Effect of Zeolite Catalyst on the Pyrolysis Kinetics of Multi-Layered Plastic Food Packaging
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Thermogravimetry
2.3. Kinetic Study
- Record the TG measurements performed at different heating rates (at least 4 or 5). The shapes of the TG and DTG (first-order derivative of TG data) curves can indicate the reaction path. When the residual mass varies with the heating rate, it usually indicates branching in the reaction path; otherwise, the reaction path remains unbranched.
- Process the experimental TG data to calculate the activation energy associated with degradation steps by isoconversional methods. According to ICTAC’s guidelines, a kinetic study should start with the precise determination of one parameter without any assumption of a kinetic model (a mechanism). Model-free isoconversional approaches make this achievable. Isoconversional model-free approaches such as those of Ozawa–Flynn–Wall and Kissinger–Akahira–Sunose (integral methods) [40] and Friedman (differential method) [41] are the most commonly utilized methods for kinetic analysis of solid-waste pyrolysis processes. Model-fitting methods are also often used, with the Coats–Redfern method dominating solid-waste pyrolysis research [42,43]. The differential Friedman method was used in this research. Friedman’s differential model-free isoconversional method employs the logarithmic form of the fundamental kinetic equation:
- 3.
- Plot the obtained activation energy against the degree of conversion. If the highest and lowest calculated values of activation energy values vary by more than 30% from the average value, it is implied that the process is complex and occurs in multiple stages [44]. This demands multivariate non-linear model-fitting regression methods. Otherwise, if it does not vary significantly, the process is simple, and the kinetic model can be determined by using linear model-fitting regression methods to the experimental data.
- 4.
- Obtain Friedman plots from the experimental data (Equation (3)). It is very important to compare the slopes of the experimental data and isoconversional lines by the Friedman method at the beginning of the reaction (0.01 < α < 0.10) since this will give insight into the most probable process at the initial reaction stage:
- The slopes are comparably similar: reaction-order or phase-boundary reaction;
- The slope of the experimental data is lower than the slope of the isoconversional lines: diffusion;
- The slope of the experimental data is steeper than the slope of the isconversional lines: autocatalytically activated reaction type of Avrami–Erofeev.
3. Results and Discussion
3.1. Thermogravimetric Analysis
3.2. Results of the Kinetic Study
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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No. | Composition | Thickness/μm | PET/PE/PP/% | Description and Use |
---|---|---|---|---|
1 | APET/PE | 450/50 | 90.0/10.0/0 | Transparent rigid film used in fresh meat, salami, and quick-prep food packaging |
2 | PET/boPP metallized | 12/20 | 37.5/0/62.5 | Metallized flexible film used in snacks and sweets packaging |
3 | PET/PE metallized | 12/45 | 21.1/78.9/0 | Metallized flexible film used in snacks packaging and frozen food packaging |
4 | PET/PE laminated | 12/75 | 13.8/86.2/0 | Transparent flexible film used in frozen food and sour vegetable packaging |
5 | Mixture | - | 71.9/25.1/3.0 | - |
No. | Sample | Ton/°C | T1/°C | R1/% min−1 | T2/°C | R2/% min−1 |
---|---|---|---|---|---|---|
1 | APET/PE | 398 | 433 | 19.60 | − | − |
APET/PE-catalyst | 369 | 405 | 18.49 | − | − | |
2 | PET/boPP | 369 | 436 | 10.02 | 467 | 12.52 |
PET/boPPmet-catalyst | 346 | 406 | 8.00 | 438 | 10.17 | |
3 | PET/PEmet | 386 | 433 | 6.78 | 478 | 19.9 |
PET/PEmet-catalyst | 361 | 404 | 6.46 | 442 | 16.22 | |
4 | PET/PElam | 413 | − | − | 474 | 23.83 |
PET/PElam-catalyst | 381 | − | − | 436 | 21.96 | |
5 | Mix | 387 | 428 | 12.88 | 458 | 13.71 |
Mix-catalyst | 363 | 404 | 10.58 | 436 | 12.65 |
Stage of Reaction | Parameter | Mix | Mix-Catalyst | ||
---|---|---|---|---|---|
Statistical Fit | Friedman | Statistical Fit | Friedman | ||
Stage 1 | E1 (kJ mol−1) | 131.1 | 143.9 | 66.4 | 80.7 |
log A1 | 7.1 | 8.4 | 2.2 | 3.7 | |
n | − | − | − | − | |
Model | D3 | − | D3 | − | |
Conversion range | 0.00–0.05 | 0.00–0.04 | |||
Stage 2 | E2 (kJ mol−1) | 200.0 | 191.9 | 197.1 | 177.3 |
log A2 | 12.7 | 11.8 | 13.1 | 11.1 | |
n | 0.69 | − | 0.82 | − | |
Model | An | − | An | − | |
Conversion range | 0.10–0.65 | 0.05–0.60 | |||
Stage 3 | E3 (kJ mol−1) | 218.6 | 213.5 | 213.0 | 210.5 |
log A3 | 13.1 | 13.3 | 13.2 | 13.6 | |
n | 4.0 | − | 3.9 | − | |
Model | An | − | An | − | |
Conversion range | 0.70–0.95 | 0.65–0.95 |
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Kremer, I.; Tomić, T.; Katančić, Z.; Hrnjak-Murgić, Z.; Erceg, M.; Vecchio Ciprioti, S.; Schneider, D.R. Effect of Zeolite Catalyst on the Pyrolysis Kinetics of Multi-Layered Plastic Food Packaging. Symmetry 2022, 14, 1362. https://doi.org/10.3390/sym14071362
Kremer I, Tomić T, Katančić Z, Hrnjak-Murgić Z, Erceg M, Vecchio Ciprioti S, Schneider DR. Effect of Zeolite Catalyst on the Pyrolysis Kinetics of Multi-Layered Plastic Food Packaging. Symmetry. 2022; 14(7):1362. https://doi.org/10.3390/sym14071362
Chicago/Turabian StyleKremer, Irma, Tihomir Tomić, Zvonimir Katančić, Zlata Hrnjak-Murgić, Matko Erceg, Stefano Vecchio Ciprioti, and Daniel Rolph Schneider. 2022. "Effect of Zeolite Catalyst on the Pyrolysis Kinetics of Multi-Layered Plastic Food Packaging" Symmetry 14, no. 7: 1362. https://doi.org/10.3390/sym14071362