Kinetic model for the pyrolysis and combustion of poly-(ethylene terephthalate) (PET)

Martı́n-Gullón, Ignacio; Esperanza, M.; Font, R.

doi:10.1016/s0165-2370(00)00141-8

Cited by 140 publications

(88 citation statements)

References 13 publications

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“…During the first stage (Figures 4d and 5d) at <80% conversion, with an apparent activation energy of 193 kJ/mol, PET decomposes mainly by β-H transfer reactions, where hydrogen atoms in β position are transferred to a more stable carbon with subsequent scission of the molecule; rearrangement reactions leading to formation of new ester links and decarboxylation reactions (CO2 evolution) occur as well to obtain the major products, benzoic acid and vinyl terephthalate [76]. The increasing apparent activation energy above 80% conversion (Table 3 and Figure 5d) is signature of char formation [77,78], as mentioned above.…”

Section: Pyrolysis Kinetics and Thermodynamicsmentioning

confidence: 98%

“…For synthetic polymers, and PMMA in particular, dissociation of C-C bonds located at both the extreme of the chain (end-chain scission) and at any other point in the chain (random scission) have been taken into account. In the case of PET, we considered homolytic scission of the C-O bond [77,78,89,90]. The enthalpies that characterize biomass pyrolysis were evaluated by taking into account its lignocellulosic character and the primary depolymerization stages that occur through the rupture of main covalent bonds between monomers.…”

Section: Structure-reactivity Relationshipmentioning

confidence: 99%

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Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Larraín

Carrier

Radović

2017

Journal of Analytical and Applied Pyrolysis

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Highlights• Global activation energy depends on conversion in pyrolysis of all polymers.• Activation energy variability is proportional to chemical complexity of polymers.• An Evans-Polanyi relationship for initiation reactions of polymer pyrolysis is proposed. AbstractRecent advances in plastics recycling confirm the high potential of pyrolysis technologies to enhance recovery and selectivity rates. Modelling the kinetics of this complex process to stimulate scaling-up opportunities remains a major challenge.This study is an attempt to develop practical quantitative reactivity indices for the pyrolysis of natural and synthetic polymers. Representative samples from both categories (coal and pine vs. PET, PE and PMMA) were selected. Their weight loss during pyrolysis was determined experimentally and analyzed using judicious lumping procedures for its initiation, propagation and termination steps. The combined experimental and theoretical approach allowed us to determine apparent activation energies using the isoconversional Friedman method; and the use of Benson's group contribution method generated reaction enthalpies for the initiation reactions. Increasing activation energies with conversion in each case indicated that bond scission proceeds in order of increasing bond strength. The greater chemical complexity of natural polymers was reflected in the higher coefficients of variability for activation energy and wider ranges of reaction enthalpies. A structure-reactivity relationship based on the Evans-Polanyi theory was used to test the hypothesis that primary pyrolysis kinetics is controlled by cleavage of weakest chemical bonds. While the results show that this approach is promising, especially if confirmed by extension to a larger data set, they also suggest the need to compare the relative kinetic importance of initiation and propagation steps in the sequence of polymer pyrolysis reactions.

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Section: Pyrolysis Kinetics and Thermodynamicsmentioning

confidence: 98%

Section: Structure-reactivity Relationshipmentioning

confidence: 99%

Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Larraín

Carrier

Radović

2017

Journal of Analytical and Applied Pyrolysis

View full text Add to dashboard Cite

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“…Taking into account the behavior commented above, the oxygen to be included in the decomposition law has been considered, as has been done with other materials [15][16].…”

Section: Combustion Modelmentioning

confidence: 99%

Thermogravimetric analysis during the decomposition of cotton fabrics in an inert and air environment

Moltó

Font

Conesa

et al. 2006

Journal of Analytical and Applied Pyrolysis

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The thermal degradation of samples of used cotton fabrics has been investigated using thermogravimetric analysis (TGA) between room temperature and 700 8C. Experiments were carried out with about 5 mg of sample in three different atmospheres: helium, 20% oxygen in helium and 10% oxygen in helium. Three different heating rates were used at each atmosphere condition. A kinetic model for the decomposition of used cotton fabrics explaining the behavior of all the runs performed has been proposed and tested. For the pyrolysis of the cotton, the model comprises two parallel reactions. For the combustion process, one competitive reaction was added to each parallel reaction of the pyrolysis model and four combustion reactions of the different solid fractions to obtain volatiles. One single set of parameters can explain all the experiments (pyrolysis, oxidative pyrolysis and combustion) at the three different heating rates used.

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“…Approximately 15 million tonnes of the used plastic waste are generated every year across Europe. Of this volume, a mere 7% [1][2][3] is recycled and the remainder is deposited or incinerated [4]. Polyethylene terephthalate (PET, systematic name poly(oxy-1,2-ethanediyloxycarbonyl-1,4-phenylenecarbonyl)) is a highly thermally stable polymer with many uses, most frequently as packaging material for beverages [5] in the form of the well known PET bottles.…”

Section: Introductionmentioning

confidence: 99%

A study of thermal decomposition and combustion products of disposable polyethylene terephthalate (PET) plastic using high resolution fourier transform infrared spectroscopy, selected ion flow tube mass spectrometry and gas chromatography mass spectrometry

et al. 2008

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Kinetic model for the pyrolysis and combustion of poly-(ethylene terephthalate) (PET)

Cited by 140 publications

References 13 publications

Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Thermogravimetric analysis during the decomposition of cotton fabrics in an inert and air environment

A study of thermal decomposition and combustion products of disposable polyethylene terephthalate (PET) plastic using high resolution fourier transform infrared spectroscopy, selected ion flow tube mass spectrometry and gas chromatography mass spectrometry

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