| Summary: | Expanded polystyrene (EPS) has excellent thermal insulation properties and is widely applied in building energy conservation. However, these thermal insulation materials have caused numerous fires because of flammability. Pyrolysis is necessary to support combustion, and more attention should be paid to the pyrolysis characteristics of EPS. Moreover, pyrolysis is considered to be an effective method for recycling solid waste. Pyrolysis kinetics of EPS were analyzed by thermogravimetric experiments, both in nitrogen and air atmospheres. A new method was proposed to couple the Flynn–Wall–Ozawa model-free method and the model-fitting method called the Coats–Redfern as well as the particle swarm optimization (PSO) global algorithm to establish reaction mechanisms and their corresponding kinetic parameters. It was found that the pyrolysis temperature of EPS was concentrated at 525–800 K. The activation energy of EPS in nitrogen was about 163 kJ/mol, which was higher than that in air (109.63 kJ/mol). Furthermore, coupled with Coats–Redfern method, reaction functions <i>g(α) = 1 − (1 − α)<sup>3</sup></i> and <i>g(α) = 1 − (1 − α)<sup>1/4</sup></i> should be responsible for nitrogen and air reactions, respectively. The PSO algorithm was applied to compute detailed pyrolysis kinetic parameters. Kinetic parameters could be used in further large-scale fire simulation and provide guidance for reactor design.
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