β-O-4型木质素二聚体热解历程的密度泛函理论研究

doi:10.3969/j.issn.0253-2417.2016.01.003

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (1): 20-26.doi: 10.3969/j.issn.0253-2417.2016.01.003

β-O-4型木质素二聚体热解历程的密度泛函理论研究

蒋晓燕, 陆强, 董晓晨, 胡斌, 董长青

华北电力大学可再生能源学院生物质发电成套设备国家工程实验室, 北京 102206

收稿日期:2014-12-29 出版日期:2016-02-25 发布日期:2016-03-18
通讯作者: 陆强,副教授,硕士生导师,主要从事生物质高效热化学转化研究;E-mail:qianglu@mail.ustc.edu.cn。 E-mail:qianglu@mail.ustc.edu.cn
作者简介:蒋晓燕 (1990-),女,江苏江阴人,博士生,主要从事生物质高效热化学转化机理研究
基金资助:
国家火炬计划项目(2013GH561645);国家自然科学基金资助项目(51276062)

Studies on Pyrolysis Process of β-O-4 Type Lignin Model Dimer Using Density Functional Theory

JIANG Xiao-yan, LU Qiang, DONG Xiao-chen, HU Bin, DONG Chang-qing

National Engineering Laboratory for Biomass Power Generation Equipment, Renewable Energy School, North China Electric Power University, Beijing 102206, China

Received:2014-12-29 Online:2016-02-25 Published:2016-03-18

摘要/Abstract

摘要： 为了解木质素的热解机理,利用密度泛函理论B3LYP方法,在6-31++G(d,p)基组水平上对含有C_α位羰基的β-O-4型木质素二聚体模型化合物(3-羟基-1-(4-羟基苯基)-2-苯氧基-1-丙酮)的热解过程进行了理论计算和分析。结果表明,C_α位上的羰基取代基可大大降低C_β-O的键解离能,提高C_α-C_β的键解离能,使得C_β-O的键解离能比C_α-C_β低91.5 kJ/mol,因此该二聚体主要通过C_β-O键均裂的方式发生热解反应,其主要酚类热解产物是苯酚和4-羟基苯甲醛,次要产物是4-羟基苯乙酮,生成4-羟基苯甲醛的动力学最优路径是R7-a,其反应能垒为236.6 kJ/mol。

关键词: 木质素, β-O-4型二聚体, 热解机理, 密度泛函理论

Abstract: In order to understand the pyrolysis mechanism of lignin, 3-hydroxy-1-(4-hydroxyphenyl)-2-phenoxypropan-1-one with C_α carbonyl group was selected as a β-O-4 type lignin model dimer, and its pyrolysis process was theoretically calculated by density functional theory methods at B3LYP level with 6-31++G(d, p) basis set.The calculation results indicated that the carbonyl substituent on the C_α dramatically could significantly decrease the bond dissociation energy (E_BD) of C_β-O, while the bond dissociation energy of C_α-C_β was augmented.The bond dissociation energy of C_β-O was 91.5 kJ/mol lower than that of C_α-C_β.Thus, it could be deduced that the dimer was mainly decomposed through the homolytic cleavage of the C_β-O linkage, and major phenolic pyrolytic products of phenol and 4-hydroxybenzaldehyde, minor parts of 4-hydroxyacetophenone were formed in this process. The R7-a kinetic way was considered as the optimum way to form 4-hydroxybenzaldehyde, and the energy barrier was 236.6 kJ/mol.

Key words: lignin, β-O-4 linkage dimer, pyrolysis mechanism, density functional theory

中图分类号:

TQ35
TK6

蒋晓燕, 陆强, 董晓晨, 胡斌, 董长青. β-O-4型木质素二聚体热解历程的密度泛函理论研究[J]. 林产化学与工业, 2016, 36(1): 20-26.

JIANG Xiao-yan, LU Qiang, DONG Xiao-chen, HU Bin, DONG Chang-qing. Studies on Pyrolysis Process of β-O-4 Type Lignin Model Dimer Using Density Functional Theory[J]. Chemistry and Industry of Forest Products, 2016, 36(1): 20-26.

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β-O-4型木质素二聚体热解历程的密度泛函理论研究

Studies on Pyrolysis Process of β-O-4 Type Lignin Model Dimer Using Density Functional Theory

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