Thermal Behavior of Mixed Plastics at Different Heating Rates: I. Pyrolysis Kinetics

The amount of generated plastic waste has increased dramatically, up to 20 times, over the past 70 years. More than 50% of municipal plastic waste is composed of polystyrene (PS), polypropylene (PP), and low-density polyethylene (LDPE) products. Therefore, this work has developed a kinetic model that can fully describe the thermal decomposition of plastic mixtures, contributing significantly towards the efficiency of plastic waste management and helping to save the environment. In this work, the pyrolysis of different plastic mixtures, consisting of PP, PS, and LDPE, was performed using a thermogravimetric analyzer (TGA) at three different heating rates (5, 20, and 40 K/min). Four isoconversional models, namely Friedman, Flynn–Wall–Qzawa (FWO), Kissinger–Akahira–Sunose (KAS), and Starink, have been used to obtain the kinetic parameters of the pyrolysis of different plastic mixtures with different compositions. For the equi-mass binary mixtures of PP and PS, the average values of the activation energies were 181, 144 ± 2 kJ/mol obtained using the Freidman and integral (FWO, KAS, and Starink) models, respectively. However, higher values were obtained for the equi-mass ternary plastic mixtures of PP, PS, and LDPE (Freidman: 255 kJ/mol, FWO: 222 kJ/mol, KAS: 223 kJ/mol, and Starink: 222 kJ/mol). The most suitable reaction mechanisms were obtained using the Coats–Redfern model. The results confirm that the most controlling reaction mechanisms obey the first-order (F1) and the third-order (F3) reactions for the pyrolysis of the equi-mass binary (PS and PP) and equi-mass ternary (PS, PP, and LDPE) mixtures, respectively. Finally, the values of the pre-exponential factor (A) were obtained using the four isoconversional models and the linear relationship between ln A and the activation energy was confirmed.

Distributed Activation Energy Model for Thermal Decomposition of Polypropylene Waste

Thermal decomposition kinetics of Polypropylene (PP) waste is extremely important with respect to valorisation of waste plastics and production of utilizable components viz. chemicals, fuel oil & gas. The present research study focuses on pyrolysis kinetics of PP waste, which is present as a fraction of municipal plastic waste through distributed activation energy model (DAEM). The decomposition kinetics for PP follows a Gaussian distribution, where the normal distribution curves were centred corresponding to activation energy of 224 kJ/mol. The standard deviation of the distribution for the PP sample was found to be 22 kJ/mol indicating its wider distribution of decomposition range. The data validation has been carried out by comparing the rate parameter and extent of conversion values calculated through DAEM model with the Thermogravimetric analysis (TGA) experiments carried out for PP at various heating rates of 5, 10, 20 and 40 °C/min.

High Temperature Pyrolysis of Municipal Plastic Waste Using Me/Ni/ZSM-5 Catalysts: The Effect of Metal/Nickel Ratio

This work is dedicated to the high temperature pyrolysis of municipal plastic waste using Me/Ni/ZSM-5 catalysts. Catalysts were synthetized by wet impregnation. In addition to nickel, synthetic zeolite catalysts contain calcium, ceria, lanthanum, magnesia or manganese. Catalysts were prepared and tested using 0.1, 0.5 and 2.0 Me/Ni ratios. Catalyst morphology was investigated by SEM and surface analysis. Higher concentrations of second metals can block catalyst pore channels due to the more coke formation, which leads to smaller surface area. Furthermore, the chemicals used for the impregnation were among the catalyst grains, especially in case of 2.0 Me/Ni ratios. For pyrolysis, a horizontal tubular furnace reactor was used at 700 °C. The highest hydrogen and syngas yields were observed using ceria- and lanthanum-covered catalysts. The maximum production of syngas and hydrogen (69.8 and 49.2 mmol/g raw material) was found in the presence of Ce/Ni/ZSM-5 catalyst with a 0.5 Me/Ni ratio.