Process and kinetics studies of catalytic cyclodehydration of galactaric acid to 2,5-furandicarboxylic acid

doi:10.11949/0438-1157.20191239

Abstract

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.

Key words: galactaric acid, 2,5-furandicarboxylic acid, catalytic, cyclodehydration, kinetics

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

CLC Number:

TQ 352.2

Haifeng XU, Liping ZHENG, Hongying WANG, Xilei LYU, Xujie CHEN, Ling XU, Yanchen LI, Yuxi JIANG, Xiuyang LYU. Process and kinetics studies of catalytic cyclodehydration of galactaric acid to 2,5-furandicarboxylic acid[J]. CIESC Journal, 2020, 71(5): 2240-2247.

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.

Figures/Tables 12

Fig.1 Results of repeated experiments (130℃, 10%(mass)H2SO4)

Fig.2 Effect of different catalysts on reaction (130℃, sulfone, 24 h)

Fig.3 Effect of different solvents on reaction(130℃, 10%(mass)H2SO4, 24 h)

Fig.4 Effect of initial concentration on reaction (130℃, 10%(mass)H2SO4, 24 h)

Fig.5 Conversion of galactaric acid and yield of 2,5-FDCA,2-furoic acid,HOPC as a function of time under different concentration of sulfuric acid (130℃)

Fig.6 Conversion of galactaric acid and yield of 2,5-FDCA,2-furoic acid,HOPC as a function of time under different temperatures(15%(mass) H2SO4)

Fig.7 Conversion of 2,5-FDCA as a function of time under different temperatures(15%(mass) H2SO4)

Fig.8 Reaction pathway for conversion of galactaric acid to 2,5-FDCA

Fig.9 Degradation kinetics of 2,5-FDCA

Table 1 Reaction rate constant at different temperatures (15%(mass) H2SO4)

Temperature/℃	k₁/h^-1	k₂/h^-1	k₃/h^-1
110	0.0572	0.0561	0.000647
120	0.0815	0.0796	0.00183
130	0.141	0.124	0.00481
140	0.206	0.175	0.0129

Fig.10 Surface plot of 2,5-FDCA yield with temperature and time

References 17

1	阎立峰, 朱清时. 以生物质为原材料的化学化工[J]. 化工学报, 2004, 55(12): 1938-1943.
	Yan L F, Zhu Q S. New chemical industry based on biomass[J]. Journal of Chemical Industry and Engineering(China), 2004, 55(12): 1938-1943.
2	吴志强, 张博, 杨伯伦. 生物质化学链转化技术研究进展[J]. 化工学报, 2019, 70(8): 2835-2853.
	Wu Z Q, Zhang B, Yang B L. Research progress on biomass chemical-looping conversion technology[J]. CIESC Journal, 2019, 70(8): 2835-2853.
3	周晨, 龚党生, 李学敏, 等. 呋喃二甲酸的合成研究进展及其应用前景[J]. 染料与染色, 2018, 55(2): 38-42, 61.
	Zhou C, Gong D S, Li X M, et al. Synthesis research progress and application prospects of 2,5-furandicarboxylic acid[J]. Dyestuffs and Coloration, 2018, 55(2): 38-42, 61.
4	Sousa A F, Vilela C, Fonseca A C, et al. Biobased polyesters and other polymers from 2,5-furandicarboxylic acid: a tribute to furan excellency[J]. Polymer Chemistry, 2015, 6(33): 5961-5983.
5	Eerhart A J J E, Faaij A P C, Patel M K. Replacing fossil based PET with biobased PEF; process analysis, energy and GHG balance[J]. Energy & Environmental Science, 2012, 5(4): 6407-6422.
6	Xu S, Zhou P, Zhang Z H, et al. Selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid using O₂ and a photocatalyst of Co-thioporphyrazine bonded to g-C₃N₄[J]. Journal of the American Chemical Society, 2017, 139(41): 14775-14782.
7	Sajid M, Zhao X B, Liu D H. Production of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF): recent progress focusing on the chemical-catalytic routes[J]. Green Chemistry, 2018, 20(24): 5427-5453.
8	Donen S, Hash K, Smitth T. Oxidation process: US135005[P]. 2016-04-21.
9	Smith T N, Hash K, Davey C L, et al. Modifications in the nitric acid oxidation of D-glucose[J]. Carbohydrate Research, 2012, 350(1): 6-13.
10	Su H H, Guo Z W, Wu X L, et al. Efficient bioconversion of sucrose to high-value-added glucaric acid by in vitro metabolic engineering[J]. ChemSusChem, 2019, 12(10): 2278-2285.
11	Zheng S, Hou J, Zhou Y, et al. One-pot two-strain system based on glucaric acid biosensor for rapid screening of myo-inositol oxygenase mutations and glucaric acid production in recombinant cells[J]. Metabolic Engineering, 2018, 49： 212-219.
12	Bratulescu G. New synthesis method for 2,5-bis(alkoxycarbonyl)furans in one single step[J]. Journal de la Société Algérienne de Chimie, 2000, 10(1): 135-137.
13	Bratulescu G. Cyclisation under the action of microwaves of the D-saccaric acid to 2,5-furandicarboxylic acid[J]. Revue Roumaine de Chimie, 2000, 45(9): 883-885.
14	Lewkowski J. Convenient synthesis of furan-2,5-dicarboxylic acid and its derivatives[J]. Polish Journal of Chemistry, 2001, 75(12): 1943-1946.
15	Taguchi Y, Oishi A, Iida H. One-step synthesis of dibutyl furandicarboxylates from galactaric acid[J]. Chemistry Letters, 2008, 37(1): 50-51.
16	Zhao D Y, Delbecq F, Len C. One-pot FDCA diester synthesis from mucic acid and their solvent-free regioselective polytransesterification for production of glycerol-based furanic polyesters[J]. Molecules, 2019, 24(6): 1030-1044.
17	Guo N. Acid-catalyzed dehydration of glucaric acid to2,5-furandicarboxylic acid (FDCA): US060975[P]. 2016-08-11.

