Page 220 - 《精细化工》2021年第5期

第 38 卷第 5 期 精 细 化 工 Vol.38, No.5
202 1 年 5 月 FINE CHEMICALS May 2021

精细化工中间体
丙酮液相氨肟化连续流反应

刘建武，张 跃

（常州大学 药学院，江苏 常州 213164）

摘要：液相条件下，以丙酮、氨水和双氧水为原料，钛硅分子筛（TS-1）为催化剂，溴化钠为助催化剂，叔丁
醇为溶剂，在具有特殊微结构的连续流微通道反应器（AFR）中一步氧化合成了丙酮肟。考察了双氧水质量分
数、氨水/丙酮物质的量比、双氧水/丙酮物质的量比、溶剂/丙酮物质的量比、催化剂和助催化剂用量、温度以
及停留时间对氨肟化的影响。结果表明，AFR 出口压力 500 kPa、反应温度 100 ℃、n(氨水)∶n(双氧水)∶n(叔
丁醇)∶n(丙酮)=3.0∶1.1∶6.0∶1.0、双氧水质量分数 70%、氨水质量分数 25%、催化剂用量 8 g（以 58.08 g 丙
酮的质量为基准，下同）、助催化剂用量 3 mg、停留时间 72 s 条件下，丙酮转化率为 75.7%、丙酮肟选择性和
收率分别为 96.8%和 73.5%。AFR 具有持液量小、停留时间短、强传质传热等特点，强化了反应物料和催化体
系之间的协同效应，提高了氨肟化反应速率。
关键词：丙酮；氨肟化；连续流；钛硅分子筛；丙酮肟；精细化工中间体
中图分类号：TQ224.4 文献标识码：A 文章编号：1003-5214 (2021) 05-1074-08

Continuous flow process for ammoximation of acetone in liquid phase

LIU Jianwu, ZHANG Yue
（School of Pharmacy, Changzhou University, Changzhou 213164, Jiangsu, China）

Abstract: Acetoxime was synthesized by one-step oxidation in a continuous flow micro-channel reactor
(AFR) with special micro-structure using acetone, ammonia and hydrogen peroxide as raw materials,
titanium silicalite (TS-1) as catalyst, sodium bromide as co-catalyst, and tertbutanol as solvent. The effects
of hydrogen peroxide mass fraction, ammonia/acetone molar ratio, hydrogen peroxide/acetone molar ratio,
solvent/acetone molar ratio, catalyst dosage, co-catalyst dosage, and temperature and residence time on
ammoximation were investigated. The results showed that under conditions of outlet pressure of AFR of 500
kPa, temperature of 100 ℃, n(ammonia)∶n(hydrogen peroxide)∶n(tertbutanol)∶n(acetone)=3.0∶1.1∶
6.0∶1.0, mass fraction of hydrogen peroxide and ammonia of 70% and 25%, respectively, catalyst dosage
of 8 g (based on the mass of 58.08 g acetone, the same below), co-catalyst dosage of 3 mg and residence
time of 72 s, the conversion of acetone reached 75.7%, the selectivity and yield of acetoxime reached 96.8%
and 73.5%. AFR had significant advantages, including small liquid holding capacity, short residence time,
strong mass transfer and heat transfer, which strengthens coordination effect between reaction material and
catalytic system, so increases the reaction rate of ammoximation.
Key words: acetone; ammoximation; continuous flow; TS-1; acetoxime; fine chemical intermediates

[2]
丙酮肟别名二甲基酮肟，具有低毒性、环境友 丙酮肟传统生产方法主要有盐酸羟胺法 和亚
[3]
好、高还原性能等优点，是一种优良的还原剂，可 硝酸钠法 。盐酸羟胺法是由盐酸羟胺溶液滴加于
替代联氨和毒性较大的肼作为锅炉给水的除氧剂和 丙酮中发生肟化反应，肟化液经调碱、冷却过滤、
缓蚀剂，也可作为聚氨酯封闭剂、医药、农药、染 蒸馏、结晶制得丙酮肟。亚硝酸钠法是在冰水浴中
[1]
料及有机硅偶联剂的原料 。 先将无水碳酸钠通入二氧化硫制成亚硫酸氢钠饱和

收稿日期：2020-08-29; 定用日期：2020-10-23; DOI: 10.13550/j.jxhg.20200807
基金项目：江苏省产学研前瞻性联合研究项目（BY2014037-19）
作者简介：刘建武（1973—），男，高级工程师，E-mail: liujianwu@cczu.edu.cn。