过渡金属离子双相体系催化纤维素制备5-羟甲基糠醛的机理及应用研究

项目名称： 过渡金属离子双相体系催化纤维素制备5-羟甲基糠醛的机理及应用研究

项目编号： No.21506137

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 有机化学

项目作者： 严立石

作者单位： 苏州科技大学

项目金额： 21万元

中文摘要： 5-羟甲基糠醛(HMF)是重要的平台化合物，用于合成许多有用化合物及燃料。利用生物质衍生的纤维素代替来源有限的果糖制备HMF，是实现其工业化的有效途径。然而，由于目前纤维素很难简单高效的转化HMF，制约了其工业化进程。过渡金属离子由于其均相特质、倾向于削弱多糖糖苷键、促进吡喃糖转化呋喃糖等特点，有望实现一步催化纤维素制备HMF。本课题利用过渡金属离子在较廉价的双相体系中催化纤维素制备HMF。针对纤维素降解过程中三个重要反应：纤维素水解、葡萄糖脱水产 HMF以及葡萄糖反羟醛缩合产乳酸等副产物，选取合适过渡金属离子，考察不同过渡金属离子与纤维素及葡萄糖的配合机制及对这三个反应的影响，探究反应机理。获得利于纤维素定向转化制备HMF的催化剂信息。同时探究有机相对HMF的萃取效率以及HMF在双相体系中反应动力学，掌握定向转化纤维素制备HMF的调控方法。本课题对实现纤维素一步转化HMF有重要意义。

中文关键词： 5-羟甲基糠醛；过渡金属离子；水解；脱水；反羟醛缩合

英文摘要： 5-hydroxymethylfurfural (HMF) is an important platform intermediate due to its potential availability for the synthesis of varied chemicals and fuels. The current feedstock for HMF production is primarily dependent on fructose. Nevertheless, the resources of fructose are limited, impeding its application in industry. Applying biomass derived cellulose instead of fructose to produce HMF is a promising way for the industrialization of HMF. However, cellulose is insusceptible to be effectively converted into HMF by current approach, therefore limiting its industrialization process. Transition metal ions have shown promising efficiency for one-pot conversion of cellulose to HMF due to their homogeneous properties, ability to attenuate glycosidic bond and transform pyranose to furanose. This work will select appropriate transition metal ions as catalyst for cellulose conversion to HMF in biphasic systems. The effects of varied transition metal ions on cellulose hydrolysis, glucose dehydration to HMF, and glucose retro-aldol to lactic acid and other byproducts will be studied. Particularly, the coordination of metal ions with cellulose and glucose will be investigated to depicture the mechanism of cellulose degradation catalyzed by transition metal ions. This research will obtain significant information regarding optimal transition metal ions for cellulose conversion to HMF. In addition, the effects of organic solvent on extraction efficiency of HMF, the kinetics of HMF production will be studied as well to master the degradation module of cellulose to HMF in biphasic systems. This work will play an important role in realizing one-pot conversion of cellulose to HMF.

英文关键词： 5-hydroxymethylfurfural;transition metal ions;hydrolysis;dehydration;retro-aldol