Computational study on pyrolysis mechanism of β-5 linked lignin dimers

Lignin is a highly complex amorphous three-dimensional network polymer connected by C—O bond and C—C bond. Understanding the bond cleavage mechanism during lignin pyrolysis is crucial for advancing efficient pyrolysis technology, as it serves as a significant avenue to harness lignin′s potential. In...

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Main Authors: LI Wentao, GAO Lijuan, ZHOU Guanzheng, CHAI Baohua, WANG Meijing, HU Bin*, LIU Ji, LU Qiang
Format: Article
Language:zho
Published: Editorial Office of Energy Environmental Protection 2024-04-01
Series:能源环境保护
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Online Access:https://eep1987.com/en/article/4869
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author LI Wentao
GAO Lijuan
ZHOU Guanzheng
CHAI Baohua
WANG Meijing
HU Bin*
LIU Ji
LU Qiang
author_facet LI Wentao
GAO Lijuan
ZHOU Guanzheng
CHAI Baohua
WANG Meijing
HU Bin*
LIU Ji
LU Qiang
author_sort LI Wentao
collection DOAJ
description Lignin is a highly complex amorphous three-dimensional network polymer connected by C—O bond and C—C bond. Understanding the bond cleavage mechanism during lignin pyrolysis is crucial for advancing efficient pyrolysis technology, as it serves as a significant avenue to harness lignin′s potential. In this paper, the density functional theory method was employed to investigate the process of alignin dimer model compound that contains β-5 linkages. The calculation results show that the most likely initial reaction is the five-membered ring-opening reaction between benzene rings, in which the bond dissociation energies (BDEs) of the Cα—O bond and Cα—Cβ bond are 163.9 kJ/ mol and 212.9kJ/ mol, respectively. These reactions are the main ring-opening reactions. By comparing the cleavage of β-5 linkages among the dimers that carry methyl, methoxy, hydroxyl, n-propyl, and other branched chains, it is found that the BDEs of the Cα—O bond and Cα—Cβ bond are at a minimum when hydroxyl, propyl, and hydroxymethyl groups are attached to the two benzene rings and the five-membered ring, respectively. Homolytic cleavage of the Cα—O bond is always the initial reaction, and the continuous fracture of the Cα—O and Cα—Cβ bonds is the main path to break the five-membered ring.
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id doaj-art-453bf10efe674db5bb8686863415997c
institution DOAJ
issn 2097-4183
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publishDate 2024-04-01
publisher Editorial Office of Energy Environmental Protection
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series 能源环境保护
spelling doaj-art-453bf10efe674db5bb8686863415997c2025-08-20T02:53:34ZzhoEditorial Office of Energy Environmental Protection能源环境保护2097-41832024-04-0138220821410.20078/j.eep.20240104Computational study on pyrolysis mechanism of β-5 linked lignin dimersLI Wentao0GAO Lijuan1ZHOU Guanzheng2CHAI Baohua3WANG Meijing4HU Bin*5LIU Ji6LU Qiang71. Power China Northwest Engineering Corporation Limited; 2. National Engineering Research Center of New Energy Power Generation, North China Electric Power UniversityPower China Northwest Engineering Corporation LimitedNational Engineering Research Center of New Energy Power Generation, North China Electric Power UniversityPower China Northwest Engineering Corporation LimitedPower China Northwest Engineering Corporation LimitedNational Engineering Research Center of New Energy Power Generation, North China Electric Power UniversityNational Engineering Research Center of New Energy Power Generation, North China Electric Power UniversityNational Engineering Research Center of New Energy Power Generation, North China Electric Power UniversityLignin is a highly complex amorphous three-dimensional network polymer connected by C—O bond and C—C bond. Understanding the bond cleavage mechanism during lignin pyrolysis is crucial for advancing efficient pyrolysis technology, as it serves as a significant avenue to harness lignin′s potential. In this paper, the density functional theory method was employed to investigate the process of alignin dimer model compound that contains β-5 linkages. The calculation results show that the most likely initial reaction is the five-membered ring-opening reaction between benzene rings, in which the bond dissociation energies (BDEs) of the Cα—O bond and Cα—Cβ bond are 163.9 kJ/ mol and 212.9kJ/ mol, respectively. These reactions are the main ring-opening reactions. By comparing the cleavage of β-5 linkages among the dimers that carry methyl, methoxy, hydroxyl, n-propyl, and other branched chains, it is found that the BDEs of the Cα—O bond and Cα—Cβ bond are at a minimum when hydroxyl, propyl, and hydroxymethyl groups are attached to the two benzene rings and the five-membered ring, respectively. Homolytic cleavage of the Cα—O bond is always the initial reaction, and the continuous fracture of the Cα—O and Cα—Cβ bonds is the main path to break the five-membered ring.https://eep1987.com/en/article/4869ligninβ-5 linkagedensity functional theorymodel compoundspyrolysis mechanism
spellingShingle LI Wentao
GAO Lijuan
ZHOU Guanzheng
CHAI Baohua
WANG Meijing
HU Bin*
LIU Ji
LU Qiang
Computational study on pyrolysis mechanism of β-5 linked lignin dimers
能源环境保护
lignin
β-5 linkage
density functional theory
model compounds
pyrolysis mechanism
title Computational study on pyrolysis mechanism of β-5 linked lignin dimers
title_full Computational study on pyrolysis mechanism of β-5 linked lignin dimers
title_fullStr Computational study on pyrolysis mechanism of β-5 linked lignin dimers
title_full_unstemmed Computational study on pyrolysis mechanism of β-5 linked lignin dimers
title_short Computational study on pyrolysis mechanism of β-5 linked lignin dimers
title_sort computational study on pyrolysis mechanism of β 5 linked lignin dimers
topic lignin
β-5 linkage
density functional theory
model compounds
pyrolysis mechanism
url https://eep1987.com/en/article/4869
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AT chaibaohua computationalstudyonpyrolysismechanismofb5linkedlignindimers
AT wangmeijing computationalstudyonpyrolysismechanismofb5linkedlignindimers
AT hubin computationalstudyonpyrolysismechanismofb5linkedlignindimers
AT liuji computationalstudyonpyrolysismechanismofb5linkedlignindimers
AT luqiang computationalstudyonpyrolysismechanismofb5linkedlignindimers