Pyrolysis of wood and PVC mixtures: thermal behaviour and kinetic modelling

Wood waste containing halogenated compounds such as polyvinyl chloride (PVC) is in abundant supply, although the pyrolysis of such waste feedstock for energy production may cause corrosion and environmental problems due to the release of HCl gas. Hence, there is a need to understand the pyrolysis behaviour of chlorine-contaminated wood in order to develop methods that minimise the impact of chloride species on pyrolysis equipment and product quality. In literature, few studies exist on the kinetic analysis of wood and PVC co-pyrolysis. The existing models assume a single-step reaction with an n-order reaction mechanism for the entire process, which may lead to large errors in the kinetic parameters estimated. Therefore, in this paper, we develop and validate a multi-step kinetic model that predicts the pyrolysis behaviour and reaction mechanismof poplar wood (PW) pellet with different contents of PVC (0, 1, 5, 10, 100 wt%). Using data from thermogravimetric analysis of the pellets at heating rates of 5, 10 and 20 degrees C/min, we determined the apparent kinetic parameters by combining Fraser-Suzuki deconvolution, isoconversional methods and master plot procedures. Our model fitted the experimental data well with a deviation of less than 4.5%. Our results show that the addition of 1 wt% PVC to PWdecreases the activation energy of hemicellulose and cellulose pyrolysis in PW from 136.3 to 101.6 kJ/mol and from 216.7 to 108.2 kJ/mol, respectively. This demonstrates the importance of acid hydrolysis reactions between the cellulosic fibres of PW and HCl released from PVC dehydrochlorination. Furthermore, we found that a nucleation and growth mechanism best represents the rate-limiting interactions between PVC and PW, which we linked to the formation of metal chloride crystals from acid-base reactions between HCl and PW minerals. Our kinetic model is an improvement of current models for the co-pyrolysis of wood and PVC, and can be readily used in a reactor-scale model of a pyrolyser or gasifier due to its relative simplicity.