Fast Pyrolysis of Hemicelluloses into Short-Chain Acids: An Investigation on Concerted Mechanisms

Marion Carrier, René Fournet, Baptiste Sirjean, Sam Amsbury, Yoselin Benitez Alfonso, Pierre-Yves Pontalier, Anthony Bridgwater

Research output: Contribution to journalArticlepeer-review


The nature of the main primary mechanisms involved in lignocellulosic fast pyrolysis is often assumed to be radical mechanisms. Here we demonstrate that thermal depolymerization of native hemicelluloses can undergo several primary and secondary concerted reactions leading to light oxygenates that can compete with radical mechanisms. To model these reactions at a microscopic level, we used high-level quantum calculations based on functional theory. In parallel, a set of experimental data was collected to confirm the main structural features of extracted and purified hemicelluloses and to describe chemical variations within fast pyrolysis products released from various hemicellulosic fractions at 823 K. In general, the barriers computed at 800 K for pericyclic reactions were found to be reasonably low competing with these of homolytic reactions. The critical role of hydrogen bonding and spatial arrangement on product distribution was clearly demonstrated, stabilizing effects depending greatly on temperature. We reported a useful data set of intrinsic kinetic parameters and a reaction network readily available to complete kinetic models for “primary” and “secondary” fast pyrolysis of hemicelluloses.
Original languageEnglish
Pages (from-to)14232-14248
Number of pages17
JournalEnergy and Fuels
Issue number11
Early online date16 Oct 2020
Publication statusPublished - 19 Nov 2020

Bibliographical note

This is an open access article published under an ACS AuthorChoice License, which permits
copying and redistribution of the article or any adaptations for non-commercial purposes.

Funding: Action H2020-MSCA-IF-2014, Pyrochem, Grant 656967,
entitled “Biopolymers 13C Tracking during Fast Pyrolysis of
Biomass - A 2-Level Mechanistic Investigation”.


  • Fuel Technology
  • Energy Engineering and Power Technology
  • General Chemical Engineering


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