The formation process of aromatic hydrocarbon tar during the pyrolysis process of biomass components of cel-lulose and lignin was carried out by quantum chemical calculation based on density functional theory method B...The formation process of aromatic hydrocarbon tar during the pyrolysis process of biomass components of cel-lulose and lignin was carried out by quantum chemical calculation based on density functional theory method B3LYP/6-31G++(d,p).5 Hydroxymethylfurfural was chosen as the model compound of cellulose and hemicel-lulose,and syringa ldehyde was chosen as the model compound of lignin.The calculation results show that the formation process of cellulose monocyclic aromatic hydrocarbon tar is the conversion process of benzene ring from furan ring,and the highest reaction energy barrier appears in the process of decarbonylation,which is 370.8 kJ/mol.The formation of lignin monocyclic aromatic hydrocarbon tar is mainly the process of side chains removal and the formation of phenol,The highest reaction energy barrier appears in the process of decarbonyla-tion,which is 374.9 kJ/mol.The reaction mechanism of phenanthrene formation from naphthalene was selected as the formation of cellulose and lignin polycydic aromatic hydrocarbon tar.The calculation results show that he total barrier of the pathway that naphthalene dehydrogenates to form naphthalene free radicals and then reacts with ethylene twice by addition action,finally occurs cydization reactions and isomerizes to produce phenan-threne is lowest,that is 38.6 kJ/mol.So it is proved that the evolution of tar is the process of deoxygenation and cyclization with the increase of the temperature from a theoretical point of view.展开更多
基金supported by 2021–2022 Hunan Province Enterprise Science and Technology Commissioner Program Project under the Contract No.2021GK5046the project supported by Scientific Research Fund of Hunan Provincial Education Department under the Contract No.19C0476the project supported by Scientific Research Fund of Hunan Institute of Engineering under the Contract No.XJ1902.
文摘The formation process of aromatic hydrocarbon tar during the pyrolysis process of biomass components of cel-lulose and lignin was carried out by quantum chemical calculation based on density functional theory method B3LYP/6-31G++(d,p).5 Hydroxymethylfurfural was chosen as the model compound of cellulose and hemicel-lulose,and syringa ldehyde was chosen as the model compound of lignin.The calculation results show that the formation process of cellulose monocyclic aromatic hydrocarbon tar is the conversion process of benzene ring from furan ring,and the highest reaction energy barrier appears in the process of decarbonylation,which is 370.8 kJ/mol.The formation of lignin monocyclic aromatic hydrocarbon tar is mainly the process of side chains removal and the formation of phenol,The highest reaction energy barrier appears in the process of decarbonyla-tion,which is 374.9 kJ/mol.The reaction mechanism of phenanthrene formation from naphthalene was selected as the formation of cellulose and lignin polycydic aromatic hydrocarbon tar.The calculation results show that he total barrier of the pathway that naphthalene dehydrogenates to form naphthalene free radicals and then reacts with ethylene twice by addition action,finally occurs cydization reactions and isomerizes to produce phenan-threne is lowest,that is 38.6 kJ/mol.So it is proved that the evolution of tar is the process of deoxygenation and cyclization with the increase of the temperature from a theoretical point of view.
