Thermal decomposition mechanism of levoglucosan during cellulose pyrolysis

Xiaolei Zhang, Weihong Yang, Wlodzimierz Blasiak

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

Levoglucosan (1,6-anhydro-β-d-glucopyranose) decomposition is an important step during cellulose pyrolysis and for secondary tar reactions. The mechanism of levoglucosan thermal decomposition was studied in this paper using density functional theory methods. The decomposition included direct CO bond breaking, direct CC bond breaking, and dehydration. In total, 9 different pathways, including 16 elementary reactions, were studied, in which levoglucosan serves as a reactant. The properties of the reactants, transition states, intermediates, and products for every elementary reaction were obtained. It was found that 1-pentene-3,4-dione, acetaldehyde, 2,3-dihydroxypropanal, and propanedialdehyde can be formed from the CO bond breaking decomposition reactions. 1,2-Dihydroxyethene and hydroxyacetic acid vinyl ester can be formed from the CC bond breaking decomposition reactions. It was concluded that CO bond breaking is easier than CC bond breaking due to a lower activation energy and a higher released energy. During the 6 levoglucosan dehydration pathways, one water molecule which composed of a hydrogen atom from C3 and a hydroxyl group from C2 is the preferred pathway due to a lower activation energy and higher product stability.
LanguageEnglish
Pages110-119
Number of pages10
JournalJournal of analytical and applied pyrolysis
Volume96
DOIs
Publication statusPublished - 31 Jul 2012

Fingerprint

Cellulose
Pyrolysis
Carbon Monoxide
Decomposition
glycolic acid
Dehydration
Activation energy
Tars
Acetaldehyde
Hydroxyl Radical
Density functional theory
Hydrogen
Esters
Atoms
Molecules
1,6-anhydro-beta-glucopyranose
Water

Keywords

  • levoglucosan
  • cellulose
  • pyrolysis
  • density functional theory (DFT)

Cite this

Zhang, Xiaolei ; Yang, Weihong ; Blasiak, Wlodzimierz. / Thermal decomposition mechanism of levoglucosan during cellulose pyrolysis. 2012 ; Vol. 96. pp. 110-119.
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Thermal decomposition mechanism of levoglucosan during cellulose pyrolysis. / Zhang, Xiaolei; Yang, Weihong; Blasiak, Wlodzimierz.

Vol. 96, 31.07.2012, p. 110-119.

Research output: Contribution to journalArticle

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AU - Zhang, Xiaolei

AU - Yang, Weihong

AU - Blasiak, Wlodzimierz

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Y1 - 2012/7/31

N2 - Levoglucosan (1,6-anhydro-β-d-glucopyranose) decomposition is an important step during cellulose pyrolysis and for secondary tar reactions. The mechanism of levoglucosan thermal decomposition was studied in this paper using density functional theory methods. The decomposition included direct CO bond breaking, direct CC bond breaking, and dehydration. In total, 9 different pathways, including 16 elementary reactions, were studied, in which levoglucosan serves as a reactant. The properties of the reactants, transition states, intermediates, and products for every elementary reaction were obtained. It was found that 1-pentene-3,4-dione, acetaldehyde, 2,3-dihydroxypropanal, and propanedialdehyde can be formed from the CO bond breaking decomposition reactions. 1,2-Dihydroxyethene and hydroxyacetic acid vinyl ester can be formed from the CC bond breaking decomposition reactions. It was concluded that CO bond breaking is easier than CC bond breaking due to a lower activation energy and a higher released energy. During the 6 levoglucosan dehydration pathways, one water molecule which composed of a hydrogen atom from C3 and a hydroxyl group from C2 is the preferred pathway due to a lower activation energy and higher product stability.

AB - Levoglucosan (1,6-anhydro-β-d-glucopyranose) decomposition is an important step during cellulose pyrolysis and for secondary tar reactions. The mechanism of levoglucosan thermal decomposition was studied in this paper using density functional theory methods. The decomposition included direct CO bond breaking, direct CC bond breaking, and dehydration. In total, 9 different pathways, including 16 elementary reactions, were studied, in which levoglucosan serves as a reactant. The properties of the reactants, transition states, intermediates, and products for every elementary reaction were obtained. It was found that 1-pentene-3,4-dione, acetaldehyde, 2,3-dihydroxypropanal, and propanedialdehyde can be formed from the CO bond breaking decomposition reactions. 1,2-Dihydroxyethene and hydroxyacetic acid vinyl ester can be formed from the CC bond breaking decomposition reactions. It was concluded that CO bond breaking is easier than CC bond breaking due to a lower activation energy and a higher released energy. During the 6 levoglucosan dehydration pathways, one water molecule which composed of a hydrogen atom from C3 and a hydroxyl group from C2 is the preferred pathway due to a lower activation energy and higher product stability.

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