Kinetics, Product Distribution, and Chlorine Release Behavior During Cogasification of Pine Sawdust and Polyvinyl Chloride

The cogasification of forestry biomass and waste plastics offers a promising pathway for low‐carbon conversion and pollutant reduction. This study investigated the kinetics, product distribution, and chlorine migration during copyrolysis and low‐temperature (≤750°C) cogasification of pine sawdust (PS) and polyvinyl chloride (PVC). Thermogravimetric analysis revealed multistage devolatilization and notable synergistic/inhibitory interactions influenced by mixing ratio and temperature. Kinetic evaluation using Flynn–Wall–Ozawa, Friedman, and master‐plot methods showed that PVC addition reduces apparent activation energy, with reaction mechanisms shifting from early three‐dimensional diffusion to late‐stage R3 random nucleation. Fluidized‐bed experiments demonstrated that higher temperatures enhanced CO, H 2 , and HCl release, yielding a peak cold‐gas efficiency of 33.1% at 700°C, while excessive equivalence ratio lowered syngas quality. A 50:50 PS/PVC blend provided optimal gasification performance. Tar analysis showed increased formation of aromatic and chlorinated compounds at elevated temperatures, particularly 3,4‐dimethylbenzyl chloride above 650°C. X‐ray photoelectron spectroscopy results indicated that aromatic carbon and stable organochlorine species dominated in the residual char. These findings deepen understanding of chlorine evolution and guide optimization of biomass–plastic cogasification for more efficient energy recovery and cleaner conversion.