Kinetic Analysis for the Catalytic Pyrolysis of Polypropylene over Low Cost Mineral Catalysts
Young‐Min Kim, Sumin Pyo, Hanie Hakimian, Kyung-Seun Yoo, Gwang-Hoon Rhee, Young-Kwon Park
Abstract
A kinetic analysis of non-catalytic pyrolysis (NCP) and catalytic pyrolysis (CP) of polypropylene (PP) with different catalysts was performed using thermogravimetric analysis (TGA) and kinetic models. Three kinds of low-cost natural catalysts were used to maximize the cost-effectiveness of the process: natural zeolite (NZ), bentonite, olivine, and a mesoporous catalyst, Al-MCM-41. The decomposition temperature of PP and apparent activation energy (Ea) were obtained from the TGA results at multiple heating rates, and a model-free kinetic analysis was performed using the Flynn–Wall–Ozawa model. TGA indicated that the maximum decomposition temperature (Tmax) of the PP was shifted from 464 °C to 347 °C with Al-MCM-41 and 348 °C with bentonite, largely due to their strong acidity and large pore size. Although olivine had a large pore size, the Tmax of PP was only shifted to 456 °C, because of its low acidity. The differential TG (DTG) curve of PP over NZ revealed a two-step mechanism. The Tmax of the first peak on the DTG curve of PP with NZ was 376 °C due to the high acidity of NZ. On the other hand, that of the second peak was higher (474 °C) than the non-catalytic reaction. The Ea values at each conversion were also decreased when using the catalysts, except olivine. At <0.5 conversion, the Ea obtained from the CP of PP with NZ was lower than that with the other catalysts: Al-MCM-41, bentonite, and olivine, in that order. The Ea for the CP of PP with NZ increased more rapidly, to 193 kJ/mol at 0.9 conversion, than the other catalysts.