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过程工程学报 ›› 2019, Vol. 19 ›› Issue (1): 25-34.DOI: 10.12034/j.issn.1009-606X.218161

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酸催化山梨醇脱水制异山梨醇的研究进展

邓 洁1, 袁 静1, 童 琴1, 代卫国1, 赵昆峰1, 王耀锋2, 徐宝华2, 何丹农1,3*   

  1. 1. 纳米技术及应用国家工程研究中心,上海 200241 2. 中国科学院过程工程研究所离子液体与绿色工程研究部,北京 100190 3. 上海交通大学材料科学与工程学院,上海 200240
  • 收稿日期:2018-03-27 修回日期:2018-07-03 出版日期:2019-02-22 发布日期:2019-02-12
  • 通讯作者: 邓洁 dengjie_94@163.com
  • 基金资助:
    国家重大科学研究计划项目;国家重大科学研究计划课题;上海市青年科技启明星计划项目B

Research progress on acidic catalyzed dehydrative formation of isosorbide from sorbitol

Jie DENG1, Jing YUAN1, Qin TONG1, Weiguo DAI1, Kunfeng ZHAO1, Yaofeng WANG2, Baohua XU2, Dannong HE1,3*   

  1. 1. National Engineering Research Center for Nanotechnology, Shanghai 200241, China 
    2. Key Laboratory of Ionic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 
    3. School of Materials Science and Engineering, Shanghai Jiaotong University, Shanghai 200240, China
  • Received:2018-03-27 Revised:2018-07-03 Online:2019-02-22 Published:2019-02-12

摘要: 异山梨醇是一种生物基功能性二元醇,近年来因其在聚合物工业中的潜在应用价值而备受关注。山梨醇脱水反应是生物质转化合成异山梨醇的关键步骤,目前普遍采用酸催化体系,且在酸性催化剂开发及工艺研究方面均取得了良好进展。本工作主要介绍了已报道的酸性催化剂结构与性质对催化活性及选择性的影响,指出强酸性均相催化剂具有高催化活性,但腐蚀性强,且不易循环利用;多相催化剂催化活性与酸性位点、酸度、酸容量、孔结构、表面性质和结构等都有关系,且这些性质随催化剂组成和结构改变而相互影响。针对目前山梨醇脱水反应催化剂均相催化腐蚀性强、催化剂循环性差,多相催化剂催化活性不高的现状,高催化活性可循环使用的离子液体催化剂是一种具有发展潜力的均相催化剂,对多相催化剂构效关系还应进行更多的研究以指导新型催化剂的开发。

关键词: 异山梨醇, 山梨醇, 脱水, 均相催化, 多相催化, 构效关系

Abstract: Isosorbide is a biomass-derived functional diol, with wide applications in the synthesis of several pharmaceutical molecules and fine chemicals. It attracted much attention recently due to its potential applications in the polymer industry. The catalytic dehydration of sorbitol represents a key and challenging step in the synthesis of isosorbide from biomass. Up to now, the acid catalytic system has been extensively explored and significant progresses were made with respect to both of catalyst designing and process optimization. This review mainly provides the relationship between structure and activity of different acid catalyst types. The first section comprehensively introduces the acid-catalyzed dehydration of sorbitol to isosorbide and the mechanism involved. The following two sections describe the progresses made in the homogenous and heterogeneous catalysts, respectively. The homogeneous catalyst mainly includes Br?nsted mineral acids, Lewis acids and ionic liquids, and the focus of was put on the influence of acid sites, acidity, stability and reaction solvent to sorbitol dehydration. The heterogeneous catalyst mainly includes acid resin, zeolite, supported metal oxide, heteropolyacid, sulphate and phosphate metal oxides, acid polymer and macromolecule catalyst. In addition to acid sites, acidity and stability, the acid capacity, pore structure, and surface structure and nature also have importantly effects on the activity of heterogeneous catalyst. Moreover, the effects of preparation methods of heterogeneous catalysts on their properties will be discussed. This article pointed out that Br?nsted mineral acids of strong acidity provided better catalytic activity, which, however, had the worst corrodibility and are difficult to be recycled. Latest reported acidic ionic liquids with tunable acidity and non-volatility in principle enables catalyst recycling, which may become competitive catalysts to replace mineral acids. For the heterogeneous catalytic system, the catalytic activity is closely related to the composition and structure of catalysts launched. More researches about the relationship between structure and activity needs to be carried out to develop efficient solid catalyst.

Key words: isosorbide, sorbitol, dehydration, homogeneous catalysis, heterogeneous catalysis, the structure-activity relationship