Citation: DUAN Yu, CHENG Hao, WU Shu-bin. Density functional theory study on the effect of C_α-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(12): 1440-1449. shu

Density functional theory study on the effect of C_α-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer

DUAN Yu ^1,2 ,
CHENG Hao ^1,2 ,
WU Shu-bin ^1,2,,

1.
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
2.
Experimental Teaching Demonstration Center of Light Industry and Food Science, South China University of Technology, Guangzhou 510640, China

Corresponding author: WU Shu-bin, shubinwu@scut.edu.cn
Received Date: 29 August 2019
Revised Date: 5 November 2019

Fund Project: The project was supported by the Natural Sciences Foundation of China (31870558, 31670582)the Natural Sciences Foundation of China 31670582the Natural Sciences Foundation of China 31870558

Figures(7)

Density functional theory method was used to calculate the bond dissociation energies of the C_aromatic-C_α, C_α-C_β, C_β-O bond, and C_aromatic-O bonds in four lignin dimer model compounds, viz., (2-(2-methoxyphenoxy)-1-phenylethan-1-ol, 2-(2-methoxyphenoxy)-1-phenylethan-1-one, 1-methoxy-2-(2-methoxy-2-phenylethoxy)benzene, and 2-(2-methoxyphenoxy)-1-phenylethyl acetate; the homolytic cracking reaction during pyrolysis of these dimers was then invetigated and the formation pathways of pyrolysis products of different dimers were analyzed. The results show that the homogenization of C_β-O bond is the main reaction in the initial pyrolysis of dimer, whereas the homolysis of C_α-C_β bond is a competitive reaction. After the oxidation and acetylation of C_α-OH, the bond dissociation energy of C_β-O bond decreases, whereas the dissociation energy of C_α-C_β bond increases, ccompanied with an increase in the probability of the C_β-O bond dissociation and a decrease in the competitive ability of C_α-C_β bond homolysis. For the pyrolysis of four model compounds, the main aromatic products include benzyl alcohol, toluene, benzaldehyde, guaiacol, etc. The selective modification of the C_α-OH functional groups can regulate the types of pyrolysis products. In particular, the product types for the pyrolysis of model compounds modified by oxidation become less, accompanied with an increase in the selectivity to ceratin products. Ethylbenzene and toluene can be produced from the hydrolysis of dimers modified by methylation and acetylation.
- lignin,
- pyrolysis,
- homolysis,
- C_α-OH functional group,
- β-O-4 bonding,
- density functional theory
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沈阳化工大学材料科学与工程学院沈阳 110142

Density functional theory study on the effect of Cα-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer

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通讯作者: 陈斌, bchen63@163.com

Density functional theory study on the effect of C_α-OH functional group modification on the homolytic cracking reaction routes during the pyrolysis of lignin dimer