当归内酯和2-甲基呋喃合成可再生生物柴油前驱体  

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

作　　者：王伟[1,2] 季晓晖 葛红光[1] 李志洲[1] 邵先钊[1] 张强[1] WANG Wei JI Xiaohui GE Hongguang LI Zhizhou SHAO Xianzhao ZHANG Qiang(School of Chemistry and Environment Science,Shaanxi University of Technology, Hanzhong 723001, China Shaanxi Key Laboratory of Catalysis, Shaanxi Province, Hanzhong 723001, China)

机构地区：[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

出　　处：《生物质化学工程》2017年第5期1-6,共6页Biomass Chemical Engineering

基　　金：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)

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。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-l-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 rain. 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-tetrabydrofuran-2-yl）pentan-l-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-l-ol and bis （ 5-methyl-tetrahydrofuran-2-yl ） ethane can be used as bio-diesel precursors.

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 

分 类 号：TE667[石油与天然气工程—油气加工工程]