Catalytic stepwise pyrolysis for dechlorination and chemical recycling of PVC-containing mixed plastic wastes: Influence of temperature, heating rate, and catalyst

Abstract

The viability of pyrolysis technology for chemical recycling of plastics is challenged by the presence of PVC in real-world mixed plastic wastes. This study aims to investigate catalytic stepwise pyrolysis as a pretreatment step to remove chlorine from PVC-containing plastic wastes prior to further processing. TG-FTIR and Py-GCMS analysis as well as experiments on a lab-scale pyrolysis system were conducted to study the influence of key processing parameters on the pretreatment including temperature, heating rate, and catalysts. Py-GCMS results indicated 300 °C to be the best pretreatment temperature in terms of balancing Cl removal and avoidance of organochloride formation. Metal oxides, i.e., CaO and Fe2O3, mainly acted as adsorbents of HCl gases with little cracking effect, and their adsorption effects are positively correlated with alkalinity. ZSM-5 catalysts promoted the release of HCl, and the dechlorination effect was more pronounced with ZSM-5 of higher acidity. In contrast, in the lab-scale pyrolysis system, 350 °C pretreatment achieved the highest HCl generation ratio, i.e., 43.60 %. The addition of zeolite catalyst significantly reduced the content of organochloride in the pyrolysis oil in contrast to the performance of metal oxides, but also absorbed most HCl instead of promoting HCl release as in Py-GCMS tests. Mass balance analyses revealed that the majority of chlorine was retained in the solid residues following the catalytic stepwise pyrolysis process, with the notable exception of Fe2O3. ZSM-5(25) catalyst combined with 350 °C pretreatment temperature and 550 °C final pyrolysis achieved the lowest chlorine content in the pyrolysis oil, i.e., 20 ppm, among different process conditions.