留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

木质素模化物紫丁香酚热解机理的量子化学研究

黄金保,  刘朝,  任丽蓉,  童红,  李伟民,  伍丹

downloadPDF
文章导航 > 燃料化学学报（中英文）  > 2013 >  41(06): 657-666
黄金保, 刘朝, 任丽蓉, 童红, 李伟民, 伍丹. 木质素模化物紫丁香酚热解机理的量子化学研究[J]. 燃料化学学报（中英文）, 2013, 41(06): 657-666.
引用本文: 黄金保, 刘朝, 任丽蓉, 童红, 李伟民, 伍丹. 木质素模化物紫丁香酚热解机理的量子化学研究[J]. 燃料化学学报（中英文）, 2013, 41(06): 657-666.
shu
HUANG Jin-bao, LIU Chao, REN Li-rong, TONG Hong, LI Wei-min, WU Dan. Studies on pyrolysis mechanism of syringol as lignin model compound by quantum chemistry[J]. Journal of Fuel Chemistry and Technology, 2013, 41(06): 657-666.
Citation: HUANG Jin-bao, LIU Chao, REN Li-rong, TONG Hong, LI Wei-min, WU Dan. Studies on pyrolysis mechanism of syringol as lignin model compound by quantum chemistry[J]. Journal of Fuel Chemistry and Technology, 2013, 41(06): 657-666.
shu

木质素模化物紫丁香酚热解机理的量子化学研究

  • 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.

    贵州民族大学化学与环境科学学院, 贵州 贵阳 550025

基金项目: 国家自然科学基金(51266002);贵州省科学技术基金(黔科合J字[2012]2188号);低品位能源利用技术及系统教育部重点实验室开放基金(LLEUTS-201303)。
详细信息
    通讯作者:

    黄金保(1976-), 男, 江西宁都人, 博士, 副教授, 主要从事生物质能开发利用及分子模拟方面的研究。 E-mail: huangjinbao76@126.com。

  • 中图分类号: TK6;O642

Studies on pyrolysis mechanism of syringol as lignin model compound by quantum chemistry

  • 1.

    School of Science, Guizhou Minzu University, 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 Chemistry and Environmental Science, Guizhou Minzu University, Guiyang 550025, China

