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林产化学与工业 ›› 2021, Vol. 41 ›› Issue (4): 62-68.doi: 10.3969/j.issn.0253-2417.2021.04.009

• 研究报告 • 上一篇    下一篇

炭基固体酸H-Al/AC的制备、表征及其催化葡萄糖制5-HMF

杜雅东, 马春慧, 尹钰, 李伟, 罗沙, 刘守新()   

  1. 东北林业大学 材料科学与工程学院, 生物质材料科学与技术教育部重点实验室, 黑龙江 哈尔滨 150040
  • 收稿日期:2021-03-08 出版日期:2021-08-28 发布日期:2021-08-31
  • 通讯作者: 刘守新 E-mail:liushouxin@126.com
  • 作者简介:刘守新, 教授, 博士生导师, 研究领域为炭材料; E-mail: liushouxin@126.com
    杜雅东(1995-), 男, 辽宁朝阳人, 硕士生, 主要从事生物质材料研究工作
  • 基金资助:
    国家自然科学基金资助项目(31890773);中央高校基本科研业务费(2572019BB02)

Catalytic Performance of Carbon-based Solid Acid H-Al/AC in Glucose to 5-Hydroxymethylfurfural Reaction

Yadong DU, Chunhui MA, Yu YIN, Wei LI, Sha LUO, Shouxin LIU()   

  1. Material Science and Engineering College, Northeast Forestry University; Key Laboratory of Bio-based Material Science&Technology, Ministry of Education, Harbin 150040, China
  • Received:2021-03-08 Online:2021-08-28 Published:2021-08-31
  • Contact: Shouxin LIU E-mail:liushouxin@126.com

摘要:

以椰壳活性炭为载体,经H2SO4磺化及负载AlCl3制备了含有Brønsted(B)酸和Lewis(L)酸的炭基固体酸催化剂H-Al/AC,将其用于水/2-仲丁基苯酚(SBP)双相体系中葡萄糖水热制备5-羟甲基糠醛(5-HMF)。以SEM、XRD、NH3-TPD和吡啶红外对催化剂进行表征,探究了制备条件对催化剂结构和活性的影响。研究结果表明:经质量分数为98%的H2SO4磺化,AlCl3饱和溶液中浸渍时间4 h时,制备的催化剂活性最高;催化剂为非晶态无定形炭结构,比表面积1 139.31 m2/g,B酸酸量为4.213 μmol/g,L酸酸量为29.97 μmol/g。当水热反应温度180℃,反应时间210 min,催化剂用量0.025 g,水相与有机相的体积比1:2时,5-HMF的产率最高(25.14%)。葡萄糖转化制备5-HMF的反应路径为:葡萄糖在水相中发生反应,在L酸的作用下异构化生成果糖,果糖在B酸的催化作用下脱水生成5-HMF,5-HMF被萃取到2-仲丁基苯酚中,生成的水保留在水相之中。催化剂循环稳定性测试表明,在重复使用5次后催化剂的活性为初始活性的86%。

关键词: 炭基固体酸, 葡萄糖, 5-羟甲基糠醛, 双相, 水热

Abstract:

A carbon-based solid acid catalyst(H-Al/AC) containing Brønsted(B) acid and Lewis(L) acid was prepared by H2SO4 sulfonation and AlCl3 immersion using coconut shell activated carbon(AC) as carrier. This catalyst was used to prepare 5-hydroxymethylfurfural(5-HMF) from glucose in a biphasic system(water/2-sec-butylphenol) by hydrothermal rection. The catalyst was characterized by SEM, BET, XRD, NH3-TPD and pyridine infrared to investigate the influence of preparation conditions on the structure and activity of the catalyst. The results showed that the catalyst activity reached the highest after being sulfonated with 98% H2SO4 and immersed in saturated AlCl3 solution for 4 h. The catalyst showed an amorphous carbon structure with the specific surface area of 1 139.31 m2/g, B acid amount 4.213 μmol/g and L acid amount 29.97 μmol/g, respectively. The catalytic performance of the prepared catalyst was investigated for the conversion of glucose to 5-HMF in biphasic system when the ratio of aqueous phase to organic phase was 1:2, and the results showed that the highest 5-HMF yield of 25.14% were obtained at 180℃ for 210 min with 0.025 g of catalyst. The reaction path of glucose conversion to 5-HMF was as follows: glucose was isomerized into fructose under the action of Lewis acid in the aqueous phase. Fructose was dehydrated under the catalysis of Brønsted acid to generate 5-HMF. 5-HMF was extracted into 2-sec-butylphenol(SBP), and the generated water was retained in the aqueous phase. The catalyst cycle stability test showed that the activity of the catalyst was 86% of the initial activity after repeated use for five times.

Key words: carbon-based solid acid, glucose, 5-hydroxymethyl furfural, biphasic system, hydrothermal

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