Kinetic and thermodynamic behavior of co-pyrolysis of olive pomace and thermoplastic waste via thermogravimetric analysis

This work represents the first attempt to analyze kinetics, thermodynamics and reaction mechanism of olive pomace (OP) and waste plastic materials (PM) co-pyrolysis. Among PM, polypropylene (PP), polystyrene (PS), high density polypropylene (HDPE), polyvinyl chloride (PVC) and poly (ethylene terephthalate) glycol (PETG) were selected. Non-isothermal TG experiments were carried out under inert conditions at four heating rates, namely 5, 10, 20 and 40 °C/min. The kinetic triplet for raw materials and their blends was determined using Starink, Kissinger-Akahira-Sunose and Ozawa-Flynn-Wall iso-conversional models. Pyrolysis mechanism reactions were explained by diverse models, depending on thermal degradation progress. Results shown that co-pyrolysis followed a complex multi-step reaction mechanism. A synergistic effect was detected during co-pyrolysis of OP/PM mixtures. The addition of 50 % (w/w) OP biomass to PM waste decreased the energy of activation (Ea) from 50 to 25 % for all blends, except for PVC/OP. Thermodynamic analysis reveals that adding OP generally reduces the energy barrier (ΔH), except for PS-OP, and improves energy efficiency (ΔG) by facilitating radical formation and molecular chain cleavage. As a conclusion, this study may open up new avenues for waste valorization and resource recovery. Thus, it may contribute to the transition towards a circular and sustainable economy, through zero waste goal.