the hydrolysis of ketone oxime were also discussed. Finally, the development of new reaction and separation technologies such as reaction-extraction coupling for the hydrolysis of ketonoxime under mild conditions and efficient, clean and one-pot synthesis of hydroxylamine as well as its salt may become the research trends in the future.

Key words: hydroxylamine, one-step synthesis, ketoxime, hydrolysis, catalyst, reactive distillation, distillation

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