Research on the thermal and thermo-oxidative degradation of polyacetals allows for the development of effective methods of utilization of the waste of these polymers towards the recovery of monomers. For this purpose, in addition to qualitative analysis, it is necessary to understand the mechanisms of chemical reactions accompanying the decomposition process under the influence of temperature. Therefore, in this article, with the experimental results from the thermal analysis of the POM homopolymer of three various stages of life—POM-P—unprocessed sample; POM-R—recycled sample, and POM-O—sample waste—we took steps to determine the basic kinetic parameters using two well-known and commonly used kinetic models: Friedman and Ozawa-Flynn-Wall (OFW). Knowing the values of the course of changes in apparent activation energy as a function of partial mass loss, theoretical curves were fitted to the experimental data. The applied calculation models turned out to be consistent in terms of the nature of the curve changes and similar in terms of Ea in the entire range of mass loss. Both kinetic models showed a very similar course of the Ea curves. The samples that decompose under oxidative conditions obtained the best fit for the reaction of nth order with autocatalysis by product B model and the samples that decompose under inert conditions for the n-dimensional nucleation according to the Avrami–Erofeev model.
This paper presents the application of two versions of the multilayer fluidized bed made out of two materials with significantly different densities. The first type of fluidized bed was composed of raw cenospheres and quartz sand. The second type of fluidized bed was composed of cenospheres coated with iron oxides and quartz sand. A variable vertical density profiles in the prepared fluidized beds were confirmed, making them suitable for processing polymeric materials, specifically, polyolefins with a density below 1 g/cm3. The polyolefin pyrolysis process was investigated in both versions of the fluidized bed at temperatures of 520, 540, 560, and 590 °C. The products of the pyrolysis were monitored using high-resolution infrared spectroscopy (with a resolution of 1 cm−1). While the process is organized in these fluidized beds, the absence of the accumulation of solid residues is notable. The results show that the pyrolytic gaseous mixture is composed of numerous compounds, namely, unsaturated and saturated aliphatic hydrocarbons and benzene. The possibility of producing a gas rich in ethylene, propylene, and 1-butene during the pyrolysis was demonstrated. Additionally, during the pyrolysis of both polymers, the production of benzene was shown with yields, ranging from 5%wt. in the fluidized bed made out of raw cenospheres to 11 %wt. in the fluidized bed made out of cenospheres modified by iron oxides. Due to the complex nature of the resulting pyrolytic gas, it is suggested that we process the created gaseous mixtures entirely in a steam conversion process, making them a potential source of hydrogen.