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林产化学与工业 ›› 2020, Vol. 40 ›› Issue (5): 27-33.doi: 10.3969/j.issn.0253-2417.2020.05.004

• 研究报告 • 上一篇    下一篇

5-羟甲基糠醛热解行为的理论研究

陈波1,刘波2,*(),时章明3   

  1. 1. 湖南工程学院 机械工程学院, 湖南 湘潭 411104
    2. 湖南工程学院 电气信息学院, 湖南 湘潭 411104
    3. 中南大学 能源科学与工程学院, 湖南 长沙 410083
  • 收稿日期:2020-05-18 出版日期:2020-10-28 发布日期:2020-10-31
  • 通讯作者: 刘波 E-mail:19704758@qq.com
  • 作者简介:陈波(1986—),男,湖南邵阳人,讲师,博士,主要从事生物质能利用方面的研究
  • 基金资助:
    湖南省教育厅资助科研项目(19C0476);湘潭市科技局资助科研项目(CG-YB20201010);湖南工程学院青年科研重点项目(XJ1902)

Theoretical Study on Pyrolysis Behavior of 5-HMF

Bo CHEN1,Bo LIU2,*(),Zhangming SHI3   

  1. 1. School of Mechanical Engineering, Hunan institute of Engineering, Xiangtan 411104, China
    2. School of Electrical and Information Engineering, Hunan institute of Engineering, Xiangtan 411104, China
    3. School of Energy Science and Engineering, Central South University, Changsha 410083, China
  • Received:2020-05-18 Online:2020-10-28 Published:2020-10-31
  • Contact: Bo LIU E-mail:19704758@qq.com

摘要:

采用密度泛函理论方法B3LYP/6-31G++(d,p)对5-羟甲基糠醛(5-HMF)的热解反应机理进行量子化学理论研究。研究结果表明:5-HMF可以脱去羟基侧链生成糠醛,反应能垒为322.8 kJ/mol;也可脱去醛基侧链生成2-糠醇,反应能垒为375.4 kJ/mol,说明在5-HMF的热解过程中糠醛的出现比2-糠醇要早。糠醛进一步热解可发生开环生成苯环,反应能垒为370.8 kJ/mol,说明呋喃环能够发生脱氧环化反应。5-HMF直接发生开环反应有水参与时生成链式烯醇类物质,无水参与时生成链式烯酮类物质,有/无水分子参与的反应能垒分别为287.6和279.1 kJ/mol,说明水分子的参与不利于5-HMF的开环。

关键词: 5-羟甲基糠醛, 糠醛, 2-糠醇, 苯, 热解机理, 量子化学

Abstract:

The mechanism of 5-hydroxymethylfurfural(5-HMF) pyrolysis was studied by density functional theory B3LYP/6-31G++(d, p). The results show that the energy barrier of generating furfural by hydroxy side chain removal of 5-HMF is 322.8 kJ/mol, and the energy barrier of 2-furfuryl alcohol by aldehyde group side chain removal of 5-HMF is 375.4 kJ/mol. It is indicated that the appearance of furfuryl is earlier than 2-furfural in the pyrolysis process of 5-HMF. Further pyrolysis of furfural can occur the ring-opening reaction to form benzene ring with the reaction energy barrier of 370.8 kJ/mol, which explains that the furan ring can undergo deoxygenation and cyclization reaction. 5-HMF can directly generate ring-opening reaction in the case of H2O participation or without H2O participation to obtain enol compounds or enone compounds. The energy barrier of ring-opening reaction with H2O participation is 287.6 kJ/mol, and the energy barrier of ring-opening reaction without H2O participation is 279.1 kJ/mol. Thus, the participation of water molecules is not conducive to the ring opening of 5-HMF.

Key words: 5-HMF, furfural, 2-furfuryl, benzene, pyrolysis mechanisms, quantum chemistry

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