[1]	Cheng CHENG, Zhongdi DUAN, Haoran SUN, Haitao HU, Hongxiang XUE. Lattice Boltzmann simulation of surface microstructure effect on crystallization fouling [J]. CIESC Journal, 2023, 74(S1): 74-86.
[2]	Xiaoxiong FAN, Lifang HAO, Chuigang FAN, Songgeng LI. Study on the catalytic denitrification performance of low-temperature NH₃-SCR over LaMnO₃/biochar catalyst [J]. CIESC Journal, 2023, 74(9): 3821-3830.
[3]	Lei WU, Jiao LIU, Changcong LI, Jun ZHOU, Gan YE, Tiantian LIU, Ruiyu ZHU, Qiuli ZHANG, Yonghui SONG. Catalytic microwave pyrolysis of low-rank pulverized coal for preparation of high value-added modified bluecoke powders containing carbon nanotubes [J]. CIESC Journal, 2023, 74(9): 3956-3967.
[4]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[5]	Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries [J]. CIESC Journal, 2023, 74(7): 3116-3126.
[6]	Pan LI, Junyang MA, Zhihao CHEN, Li WANG, Yun GUO. Effect of the morphology of Ru/α-MnO₂ on NH₃-SCO performance [J]. CIESC Journal, 2023, 74(7): 2908-2918.
[7]	Yuming TU, Gaoyan SHAO, Jianjie CHEN, Feng LIU, Shichao TIAN, Zhiyong ZHOU, Zhongqi REN. Advances in the design, synthesis and application of calcium-based catalysts [J]. CIESC Journal, 2023, 74(7): 2717-2734.
[8]	Guangyu WANG, Kai ZHANG, Kaihua ZHANG, Dongke ZHANG. Heat and mass transfer and energy consumption for microwave drying of coal slime [J]. CIESC Journal, 2023, 74(6): 2382-2390.
[9]	Jipeng ZHOU, Wenjun HE, Tao LI. Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts [J]. CIESC Journal, 2023, 74(6): 2416-2426.
[10]	Chen WANG, Xiufeng SHI, Xianfeng WU, Fangjia WEI, Haohong ZHANG, Yin CHE, Xu WU. Preparation of Mn₃O₄ catalyst by redox method and study on its catalytic oxidation performance and mechanism of toluene [J]. CIESC Journal, 2023, 74(6): 2447-2457.
[11]	Quanbi ZHANG, Yijin YANG, Xujing GUO. Catalytic degradation of dissolved organic matter in rifampicin pharmaceutical wastewater by Fenton oxidation process [J]. CIESC Journal, 2023, 74(5): 2217-2227.
[12]	Simin YI, Yali MA, Weiqiang LIU, Jinshuai ZHANG, Yan YUE, Qiang ZHENG, Songyan JIA, Xue LI. Study on ammonia evaporation and hydration kinetics of microcrystalline magnesite [J]. CIESC Journal, 2023, 74(4): 1578-1586.
[13]	Jian JIAN, Jiaming ZHANG, Xiang SHE, Hu ZHOU, Kuiyi YOU, Hean LUO. Correlation with the redox V⁴⁺/V⁵⁺ ratio in VPO catalysts for oxidation of cyclohexane by NO₂ [J]. CIESC Journal, 2023, 74(4): 1570-1577.
[14]	Jin YU, Binbin YU, Xinsheng JIANG. Study on quantification methodology and analysis of chemical effects of combustion control based on fictitious species [J]. CIESC Journal, 2023, 74(3): 1303-1312.
[15]	Qingyun YANG, Qingsong LI, Zeming CHEN, Jing DENG, Yuying LI, Fan YANG, Guoyuan CHEN, Guoxin LI. Degradation of methylparaben by UV/PMS, UV/PDS and UV/SPC process [J]. CIESC Journal, 2023, 74(3): 1322-1331.