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Pyrolysis kinetics and estimation of chemical composition of Quercus cerris cork

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Abstract

Pyrolysis kinetics of Quercus cerris cork was investigated using thermogravimetric analysis with heating rates of 10, 20, 50, and 100 °C min−1. The activation energies and chemical compositions of cork components were determined by different model-fitting methods, isoconversional Kissinger-Akahira-Sunose (KAS) method, and Lorentzian multi-peak fitting. Wet chemical analysis of cork was conducted to compare with the chemical compositions predicted by the kinetic models and Lorentzian multi-peak fitting. The results show that pyrolysis of Quercus cerris cork possibly follows nth-order kinetics, and best fits to the experimental data were obtained by three-halves kinetics followed by first-order and contracting sphere models. The fit qualities of the different models were close implying that the first order models could be used for practical applications. Six pseudo-components approximation used in these models suggested that while cork hemicelluloses and cellulose undergo thermal decompositions similar as in wood, cork suberin decomposes in two distinct steps, i.e., cellulose-like and lignin-like decompositions. Isoconversional KAS method showed that the average activation energy of Quercus cerris cork is approximately 298 kJ mol−1. The reconstructed mass loss curves after Lorentzian multi-peak fitting resulted in smaller activation energies for cork components.

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Abbreviations

Activation energy:

Ea J mol−1

Universal gas constant:

R 8.314 J mol−1 K−1

Heating rate:

HR, β °C min−1

Temperature:

T K, °C

Time:

t min

Central peak temperature:

Tc °C

Peak width:

w °C

Peak area:

A 0.5 °C (% min−1)

Heat transfer coefficient:

h W m−2 K−1

Thermal conductivity:

k W m−1 K−1

Thermogravimetric analysis:

TGA

Differential thermogravimetry:

DTG

Conversion degree:

α

Pre-exponential factor:

k 0 , A α

Biomass fraction:

xi

Residual sum of squares:

RSS

Lorentzian multi-peak fitting:

LMPF

Kissinger-Akahira-Sunose:

KAS

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Acknowledgments

Forest Research Centre (CEF) is a research unit funded by the Fundação para a Ciência e a Tecnologia (FCT) (UIDB/00239/2020). A. Umut Sen acknowledges the postdoctoral fellowship from FCT (SFRH/BPD/87632/2012) and thanks the Chemical Engineering Department of Instituto Superior Técnico for the laboratorial use. The authors thank Joaquina Martins for her help in chemical analysis. F. G. Fonseca is a member of the BBW ForWerts Graduate Program.

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Authors and Affiliations

  1. Centro de Estudos Florestais, Instituto Superior de Agronomia, Universidade de Lisboa, Tapada da Ajuda, 1349-017, Lisbon, Portugal

    A. Umut Şen & Helena Pereira

  2. Karlsruhe Institute of Technology, Institute of Catalysis Research and Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

    Frederico G. Fonseca & Axel Funke

  3. CERENA/Chemical Engineering Department, Instituto Superior Técnico, Universidade de Lisboa, 1049-001, Lisbon, Portugal

    Francisco Lemos

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  1. A. Umut Şen
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Correspondence to A. Umut Şen.

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Şen, A.U., Fonseca, F.G., Funke, A. et al. Pyrolysis kinetics and estimation of chemical composition of Quercus cerris cork. Biomass Conv. Bioref. 12, 4835–4845 (2022). https://doi.org/10.1007/s13399-020-00964-y

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