化学学报 ›› 2012, Vol. 70 ›› Issue (02): 114-120.DOI: 10.6023/A1109252 上一篇    下一篇

研究论文

微波裂解硬脂酸钠脱羧成烃机理研究

王允圃a,b, 刘玉环a,b, 阮榕生a,b, 万益琴a, 张锦胜a,b, 彭红a   

  1. a. 南昌大学生物质转化教育部工程研究中心 南昌 330047;
    b. 南昌大学食品科学与技术国家重点实验室 南昌 330047
  • 投稿日期:2011-09-25 修回日期:2011-11-30 发布日期:2012-02-25
  • 通讯作者: 刘玉环 E-mail:liuyuhuan@ncu.edu.cn
  • 基金资助:

    江西省国际合作(No.20101208);科技部国际合作(No.2010DFB63750);江西省自然科学基金(No.2008GZH0047);江西省科技厅产业化关键技术攻关(No.2007BN12100);国家自然科学基金(No.30960304);国家林业局(No.9482010-4-09)和食品科学与技术国家重点实验室自由探索(Nos.SKLF-TS-201111, KLF-TS-200814)资助项目.

Mechanism of Hydrocarbon Generation from Sodium Stearate Decarboxylation by Microwave Assisted Pyrolysis

Wang Yunpua,b, Liu Yuhuana,b, Ruan Rongshenga,b, Wan Yiqina, Zhang Jinshenga,b, Peng Honga   

  1. a. Nanchang University, Engineering Research Center for Biomass Conversion, Ministry of Education, Nanchang 330047;
    b. Nanchang University, State Key Laboratory of Food Science and Technology, Nanchang 330047
  • Received:2011-09-25 Revised:2011-11-30 Published:2012-02-25
  • Supported by:

    Project supported by International Cooperation of Jiangxi Province (No.20101208);International Science & Technology Cooperation Program of China (No.2010DFB63750);Natural Science Foundation of Jiangxi Province (No.2008GZH0047);Jiangxi Province Department of Science and Technology (No.2007BN12100);National Natural Science Foundation of China (No.30960304);State Forestry Administration;P. R. China (No.9482010-4-09) and State Key Laboratory of Food Science and Technology (Nos.SKLF-TS-201111;KLF-TS-200814).

可再生烃类燃料相对于脂肪酸甲酯(生物柴油)有显著优势. 本研究以硬脂酸钠为研究对象, 采用微波裂解技术开展脂肪酸盐脱羧成烃机理的研究, 通过气质联用等手段对裂解产物进行分析, 研究结果表明微波能选择性作用于硬脂酸钠羧基端, 导致其在微波场中发生偶极转向极化和界面极化. 离子或极性分子的Lorentz 力按照电磁波作用的方式运动, 有助于碳负离子的形成, 有效推动了脱羧反应的进行; 添加于反应体系中的甘油具有很高的介电常数, 在微波场中形成“高热位点”, 降低了脱羧反应活化能并为硬脂酸钠脱羧起到了供氢体的作用. 液体产物中端烯烃和正构烷烃系列从C8~C20有规律的分布, 符合烃类裂解的规律. 研究结果证实了由脂肪酸盐在微波作用和甘油做为供氢体的条件下, 脱羧裂解生产优质替代性烃类燃料和绿色化学品的可行性.

关键词: 微波裂解, 硬脂酸钠, 极化, 脱羧, 烃类

Renewable hydrocarbon fuel have significant advantage to biodiesel (fatty acid methyl ester). The purpose of present study was to explore decarboxylation mechanism of fatty acid sodium salt with microwave radiation. Sodium stearate (C18) was chosen as a model compound, the carboxy-terminal of this dipolar molecular was further polarized with microwave radiation. The Lorentz force of ions or dipolar molecules were moved in accordance with the way of electromagnetic waves, contributing to the formation of carbanion, which effectively promote the decarboxylation reaction. Glycerol possessing high dielectric constant were added which formed a “high-temperature locus” that lowed the activation energy of decarboxylation reaction and played a role as the hydrogen donor. The liquid products were analysed and the results showed C8~C20 n-alkanes and n-alk-1-enes were arranged regularly which complied with the law of hydrocarbon pyrolysis. All the work proved the feasibility of deriving renewable hydrocarbon fuel from fatty acid sodium salt by microwave pyrolysis.

Key words: microwave pyrolysis, sodium stearate, polarization, decarboxylation, hydrocarbon