Product distribution and conversion mechanism of fossil-based biodegradable plastics during rapid pyrolysis

Fast pyrolysis has emerged as a promising technology for converting fossil-based biodegradable plastics (FBBPs) into clean energy and high-value products with rapid volume reduction and efficient utilisation. The degradation mechanism during pyrolysis is crucial, and different chemical structures and reaction processes directly affect the treatment efficiency and economic benefits. In this study, three typical FBBPs, including poly(butylene adipate-co-terephthalate) (PBAT), polybutylene succinate (PBS) and poly(epsilon-caprolactone) (PCL), have been analyzed in rapid pyrolysis experiments and corresponding products. Being pyrolyzed at 550℃, three kinds of FBBPs exhibited distinctly different decomposition behaviors and characteristics. These differences can be attributed to the bond-breaking ways and pyrolysis mechanisms, which enhance the value of products. Specifically, PBS exhibited the highest abundance of bio-oils and particulate matter (total 90.58%) compared to PBAT and PCL, mainly converted to ketones and acids with a homogeneous component distribution, which was likely to help facilitate further utilisation. In addition, the oxygen of PBS remained in the bio-oil fraction while showing high levels of CO in the bio-gas. Moreover, PCL had the highest amount of bio-gas (21.76%) among the three FBBPs, indicating that it was more likely to break into small molecule products. Notably, the broken chains or macro-molecules of PCL were primarily converted into esters, with di(but-2-en-1-yl) adipate accounting for 57.5% of bio-oils. This work elucidated the transformation pathways and mechanism of FBBP pyrolysis, providing guidance for the treatment and resource utilisation of FBBPs.