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生物质化学工程 ›› 2017, Vol. 51 ›› Issue (5): 1-6.doi: 10.3969/j.issn.1673-5854.2017.05.001

• 研究报告 •    下一篇

当归内酯和2-甲基呋喃合成可再生生物柴油前驱体

王伟1,2, 季晓晖1, 葛红光1, 李志洲1, 邵先钊1, 张强1   

  1. 1. 陕西理工大学 化学与环境科学学院, 陕西 汉中 723001;
    2. 陕西省催化基础与应用重点实验室, 陕西 汉中 723001
  • 收稿日期:2017-02-28 出版日期:2017-09-30 发布日期:2017-09-30
  • 作者简介:王伟(1980—),男,讲师,博士,主要从事生物质催化转化;E-mail:wangwei@snut.edu.cn
  • 基金资助:
    国家自然科学基金资助项目(21503125,21502109);陕西省教育厅专项项目(16JK1146);陕西理工大学科研计划资助项目(SLGQD13(2)-1)

Synthesis of Renewable Bio-diesel Precursors with Angelica Lactone and 2-Methylfuran

WANG Wei1,2, JI Xiaohui1, GE Hongguang1, LI Zhizhou1, SHAO Xianzhao1, ZHANG Qiang1   

  1. 1. School of Chemistry and Environment Science, Shaanxi University of Technology, Hanzhong 723001, China;
    2. Shaanxi Key Laboratory of Catalysis, Shaanxi Province, Hanzhong 723001, China
  • Received:2017-02-28 Online:2017-09-30 Published:2017-09-30

摘要: 以生物质衍生的当归内酯与2-甲基呋喃为原料,杂多酸为催化剂,经羟烷基化或烷基化反应生成4,4-二(5-甲基呋喃-2-基)戊酸,然后加氢制得可再生生物柴油前驱体4,4-二(5-甲基四氢呋喃-2-基)-1-戊醇和双(5-甲基四氢呋喃-2-基)乙烷。首先,考察了硅钨酸、磷钼酸和硅钼酸催化剂对羟烷基化/烷基化反应的影响,并对催化剂用量、反应温度和时间进行了优化,结果表明,硅钨酸的催化性最高,在反应温度为60 ℃、硅钨酸的用量为0.05 g、反应时间为60 min条件下4,4-二(5-甲基呋喃-2-基)戊酸产率达到70.5%。然后,考察了Pd/C、Ru/C和Pt/C催化剂对当归内酯与2-甲基呋喃羟烷基化/烷基化产物的加氢反应,Ru/C催化剂表现出最好的活性和选择性,4,4-二(5-甲基四氢呋喃-2-基)-1-戊醇和双(5-甲基四氢呋喃-2-基)乙烷产率分别为60.5%和24.6%。最后对Ru/C催化剂的稳定性进行了考察,在24 h的反应时间内催化剂表现出良好的稳定性,活性没有明显下降。获得的4,4-二(5-甲基四氢呋喃-2-基)-1-戊醇和双(5-甲基四氢呋喃-2-基)乙烷混合物可作为柴油前驱体。

关键词: 羟烷基化/烷基化, 加氢, 生物柴油前驱体, 当归内酯, 2-甲基呋喃

Abstract: Hydroxylalkylation/alkylation of angelica lactone and 2-methylfuran derived from biomass was processed with heteropoly acid as catalyst to obtained 4,4-bis(5-methylfuran-2-yl)pentanoic acid. Renewable bio-diesel precursors, 4,4-bis(5-methyl-tetrahydrofuran-2-yl)pentan-1-ol and bis(5-methyl-tetrahydrofuran-2-yl)ethane, were produced by hydrogenation of the 4,4-bis(5-methylfuran-2-yl)pentanoic acid. First of all, the effects of silicotungstic acid, phosphomolybdic acid and silicomolybdic acid catalyst on hydroxylalkylation/alkylation yield were studied. Reaction temperature, catalyst dosage and reaction time were optimized. The yield of 4,4-bis(5-methylfuran-2-yl)pentanoic acid reached 70.5% under the reaction temperature 60 ℃, the dosage of silicotungstic acid 0.05 g, and the reaction time 60 min. Afterwards, the hydrogenation of hydroxylalkylation/alkylation product of angelica lactone and 2-methylfuran on the Pd/C, Ru/C and Pt/C catalyst was also investigated. Ru/C catalyst showed the best activity and selectivity. Yields of 4,4-bis(5-methyl-tetrahydrofuran-2-yl)pentan-1-ol and bis(5-methyl-tetrahydrofuran-2-yl)ethane were 60.5% and 24.6%, respectively. Finally, the stability of Ru/C catalyst was investigated, and the reaction time of 24 h showed good stability. The obtained mixture of 4,4-bis(5-methyl-tetrahydrofuran-2-yl)pentan-1-ol and bis(5-methyl-tetrahydrofuran-2-yl)ethane can be used as bio-diesel precursors.

Key words: hydroxylalkylation/alkylation, hydrogenation, bio-diesel precursors, angelica lactone, 2-methylfuran

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