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Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Energy and Furnace Technology.
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Energy and Furnace Technology.ORCID iD: 0000-0002-1837-5439
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Energy and Furnace Technology.
2013 (English)In: Fuel, ISSN 0016-2361, Vol. 109, 476-483 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
Elsevier, 2013. Vol. 109, 476-483 p.
Keyword [en]
Rate constant, Cellulose pyrolysis, Levoglucosan decomposition, Dehydration
National Category
Energy Engineering
URN: urn:nbn:se:kth:diva-120082DOI: 10.1016/j.fuel.2013.03.035ISI: 000320651700061ScopusID: 2-s2.0-84879100732OAI: diva2:613344
Swedish Research Council

QC 20130802. Updated from accepted to published.

Available from: 2013-03-27 Created: 2013-03-27 Last updated: 2013-08-02Bibliographically approved
In thesis
1. Micro-reaction Mechanism Study of the Biomass Thermal Conversion Process using Density Functional Theory
Open this publication in new window or tab >>Micro-reaction Mechanism Study of the Biomass Thermal Conversion Process using Density Functional Theory
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Biomass, or bio-energy, is one of the most important alternative energies because of environmental concerns and the future shortage of fossil fuels. Multi-scaled bioenergy studies have been performed in the division of Energy and Furnace Technology, which included studies of macroscopic systems such as systems and reactors, modeling of computational fluid dynamics (CFD), and atomic/molecular level studies. The present thesis focus on the atomic/molecular level that based on quantum chemistry methods.

The microscopic structure study of biomass is the first and an important step for the investigation of the biomass thermal conversion mechanism. Cellulose, hemicellulose, and lignin are the three most important components for biomass. The atomic interactions among these three main components were studied, including the hydrogen bond linkages between cellulose and hemicellulose, and the covalent bond linkages between hemicellulose and lignin.

The decomposition of biomass is complicated and includes cellulose decomposition, hemicellulose decomposition, and lignin decomposition. As the main component of biomass, the mechanism of cellulose pyrolysis mechanism was focused on in this thesis. The study of this mechanism included an investigation of the pathways from cellulose to levoglucosan then to lower-molecular-weight species. Three different pathways were studied for the formation of levoglucosan from cellulose, and three different pathways were studied for the levoglucosan decomposition. The thermal properties for every reactant, intermediate, and product were obtained. The kinetics parameters (rate constant, pre-exponential factor, and activation energy) for every elementary step and pathway were calculated. For the formation of levoglucosan, the levoglucosan chain-end mechanism is the favored pathway due to the lower energy barrier; for the subsequent levoglucosan decomposition process, dehydration is a preferred first step and C-C bond scission is the most difficult pathway due to the strength of the C-C bonds.

The biomass gasification process includes pyrolysis, char gasification, and a gas-phase reaction; Char gasification is considered to be the rate-controlling step because of its slower reaction rate. Char steam gasification can be described as the adsorption of steam on the char surface to form a surface complex, which may transfer to another surface complex, which then desorbs to give the gaseous products (CO and H2) and the solid product of the remaining char. The influences of several radicals (O, H, and OH) and molecules (H2 and O2) on steam adsorption were investigated. It was concluded that the reactivity order for these particles adsorbed onto both zigzag and armchair surfaces is O > H2 > H > OH > O2. For water adsorbs on both zigzag and armchair carbon surfaces, O and OH radicals accelerate water adsorption, but H, O2, and H2 have no significant influence on water adsorption.

It was also shown that quantum chemistry (also known as molecular modeling) can be used to investigate the reaction mechanism of a macroscopic system. Detailed atomic/molecular descriptions can provide further understanding of the reaction process and possible products.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. x, 58 p.
biomass thermal conversion, cellulose pyrolysis, char steam gasification, adsorption, interaction, mechanism, quantum chemistry, density functional theory
National Category
urn:nbn:se:kth:diva-120071 (URN)978-91-7501-656-6 (ISBN)
Public defence
2013-04-22, Sal F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)

QC 20130327

Available from: 2013-03-27 Created: 2013-03-27 Last updated: 2013-03-27Bibliographically approved

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Zhang, XiaoleiYang, WeihongBlasiak, Wlodzimierz
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