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

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Abstract

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 mechanism of 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 °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 PW decreases 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.

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Acknowledgments

The authors gratefully thank our colleagues at RAPSODEE research centre for technical help.

Funding

The study was financially supported by Suez Environnement (France) and IMT Mines Albi.

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Authors and Affiliations

  1. Université de Toulouse, IMT Mines Albi, UMR CNRS 5302, Centre RAPSODEE, Campus Jarlard, F-81013, cedex 09, Albi, France

    Augustina Ephraim, Patrick Sharrock, Ange Nzihou & Doan Pham Minh

  2. LGPM, Centrale Supelec, Université Paris-Saclay, SFR Condorcet FR CNRS 3417, Centre Européen de Biotechnologie et de Bioéconomie (CEBB), 3 rue des Rouges Terres, 51110, Pomacle, France

    Victor Pozzobon

  3. SUEZ, 38, rue du Président Wilson, 78230, Le Pecq, France

    Damien Lebonnois & Carlos Peregrina

  4. Institute of Research and Development, Duy Tan University, Da Nang, 550000, Vietnam

    Doan Pham Minh

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  1. Augustina Ephraim
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Ephraim, A., Pozzobon, V., Lebonnois, D. et al. Pyrolysis of wood and PVC mixtures: thermal behaviour and kinetic modelling. Biomass Conv. Bioref. 13, 8669–8683 (2023). https://doi.org/10.1007/s13399-020-00952-2

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