响应面优化脂肪酶催化Baeyer-Villiger反应制备ε-己内酯  

Optimization of Baeyer-Villiger reaction mediated by lipase for preparation of ε-caprolactone using response surface methodology

作　　者：许慧 薛晓 李楷原 刘翠 邓雅姗 张媛媛[1] XU Hui;XUE Xiao;LI Kai-yuan;LIU Cui;DENG Ya-shan;ZHANG Yuan-yuan(College of Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266042,China)

机构地区：[1]青岛科技大学化工学院,山东青岛266042

出　　处：《兰州理工大学学报》2022年第6期67-73,共7页Journal of Lanzhou University of Technology

基　　金：国家自然科学基金(21546004,21576145)。

摘　　要：固定化T.laibaccii脂肪酶介导化学-酶Baeyer-Villiger氧化法制备ε-己内酯.运用响应面法进行了实验设计,获得了最优反应条件:环己酮初始浓度为1.22 mol/L,环己酮与过氧化氢脲的物质的量比为1∶1.3,反应温度为56.5℃,产率达到98.06%,浓度高达1.2 mol/L.在环己酮、乙酸乙酯反应体系中有三个反应,其中第三个反应是过氧化氢脲通过固定化脂肪酶的作用与中间产物乙酸反应,乙酸原位生成过氧乙酸.建立了二次多项式模型,其R2值为0.998 8,可以准确地预测ε-己内酯产率.该模型考虑了环己酮的初始浓度、环己酮与过氧化氢脲的物质的量比和反应温度对ε-己内酯产率的影响,环己酮与过氧化氢脲的物质的量比对ε-己内酯的产率有非常显著的影响(p<0.000 6).Immobilized T. laibaccii lipase-mediated chemical-enzyme Baeyer-Villiger oxidation method can prepare ε-caprolactone. The experimental design was carried out by response surface method, and the optimal reaction conditions were obtained, which the concentration of cyclohexanone was 1.22 mol/L, the molar ratio of cyclohexanone to urea hydrogen peroxide was 1∶1.3, the reaction temperature was 56.5 ℃, the yield reached 98.06%, and the concentration was as high as 1.2 mol/L. There are three reactions in the reaction system of cyclohexanone and ethyl acetate, which the third reaction is that urea hydrogen peroxide reacts with the intermediate acetic acid under the action of immobilized lipase, and acetic acid generates peracetic acid in situ. The quadratic polynomial model was established with the R~2 value of 0.998 8, which can accurately predict the yield of ε-caprolactone. In this model, the effect of initial concentration of cyclohexone, the ratio of cyclohexone to urea hydrogen peroxide and reaction temperature on ε-caprolactone yield are considered. The molar ratio of cyclohexone to urea hydrogen peroxide has a very significant effect on the yield of ε-caprolactone(p<0.000 6).

关 键 词：化学-酶Baeyer-Villiger氧化 固定化脂肪酶 己内酯 最优化 响应面法 

分 类 号：TQ317[化学工程—高聚物工业]