Abstract
Pyrolysis is a promising technology for the valorisation of plastic waste by converting it into valuable products, such as fuels and chemicals. This study aims to assess the thermogravimetric behaviour and kinetic parameters of the real-world plastic waste mixture with added nickel- and iron-based catalysts on gamma-aluminium oxide as support. Thermogravimetric measurements were carried out in a nitrogen atmosphere over a set of heating rates (5, 10, 15 and 20 °C/min) within a temperature range 40–600 °C. Kinetic analysis was performed through a combined approach by using the model-free isoconversional Friedman method and regression methods (linear and multivariate nonlinear). The kinetic analysis results showed a complex decomposition mechanism of the real-world plastic waste mixture. The average apparent activation energy for the real-world plastic waste mixture (22% high-density polyethylene, 31% low-density polyethylene, 35% polypropylene, 12% polystyrene) was 205 kJ/mol. The initial value decreased by 15.6% with the addition of iron-based gamma-aluminium oxide catalyst and only 9.8% with nickel-based gamma-aluminium oxide catalyst.
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- HDPE:
-
High-density polyethylene
- LDPE:
-
Low-density polyethylene
- PP:
-
Polypropylene
- PS:
-
Polystyrene
- PVC:
-
Polyvinyl chloride
- PET:
-
Polyethylene terephthalate
- TGA:
-
Thermogravimetric analysis
- DTG:
-
Differential thermogravimetry
- α :
-
Degree of conversion (dimensionless)
- β :
-
Linear heating rate (°C/min)
- A :
-
Frequency or pre-exponential factor (min−1)
- E :
-
Energy of activation (J/mol)
- f(α):
-
Mechanism of reaction; kinetic model (dimensionless)
- m 0 :
-
Initial mass of the sample (wt%)
- m f :
-
Residual mass of the sample; final mass of the residue (wt%)
- R :
-
General gas constant (J/mol K)
- r max :
-
Maximum peak rate (%/min)
- T :
-
Absolute temperature (K)
- T max :
-
Temperature of maximum decomposition rate and peak rate (°C)
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Acknowledgements
This work has been fully supported by the Croatian Science Foundation under the Project Neoplast (IP-2018-3200) and the project Career development of young researchers—the training of new Doctors of Science (DOK-2018-09-6944). This support is gratefully acknowledged.
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Appendix
Appendix
Tables 5 and 6 present data containing the values of temperature maximum decomposition rate, maximum peak rate and final mass of the residue for the four heating rates of thermal decomposition of neat polymers (Table 5), and mixtures of polymers with and without catalyst used (Table 6). Bolded values in Table 6 show a significant change that occurred after the addition of catalysts to Mix 2 sample. Figure 9 shows thermogravimetric and derivative thermogravimetric plots of neat polymers at four heating rates. In Fig. 10 thermogravimetric and derivative thermogravimetric curves of neat polymers are compared at the heating rate of 10 °C/min.
Thermogravimetric and derivative thermogravimetric plots for HDPE, LDPE, PP and PS at 5, 10, 15 and 20 °C/min
a Thermogravimetric and b derivative thermogravimetric plot for HDPE, LDPE, PP and PS at 10 °C/min
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Kremer, I., Tomić, T., Katančić, Z. et al. Catalytic decomposition and kinetic study of mixed plastic waste. Clean Techn Environ Policy 23, 811–827 (2021). https://doi.org/10.1007/s10098-020-01930-y
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DOI: https://doi.org/10.1007/s10098-020-01930-y