高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (5): 1029-1036.doi: 10.7503/cjcu20180668

• 物理化学 • 上一篇    下一篇

功能特异性杂多酸离子液体催化丁二酸水溶液直接酯化

丁中协1, 梁金花2, 刘振1, 沈节灿1, 张峰2, 任晓乾1(), 姜岷3   

  1. 1. 南京工业大学化工学院
    2. 生物技术与制药工程学院
    3. 材料化学工程国家重点实验室, 南京 210009
  • 收稿日期:2018-09-29 出版日期:2019-04-12 发布日期:2019-04-12
  • 作者简介:

    联系人简介: 任晓乾, 男, 博士, 副教授, 主要从事绿色化学及工业催化研究. E-mail: xqren@njtech.edu.cn

  • 基金资助:
    国家“八六三”计划项目(批准号: 2014AA021205)和材料化学工程国家重点实验室开放课题(批准号: KL14-09)资助.

Functional Specific Heteropoly Acid Ionic Liquid Catalyzed Direct Esterification of Aqueous Succinate Solution

DING Zhongxie1, LIANG Jinhua2, LIU Zhen1, SHEN Jiecan1, ZHANG Feng2, REN Xiaoqian1,*(), JIANG Min3   

  1. 1. College of Chemical Engineering
    2. College of Biotechnology and Pharmaceutical Engineerin
    3. State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, China
  • Received:2018-09-29 Online:2019-04-12 Published:2019-04-12
  • Contact: REN Xiaoqian E-mail:xqren@njtech.edu.cn
  • Supported by:
    † Supported by the National High Technology Research and Development Program of China(No.2014AA021205) and the Open Project of State Key Laboratory of Materials Chemical Engineering, China(No.KL14-09)

摘要:

将以磺化六亚甲基四胺([HMT-4PS])制备的阳离子与以杂多酸([HPA])制备的阴离子结合, 制备了一系列功能特异性离子液体催化剂([HMT-4PS][HPA]); 将其用于催化甲醇(MeOH)与丁二酸(SA)水溶液的直接酯化反应. 结果表明, 该系列离子液体在反应过程中以“乳状液”的形式均匀分散在体系中. 反应结束后, 通过降低体系极性即可实现催化剂的快速分离. 在合成的系列催化剂中, [HMT-4PS]3[PW]4表现出最佳的催化活性. 分别探讨了反应温度、 催化剂用量、 酸醇摩尔比和反应时间等因素对反应的影响, 确定了最优反应条件: 温度80 ℃, 催化剂用量5%(质量分数, 按丁二酸水溶液计), n(SA)∶n(MeOH)=1∶30, 反应时间8 h. 最优条件下丁二酸的转化率达到79.3%, 二酯选择性达到92.9%; 该催化剂重复使用5次后, 丁二酸转化率及二酯选择性仍分别保持在77%及90%以上.

关键词: 丁二酸水溶液, 杂多酸, 多相催化, Keggin结构, 离子液体

Abstract:

A series of functionally specific acid ionic liquid catalysts([HMT-4PS][HPA]) was synthesized by combining sulfonated hexamethylenetetramine[HMT-4PS] with heteropoly acid anions, and then used for catalyzing the direct esterification of methanol with aqueous succinic acid(SA) solution. The results indicated that the series of ionic liquids were uniformly dispersed in the system as “emulsion” during the reaction. After the reaction was completed, the rapid separation of the catalyst could be accomplished by reducing the polarity of the system. [HMT-4PS]3[PW]4 exhibited the best catalytic activity during the series of synthesized catalysts. The effects of temperature, amount of catalyst, molar ratio of acid to alcohol and reaction time were fully investigated. The optimal reaction conditions were determined: reaction temperature 80 ℃, catalyst mass fraction of 5%(based on SA aqueous solution), n(SA)∶n(MeOH) = 1∶30, reaction time 8 h. The conversion of succinic acid could reach 79.3%, the diester selectivity could reach 92.9%. After 5 times reused, the conversion of succinic acid and the selectivity of the diester still reached above 77% and 90%.

Key words: Succinic acid aqueous solution, Heteropoly acid, Heterogeneous catalysis, Keggin structure, Ionic liquid

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