Biochar gasification: Insights from pyrolysis atmospheres and gasification heating rates

Gasification is a promising technology for the synthesis of syngas and hydrogen, with char reactivity being a pivotal factor in the design of industrial gasifiers. Despite extensive studies on the gasification characteristics of biochar, the influence of the pyrolysis atmospheres on the evolution of biochar pore structure and its reactivity in gasification remains poorly understood. This study aims to bridge this gap by comprehensively investigating the effects of char preparation atmospheres (i.e., CO2, H2O, and N2) on ensuring gasification reactivities at varied heating rates. Biochars were synthesized in a horizontal tube furnace at 700 °C with a low heating rate (10 °C min−1) under three different atmospheres: N2, CO2, and H2O. Subsequent gasification reactivities were investigated using i) a thermogravimetric analyzer (TGA) at a low heating rate (10 °C min−1) and ii) a wire mesh reactor (WMR) at a high heating rate (1000 °C s−1), both under CO2 atmosphere at 950 °C. The results showed that the presence of an active atmosphere (CO2 and H2O) during pyrolysis significantly impacts the biochar's aromaticity, crystalline structure, and surface morphology. The functional group concentration and surface area trends indicated that CO2 and H2O atmospheres during pyrolysis enhance biochar reactivity compared to the N2 atmosphere, with the highest reactivity observed for biochars produced under H2O. Furthermore, biochar gasification reactivity was markedly higher using the WMR compared to TGA, underscoring the pronounced effects of heating rate on gasification behavior. The high heating rate in WMR preserved the biochar's porous and amorphous structure, whereas the TGA gasification encountered diffusional limitations and thermal annealing effects. These insights underscore the need to consider pyrolysis atmosphere and heating rate in gasification studies, offering a more comprehensive understanding of biochar's behavior under practical gasification conditions.