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左旋葡聚糖热解机理的密度泛函理论研究

黄金保,  刘朝,  曾桂生,  谢宇,  童红,  李伟民

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文章导航 > 燃料化学学报（中英文）  > 2012 >  40(07): 807-815
黄金保, 刘朝, 曾桂生, 谢宇, 童红, 李伟民. 左旋葡聚糖热解机理的密度泛函理论研究[J]. 燃料化学学报（中英文）, 2012, 40(07): 807-815.
引用本文: 黄金保, 刘朝, 曾桂生, 谢宇, 童红, 李伟民. 左旋葡聚糖热解机理的密度泛函理论研究[J]. 燃料化学学报（中英文）, 2012, 40(07): 807-815.
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HUANG Jin-bao, LIU Chao, ZENG Gui-sheng, XIE Yu, TONG Hong, LI Wei-min. A density functional theory study on the mechanism of levoglucosan pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2012, 40(07): 807-815.
Citation: HUANG Jin-bao, LIU Chao, ZENG Gui-sheng, XIE Yu, TONG Hong, LI Wei-min. A density functional theory study on the mechanism of levoglucosan pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2012, 40(07): 807-815.
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左旋葡聚糖热解机理的密度泛函理论研究

  • 1.

    贵州民族大学 理学院, 贵州 贵阳 550025;

  • 2.

    重庆大学 低品位能源利用技术及系统教育部重点实验室, 重庆 400044;

  • 3.

    南昌航空大学 环境与化学工程学院 江西 南昌 330063;

  • 4.

    华南理工大学 制浆造纸工程国家重点实验室, 广东 广州 510640

基金项目: 贵州省科学技术基金(黔科合J字[2012]2188号); 制浆造纸工程国家重点实验室开放基金(200928); 贵州省科技厅与贵州民族学院联合基金(黔科合J字LKM[2011]22号); 贵州民族大学引进人才科研基金资助项目。
详细信息
    通讯作者:

    黄金保(1976-), 男, 江西宁都人, 博士, 副教授, 主要从事能源利用及分子模拟方面的研究.E-mail: huangjinbao76@126.com.

  • 中图分类号: TK6;O642

A density functional theory study on the mechanism of levoglucosan pyrolysis

  • 1.

    School of Science, Guizhou University for Nationalities, Guiyang 550025, China;

  • 2.

    Key Laboratory of Low-grade Energy Utilization Technologies and Systems of Ministry of Education, Chongqing University, Chongqing 400044, China;

  • 3.

    School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063, China;

  • 4.

    State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China

    摘要
  • 摘要: 采用密度泛函理论B3LYP/6-31++G(d,p)方法,对纤维素热解的主要产物左旋葡聚糖的热解反应机理进行了理论计算分析,设计了四种可能的热解反应途径, 对各种反应的反应物、产物和过渡态的结构进行了能量梯度全优化。计算结果表明,左旋葡聚糖开环成链状中间体时,首先,左旋葡聚糖中的两个半缩醛键C(1)-O(7)和C(6)-O(8)断裂,经过渡态TS1形成中间体IM1,同时,C(6)-O(7)结合成键使C(5)-C(6)-O(7)形成环状结构,该反应的能垒较高,为296.53 kJ/mol,然后IM1经过渡态TS2转变为中间体IM2,该反应的能垒为234.09 kJ/mol;对IM2设计了四条可能的反应路径,反应路径2和3能垒较低,是IM2最可能的热解反应途径;在反应路径1和4中都包含了脱羰基反应,其反应能垒较高,不易发生。
    Abstract: The pyrolysis mechanism of levoglucosan (one of the major product from cellulose pyrolysis) was investigated by using density functional theory at B3LYP/6-31++G(d,p) level. Four possible reaction pathways were proposed and the geometries of reactant, transition states, intermediates and products for each pathway were fully optimized; the standard thermodynamic and kinetic parameters of each reaction at different temperatures were calculated. The results showed that levoglucosan is converted to intermediate IM1 via transition state TS1 with an activation energy of 296.53 kJ/mol by breakage of C(1)-O(7) and C(6)-O(8) hemiacetal linkages and formation of C(5)-C(6)-O(7) circular structure, and then IM1 is converted to intermediate IM2 via transition state TS2 with an activation energy of 234.09 kJ/mol. IM2 can be further decomposed via four different pathways. Pathways 1 and 4 involve decarbonylation reactions with high energy barriers, and as a result, they are unlikely to occur; on the other side, the energy barriers for the rate-determining steps of pathways 2 and 3 are much lower, which are kinetically favorable and possible the major reaction channels for IM2 pyrolysis.
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    • 参考文献(17)
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出版历程
  • 收稿日期:  2011-09-17
  • 修回日期:  2011-11-25
  • 刊出日期:  2012-07-31

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