Evolution of Char Structure and Its Influence on Reactivity During Biomass Pyrolysis: Spatial Scale Effects from Pellet Size to Intra-Pellet Location.

Biomass, composed of natural polymers such as cellulose, hemicellulose, and lignin, can be converted into circular chemical feedstocks through thermochemical conversion processes like pyrolysis. Char conversion is the rate-limiting step in the thermochemical conversion process, and thus, char reactivity is essential for determining the overall efficiency of pellet-based thermochemical processes. Pyrolysis experiments were conducted on rice straw pellets of different sizes (i.e., 8, 10, and 12 mm) in a vertical quartz tube reactor at 700 °C, and then the chemical structure of chars sampled at different stages and locations within a 10 mm pellet was analyzed using Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). The results indicate that increasing the pellet size facilitates the growth of polycyclic aromatic structures, as evidenced by the observed variations in the abundance of typical aromatic compounds in bio-oil. This also promotes volatile-char interactions, leading to greater deposition of large aromatic structures on the char surface, thereby enhancing char aromatization. Analogous to the spatial scale effect of pellet size on char structure, the evolution of the char structure within a single pellet exhibits distinct spatial heterogeneity during the initial devolatilization and subsequent char aromatization stages due to the location-dependent coupling of heat/mass transfer limitations and aromatization reactions during pyrolysis. Furthermore, the spatiotemporal evolution of the char structure leads to differences in the specific reactivity: during the devolatilization stage at 75 s, the center exhibits the highest reactivity, whereas the outer surface becomes the most reactive in the subsequent char aromatization stage at 300 s.