Pyrolysis is a promising technology for transforming waste plastics (WPs) into high-value products. In the near future it will play a key role in the circular economy, as a sustainable and environmentally friendly method of managing this waste. Although the literature reports on the pyrolysis of plastics, it is focused on pure polymers. On the other hand, the state-of-the-art knowledge about the pyrolysis of mixed and contaminated WPs is still scarce. Industrial waste processing usually uses polymer mixtures containing various impurities that influence the pyrolysis process during chemical WPs recycling. In the paper the pyrolysis of three types of WPs: low density polyethylene (LDPE), polyvinyl chloride (PVC) and polyvinyl butyral (PVB) from repeated mechanical recycling of plastics, as well as their binary and ternary mixtures, is considered. The influence of particular components on the pyrolysis process is analyzed. The aim is to determine synergistic behavior of the mixtures during the pyrolysis process, which is important for increasing the efficiency and quality of the obtained bioproducts. Methods such as thermogravimetric (TG/DTG) analysis coupled with Fourier transform infrared spectroscopy (FTIR) and mass spectroscopy (MS) are used. The variations in the initial and final temperature of pyrolysis, mass loss and mass loss rate are determined. The content of PVC significantly lowers the initial temperature and mass loss and increases the final temperature. The pyrolysis of the considered mixtures shows a noticeable synergism—in the initial stage of pyrolysis up to a temperature around 450 °C, the mass loss is accelerated compared to what is predicted by simple superposition. The inhomogeneity of the mixtures as well as the waste origin causes a significant variation in the activation energy. Three main conclusions are obtained: (i) if the waste does not contain PVC, the pyrolysis is nearly complete at a temperature around 500 °C at a heating rate of 10 °C/min, whereas PVC is not fully processed even at 995 °C; (ii) the synergistic effects affect significantly the pyrolysis process by accelerating some steps and lowering the activation energy; and (iii) the presence of PVC noticeably lowers the temperature of the first stage of PVB pyrolysis. The investigation results prove that chemical recycling of mixed LDPE, PVC and PVB waste can be an effective method of plastic waste management.
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