叔丁醇体系中化学酶法催化α-蒎烯环氧化  

Chemoenzymatic epoxidation of α-pinene in tert-butanol system

作　　者：刘永飞 苏伟 梁琪琪 李青云[1,2] 刘幽燕 唐爱星[1,2] LIU Yongfei;SU Wei;LIANG Qiqi;LI Qingyun;LIU Youyan;TANG Aixing(College of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,Guangxi,China;Key Laboratory of Guangxi Biorefinery,Nanning 530007,Guangxi,China)

机构地区：[1]广西大学化学化工学院,广西南宁530004 [2]广西生物炼制重点实验室,广西南宁530007

出　　处：《化工进展》2022年第6期3002-3009,共8页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(21966007);广西自然科学基金(2018GXNSFAA281278)。

摘　　要：采用叔丁醇作为α-蒎烯环氧化的反应溶剂,使过氧化氢水溶液和其他疏水性反应底物形成均相,构建单相体系以代替传统有机-水“双相”系统。首先在摇瓶中对单相体系进行优化,在α-蒎烯浓度为0.3mol/L时,乙酸乙酯的最适浓度为3.5mol/L,过氧化氢的最适浓度为0.5mol/L,束酸剂为柠檬酸三钠,在40℃下,反应90min,环氧化转化率为92%,收率为88%。此工艺条件下Novozym435重复使用6次后,仍保持64%的相对活力。然后以摇瓶实验为基础,构建了一种连续搅拌釜式反应器(CSTR),探索反应器的最适运行条件,测试了其长期运行性能,结果表明:当Novozym435酶量为2.0g、过氧化氢浓度为0.5mol/L、停留时间为3h时,釜式反应器的运行效果最好,其转化率可达83%,收率可达79%,在此条件下反应器连续运行十天后依然可以保持70%以上的转化率和55%以上的收率。Using tert-butanol as the reaction solvent, aqueous hydrogen peroxide was fused with other hydrophobic reaction substrates to construct a single-phase reaction system for epoxidation of α-pinene to replace the traditional organic-water “two-phase” system. Firstly, the single-phase system was optimized in shaking flask. When the concentration of α-pinene was 0.3mol/L, the optimum concentration of ethyl acetate and hydrogen peroxide was 3.5mol/L and 0.5mol/L, respectively, trisodium citrate was selected as the acid-trapping reagent, and the epoxidation conversion and yield at 40℃ for 90min were92% and 88%, respectively. Under this process conditions, Novozym435 could still maintain 64% relative activity after being reused 6 times. Then, based on the shaking flask experiment, a continuous stirred tank reactor(CSTR) was constructed, the optimal operating conditions of the reactor were studied, and its longterm operating performance was tested. The results showed that: when the amount of Novozym435 enzyme was 2.0g, the concentration of hydrogen peroxide was 0.5mol/L and the residence time was 3h, the tank reactor had the best operating effect with a conversion of 83% and a yield of 79%. Under these conditions,the reactor could still maintain more than 70% conversion and more than 55% yield after 10 days of continuous operation.

关 键 词：溶剂 蒎烯 催化 环氧化 化学反应器 

分 类 号：Q503[生物学—生物化学]