Page 103 - 精细化工2019年第8期

第 36 卷第 8 期 精 细 化 工 Vol.36, No.8
201 9 年 8 月 FINE CHEMICALS Aug. 2019

催化与分离提纯技术
壳聚糖基固体酸催化果糖合成 5-羟甲基糠醛

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杨莎莎 ，张江华 1,2,3* ，李红艳 ，蔡伟杰 ，阴法文 ，
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崔 励 ，蔡迪迪 ，周大勇
（1. 大连工业大学 轻工与化学工程学院，辽宁 大连 116034；2. 大连工业大学 国家海洋食品工程技术
研究中心，辽宁 大连 116034；3. 大连理工大学 精细化工国家重点实验室，辽宁 大连 116024；4. 辽
宁中医药大学 药学院，辽宁 大连 116600）
摘要：以壳聚糖为原料，采用一步水热碳化和磺化法合成壳聚糖基固体酸材料（CASA），并将其用于催化无溶
剂条件下果糖脱水合成 5-羟甲基糠醛（5-HMF），考察了催化剂用量、反应温度、反应时间及催化剂循环利用次
数对脱水反应的影响，并与甲壳素基固体酸材料（CISA）进行了催化性能比较。采用 X 射线衍射、扫描电镜、
吡啶吸附红外光谱对 CASA 材料进行了结构和酸性质表征，建立了催化剂结构与性能的关系。结果表明，CASA
材料含有大量的表面强 Brӧnsted 酸性位点，因而其催化性能较 CISA 突出；当 m(果糖)∶m(CASA)=6∶1、120 ℃
反应 5 h 时，5-HMF 的收率高达 63.2%，且 CASA 可重复利用 4 次而无明显失活。
关键词：壳聚糖；5-羟甲基糠醛；果糖；固体酸；无溶剂；催化技术
中图分类号：O643.36; O643.322 文献标识码：A 文章编号：1003-5214 (2019) 08-1591-07

Chitosan-derived Solid Acid as a Catalyst for Fructose
Dehydration into 5-Hydroxymethylfurural

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YANG Sha-sha , ZHANG Jiang-hua 1,2,3* , LI Hong-yan , CAI Wei-jie ,
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YIN Fa-wen , CUI Li , CAI Di-di , ZHOU Da-yong
（1. College of Light Industry and Chemical Engineering, Dalian Polytechnic University, Dalian 116034, Liaoning,
China; 2. National Engineering Research Center of Seafood, Dalian Polytechnic University, Dalian 116034, Liaoning,
China; 3. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China;
4. Pharmaceutical College, Liaoning University of Traditional Chinese Medicine, Dalian 116600, Liaoning, China）
Abstract: A kind of chitosan-derived solid acid (CASA) material was successfully synthesized via in situ
partially hydrothermal carbonization followed by sulfonation with chitosan as raw materials. Subsequently,
the CASA material was used for catalytic fructose dehydration to 5-hydroxymethylfurfural (5-HMF) under
solvent-free conditions. The effects of catalyst amount, reaction temperature, reaction time and catalyst
recyclability on the dehydration were studied in detail. Meanwhile, its catalytic activity was compared with
that of chitin-derived solid acid (CISA) material. The obtained CASA material was characterized by various
techniques, such as X-ray diffraction, scanning electron microscopy and infrared spectra of pyridine
adsorption. A relationship between the catalyst structure and properties was established. The results
suggested that there were a lot of strong Brӧnsted acid sites on the CASA surface. Therefore, its catalytic
performance was more outstanding than that of CISA. The 5-HMF yield was up to 63.2% at 120 ℃ within
5 h when the mass ratio of fructose to CASA material was 6∶1. Moreover, the CASA catalyst could be
recycled up to 4 times without any obvious deactivation.
Key words: chitosan; 5-hydroxymethylfurfural; fructose; solid acid; solvent-free; catalysis technology

收稿日期：2019-05-04; 定用日期：2019-06-27; DOI: 10.13550/j.jxhg.20190390
基金项目：国家自然科学基金（31801546）；中国博士后科学基金资助项目（2017M621119）；辽宁省自然科学基金计划重点项目
（20170520220）；国家重点研发计划课题（2017YFB0308701）；大连理工大学精细化工国家重点实验室开放课题基金项目（KF1416）
作者简介：杨莎莎（1995—），女，硕士生。联系人：张江华（1980—），女，讲师，E-mail：zhang_jh@dlpu.edu.cn；周大勇（1977—），
男，教授，E-mail：zdyzf1@163.com。