硫酸铁协同离子液体催化果糖选择性制备5-羟甲基糠醛的作用机制研究

楚雄师范学院学报 ›› 2023, Vol. 38 ›› Issue (3): 9-16.

硫酸铁协同离子液体催化果糖选择性制备5-羟甲基糠醛的作用机制研究

宋向波^1,2, 范书怡¹, 陈凯思¹, 熊婉婷¹, 郭正熙¹, 解增¹

1.楚雄师范学院物理与电子科学学院,云南楚雄 675000;
2.中国科学院广州能源研究所,广东广州 510640

收稿日期:2023-01-15 出版日期:2023-05-20 发布日期:2023-08-07
作者简介:宋向波（1990–）,男,博士,讲师,研究方向为生物质能源转化与利用技术。E-mail： 20210101010@cxtc.edu.cn
基金资助:
云南省地方本科高校基础研究联合项目（No. 202101BA070001-190）; 2022年国家级大学生创新创业训练计划项目（No. 202211391015）; 云南省教育厅科学研究基金项目（No. 2022J0837）; 楚雄师范学院博士科研启动项目（No. BSQD2109）

Selective Production of 5-Hydroxymethylfurfural from Fructose Catalyzed by Ferric Sulfate with Ionic Liquid Additive and Its Mechanism

SONG Xiangbo^1,2, FAN Shuyi¹, CHEN Kaisi¹, XIONG Wanting¹, GUO Zhengxi¹, XIE Zeng¹

1. School of Physics and Electronic Science, Chuxiong Normal University, Chuxiong, Yunnan Province 675000;
2. Chinese Academy of Sciences, Guangzhou Institute of Energy Resources, Guangzhou,Guangdong Province 510640

Received:2023-01-15 Online:2023-05-20 Published:2023-08-07

摘要/Abstract

摘要： 5-羟甲基糠醛（HMF）是一种用途范围较广的高值平台化合物。以可再生的生物质基糖类为原料选择性制备HMF对生物质资源的综合开发与利用具有重要意义。本文以生物质基果糖为原料,采用廉价无毒的硫酸铁协同1-丁基-3甲基咪唑氯盐离子液体（[Bmim]Cl）作为催化剂体系用于催化果糖选择性制备HMF。通过对反应工艺参数进行详细的考察,探究了硫酸铁与[Bmim]Cl的协同催化性能。结果表明：当反应温度维持140 ^oC并反应1.5 h时,在纯水体系中HMF的最大收率接近55%;在水-THF混合体系中可提高至63%。此外,通过溶剂效应实验对硫酸铁催化果糖转化的作用机制进行了探究,提出了硫酸铁在水的作用下发生水解并释放活性物质H⁺催化果糖转化的作用机制。

关键词: 生物质, 5-羟甲基糠醛, 离子液体, 硫酸铁, 选择性

Abstract: 5-Hydroxymethylfurfural (HMF) is a high value platform compound with a wide range of applications. Selective production of HMF from renewable biomass-based sugars is of great significance for comprehensive development and utilization of biomass resources. In this paper, the bio-based fructose is used as raw material, and the cheap and non-toxic ferric sulfate combined with 1-butyl-3-methylimidazole chloride ionic liquid ([Bmim]Cl) is used as catalyst system to catalyze selective conversion of fructose to HMF. The synergistic catalytic performance of ferric sulfate and [Bmim]Cl is investigated through the detailed investigation of reaction process parameters. Results show that when the reaction temperature is maintained at 140 ^oC for 1.5 h, the maximum yield of HMF from fructose in pure water system is close to 55%, while it can be increased to 63% in the water-THF miscible system. In addition, the mechanism of fructose conversion catalyzed by ferric sulfate is explored through solvent effect experiment. The mechanism of hydrolysis of ferric sulfate in the presence of water followed by releasing the H⁺ species to catalyze fructose conversion is proposed.

Key words: biomass, 5-Hydroxymethylfurfural, ionic liquids, ferric sulfate, selectivity

中图分类号:

O645.13

宋向波, 范书怡, 陈凯思, 熊婉婷, 郭正熙, 解增. 硫酸铁协同离子液体催化果糖选择性制备5-羟甲基糠醛的作用机制研究[J]. 楚雄师范学院学报, 2023, 38(3): 9-16.

