5-氯甲基糠醛水解制备5-羟甲基糠醛的工艺优化及反应动力学研究

doi:10.3969/j.issn.0253-2417.2022.03.009

摘要/Abstract

摘要：

研究了5-氯甲基糠醛(CMF)在纯水或水/丙酮体系中水解生成5-羟甲基糠醛(HMF)，探究了水解反应条件(如溶剂体系、碱中和剂、温度和CMF添加量等)对CMF水解的影响，并分析了其水解反应动力学。研究结果表明：水/丙酮体系有助于减少HMF的副反应，加入连二亚硫酸钠(Na₂S₂O₄)可以进一步阻止腐殖质的产生；1 g CMF在10 mL水/丙酮体积比为1∶4的混合液中，添加0.35 g的CaCO₃，温度353.15 K下保温反应28 min，此优化水解条件下CMF转化率为97%，HMF得率可达85%，副产物乙酰丙酸(LA)得率为6%；添加Na₂S₂O₄后，HMF的分离得率可由50%提高到86%。动力学研究结果表明：在水/丙酮体系中CMF水解反应活化能为12.3 kJ/mol，水解速率常数k₁=5.56exp(-1.23×10⁴/RT)。

关键词: 生物质, 5-氯甲基糠醛, 水解, 反应动力学, 分离提纯

Abstract:

The hydrolysis of 5-chloromethyl furfural(CMF) in pure water or water/acetone system to 5-hydroxymethyl furfural(HMF) was studied. The effects of hydrolysis reaction conditions(such as solvent system, alkali neutralizer, temperature and CMF addition amount) on the hydrolysis of CMF were investigated, and the kinetics of the hydrolysis reaction was analyzed. The results showed that the water/acetone system is helpful to reduce the side reaction of HMF, and the addition of sodium disulfite(Na₂S₂O₄) could further prevent the generation of humus. The optimal hydrolysis conditions are as follows: 1 g CMF was added with 0.35 g CaCO₃ in a mixture of 10 mL water/acetone with volume ratio of 1∶4, and incubated at 353.15 K for 28 min. Under these conditions, the CMF conversion rate was 97%, the yield of HMF was 85%, and the yield of by-product levulinic acid(LA) was 6%. The separation rate of HMF increased from 50% to 86% with the addition of Na₂S₂O₄. The kinetic study results showed that the activation energy of CMF hydrolysis was 12.3 kJ/mol and the hydrolysis rate constant k₁=5.56exp(-1.23×10⁴/RT) in water/acetone system.

Key words: biomass, 5-chloromethylfurfural, hydrolysis, reaction kinetics, separation and purification

中图分类号:

TQ35

王帅, 唐兴, 孙勇, 曾宪海, 林鹿. 5-氯甲基糠醛水解制备5-羟甲基糠醛的工艺优化及反应动力学研究[J]. 林产化学与工业, 2022, 42(3): 65-74.

Shuai WANG, Xing TANG, Yong SUN, Xianhai ZENG, Lu LIN. Optimization and Kinetics of Hydrolysis of 5-Chloromethylfurfural to 5-Hydroxymethylfurfural[J]. Chemistry and Industry of Forest Products, 2022, 42(3): 65-74.

图/表 9

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温度/K temperature	速率常数(k₁)/min^-1 rate constant	速率常数(k₂)/min^-1 rate constant
333.15	0.0672	0.0058
353.15	0.0839	0.0088
373.15	0.1081	0.0141

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