    摘要
  • 摘要: 采用密度泛函理论方法B3LYP/6-31G++(d,p),对木质素模化物紫丁香酚的热解反应机理进行了量子化学理论研究。提出了三种可能的热解反应途径,对各种反应的反应物、产物、中间体和过渡态的结构进行了能量梯度全优化。计算了各热解反应途径的标准动力学参数,分析了各种主要热解产物的形成演化机理。键离解能计算结果表明,紫丁香酚中CH3-O键的键离解能最小,各种键离解能的大小顺序为CH3-O < O-H < CH3O-Caromatic < CH2-H < HO-Caromatic < Caromatic-H。在反应路径(1)中,主要热解产物是3-甲氧基邻苯二酚,其形成反应的总能垒为366.6 kJ/mol;在反应路径(2)中主要热解产物是2-甲氧基-6-甲基苯酚,其形成反应的总能垒为474.8 kJ/mol;在反应路径(3)中形成邻甲氧基苯酚的总能垒很低,为21.4 kJ/mol,这表明,在连接甲氧基的碳原子上加氢后能够有效地降低木质素芳环模化物紫丁香酚去甲氧基反应的反应能垒。
    Abstract: The pyrolysis of syringol as lignin model compound was investigated using density functional theory methods at B3LYP/6-31G++ (d, p) level. Three possible pyrolytic pathways were proposed and the equilibrium geometries of the reactants, transition states, intermediate and products were fully optimized. The standard kinetic parameters in each reaction pathway were calculated and the formation and evolution mechanism of main pyrolysis products were analyzed. Bond dissociation energies calculation results show that the bond dissociation energy of CH3-O of syringol is the lowest and the order of all kinds of bond dissociation energy is CH3-O < O-H < CH3O-Caromatic < CH2-H < HO-Caromatic < Caromatic-H. In reaction pathway 1 and 2, the main pyrolysis product is 3-methoxycatechol and 2-methoxy-6-methylphenol, respectively. The total energy barrier is 366.6 and 474.8 kJ/mol in pathway 1 and 2, respectively. For reaction pathway 3, the total energy barrier of o-methoxyphenol formation is as low as 21.4 kJ/mol, which shows that addition of hydrogen to the carbon atom connected with methoxyl can effectively lower the reaction energy barrier of demethoxy reaction of lignin model syringol.
    • HTML全文
    • 参考文献(21)
  • MCKENDRY P. Energy production from biomass (part 1): Overview of biomass[J]. Bioresour Technol, 2002, 83(1): 37-46.
    MAHINPEV N, MURUGAN P, MANI T, RAINA R. Analysis of bio-oil, biogas, and biochar from pressurized pyrolysis of wheat straw using a tubular reactor[J]. Energy Fuels, 2009, 23(5): 2736-2742.
    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, 2012, 40(7): 807-815. (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(7): 807-815.)
    黄金保, 童红, 李伟民, 伍丹. 木质素热解机理的分子动力学模拟研究[J]. 材料导报, 2012, 26(10): 138-142. (HUANG Jin-bao, TONG Hong, LI Wei-min, WU Dan. Molecular dynamic simulation study on thermal decomposition mechanism of lignin[J]. Materials Review, 2012, 26(10): 138-142.)
    刘军利, 蒋剑春, 黄海涛. 木质素CP-GC-MS法裂解行为研究[J]. 林产化学与工业, 2009, 29(s): 1-6. (LIU Jun-li, JIANG Jian-chun, HUANG Hai-tao. Study on thermal transformations of lignin under curie-point pyrolysis-GC-MS conditions[J]. Chemisty and Industry of Forest Products, 2009, 29(s): 1-6.)
    CABALLERO J A, FONT R, MARCILLA A. Study of the primary pyrolysis of kratf 1ignin at high heating rates: Yields and kineties[J]. J Anal Appl Pyrolysis, 1996, 36(2): 159-178.
    谭洪, 王树荣, 骆仲泱, 余春江, 岑可法. 木质素快速热裂解试验研究[J]. 浙江大学学报(工学版), 2005, 39(5): 710-714. (TAN Hong, WANG Shu-rong, LUO Zhong-yang, YU Chun-jiang, CEN Ke-fa. Experimental study of lignin flash pyrolysis[J]. Journal Zhejiang University (Engineering Science), 2005, 39(5): 710-714.)
    LIU Q, WANG S, ZHENG Y, LUO Z, CEN K. Mechanism study of wood lignin pyrolysis by using TG-FTIR analysis[J]. J Anal Appl Pyrolysis, 2008, 82(1): 170-177.
    NUNN T R, HOWARD J B, LONGWLL J P, PETERS W A. Product compositions and kinetics in the rapid pyrolysis of milled wood lignin[J]. Ind Eng Chem Process Des Dev, 1985, 24(3): 844-852.
    BESTE A, BUCHANAN III A C. Computational study of bond dissociation enthalpies for lignin model compounds: Substituent effects in phenethyl phenyl ethers[J]. J Org Chem, 2009, 74(7): 2837-2841.
    HUANG X, LIU C, HUANG J, LI H. Theory studies on pyrolysis mechanism of phenethyl phenyl ether[J]. Comput Theor Chem, 2011, 976(1-3): 51-59.
    蒋挺大. 木质素[M]. 北京: 化学工业出版社, 2001. (JIANG Ting-da. Lignin[M]. Beijing: Chemistry Industry Press, 2001.)
    SURYAN M M, KAFAFI S A, STEIN S E. The thermal decomposition of hydroxy-and methoxy-substituted anisoles[J]. J Am Chem Soc, 1989, 111(4): 1423-1429.
    DORRESTIJN E, MULDER P. The radical-induced decomposition of 2-methoxyphenol[J]. J Chem Soc Perkin Trans, 1999, (2): 777-780.
    Gaussian 03. Gaussian, Inc. Pittsburgh PA, 2003.
    HUANG J B, LIU C, TONG H, LI W M, WU D. Theoretical studies on pyrolysis mechanism of xylopyranose[J]. Computa Theore Chem, 2012, 1001: 44-50.
    黄金保, 刘朝, 魏顺安, 黄晓露, 李豪杰. 纤维素热解形成左旋葡聚糖机理的理论研究[J]. 燃料化学学报, 2011, 39(8): 590-594. (HUANG Jin-bao, LIU Chao, WEI Shun-an, HUANG Xiao-lu, LI Hao-jie. A theoretical study on the mechanism of levoglucosan formation in cellulose pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2011, 39(8): 590-594.)
    张芳沛, 程新路, 刘子江, 胡栋, 刘永刚. 硝酸丙酯键离解能和热解机理的密度泛函理论研究[J]. 高压物理学报, 2005, 19(2): 189-192. (ZHANG Fang-pei, CHENG Xin-lu, LIU Zi-jiang, HU Dong, LIU Yong-gang. Density functional studies on the bond dissociation energy and pyrolysis mechanism of propyl nitrate[J]. Chinese Journal of High Pressure Physics, 2005, 19(2): 189-192.)
    沈文浩, 陈小泉, 刘鸿斌, 武书彬. 木素模型物愈疮木酚结构和热解机理的量子化学研究[J]. 造纸科学与技术, 2010, 29(3): 73-78. (SHEN Wen-hao, CHEN Xiao-quan, LIU Hong-bin, WU Shu-bin. Quantum chemistry research on guaiacol lignin model compound structure and pyrolysis mechanism[J]. Paper Science & Technology, 2010, 29(3): 73-78.)
    ASMADI M, KAWAMOTO H, SAKA S. Thermal reactions of guaiacol and syringol as lignin model aromatic nuclei[J]. J Anal Appl Pyrolysis, 2011, 92(1): 88-98.
    ASMADI M, KAWAMOTO H, SAKA S. Thermal reactivities of catechols/pyrogallols and cresols/xylenols as lignin pyrolysis intermediates[J]. J Anal Appl Pyrolysis, 2011, 92(1): 76-87.
    • 相关文章
    • 施引文献
  • 资源附件(0)
  • 加载中
WeChat 点击查看大图
计量
  • 文章访问数:  1932
  • HTML全文浏览量:  34
  • PDF下载量:  979
  • 被引次数: 0
出版历程
  • 收稿日期:  2013-01-29
  • 修回日期:  2013-03-18
  • 刊出日期:  2013-06-30

目录

    /

    返回文章
    返回
    友情链接： 新型炭材料 中国科学院 中国知网 万方论文查重系统

    主办单位：中国科学院山西煤炭化学研究所 中国化学会主编：房倚天

    电子邮件：rlhx@sxicc.ac.cn

    版权所有 © 《燃料化学学报（中英文）》编辑部 本系统由 北京仁和汇智信息技术有限公司 开发    百度统计

    x 关闭 永久关闭

    2023年《燃料化学学报（中英文）》评优结果公布！