Influence of torrefaction on the characteristics and pyrolysis behavior of cellulose

The influence of torrefaction on cellulose structural characteristics and the resulting pyrolysis behavior was investigated in this study. Torrefaction reduced O/C ratio in cellulose and increased its high heating value. The crystallinity of cellulose increased slightly first and then decreased sharply with the increase of torrefaction temperature, which could be ascribed to competitive degradation between crystalline region and amorphous region, as indicated by ¹³C CP/MAS NMR analysis. Besides, the cleavage of β-1,4-glycosidic bond and the dehydration of hydroxyl were the major reactions occurring in torrefaction. Avrami-Erofeev model was found to be the most suitable kinetic reaction model for explaining the thermogravimetric weight loss during the pyrolysis of the raw and torrefied cellulose. A distributed activation energy model based on Avrami-Erofeev model was subsequently used to reveal the pyrolytic kinetics. It was found that the changes in cellulose structure influenced the kinetic parameters greatly. Torrefaction also changed pyrolytic product distribution. The yields of furfural, alicyclic ketones and anhydrosugars increased while that of 5-hydroxymethyl-furfural decreased as torrefaction temperature increased. - Highlights: • Competitive degradation of crystalline and amorphous regions caused CrI change. • Cleavage of glycosidic bond and dehydration of hydroxyl occurred during torrefaction. • Am-DAEM was used to analyze the raw and torrefied cellulose pyrolysis kinetics. • Torrefaction changed cellulose pyrolytic products distribution greatly.