Characterization of pyrolysis behavior for rigid polyurethane foam wastes with different densities through TGA-FTIR-DSC-MCC and Hill Climbing Optimization methods

Pyrolysis technology is one of the most effective thermal treatment methods recycling rigid polyurethane foam (RPUF) waste. To optimize pyrolysis recovery efficiency, quantifying the pyrolysis reaction kinetics and the heat required for the thermal treatment process is critical. This work focuses on establishing a systematic methodology to quantify pyrolysis reaction kinetics and thermodynamics for RPUF waste. RPUF waste with two different densities (RPUF rho 100 and RPUF rho 45) were investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) under anaerobic atmosphere to measure mass and heat flow information. The obtained data were inversely analyzed using a numerical framework known as ThermaKin2Ds. Pyrolysis reaction mechanisms with four and three consecutive first-order reactions were developed to reproduce the TGA data for RPUF rho 100 and RPUF rho 45, respectively. The Hill Climbing Optimization Algorithm was employed to adjust the reaction kinetics for an improved agreement between the ThermaKin2Ds-reproduced and experimental data. Based on the heat flow data from DSC tests, the specific heat capacity of each condensed-phase component was determined by using the inverse modeling method. Additionally, the micro-scale combustion calorimeter was used to generate the heat release data that served as the target data for inversely determining the heats of complete combustion, hc, of each pyrolyzate. The established pyrolysis reaction models was further validated by predicting the TGA results collected under different external heating conditions. Subsequently, the generated combustion-inhibiting gases (CO2) and combustion-promoting gases (olefins, alkanes, carboxylic acids, etc.) were characterized through TGA coupled with Fourier-transform infrared spectroscopy (TG-FTIR). This allowed us to elucidate the gas-phase combustion phenomena observed in MCC experiments. This work provides a core set of parameters for optimizing the thermal treatment conditions of RPUF waste.