Using apparent activation energy as a reactivity criterion for biomass pyrolysis

Marion Carrier, Lidia Auret, Anthony Bridgwater, Johannes H. Knoetze

Research output: Contribution to journalSpecial issue

Abstract

The reactivity of chemically isolated lignocellulosic blocks, namely, α-cellulose, holocellulose, and lignin, has been rationalized on the basis of the dependence of the effective activation energy (Eα) upon conversion (α) determined via the popular isoconversional kinetic analysis, Friedman’s method. First of all, a detailed procedure for the thermogravimetric data preparation, kinetic calculation, and uncertainty estimation was implemented. Resulting Eα dependencies obtained for the slow pyrolysis of the extractive-free Eucalyptus grandis isolated α-cellulose and holocellulose remained constant for 0.05 < α < 0.80 and equal to 173 ± 10, 208 ± 11, and 197 ± 118 kJ/mol, thus confirming the single-step nature of pyrolysis. On the other hand, large and significant variations in Eα with α from 174 ± 10 to 322 ± 11 kJ/mol in the region of 0.05 and 0.79 were obtained for the Klason lignin and reported for the first time. The non-monotonic nature of weight loss at low and high conversions had a direct consequence on the confidence levels of Eα. The new experimental and calculation guidelines applied led to more accurate estimates of Eα values than those reported earlier. The increasing Eα dependency trend confirms that lignin is converted into a thermally more stable carbonaceous material.
Original languageEnglish
Pages (from-to)7834-7841
Number of pages8
JournalEnergy and Fuels
Volume30
Issue number10
Early online date24 May 2016
DOIs
Publication statusPublished - 20 Oct 2016

Fingerprint

Lignin
Biomass
Pyrolysis
Activation energy
Cellulose
Kinetics

Bibliographical note

This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

Funding: European Union and Horizon 2020 to financially support the action H2020-MSCA-IF-2014, Pyrochem, Grant 656967 "Biopolymers (13)C Tracking
during Fast Pyrolysis of Biomass-A 2-Level Mechanistic Investigation”.

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.energy-fuels.6b00794

Keywords

  • pyrolysis kinetics
  • biomass
  • lignin
  • holocellulose

Cite this

Carrier, Marion ; Auret, Lidia ; Bridgwater, Anthony ; Knoetze, Johannes H. / Using apparent activation energy as a reactivity criterion for biomass pyrolysis. In: Energy and Fuels. 2016 ; Vol. 30, No. 10. pp. 7834-7841.
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Using apparent activation energy as a reactivity criterion for biomass pyrolysis. / Carrier, Marion; Auret, Lidia; Bridgwater, Anthony; Knoetze, Johannes H.

In: Energy and Fuels, Vol. 30, No. 10, 20.10.2016, p. 7834-7841.

Research output: Contribution to journalSpecial issue

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AU - Carrier, Marion

AU - Auret, Lidia

AU - Bridgwater, Anthony

AU - Knoetze, Johannes H.

N1 - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Funding: European Union and Horizon 2020 to financially support the action H2020-MSCA-IF-2014, Pyrochem, Grant 656967 "Biopolymers (13)C Tracking during Fast Pyrolysis of Biomass-A 2-Level Mechanistic Investigation”. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.energy-fuels.6b00794

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N2 - The reactivity of chemically isolated lignocellulosic blocks, namely, α-cellulose, holocellulose, and lignin, has been rationalized on the basis of the dependence of the effective activation energy (Eα) upon conversion (α) determined via the popular isoconversional kinetic analysis, Friedman’s method. First of all, a detailed procedure for the thermogravimetric data preparation, kinetic calculation, and uncertainty estimation was implemented. Resulting Eα dependencies obtained for the slow pyrolysis of the extractive-free Eucalyptus grandis isolated α-cellulose and holocellulose remained constant for 0.05 < α < 0.80 and equal to 173 ± 10, 208 ± 11, and 197 ± 118 kJ/mol, thus confirming the single-step nature of pyrolysis. On the other hand, large and significant variations in Eα with α from 174 ± 10 to 322 ± 11 kJ/mol in the region of 0.05 and 0.79 were obtained for the Klason lignin and reported for the first time. The non-monotonic nature of weight loss at low and high conversions had a direct consequence on the confidence levels of Eα. The new experimental and calculation guidelines applied led to more accurate estimates of Eα values than those reported earlier. The increasing Eα dependency trend confirms that lignin is converted into a thermally more stable carbonaceous material.

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