Effect of traditional solvent on thermal decomposition mechanism of lignin: A density functional theory study

IF 7.2 2区 工程技术 Q1 CHEMISTRY, APPLIED
Xiaosong Luo, Qibin Li
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引用次数: 0

Abstract

In order to understand the effect of traditional solvents on lignin pyrolysis, the decarbonylation and decarboxylation reactions of various phenylic lignin model compounds were theoretically investigated using DFT methods at M06-2×/6–31++G(d,p) level. The calculation results show that activation energy of the decarbonylation and decarboxylation reactions of lignin model compounds can be reduced when H2O/CH3OH existed. There are two types of reaction for the H2O/CH3OH during the pyrolysis. For first type, the synergistic reaction of lignin with H2O/CH3OH as hydrogen transfer carrier. The energy barriers of the main elemental reaction steps during this type of pyrolysis are about 285.0–300.0 kJ/mol (H2O) and 275.0–290.0 kJ/mol (CH3OH) (decarbonylation), 170.0–210.0 kJ/mol and 155.0–200.0 kJ/mol (decarboxylation). For another type, the synergistic reaction of lignin with H2O/CH3OH as hydrogen source. The energy barriers of the main elemental reaction steps during this type of pyrolysis are about 260.0–278.0 kJ/mol and 240.0–260.0 kJ/mol, 303.0–312.0 kJ/mol and 291.0–297.0 kJ/mol. Furthermore, the reaction temperature has the most significant impact on decomposition reaction of lignin in a methanol medium, suggesting that the reaction in the methanol medium is better than that in the water environment.

传统溶剂对木质素热分解机理的影响:密度泛函理论研究
为了了解传统溶剂对木质素热解的影响,在M06-2×/6-31++G(d,p)水平上采用DFT方法对多种苯基木质素模型化合物的脱羰基和脱羧反应进行了理论研究。计算结果表明,当木质素模型化合物中存在 H2O/CH3OH 时,其脱羰基和脱羧反应的活化能会降低。在热解过程中,H2O/CH3OH 会发生两种反应。第一种是木质素与作为氢转移载体的 H2O/CH3OH 的协同反应。这种热解过程中主要元素反应步骤的能量势垒约为 285.0-300.0 kJ/mol(H2O)和 275.0-290.0 kJ/mol(CH3OH)(脱碳)、170.0-210.0 kJ/mol和 155.0-200.0 kJ/mol(脱羧)。另一类是木质素与作为氢源的 H2O/CH3OH 的协同反应。这类热解过程中主要元素反应步骤的能量势垒分别约为 260.0-278.0 kJ/mol 和 240.0-260.0 kJ/mol、303.0-312.0 kJ/mol 和 291.0-297.0 kJ/mol。此外,反应温度对木质素在甲醇介质中的分解反应影响最大,表明在甲醇介质中的反应优于在水环境中的反应。
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来源期刊
Fuel Processing Technology
Fuel Processing Technology 工程技术-工程:化工
CiteScore
13.20
自引率
9.30%
发文量
398
审稿时长
26 days
期刊介绍: Fuel Processing Technology (FPT) deals with the scientific and technological aspects of converting fossil and renewable resources to clean fuels, value-added chemicals, fuel-related advanced carbon materials and by-products. In addition to the traditional non-nuclear fossil fuels, biomass and wastes, papers on the integration of renewables such as solar and wind energy and energy storage into the fuel processing processes, as well as papers on the production and conversion of non-carbon-containing fuels such as hydrogen and ammonia, are also welcome. While chemical conversion is emphasized, papers on advanced physical conversion processes are also considered for publication in FPT. Papers on the fundamental aspects of fuel structure and properties will also be considered.
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