Dechlorination Through Torrefaction: A Pretreatment for Co-Pyrolysis of PVC-Biomass Blends

This study investigates the torrefaction of polyvinyl chloride (PVC) and cellulose, two major constituents of agricultural waste, with the aim of improving chlorine removal and enhancing the energy quality of the resulting solid products. Thermodynamic simulations using HSC Chemistry 9.0 were first conducted to predict equilibrium compositions, particularly chlorine-containing species. Thermogravimetric analysis (TGA) and coupled TGA-FTIR were employed to monitor mass loss and identify gaseous chlorine compounds. Based on these preliminary results, torrefaction experiments were carried out at temperatures of 250–300 °C and durations of 30–90 min. The results demonstrate a significant synergistic effect between cellulose and PVC during co-torrefaction, achieving 97% chlorine removal under optimal conditions (9:1 cellulose-to-PVC ratio, 250 °C, 30 min). This effective dechlorination helps mitigate Cl-induced corrosion and reduces the risk of dioxin formation in industrial applications, enabling the sustainable upcycling of PVC-contaminated biomass into clean solid fuels. Torrefaction temperature exerted a stronger influence than time on mass loss, yielding approximately 40% solid residue at 300 °C. While both solid and energy yields decreased with increasing temperature and time, the O/C and H/C atomic ratios decreased by 56% and 48%, respectively, indicating a substantial improvement in fuel properties. The observed synergy is attributed to cellulose-derived hydroxyl radicals promoting PVC dehydrochlorination. This process offers a scalable and economically viable pretreatment route for PVC-containing biomass, potentially reducing boiler corrosion and hazardous emissions.