Detailed chemical kinetic modelling of vapour-phase cracking of multi-component molecular mixtures derived from the fast pyrolysis of cellulose

Norinaga, Koyo; Tanaka, Shōji; Kudo, Shinji; Hayashi, Jun Ichiro

doi:10.1016/j.fuel.2011.07.045

Cited by 69 publications

(104 citation statements)

References 29 publications

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“…Furan, 2-methylfuran and 2,5-dimethylfuran are also know intermediates and model compounds considered in the pyrolysis of biomass 82,83 and coals, 17 and the kinetic scheme developed herein is likely to be useful in kinetic modelling work in these areas. Furan, 2-methylfuran and 2,5-dimethylfuran are also know intermediates and model compounds considered in the pyrolysis of biomass 82,83 and coals, 17 and the kinetic scheme developed herein is likely to be useful in kinetic modelling work in these areas.…”

Section: Discussionmentioning

confidence: 99%

The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study

Somers

Simmie

Metcalfe

et al. 2014

Phys. Chem. Chem. Phys.

107

137

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Due to the rapidly growing interest in the use of biomass derived furanic compounds as potential platform chemicals and fossil fuel replacements, there is a simultaneous need to understand the pyrolysis and combustion properties of such molecules. To this end, the potential energy surfaces for the pyrolysis relevant reactions of the biofuel candidate 2-methylfuran have been characterized using quantum chemical methods (CBS-QB3, CBS-APNO and G3). Canonical transition state theory is employed to determine the high-pressure limiting kinetics, k(T), of elementary reactions. Rice-Ramsperger-Kassel-Marcus theory with an energy grained master equation is used to compute pressure-dependent rate constants, k(T,p), and product branching fractions for the multiple-well, multiple-channel reaction pathways which typify the pyrolysis reactions of the title species. The unimolecular decomposition of 2-methylfuran is shown to proceed via hydrogen atom transfer reactions through singlet carbene intermediates which readily undergo ring opening to form collisionally stabilised acyclic C5H6O isomers before further decomposition to C1-C4 species. Rate constants for abstraction by the hydrogen atom and methyl radical are reported, with abstraction from the alkyl side chain calculated to dominate. The fate of the primary abstraction product, 2-furanylmethyl radical, is shown to be thermal decomposition to the n-butadienyl radical and carbon monoxide through a series of ring opening and hydrogen atom transfer reactions. The dominant bimolecular products of hydrogen atom addition reactions are found to be furan and methyl radical, 1-butene-1-yl radical and carbon monoxide and vinyl ketene and methyl radical. A kinetic mechanism is assembled with computer simulations in good agreement with shock tube speciation profiles taken from the literature. The kinetic mechanism developed herein can be used in future chemical kinetic modelling studies on the pyrolysis and oxidation of 2-methylfuran, or the larger molecular structures for which it is a known pyrolysis/combustion intermediate (e.g. cellulose, coals, 2,5-dimethylfuran).

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Section: Discussionmentioning

confidence: 99%

The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study

Somers

Simmie

Metcalfe

et al. 2014

Phys. Chem. Chem. Phys.

107

137

View full text Add to dashboard Cite

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“…Meanwhile, pyrolysis produces combustible gases, liquid fuels, and chemical feedstock directly from lignin or lignocellulosic biomass . The pyrolysis is roughly divided into two steps: the primary heterogeneous pyrolysis involving the volatilization from biomass solids and the secondary homogeneous vapor‐phase cracking of the released volatiles .…”

Section: Introductionmentioning

confidence: 99%

“…In case of the secondary homogeneous vapor‐phase cracking, our research group has established a DCKM involving thousands of elementary reaction channels and hundreds of chemical species . The DCKM was employed to conduct the numerical simulation of the vapor‐phase reactions of volatiles derived from fast pyrolysis of lignin at 773−1223 K .…”

Section: Introductionmentioning

confidence: 99%

Computational Study on the Thermal Decomposition of Phenol‐Type Monolignols

Furutani

Dohara

Kudo

et al. 2018

Int J of Chemical Kinetics

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A detailed chemical kinetic model has been developed to theoretically predict the pyrolysis behavior of phenol‐type monolignol compounds (1‐(4‐hydroxyphenyl)prop‐2‐en‐1‐one, HPP; p‐coumaryl alcohol, 3‐hydroxy‐1‐(4‐hydroxyphenyl)propan‐1‐one, HHPP; 1‐(4‐hydroxyphenyl)propane‐1,3‐diol, HPPD) released from the primary heterogeneous pyrolysis of lignin. The possible thermal decomposition pathways involving unimolecular decomposition, H‐addition, and H‐abstraction by H and CH3 radicals were investigated by comparing the activation energies calculated at the M06–2X/6–311++G(d,p) level of theory. The results indicated that all phenol‐type monolignol compounds convert to phenol by side‐chain cleavage. p‐Coumaryl alcohol decomposes into phenol via the formation of 4‐vinylphenol, whereas HPP, HHPP, and HPPD decompose into phenol via the formation of 4‐hydroxybenzaldehyde. The pyrolytic pathways focusing on the reactivity of the hydroxyl group in HPP and producing cyclopentadiene (cyc‐C5H6) were also investigated. The transition state theory (TST) rate constants for all the proposed elementary reaction channels were calculated at the high‐pressure limit in the temperature range of 300–1500 K. The kinetic analysis predicted the two favorable unimolecular decomposition pathways in HPP: the one is the dominant channel below 1000 K to produce cyc‐C5H6, and the other is above 1000 K to yield phenol (C6H5OH).

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“…The product distribution provides an insight into the mechanism of aromatics formation during the reaction. Because the non-catalytic process had been known to effectively produce oxygenates, including aldehydes, ketones, furfurals and phenols [128][129][130], the lighter of these species were subjected to dehydrogenation, deoxygenation and cracking over the zeolite surface. The reactions produced olefins as intermediates for cyclization and aromatization.…”

Section: Effect Of Zeolite Topology and Textural Propertiesmentioning

confidence: 99%

In situ fast pyrolysis of biomass with zeolite catalysts for bioaromatics/gasoline production: A review

Galadima

Muraza

2015

Energy Conversion and Management

214

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Detailed chemical kinetic modelling of vapour-phase cracking of multi-component molecular mixtures derived from the fast pyrolysis of cellulose

Cited by 69 publications

References 29 publications

The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study

The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study

Computational Study on the Thermal Decomposition of Phenol‐Type Monolignols

In situ fast pyrolysis of biomass with zeolite catalysts for bioaromatics/gasoline production: A review

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