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。
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 k Pa, 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.
作者
刘建武
张跃
LIU Jianwu;ZHANG Yue(School of Pharmacy,Changzhou University,Changzhou 213164,Jiangsu,China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2021年第5期1074-1080,共7页
Fine Chemicals
基金
江苏省产学研前瞻性联合研究项目(BY2014037-19)。
