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

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.