HBr-LiBr催化葡萄糖二酸单钾盐合成2,5-呋喃二甲酸工艺优化
Process optimization of 2,5-furandicarboxylic acid synthesis from potassium bisaccharate catalyzed with HBr-LiBr
吕喜蕾 1魏茜文 2任傲天 2蒋雨希 2秦雯琪 2吕秀阳2
作者信息
- 1. 浙江大学生物质化工教育部重点实验室,浙江大学 化学工程与生物工程学院,浙江 杭州 310058;浙江恒逸石化研究院有限公司,浙江 杭州 311209;杭州澜顺科技有限公司,浙江 杭州 311209
- 2. 浙江大学生物质化工教育部重点实验室,浙江大学 化学工程与生物工程学院,浙江 杭州 310058
- 折叠
摘要
2,5-呋喃二甲酸(2,5-FDCA)是一种发展潜力大的生物基聚酯单体,其中葡萄糖-葡萄糖二酸路线生产 2,5-FDCA是一条有前景的路线.为了筛选出更适合工业化的催化体系,对 HBr-LiBr 催化葡萄糖二酸单钾盐脱水环合制备2,5-FDCA的工艺条件进行了优化研究.基于溶剂筛选,发现在含O=S=O的溶剂中,反应效果较佳,提出葡萄糖二酸与环丁砜可能的成环溶剂效应机理.优化得到葡萄糖二酸单钾盐脱水环合制备 2,5-FDCA的较佳催化剂配比(质量分数):w(HBr)=2%、w(LiBr)=5%,2,5-FDCA 的收率为 81.1%.测定不同底物质量分数下葡萄糖二酸单钾盐脱水环合制备2,5-FDCA的动力学数据,反应速率常数随着底物浓度的提高逐渐减小.发现含水量是HBr-LiBr催化体系的反应敏感参数,当含水量从 2.2%提高到 8.2%时,2,5-FDCA的收率从 75.2%下降到 20.6%.研究工作为葡萄糖-葡萄糖二酸路线生产 2,5-FDCA提供了重要的基础数据.
Abstract
2,5-furandicarboxylic acid(2,5-FDCA)is a bio-based polyester monomer with great potential,and it is promising to produce 2,5-FDCA from saccharic acids.In order to find a more suitable catalytic system for industrialization,this work optimized the process of 2,5-FDCA synthesis from cyclodehydration of potassium bisaccharate catalyzed with HBr-LiBr.The solvent screening results show that solvents containing O=S=O can facilitate the reaction.A possible cyclization mechanism of solvent effects on potassium bisaccharate and sulfolane was proposed.The optimal catalyst ratio for 2,5-FDCA preparation by cyclodehydration of potassium bisaccharate was obtained as w(HBr)=2%,w(LiBr)=5%,and the yield of 2,5-FDCA was 81.1%.The kinetic data for the preparation of 2,5-FDCA from cyclodehydration of potassium bisaccharate with different substrate concentrations were determined,and the reaction rate constant decreased gradually with the increase of substrate concentration.Water content was a sensitive parameter in the HBr-LiBr catalytic system,and when the water content increased from 2.2%to 8.2%,the yield of 2,5-FDCA decreased from 75.2%to 20.6%.This work provide important basic data for the production of 2,5-FDCA from saccharic acids.
关键词
葡萄糖二酸单钾盐/2,5-呋喃二甲酸/HBr-LiBr催化/工艺优化Key words
potassium bisaccharate/2,5-furandicarboxylic acid/HBr-LiBr catalyzed/process optimization引用本文复制引用
出版年
2024
国家科技期刊平台
NSTL
万方数据