SONG Xiangbo, FAN Shuyi, CHEN Kaisi, XIONG Wanting, GUO Zhengxi, XIE Zeng. Selective Production of 5-Hydroxymethylfurfural from Fructose Catalyzed by Ferric Sulfate with Ionic Liquid Additive and Its Mechanism[J]. Journal of Chuxiong Normal University, 2023, 38(3): 9-16.

参考文献

[1] Van P R J,Van D W J C,De J E, et al. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources[J]. Chemical Reviews 2013,113(3): 1499-1597.
[2] Mittal A, Pilath H M,Johnson D K.Direct conversion of biomass carbohydrates to platform chemicals: 5-Hydroxymethylfurfural (HMF) and furfural[J]. Energy & Fuels,2020,34(3):3284-3293.
[3] Viar N,Requies J M, Agirre I,et al.HMF hydrogenolysis over carbon-supported Ni-Cu catalysts to produce hydrogenated biofuels[J]. Energy,2022,255: 124437.
[4] Costa M J F, Gonçalves A A S,Rinaldi R,et al. Highly porous niobium-containing silica glasses applied to the microwave-assisted conversion of fructose into HMF[J]. Catalysis Communications,2023,174:106577.
[5] Rodriguez Q N,Norton A M, Nguyen H,et al.Homogeneous metal salt solutions for biomass upgrading and other select organic reactions[J]. ACS Catalysis,2019,9(11):9923-9952.
[6] Cao J, Ma M, Liu J, et al. Highly effective transformation of carbohydrates to 5-Hydroxymethylfurfural with Al- montmorillonite as catalyst[J]. Applied Catalysis A: General,2019:571, 96-101.
[7] Huang T, Zhang H, Zhang X, et al. Preparation of functionalized dially limidazole ionic liquid and its application in conversion of D-fructose into HMF[J]. Journal of Molecular Liquids, 2022, 345:118233.
[8] Zhao H, Holladay J E, Brown H, et al. Metal chlorides in ionic liquid solvents convert sugars to 5-Hydroxymethylfurfural[J]. Science, 2007, 316(5831): 1597-1600.
[9] Li Y, Wang J, He L, et al. Experimental and theoretical studies on imidazolium ionic liquid-promoted conversion of fructose to 5-hydroxymethylfurfural[J]. Green Chemistry, 2012, 14(10): 2752-2758.
[10] Qi X, Watanabe M, Aida T M, et al. Fast transformation of glucose and di-/Polysaccharides into 5-Hydroxymethylfurfural by microwave heating in an ionic liquid/catalyst system[J]. Chemistry Sustainability Chemistry, 2010, 3(9):1071-1077.
[11] DaβCβL, A M, Bogel-Łukasik R. Acidic ionic liquids as sustainable approach of cellulose and lignocellulosic biomass conversion without additional catalysts[J]. Chemistry Sustainability Chemistry, 2015,8(6):947-965.
[12] Marshall W L, Franck E U.Ion product of water substance, 0~1000 °C, 1~10,000 bars new international formulation and its background[J]. Journal of Physical and Chemical Reference Data,1981,10(2): 295-304.
[13] Weingarten R, Cho J, Xing R, et al. Kinetics and reaction engineering of levulinic acid production from aqueous glucose solutions[J]. Chemistry Sustainability Chemistry, 2012,5(7):1280-1290.
[14] Horvat J, Klaić B, Metelko B, et al. Mechanism of levulinic acid formation[J]. Tetrahedron Letters,1985, 26(17):2111-2114.
[15] Guo H, Qi X, Hiraga Y, et al. Efficient conversion of fructose into 5-ethoxymethylfurfural with hydrogen sulfate ionic liquids as co-solvent and catalyst[J]. Chemical Engineering Journal,2017,314:508-514.
[16] Hoang T M C, Van E R H, Bula W P, et al. Humin based by-products from biomass processing as a potential carbonaceous source for synthesis gas production[J]. Green Chemistry,2015,17(2): 959-972.
[17] Choudhary V,Mushrif S H,Ho C, et al. Insights into the interplay of lewis and brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media[J]. Journal of the American Chemical Society,2013, 135(10):3997-4006.
[18] De S, Dutta S, Saha B.Microwave assisted conversion of carbohydrates and biopolymers to 5-hydroxymethylfurfural with aluminium chloride catalyst in water[J]. Green Chemistry,2011,13(10):2859-2868.