Chemical Industry and Engineering Progress ›› 2022, Vol. 41 ›› Issue (6): 3002-3009.DOI: 10.16085/j.issn.1000-6613.2021-1321

• Industrial catalysis • Previous Articles     Next Articles

Chemoenzymatic epoxidation of α-pinene in tert-butanol system

LIU Yongfei1(), SU Wei1, LIANG Qiqi1, LI Qingyun1,2, LIU Youyan1,2, TANG Aixing1,2()   

  1. 1.College of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
    2.Key Laboratory of Guangxi Biorefinery, Nanning 530007, Guangxi, China
  • Received:2021-06-24 Revised:2021-07-30 Online:2022-06-21 Published:2022-06-10
  • Contact: TANG Aixing

叔丁醇体系中化学酶法催化α-蒎烯环氧化

刘永飞1(), 苏伟1, 梁琪琪1, 李青云1,2, 刘幽燕1,2, 唐爱星1,2()   

  1. 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
  • 通讯作者: 唐爱星
  • 作者简介:刘永飞(1995—),男,硕士研究生,研究方向为生物化工。E-mail:lyfly2021@163.com
  • 基金资助:
    国家自然科学基金(21966007);广西自然科学基金(2018GXNSFAA281278)

Abstract:

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 were 92% 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 long-term 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.

Key words: solvents, pinene, catalysis, epoxidation, chemical reactor

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。

关键词: 溶剂, 蒎烯, 催化, 环氧化, 化学反应器

CLC Number: 

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