燃料化学学报Issue(11)：1334-1343,10.
木质素二聚体模型化合物热解机理的量子化学研究
Quantum chemistry study on pyrolysis mechanism of lignin dimer model compound
摘要
Abstract
β-O-4 is the primary type of linkages among the main lignin structure units. The pyrolysis of lignin dimer model compound of β-O-4 linkage was investigated by using density functional theory B3 LYP methods at 6-31G ( d, p ) level. Three possible pyrolysis pathways were proposed: the subsequent reactions after the homolytic cleavage of Cβ-O bond, the subsequent reactions after the homolytic cleavage of Cα-Cβbond and the concerted reactions. The equilibrium geometries of the reactants, transition states, intermediates and products were optimized and the standard kinetic parameters for each reaction pathway were calculated. The formation mechanism of the main pyrolysis products and the effect of temperature on the pyrolysis mechanism of lignin dimer were analyzed. The calculation results show that the subsequent reaction pathways after the homolytic cleavage of Cβ-O bond and the concerted reaction pathways ( 1 ) and ( 3 ) are the major reaction channels, whereas the subsequent reaction pathways after the homolytic cleavage of Cα-Cβ and the concerted reaction pathways ( 2 ) and ( 5 ) are the competitive reaction channels in the pyrolysis process. The main pyrolysis products are phenolic compounds such as guaiacol, 1-guaiacyl-3-hydroxy- acetone, 1-guaiacyl-3-hydroxy-propaldehyde and guaiacyl-formaldehyde. In the pyrolysis process of the lignin dimer, the concerted reactions dominate over the free-radical homolytic reactions at low temperature, whereas but the free-radical reactions prevail over the concerted reactions at high temperatures.关键词
木质素/β-O-4连接二聚体/热解机理/密度泛函理论Key words
ignin/β-O-4 linkage dimer/pyrolysis mechanism/density functional theory分类
能源与动力引用本文复制引用
黄金保,武书彬,雷鸣,程皓,梁嘉晋,童红..木质素二聚体模型化合物热解机理的量子化学研究[J].燃料化学学报,2015,(11):1334-1343,10.基金项目
The project was supported by the National Natural Science Foundation of China (51266002), the Major State Basic Research Development Program of China (973 Program,2013CB228101) and the Natural Science Research Funds of the Department of Education of Guizhou Province ([2013]405).国家自然科学基金(51266002),国家重点基础研究发展规划(973计划,2013CB228101),贵州省教育厅自然科学研究招标项目(黔教科研发[2013]405号)资助 （51266002）
