Co-pyrolysis of thermoplastic polyurethane with paulownia wood: Synergistic effects on product properties and kinetics

Co-pyrolysis of plastics and biomass offers an effective approach for waste disposal. In this study, the synergistic effects during the co-pyrolysis of thermoplastic polyurethane (TPU) and paulownia wood (PAW) were investigated in terms of pyrolysis kinetics and product properties using tube furnace, TG-FTIR and GC/MS. The results revealed that co-pyrolysis promoted the material pyrolysis and facilitated the pyrolysis process taking place at low temperatures. By adopting the Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO) and Starink methods, the average activation energies of pure TPU, PAW, and TPU/PAW blends with a 1:1 mass ratio were determined to be 139 kJ/mol, 288 kJ/mol, and 126 kJ/mol. It is indicated that co-pyrolysis significantly reduced the activation energies and enhanced reactivity. Tube furnace experiments demonstrated that TPU/PAW blend with 1:1 mass ratio exhibited the highest synergism. The TPU melt acted as a physical barrier, leading to increased production of char and oil, and lower production of volatile gas. In the pyrolysis oil, the synergistic effect effectively hindered a formation of alcohol phenols. In the meanwhile, the synergistic effect also boosted generations of aliphatic compounds and ketones, increasing the heat value use of pyrolysis oil. Furthermore, a reaction pathway and mechanism of co-pyrolysis of TPU and PAW was proposed. The active molecules and free radicals generated by the pyrolysis of PAW promote the hydrogen transfer cyclization of polyester polyols decomposed by TPU, and the hydrogen free radicals released by TPU promote the depolymerization and activation of PAW. Moreover, the catalytic effect of alkali metal elements in PAW promotes the synergistic effect. The results of the study provide a basis for the co-pyrolysis of waste plastics and biomass to achieve high value utilization of waste.