In this work, the pyrolysis behavior of plastic waste—TV plastic shell—was investigated, based on thermogravimetric analysis and using a combination of model-fitting and model-free methods. The possible reaction mechanism and kinetic compensation effects were also examined. Thermogravimetric analysis indicated that the decomposition of plastic waste in a helium atmosphere can be divided into three stages: the minor loss stage (20–300°C), the major loss stage (300–500°C) and the stable loss stage (500–1000°C). The corresponding weight loss at three different heating rates of 15, 25 and 35 K/min were determined to be 2.80–3.02%, 94.45–95.11% and 0.04–0.16%, respectively. The activation energy ( Ea) and correlation coefficient ( R2) profiles revealed that the kinetic parameters calculated using the Friedman and Kissinger–Akahira–Sunose method displayed a similar trend. The values from the Flynn–Wall–Ozawa and Starink methods were comparable, although the former gave higher R2 values. The Eα values gradually decreased from 269.75 kJ/mol to 184.18 kJ/mol as the degree of conversion ( α) increased from 0.1 to 0.8. Beyond this range, the Eα slightly increased to 211.31 kJ/mol. The model-fitting method of Coats–Redfern was used to predict the possible reaction mechanism, for which the first-order model resulted in higher R2 values than and comparable Eα values to those obtained from the Flynn–Wall–Ozawa method. The pre-exponential factors (ln A) were calculated based on the F1 reaction model and the Flynn–Wall–Ozawa method, and fell in the range 59.34–48.05. The study of the kinetic compensation effect confirmed that a compensation effect existed between Ea and ln A during the plastic waste pyrolysis.
In this study, the pyrolysis behaviour of nonmetal fraction of waste printed circuit boards (NMF-WPCBs) was studied based on five model-free methods and distributed activation energy model (DAEM). The possible decomposition mechanism was further probed using the Criado method. Thermogravimetric analysis indicated that the NMF-WPCBs pyrolysis process could be divided into three stages with temperatures of 37–330°C, 330–380°C and 380–1000°C. The mass loss at different heating rate was determined as 26.85–29.98%, 13.47–24.21% and 20.43–23.36% for these stages, respectively. The activation energy ( Eα) from various model-free methods first increased with degree of conversion ( α) increasing from 0.05 to 0.275, and then decreased beyond this range. The coefficient ( R) from the Flynn–Wall–Ozawa (FWO) method was higher, and the resulting Eα fell into the range of 214.947–565.660 kJ mol−1. For the DAEM method, the average Eα value was determined as 337.044 kJ mol−1, comparable with 329.664 kJ mol−1 from the FWO method. The thermal decomposition kinetics of NMF-WPCBs could be better described by the second-order reaction.
Thermal treatment offers an alternative method for the separation of aluminum foil and cathode materials during spent lithium-ion batteries recycling. In this work, the combustion kinetic of cathode was studied based on six model-free (isoconversional) methods, namely Flynn–Wall–Ozawa (FWO), Friedman, Kissinger–Akahira–Sunose, Starink, Tang, and Boswell methods. The possible decomposition mechanism was also probed using a master-plots method (Criado method). Thermogravimetric analysis showed that the whole thermal process could be divided into three stages with temperatures of 37–578°C, 578–849°C, and 849–1000°C. The activation energy ( Eα) derived from these model-free methods displayed the same trend, gradually increasing with a conversion range of 0.002–0.013, and significantly elevating beyond this range. The coefficients from the FWO method were larger, and the resulted Eα fell into the range of 10.992–40.298 kJ/mol with an average value of 20.228 kJ/mol. Comparing the theoretical master plots with an experimental curve, the thermal decomposition of cathode could be better described by the geometric contraction models.
Thermal treatment offers advantages of significant volume reduction and energy recovery for the polyurethane foam from waste refrigerators. In this work, the pyrolysis kinetics of polyurethane foam was investigated using the model-fitting, model-free and distributed activation energy model methods. The thermogravimetric analysis indicated that the polyurethane foam decomposition could be divided into three stages with temperatures of 38°C–400°C, 400°C–550°C and 550°C–1000°C. Peak temperatures for the major decomposition stage (<400°C) were determined as 324°C, 342°C and 344°C for heating rates of 5, 15 and 25 K min-1, respectively. The activation energy ( Eα) from the Friedman, Flynn–Wall–Ozawa and Tang methods increased with degree of conversion ( α) in the range of 0.05 to 0.5. The coefficients from the Flynn–Wall–Ozawa method were larger and the resulted Eα values fell into the range of 163.980–328.190 kJ mol-1 with an average of 206.099 kJ mol-1. For the Coats–Redfern method, the diffusion models offered higher coefficients, but the E values were smaller than that from the Flynn–Wall–Ozawa method. The Eα values derived from the distributed activation energy model method were determined as 163.536–334.231 kJ mol-1, with an average of 206.799 kJ mol-1. The peak of activation energy distribution curve was located at 205.929 kJ mol-1, consistent with the thermogravimetric results. The Flynn–Wall–Ozawa and distributed activation energy model methods were more reliable for describing the polyurethane foam pyrolysis process.
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