Effect of Pretreatment on the Pyrolysis Kinetics of Corn Stalk: Comparison of Inert, Oxidative, and Wet Torrefaction

This study compared the pyrolysis behaviors of corn stalk (CS) and its torrefied biomass after inert torrefaction (IT), oxidative torrefaction (OT), and wet torrefaction (WT), focused on the kinetic parameters and reaction mechanisms. Inert and oxidative torrefaction reduced volatile matter while increasing ash content and fixed carbon. Wet torrefaction reduced both volatile matter and ash content while increasing fixed carbon. Three pretreatment methods decreased oxygen content, increased carbon content, and had a higher heating value. The materials were pyrolyzed in a thermogravimetric analyzer. For CS, the average activation energy (E) values calculated by the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunosen methods were 62.5 and 60.07 kJ/mol. IT and WT showed increased trend, with values of 81.58, 81.48 kJ/mol and 69.75, 67.58 kJ/mol respectively. Conversely, OT decreased with the E values of 57.39 and 56.2 kJ/mol. Pyrolysis was divided into two stages based on various conversion rates (α) using Malek and Coats–Redfern methods. When α was below 0.5, a one-dimensional diffusion mathematical model described the pyrolysis process. When α was beyond 0.5, the pyrolysis of CS conformed to the cylindrical symmetric three-dimensional diffusion mathematical model, while IT, OT, and WT better fit the spherical symmetric three-dimensional diffusion mathematical model. However, the torrefaction atmosphere’s impact on the pyrolysis kinetic mechanism was limited, exhibiting no alterations in the diffusion model. Different torrefaction samples demonstrated a degree of homogeneity, considering the lower pretreatment temperatures and the economic feasibility of torrefaction atmospheres in oxidative torrefaction, coupled with the lowest activation energy of oxidative torrefaction products indicating more efficient pyrolysis, oxidative torrefaction was recommended as the torrefaction pretreatment process before pyrolysis engineering.