HBr-MgBr2催化己糖二酸脱水环合制备2，5-呋喃二甲酸的研究

doi:10.11949/0438-1157.20210204

摘要/Abstract

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

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

中图分类号:

TQ 352.2

陈旭杰, 吕喜蕾, 史欢欢, 郑丽萍, 魏茜文, 田鹏辉, 蒋雨希, 吕秀阳. HBr-MgBr₂催化己糖二酸脱水环合制备2，5-呋喃二甲酸的研究[J]. 化工学报, 2021, 72(9): 4658-4664.

Xujie CHEN, Xilei LYU, Huanhuan SHI, Liping ZHENG, Xiwen WEI, Penghui TIAN, Yuxi JIANG, Xiuyang LYU. Study on cyclodehydration of hexaric acids to 2,5- furandicarboxylic acid catalyzed with HBr-MgBr₂[J]. CIESC Journal, 2021, 72(9): 4658-4664.

图/表 14

图1 不同酸催化剂对D-葡萄糖二酸单钾盐脱水环合反应的影响(环丁砜、120℃、24 h)

Fig.1 Effect of different acid catalysts on the cyclodehydration of potassium bisaccharate (sulfolane, 120℃, 24 h)

图 2 HBr质量分数对D-葡萄糖二酸单钾盐脱水环合反应的影响(环丁砜、120℃、24 h)

Fig.2 Effect of HBr concentration on the cyclodehydration of potassium bisaccharate (sulfolane, 120℃, 24 h)

图3 不同助催化剂对D-葡萄糖二酸单钾盐脱水环合反应的影响[环丁砜、2.5%(质量)HBr、120℃、24 h]

Fig.3 Effect of different cocatalysts on the cyclodehydration of potassium bisaccharate [sulfolane, 2.5%(mass) HBr, 120℃, 24 h]

图 4 搅拌速率对D-葡萄糖二酸单钾盐脱水环合反应的影响[环丁砜、3%(质量)HBr-6%(质量)MgBr2、120℃、24 h]

Fig.4 Effect of rotating speed on the cyclodehydration of potassium bisaccharate [sulfolane, 3%(mass) HBr-6%(mass)MgBr2, 120℃, 24 h]

表1 全面实验因素与水平

Table 1 Factors and level of comprehensive test

水平	因素A HBr质量分数/%	因素B MgBr₂质量分数/%
1	0.5	0
2	1.0	1.0
3	1.5	2.0
4	2.0	3.0
5	2.5	4.0
6	3.0	5.0
7	3.5	6.0

图5 HBr和MgBr2的浓度对2,5-FDCA摩尔收率的影响(环丁砜、120℃、24 h)

Fig.5 Effect of HBr and MgBr2 concentrations on the yield of 2,5-FDCA (sulfolane, 120℃, 24 h)

图6 HBr和MgBr2的浓度对糠酸摩尔收率的影响(环丁砜、120℃、24 h)

Fig.6 Effect of HBr and MgBr2 concentrations on the yield of 2-furoic acid (sulfolane, 120℃, 24 h)

图7 底物浓度对D-葡萄糖二酸单钾盐脱水环合反应的影响[环丁砜、3%(质量)HBr-6%(质量)MgBr2、120℃、24 h]

Fig.7 Effect of substrate concentration on the cyclodehydration of potassium bisaccharate [sulfolane，3%(mass) HBr-6%(mass) MgBr2, 120℃, 24 h]

图8 水量的富集对D-葡萄糖二酸单钾盐脱水环合反应的影响[环丁砜、120℃、24 h;催化剂初始浓度：3%(质量)HBr-6%(质量)MgBr2]

Fig.8 Effect of water added on the cyclodehydration of potassium bisaccharate [sulfolane, 120℃, 24 h; initial catalyst concentration：3%(mass) HBr-6%(mass) MgBr2]

图9 不同己糖二酸原料对脱水环合反应的影响[环丁砜、3%(质量)HBr-6%(质量)MgBr2、120℃、24 h]

Fig.9 Effect of different hexaric acids on the cyclodehydration reaction [sulfolane, 3%(mass) HBr-6%(mass) MgBr2, 120℃, 24 h]

图10 不同温度下2,5-FDCA收率随时间的变化[环丁砜、3%(质量)HBr-6%(质量)MgBr2]

Fig.10 Yield of 2,5-FDCA as a function of time under different temperatures [sulfolane, 3%(mass) HBr-6%(mass) MgBr2]

图11 不同温度下糠酸收率随时间的变化[环丁砜、3%(质量)HBr-6%(质量)MgBr2]

Fig.11 Yield of 2-furoic acid as a function of time under different temperatures [sulfolane, 3%(mass) HBr-6%(mass) MgBr2]

图12 不同温度下2,5-FDCA的生成动力学拟合

Fig. 12 Kinetics fitting of 2,5-FDCA formation at different temperatures

表2 不同温度下反应速率常数及决定系数

Table 2 Reaction rate constant and R2 at different temperatures

T/℃	k₁/min^-1	k₂/min^-1	R²
100	0.00568	0.00073	0.99641
110	0.01353	0.00194	0.99332
120	0.03389	0.00690	0.99905
130	0.03939	0.00747	0.99170

参考文献 12

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HBr-MgBr₂催化己糖二酸脱水环合制备2，5-呋喃二甲酸的研究

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

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