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| 半乳糖二酸催化脱水环合制备2,5-呋喃二甲酸工艺及动力学 | |
| 引用本文： | 徐海峰,郑丽萍,王洪营,吕喜蕾,陈旭杰,徐玲,李彦辰,蒋雨希,吕秀阳. 半乳糖二酸催化脱水环合制备2,5-呋喃二甲酸工艺及动力学[J]. 化工学报, 2020, 71(5): 2240-2247. DOI: 10.11949/0438-1157.20191239 |
| 作者姓名： | 徐海峰 郑丽萍 王洪营 吕喜蕾 陈旭杰 徐玲 李彦辰 蒋雨希 吕秀阳 |
| 作者单位： | 1.生物质化工教育部重点实验室（浙江大学）, 浙江大学化学工程与生物工程学院，浙江 杭州 310027;2.浙江恒逸石化有限公司研发中心，浙江 杭州 311209 |
| 基金项目： | 浙江大学-恒逸全球未来先进技术研究院资助项目 |
| 摘 要： | 2,5-呋喃二甲酸(2,5-FDCA)是生物质基的平台化合物之一,在聚合物领域有广泛的应用前景。针对半乳糖二酸脱水环合制备2,5-FDCA存在的收率低、动力学数据缺乏等问题,在催化剂和溶剂筛选的基础上,开展了半乳糖二酸制备2,5-FDCA的工艺优化,得到了较佳的工艺条件为15%(质量)硫酸催化、环丁砜为溶剂、130℃下反应16 h,此时2,5-FDCA收率为49.1%。测定了不同硫酸浓度和不同温度下半乳糖二酸脱水环合制备2,5-FDCA反应动力学数据,采用一级反应动力学拟合得到了15%(质量)硫酸催化下半乳糖二酸降解反应活化能为54.4 kJ/mol、2,5-FDCA生成活化能为57.8 kJ/mol、其他副反应的活化能为50.7 kJ/mol、2,5-FDCA进一步降解反应的活化能为130.6 kJ/mol。研究工作对己糖二酸路线制备2,5-FDCA工业化进程有一定的推动作用。 |
| 关 键 词： | 半乳糖二酸 2,5-呋喃二甲酸 催化 脱水环合 动力学 |
| 收稿时间： | 2019-10-23 |
| 修稿时间： | 2020-01-01 |
Process and kinetics studies of catalytic cyclodehydration of galactaric acid to 2,5-furandicarboxylic acid |
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| XU Haifeng,ZHENG Liping,WANG Hongying,LYU Xilei,CHEN Xujie,XU Ling,LI Yanchen,JIANG Yuxi,LYU Xiuyang. Process and kinetics studies of catalytic cyclodehydration of galactaric acid to 2,5-furandicarboxylic acid[J]. Journal of Chemical Industry and Engineering(China), 2020, 71(5): 2240-2247. DOI: 10.11949/0438-1157.20191239 | |
| Authors: | XU Haifeng ZHENG Liping WANG Hongying LYU Xilei CHEN Xujie XU Ling LI Yanchen JIANG Yuxi LYU Xiuyang |
| Affiliation: | 1.Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China;2.R&D Center of Zhejiang Hengyi Petrochemical Co. , Ltd. ，Hangzhou 311209, Zhejiang, China |
| Abstract: | 2,5-Furandicarboxylic acid (2,5-FDCA) is one of the biomass-based platform compounds, which has an extensive application prospects in the field of polymers. In order to solve the problems of low yield and lack of kinetic data in the process for preparing 2,5-FDCA from galactaric acid cyclodehydration, the effects of different catalysts and solvents were investigated, and the optimized conditions were obtained: with 15%(mass) sulfuric acid as catalyst and sulfone as solvent, the yield of 2,5-FDCA was 49.1% at 130℃ and 16 h reaction time. The kinetics of galactaric acid cyclodehydration at different concentrations of sulfuric acid and different temperatures were determined. According to the first-order reaction kinetics, the degradation activation energy of galactaric acid was 54.4 kJ/mol, the generation activation energy of 2,5-FDCA was 57.8 kJ/mol, the activation energy of other side reactions was 50.7 kJ/mol, and the degradation activation energy of 2,5-FDCA was 130.6 kJ/mol, at 15%(mass) sulfuric acid. The research work has promoted the industrialization of 2,5-FDCA in hexedioic acid route. |
| Keywords: | galactaric acid 2 5-furandicarboxylic acid catalytic cyclodehydration kinetics |
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