Development of cellulose-derived HMF production catalyzed by ion exchange resin in ionic liquid

离子液体中离子交换树脂催化纤维素衍生 HMF 生产的进展

• 批准号: 22310055
• 负责人: WATANABE Masaru
• 金额: $ 11.98万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2010
• 资助国家: 日本
• 起止时间: 2010 至 2012
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-22310055/
• 关键词: グリーンケミストリー; イオン液体; セルロース; HMF; イオン交換樹脂; グルコース; フルクトース; マイクロ波; 固体酸触媒

To develop cellulose-derived HMF production process, which includes multi-step reaction (cellulose hydrolysis, glucose isomerization and fructose dehydration), heterogeneous catalysts such as ion exchange resin and ionic liquid were employed as catalysts and solvent, respectively. It was found that sequential water addition was effective for selective glucose production via cellulose hydrolysis. It was revealed that alkali catalyst, which is normally effective for glucose isomerization in aqueous solution, became inactive in ionic liquid. Probably, this can be explained by strong interactions between alkali (or alkaline-earth) metal ion in heterogeneous catalysts and Cl- in ionic liquid (such as [Bmim][Cl]) such that active sites on the materials are poisoned. In addition, glucose isomerization into fructose is equilibrium reaction and fructose yield is limited at lower temperature because of the equilibrium constraint. To overcome these issues, direct production of HMF from glucose is effective and Lewis acid catalyst must be attempted. To accomplish energetically-favorable products separation and recycle of solvent, combination of liquid-liquid extraction with distillation would be appropriate and effective.

采用离子交换树脂和离子液体等多相催化剂作为催化剂和溶剂，开发了包括纤维素水解、葡萄糖异构化和果糖脱水等多步骤反应的纤维素基HMF生产工艺。研究发现，连续加水对纤维素水解法选择性生产葡萄糖是有效的。结果表明，通常对水溶液中葡萄糖异构化反应有效的碱性催化剂在离子液体中失活。这可能是由于非均相催化剂中的碱(或碱土)金属离子与离子液体(如[Bmim][Cl])中的Cl-发生强烈的相互作用而使材料上的活性中心中毒所致。此外，葡萄糖异构化为果糖的反应是平衡反应，在较低的温度下，由于平衡约束，果糖的产量受到限制。为了克服这些问题，从葡萄糖直接生产HMF是有效的，必须尝试使用Lewis酸催化剂。采用液-液萃取与精馏相结合的方法，可以实现能量利好的产物分离和溶剂循环利用。

项目成果

High selective glucose production from cellulose hydrolysiscatalyzed by solid acid in imidazolium-based ionic liquid

咪唑基离子液体中固体酸催化纤维素水解高选择性生产葡萄糖

• 发表时间: 2011
• 作者: Kaori Ishida;Xinhua Qi;Masaru Watanabe;Taku M. Aida;Richard L.Smith Jr.
• 通讯作者: Richard L.Smith Jr.

HMF formation from sugar (fructose and glucose) and their polymer in ionic liquids (ILs)

由糖（果糖和葡萄糖）及其聚合物在离子液体 (IL) 中形成 HMF

• 发表时间: 2011
• 作者: 喜多あずさ;他3名;Masaru Watanabe
• 通讯作者: Masaru Watanabe

Catalytic conversion of cellulose into 5-hydroxymethylfurfural in high yields via a two-step process

通过两步法将纤维素高产率催化转化为 5-羟甲基糠醛

• DOI: 10.1007/s10570-011-9568-1
• 发表时间: 2011-10-01
• 期刊: CELLULOSE
• 影响因子: 5.7
• 作者: Qi, Xinhua;Watanabe, Masaru;Smith, Richard L., Jr.
• 通讯作者: Smith, Richard L., Jr.

Reaction kinetics of D-xylose in sub- and supercritical water

• DOI: 10.1016/j.supflu.2010.08.013
• 发表时间: 2010-11-01
• 期刊: JOURNAL OF SUPERCRITICAL FLUIDS
• 影响因子: 3.9
• 作者: Aida, Taku Michael;Shiraishi, Naohiro;Smith, Richard L., Jr.
• 通讯作者: Smith, Richard L., Jr.

固体酸触媒を用いたイオン液体中でのセルロース加水分解による糖の選択的合成

使用固体酸催化剂在离子液体中纤维素水解选择性合成糖

• 发表时间: 2012
• 作者: 林紀男;尾崎保夫;稲森悠平;松田詩穂,石田華緒梨,Xinhua Qi,渡邉賢,相田卓,Smith Richard
• 通讯作者: 松田詩穂,石田華緒梨,Xinhua Qi,渡邉賢,相田卓,Smith Richard