Fast pyrolysis of guaiacyl-syringyl (GS) type milled wood lignin: Product characteristics and CH4 formation mechanism study

It is anticipated that the insight into the demethylation and mechanism of CH4 formation from natural lignin using in-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ FTIR) combined with two-dimensional perturbation correlation infrared spectroscopy (2D-PCIS) and density functional theory (DFT) calculation analysis would contribute to a deeper insight of bond cleavage mechanism of lignin pyrolysis. Herein, GS-type lignin (poplar MWL) was characterized by Fourier transform infrared spectroscopy (FTIR) and heteronuclear Single-Quantum Correlation Nuclear Magnetic Resonance (HSQC), and its pyrolysis at different temperatures was performed in a lab-scale fixed-bed reactor. The biochar, gaseous and liquid products were qualitative, and quantitative analysis of gases and bio-oil is demonstrated using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The key of CH4 formation is the homolytic cleavage of the methoxyl functional group generating methyl radical and further verified via in-situ FTIR combined with 2D-PCIS and DFT calculation. The study established a new methodology based on multiple factor analysis to evaluate the CH4 formation mechanism in GS-type milled wood lignin at the molecular level, which is of positive significance for increasing lignin valorization and improving the environment.

Automated summary

This study investigated the mechanism of CH4 formation during lignin pyrolysis using in-situ FTIR, 2D-PCIS, and DFT calculation, revealing that the homolytic cleavage of the methoxyl functional group is crucial for CH4 formation. The research established a new methodology to evaluate the CH4 formation mechanism in GS-type lignin at the molecular level, offering insights for lignin valorization and environmental improvement.