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Catalytic pyrolysis and kinetic study of real-world waste plastics: multi-layered and mixed resin types of plastics

Abstract

Multi-layered and mixed resin types of plastics are a great challenge for the waste recycling industry. The majority consist of two or more types of polymers, making it difficult to recycle mechanically, which leads to landfill or incineration plant. As a way of thermochemical recycling, pyrolysis is a promising cleaner technology that could use this plastics waste stream potential and convert it into valuable products like fuels. The hypotheses of this research are that the average apparent activation energy of multi-layered and mixed resin plastic real-world waste samples can be decreased with the addition of selected iron-modified zeolite catalyst and that catalytic pyrolysis in fixed bed reactor will give products that show good potential for use as an energy vector. To evaluate activation energy, kinetic analysis was conducted using the isoconversional model-free Friedman model in conjunction with the multivariate nonlinear regression method. Pyrolysis products were analysed using nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy and calorimetry. The catalyst significantly reduced the activation energy of the flexible plastic film sample, which means that the process with catalyst requires less energy consumption. In the case of rigid plastics, the activation energy was lower at the beginning of the process with the catalyst. The catalyst reduced pyrolytic condensates’ viscosity of both samples. Analyses revealed how catalyst promoted the formation of aliphatic compounds in flexible plastics film oil, monoaromatic compounds in rigid plastics oil, and a significant decrease in polyaromatic compounds that degrade the quality of the fuel. The values of higher heating value were high (36–42 MJ/kg). Finally, the pyrolytic oil composition revealed satisfying quality and good potential for further use as an energy vector due to the high higher heating value.

Graphic abstract

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Abbreviations

α :

Degree of conversion (dimensionless)

β :

Linear heating rate (°C/min)

A :

Frequency or pre-exponential factor (min1)

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; the final weight of the residue (wt%)

R :

General gas constant (J/mol K)

HDPE:

High-density polyethylene

LDPE:

Low-density polyethylene

PP:

Polypropylene

PS:

Polystyrene

PVC:

Polyvinyl chloride

PET:

Polyethylene terephthalate

HHV:

Higher heating value

Fe-ZSM:

Iron-modified zeolite socony mobil-5 catalyst

FTIR:

Fourier transform infrared spectroscopy

TGA:

Thermogravimetric analysis

DTG:

Differential thermogravimetry

NMR:

Nuclear magnetic resonance spectroscopy

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Funding

This work has been fully supported by 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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Correspondence to Irma Kremer.

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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Kremer, I., Tomić, T., Katančić, Z. et al. Catalytic pyrolysis and kinetic study of real-world waste plastics: multi-layered and mixed resin types of plastics. Clean Techn Environ Policy (2021). https://doi.org/10.1007/s10098-021-02196-8

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Keywords

  • Multi-layered plastics
  • Mixed resin plastics
  • Thermochemical recycling
  • Pyrolysis
  • Dynamic thermogravimetric analysis
  • Kinetic study
  • Zeolite catalyst