酮肟水解反应及其羟胺产品分离的研究进展

Research progress of ketoxime hydrolysis reaction and its hydroxylamine product separation

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。

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.