Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis

Xiaolei Zhang, Weihong Yang, Wlodzimierz Blasiak

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The mechanisms and kinetics studies of the levoglucosan (LG) primary decomposition during cellulose pyrolysis have been carried out theoretically in this paper. Three decomposition mechanisms (C–O bond scission, C–C bond scission, and LG dehydration) including nine pathways and 16 elementary reactions were studied at the B3LYP/6-31 + G(D,P) level based on quantum mechanics. The variational transition-state rate constants for every elementary reaction and every pathway were calculated within 298–1550 K. The first-order Arrhenius expressions for these 16 elementary reactions and nine pathways were suggested. It was concluded that computational method using transition state theory (TST) without tunneling correction gives good description for LG decomposition by comparing with the experimental result. With the temperature range of 667–1327 K, one dehydration pathway, with one water molecule composed of a hydrogen atom from C3 and a hydroxyl group from C2, is a preferred LG decomposition pathway by fitting well with the experimental results. The calculated Arrhenius plot of C–O bond scission mechanism is better agreed with the experimental Arrhenius plot than that of C–C bond scission. This C–O bond scission mechanism starts with breaking of C1–O5 and C6–O1 bonds with formation of CO molecule (C1–O1) simultaneously. C–C bond scission mechanism is the highest energetic barrier pathway for LG decomposition.
LanguageEnglish
Pages476-483
Number of pages8
JournalFuel
Volume109
DOIs
Publication statusPublished - 31 Jul 2013

Fingerprint

Cellulose
Pyrolysis
Decomposition
Kinetics
Arrhenius plots
Dehydration
Molecules
Quantum theory
Carbon Monoxide
Computational methods
Hydroxyl Radical
Hydrogen
Rate constants
1,6-anhydro-beta-glucopyranose
Hot Temperature
Atoms
Water
Temperature

Keywords

  • rate constant
  • cellulose pyrolysis
  • levoglucosan decomposition
  • dehydration

Cite this

Zhang, Xiaolei ; Yang, Weihong ; Blasiak, Wlodzimierz. / Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis. In: Fuel. 2013 ; Vol. 109. pp. 476-483.
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Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis. / Zhang, Xiaolei; Yang, Weihong; Blasiak, Wlodzimierz.

In: Fuel, Vol. 109, 31.07.2013, p. 476-483.

Research output: Contribution to journalArticle

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N2 - The mechanisms and kinetics studies of the levoglucosan (LG) primary decomposition during cellulose pyrolysis have been carried out theoretically in this paper. Three decomposition mechanisms (C–O bond scission, C–C bond scission, and LG dehydration) including nine pathways and 16 elementary reactions were studied at the B3LYP/6-31 + G(D,P) level based on quantum mechanics. The variational transition-state rate constants for every elementary reaction and every pathway were calculated within 298–1550 K. The first-order Arrhenius expressions for these 16 elementary reactions and nine pathways were suggested. It was concluded that computational method using transition state theory (TST) without tunneling correction gives good description for LG decomposition by comparing with the experimental result. With the temperature range of 667–1327 K, one dehydration pathway, with one water molecule composed of a hydrogen atom from C3 and a hydroxyl group from C2, is a preferred LG decomposition pathway by fitting well with the experimental results. The calculated Arrhenius plot of C–O bond scission mechanism is better agreed with the experimental Arrhenius plot than that of C–C bond scission. This C–O bond scission mechanism starts with breaking of C1–O5 and C6–O1 bonds with formation of CO molecule (C1–O1) simultaneously. C–C bond scission mechanism is the highest energetic barrier pathway for LG decomposition.

AB - The mechanisms and kinetics studies of the levoglucosan (LG) primary decomposition during cellulose pyrolysis have been carried out theoretically in this paper. Three decomposition mechanisms (C–O bond scission, C–C bond scission, and LG dehydration) including nine pathways and 16 elementary reactions were studied at the B3LYP/6-31 + G(D,P) level based on quantum mechanics. The variational transition-state rate constants for every elementary reaction and every pathway were calculated within 298–1550 K. The first-order Arrhenius expressions for these 16 elementary reactions and nine pathways were suggested. It was concluded that computational method using transition state theory (TST) without tunneling correction gives good description for LG decomposition by comparing with the experimental result. With the temperature range of 667–1327 K, one dehydration pathway, with one water molecule composed of a hydrogen atom from C3 and a hydroxyl group from C2, is a preferred LG decomposition pathway by fitting well with the experimental results. The calculated Arrhenius plot of C–O bond scission mechanism is better agreed with the experimental Arrhenius plot than that of C–C bond scission. This C–O bond scission mechanism starts with breaking of C1–O5 and C6–O1 bonds with formation of CO molecule (C1–O1) simultaneously. C–C bond scission mechanism is the highest energetic barrier pathway for LG decomposition.

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