Inner-particle reaction mechanism of cellulose, hemicellulose and lignin during photo-thermal pyrolysis process: Evolution characteristics of free radicals

Based on the concentrated photo-thermal thermogravimetry analyzer (PT-TGA) reactor, the pyrolysis of the cellulose, hemicellulose and lignin with different ratios at 100 °C/min and 550–850 °C was performed. The interaction among the three components significantly reduced the reaction temperatures and increased the maximum weight loss rate. The cellulose/lignin interactions were the main reason for the increase of gas production, especially for the H2 production which reached 128.13 mL/g biomass, much higher than the calculated value of 75.35 mL/g biomass without considering the interactions. What occurred during the co-pyrolysis of cellulose/lignin was the combination of free radicals without consuming the hydrogen radicals, while the formation of chemicals in others’ interactions integrated with the hydrogen radicals inhibited the production of H2 at high temperatures. For full-component pyrolysis, the yield of C-containing gas can be calculated by adding a coefficient of interaction between two components, indicating that the effect of the three-component interaction was much lower than that of the two-component. This study established the interaction mechanism for the three components of biomass during photo-thermal pyrolysis based on free radicals. [Display omitted] •Inner-particle reaction significantly accelerated the fast pyrolysis process.•C-containing gases of components mixed in different ratios could be predicted.•Radicals from hemicellulose only promoted C-containing gas yields before 650 °C.•The combination of radicals from cellulose/lignin enhanced the production of H2.