CIESC Journal ›› 2021, Vol. 72 ›› Issue (9): 4658-4664.DOI: 10.11949/0438-1157.20210204

• Catalysis, kinetics and reactors • Previous Articles     Next Articles

Study on cyclodehydration of hexaric acids to 2,5- furandicarboxylic acid catalyzed with HBr-MgBr2

Xujie CHEN1(),Xilei LYU2(),Huanhuan SHI2,Liping ZHENG2,Xiwen WEI1,Penghui TIAN1,Yuxi JIANG1,Xiuyang LYU1()   

  1. 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
  • Received:2021-02-03 Revised:2021-03-12 Online:2021-09-05 Published:2021-09-05
  • Contact: Xilei LYU,Xiuyang LYU

HBr-MgBr2催化己糖二酸脱水环合制备2,5-呋喃二甲酸的研究

陈旭杰1(),吕喜蕾2(),史欢欢2,郑丽萍2,魏茜文1,田鹏辉1,蒋雨希1,吕秀阳1()   

  1. 1.浙江大学化学工程与生物工程学院生物质化工教育部重点实验室,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
  • 通讯作者: 吕喜蕾,吕秀阳
  • 作者简介:陈旭杰(1994—),男,硕士研究生,chenxujie.zju@qq.com
  • 基金资助:
    浙江大学-恒逸全球未来先进技术研究院项目;国家自然科学基金项目(22078290)

Abstract:

2,5-Furandicarboxylic acid (2,5-FDCA) is a monomer of biodegradable plastic polyethylene furanoate and will be in huge demand in the near future. In order to solve the problem of lower yield in the preparation of 2,5-furandicarboxylic acid during cyclodehydration of hexaric acid, higher selective catalytic systems were explored in this paper. HBr-MgBr2 and HBr-LiBr were found to have excellent catalytic ability for cyclodehydration of hexaric acid. 2,5-FDCA yield of 84.2% was achieved for potassium bisaccharate cyclodehydration catalyzed with 3%(mass)HBr-6%(mass) MgBr2 at 120℃ and 2 h reaction time. The molar yield of 2,5-FDCA remained above 80% when substrate concentration was up to 5%(mass) and actual water concentration was enriched from 3.3% to 16.5%. The kinetics of cyclodehydration of potassium bisaccharate to 2,5-FDCA at temperatures from 100℃ to 130℃ were measured with 3%(mass) HBr-6%(mass) MgBr2. The activation energy of 2,5-FDCA formation was 108.9 kJ/mol and that of by-product formation was 136.6 kJ/mol by first-order kinetic fitting. The research work has played a positive role in promoting the industrialization of 2,5-FDCA route by dehydration and cyclization of hexadecanoic acid.

Key words: hexaric acid, 2,5- furandicarboxylic acid, cyclodehydration, catalysis, reaction kinetics

摘要:

2,5-呋喃二甲酸(2,5-FDCA)是生物可降解塑料聚呋喃二甲酸乙二醇酯的聚合单体,未来需求量巨大。针对己糖二酸脱水环合制备2,5-呋喃二甲酸存在的收率低问题,开展了更高选择性催化体系的构建研究,成功筛选到了两个优良的催化体系:HBr-MgBr2、HBr-LiBr。3%(质量)HBr-6%(质量)MgBr2催化、120℃下反应2 h,D-葡萄糖二酸单钾盐脱水环合制备2,5-FDCA收率达到84.2%。当反应底物浓度低于5%(质量)以及水含量从3.3%富集到16.5%时,2,5-FDCA的摩尔收率未见明显下降,且都可维持在80%以上。测定了100~130℃温度范围内3%(质量)HBr-6%(质量)MgBr2催化D-葡萄糖二酸单钾盐脱水环合制备2,5-FDCA动力学数据,采用一级反应动力学拟合得到2,5-FDCA的生成反应活化能为108.9 kJ/mol、副产物生成活化能为136.6 kJ/mol。研究工作对己糖二酸脱水环合制备2,5-FDCA路线的工业化具有积极推动作用。

关键词: 己糖二酸, 2, 5-呋喃二甲酸, 脱水环合, 催化, 反应动力学

CLC Number: