微波助离子液体中生物质糖类催化转化为平台化合物5-羟甲基糠醛的研究

项目名称： 微波助离子液体中生物质糖类催化转化为平台化合物5-羟甲基糠醛的研究

项目编号： No.20806041

项目类型： 青年科学基金项目

立项/批准年度： 2009

项目学科： 化学工业

项目作者： 漆新华

作者单位： 南开大学

项目金额： 18万元

中文摘要： 5-羟甲基糠醛(5-HMF)是一种重要的可基于生物质资源的化工平台化合物。本项目研究了葡萄糖、果糖、木菊粉和纤维素等向5-HMF的转化行为并开发了一系列的将生物质转化为5-HMF的绿色高效过程。主要贡献和创新点如下：（1）开发了以离子液体为溶剂、树脂为催化剂的绿色过程，将果糖转化为5-HMF的反应温度从传统方法所需要的200度降低到了80度，反应时间降低到了10min，5-HMF产率达到83％以上。（2）首次实现了常温下果糖向5-HMF的高效转化。（3）开发了微波助葡萄糖催化转化为5-HMF的快速体系，在140度下反应30s即得到71％的5-HMF产率。（4）利用水和离子液体两种绿色溶剂在200度的中温下产生的协同效应，开发了无Cr催化下有效转化葡萄糖为5-HMF的绿色体系。（5）巧妙利用两种离子液体的特点，创新性地开发了一套两步法将木菊粉高效转化为5-HMF的温和绿色工艺。（6）创造性地采用在离子液体中纤维素水解过程中逐步增加体系中水的方法，获得83％的葡萄糖产率，进而获得了73％的5-HMF产率。本项目为将生物质这种可再生资源转化为可替代石化资源的化学品开辟了一条绿色高效的新路径。

中文关键词： 5-羟甲基糠醛；离子液体；葡萄糖；果糖；绿色过程

英文摘要： As a key renewable chemical for plastics, fine chemicals and biofuels, the preparation of 5-hydroxymethylfurfural (5-HMF) from biomass is an important research topic. In this work, a series of efficient green processes for the production of 5-HMF from biomass (including cellulose, inulin, glucose and fructose) are developed. The main originality and contributions including: (1) An efficient process for the dehydration of fructose into 5-HMF in ionic liquid 1-butyl-3-methyl imidazolium chloride ([BMIM][Cl]) by using a sulfonic ion-exchange resin as catalyst was developed. A fructose conversion of 98.6% with a 5-HMF yield of 83.3% was achieved in 10 min reaction time at 80 oC. (2)The conversion of fructose into 5-HMF at room temperature at quantitative yields was realized at the first time.(3)Fast transformation of glucose and di/polysaccharides into 5-HMF was achieved in ionic liquid system by microwave heating, where 71% of 5-HMF yield was obtained at 140 oC in 30 s. (4)An efficient green method for converting glucose into 5-HMF without using chromium- containing catalysts was developed. (5)An efficient one pot, two-step process was developed for the preparation of 5-HMF from inulin in ionic liquids under mild conditions, giving a 5-HMF yield of 82% in 65 min at 80 oC, which is the highest 5-HMF yield reported by thus far for an inulin feedstock.For using common cation ionic liquids [BMIM][Cl] and [BMIM][HSO4], recycle is simplified and the process is green and efficient. (6)We show an efficient two-step process for converting microcrystalline cellulose into 5-HMF with ionic liquids under mild conditions. In the first step, high glucose yields of above 80% could be obtained from the cellulose hydrolysis by a strong acidic cation exchange resin in 1-ethyl-3-methyl imidazolium chloride ([EMIM][Cl]) with gradual addition of water. In the second step, the resin was separated from the reaction mixture and CrCl3 was added which lead to a 5-HMF yield of 73% based on cellulose substrate. The strategy can allow practical conversion of biomass into bio-derived products. These work provides novel and green methods for the transformation of renewable platform chemicals from sustainable biomass resources.

英文关键词： 5-hydroxymethylfurfural; Ionic Liquids; Glucose; Fructose; Green process