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

作　　者：吕喜蕾 魏茜文 任傲天 蒋雨希 秦雯琪 吕秀阳[1] LYU Xilei;WEI Xiwen;REN Aotian;JIANG Yuxi;QIN Wenqi;LYU Xiuyang(Key Laboratory of Biomass Chemical Engineering of Ministry of Education,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310058,China;Zhejiang Hengyi Petrochemical Research Institute Co.Ltd.,Hangzhou 311209,China;Hangzhou Lanshun Technology Co.Ltd.,Hangzhou 311209,China)

机构地区：[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 [2]浙江恒逸石化研究院有限公司,浙江杭州311209 [3]杭州澜顺科技有限公司,浙江杭州311209

出　　处：《高校化学工程学报》2024年第6期890-896,共7页Journal of Chemical Engineering of Chinese Universities

基　　金：国家重点研发计划(2022YFC2104500);国家自然科学基金(22078290,22278358)。

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。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 

分 类 号：TQ032[化学工程]