微乳条件下磷酸氢锆催化环己酮液相氨肟化反应研究  

Study on Liquid-Phase Ammoximation of Cyclohexanone in Microemulsion over Zirconium Hydrogen Phosphate

作　　者：程庆彦[1] 朱响林 王延吉[1] 赵新强[1] 

机构地区：[1]河北工业大学绿色化工与高效节能河北省重点实验室,天津300130

出　　处：《复旦学报（自然科学版）》2017年第2期233-240,共8页Journal of Fudan University：Natural Science

摘　　要：针对环己酮(CYC)液相氨肟化制备环己酮肟(CHO)用到昂贵的TS-1催化剂,寻找该反应的新型催化剂是降低其成本的根本方法.以磷酸氢锆为催化剂,聚乙二醇-6000(PEG-6000)为表面活性剂,叔丁醇为助表面活性剂,水为溶剂,构建了新型的微乳反应体系.考察了表面活性剂的种类、表面活性剂的量、催化剂的量、底物物料比、双氧水添加方式、反应温度、反应时间等对环己酮氨肟化反应的影响.结果表明,在环己酮为0.01mol,反应物摩尔比n(CYC)∶n(NH3·H2O)∶n(H2O2)=1∶5∶2.3,催化剂磷酸氢锆0.5g,表面活性剂PEG-6000 1.3g,助表面活性剂叔丁醇2mL,水4mL,双氧水一次性加入,65℃反应3.5h的条件下,环己酮的转化率和环己酮肟的收率可分别达到95.3%和69.1%.Aiming at the problems of industrial production of cyclohexanone oxime catalyzed by expensive TS-1, finding a new catalyst to reduce the industrial costs is the fundamental way. This article used zirconium hydrogen phosphate as the catalyst, polyethylene glycol 6000 （PEG-6000） as the surfactant, t-butanol as the co-surfactant, and H2O as the solvent to establish a new reaction environment of microemulsion system for liquid-phase ammoximation of cyclohexanone. The effects of type of surfactant, surfactant amount, reaction temperature, catalyst amount, the molar ratio of substrate, adding method of H2O2, reaction time on ammoximation of cyclohexanone over zirconium hydrogen phosphate were investigated. The results revealed that the cyclohexanone conversion and cyclohexanone oxime yield can reached 95.3% and 69.1% respectively under the reaction conditions of n（CYC） =0.01 mol, n（CYC）∶n（NH3·H2O）∶n（H2O2）=1∶5∶2.3, catalyst 0.5 g, PECk6000 1.3 g, t butanol 2 mL, H2O 4 mL, and ammonia and hydrogen peroxide was added at onetime, 65 ℃, 3.5 h.

关 键 词：微乳液 氨肟化 磷酸氢锆 环己酮肟 聚乙二醇-6000 

分 类 号：O643.3[理学—物理化学]