Insight into biomass pyrolysis mechanism based on cellulose, hemicellulose, and lignin: Evolution of volatiles and kinetics, elucidation of reaction pathways, and characterization of gas, biochar and bio‐oil

Pyrolysis is the first step of gasification and combustion. The pyrolysis process of biomass is complicated, which is generally considered to consist of the pyrolysis of the three major components (i.e., cellulose, hemicellulose, and lignin). Understanding the pyrolysis behavior and product of each component holds a key to understanding the biomass pyrolysis mechanism. In this work, the pyrolysis behavior, pyrolysis kinetics, volatile evolution, and product characterization of the three major components are investigated. Results showed that pyrolysis characteristics and thermal stability of the three components were closely related to their unique chemical structures. During pyrolysis, the main pyrolytic volatiles of hemicellulose appeared first, followed by cellulose and then lignin volatiles in the 3D FTIR spectra. In term of pyrolysis products, gases were generated by the cracking of specific functional groups. Hemicellulose had the highest CO2 yield, whereas lignin had the highest CH4 yield due to the aromatic rings and methoxy groups in lignin structure. Whereas cellulose demonstrated the highest CO yield at high temperatures (above 550 °C). With increasing temperature, the carbon structures of carboxylic-C and O-alkyl-C in biochar decreased, while aryl-C was enhanced. This was due to the deoxygenation reactions such as dehydroxylation, decarboxylation, decarbonylation, and demethoxylation, resulting in a reduction in the number of oxygen-containing functional groups (such as –OH, –C=O, –COOH, and –OCH3), as well as the polycondensation reactions that formed more polycyclic aromatic hydrocarbon units during pyrolysis. The major components of cellulose bio-oil included anhydrosugars and furans. Whereas the bio-oils derived from hemicellulose and lignin showed the highest relative content of acids and phenols, respectively. Based on this analysis, the thermal decomposition pathways of cellulose, hemicellulose, and lignin were proposed.