Thermogravimetric pyrolysis of waste polyethylene-terephthalate and polystyrene: A critical assessment of kinetics modelling

Pyrolysis is considered as possible technique to thermally convert waste plastics into chemicals and energy. Literature on experimental findings is extensive, although experiments are mostly performed in a dynamic heating mode, using thermogravimetric analysis (TGA) and at low values of the heating rate (mostly below 30 K/min). The present research differs from literature through the application of far higher heating rates, up to 120 K/min. The use of these dynamic results to define the reaction kinetics necessitates the selection of an appropriate reaction mechanism, and 21 models have been proposed in literature considering the rate limiting step being diffusion, nucleation or the reaction itself.The current research studied the cracking of PET and PS by TGA at different heating rates (temperature ramps). Results were used to check the validity of the proposed mechanisms. Several conclusions are drawn: (i) to obtain fair results, the heating ramp should exceed a minimum value, calculated at 30 K/min for PET and 80 K/min for PS; (ii) application of the majority of the models to experimental findings demonstrated that they do not meet fundamental kinetic considerations and are questionable in their use; and (iii) simple models, with reaction order 1 or 2, provide similar results of the reaction activation energy.A further comparison with literature data for dynamic and isothermal experiments confirms the validity of these selected models. Since TGA results are obtained on a limited amount of sample, with results being a strong function of the applied heating rate, the authors believe that isothermal experiments, preferably on a large scale both towards equipment and/or sample size, are to be preferred.