A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

Tian, Z; Pitz, W J; Fournet, R; Glaude, P; Battin-Leclerc, F

doi:10.1016/j.proci.2010.06.063

A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

Conference · Fri Dec 18 04:00:00 EST 2009

DOI:https://doi.org/10.1016/j.proci.2010.06.063· OSTI ID:990420

Tian, Z; Pitz, W J; Fournet, R; Glaude, P; Battin-Leclerc, F

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene, decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C{sub 4} + C{sub 2} species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C{sub 6}H{sub 4}CH{sub 3} radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C{sub 6}H{sub 4}CH{sub 3} radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics.

View Conference

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA

Sponsoring Organization:: USDOE

DOE Contract Number:: W-7405-ENG-48

OSTI ID:: 990420

Report Number(s):: LLNL-PROC-421652

Country of Publication:: United States

Language:: English

References (26)

Experimental Study and Detailed Modeling of Toluene Degradation in a Low-Pressure Stoichiometric Premixed CH ₄ /O ₂ /N ₂ Flame ^† El Bakali, A.; Dupont, L.; Lefort, B. The Journal of Physical Chemistry A, Vol. 111, Issue 19 https://doi.org/10.1021/jp067080z	journal	May 2007
A kinetic model for the oxidation of toluene near 1200 K Emdee, J. L.; Brezinsky, K.; Glassman, I. The Journal of Physical Chemistry, Vol. 96, Issue 5 https://doi.org/10.1021/j100184a025	journal	March 1992
Detailed Kinetic Modelling of Toluene Combustion Lindstedt, R. P.; Maurice, L. Q. Combustion Science and Technology, Vol. 120, Issue 1-6 https://doi.org/10.1080/00102209608935571	journal	November 1996
Benzene formation in premixed fuel-rich 1,3-butadiene flames Hansen, Nils; Miller, James A.; Kasper, Tina Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.06.050	journal	January 2009
Experimental and Kinetic Modeling Evidences of a C ₇ H ₆ Pathway in a Rich Toluene Flame Detilleux, Valéry; Vandooren, J. The Journal of Physical Chemistry A, Vol. 113, Issue 41 https://doi.org/10.1021/jp905954g	journal	September 2009
Quantum Chemical Study of the Thermal Decomposition of o -Quinone Methide (6-Methylene-2,4-cyclohexadien-1-one) da Silva, Gabriel; Bozzelli, Joseph W. The Journal of Physical Chemistry A, Vol. 111, Issue 32 https://doi.org/10.1021/jp073335c	journal	August 2007
A lean methane premixed laminar flame doped with components of diesel fuel part III: Indane and comparison between n-butylbenzene, n-propylcyclohexane and indane Pousse, E.; Tian, Z. Y.; Glaude, P. A. Combustion and Flame, Vol. 157, Issue 7 https://doi.org/10.1016/j.combustflame.2010.03.008	journal	July 2010
The formation and oxidation of aromatics in cyclopentene and methyl-cyclopentadiene mixtures Lindstedt, R. P.; Rizos, K. -A. Proceedings of the Combustion Institute, Vol. 29, Issue 2 https://doi.org/10.1016/S1540-7489(02)80279-6	journal	January 2002
Flow time effects on hydrocarbon growth and soot formation in coflowing methane/air non-premixed flames McEnally, Charles S.; Pfefferle, Lisa D. Symposium (International) on Combustion, Vol. 27, Issue 1 https://doi.org/10.1016/S0082-0784(98)80562-6	journal	January 1998
Parabolic tunneling calculations Skodje, Rex T.; Truhlar, Donald G. The Journal of Physical Chemistry, Vol. 85, Issue 6 https://doi.org/10.1021/j150606a003	journal	March 1981
Thermodynamic and kinetic issues in the formation and oxidation of aromatic species Lindstedt, Peter; Maurice, Lourdes; Meyer, Michael Faraday Discussions, Vol. 119, Issue 1 https://doi.org/10.1039/b104056c	journal	November 2001
High-Temperature Reactions of OH Radicals with Benzene and Toluene Seta, Takamasa; Nakajima, Masakazu; Miyoshi, Akira The Journal of Physical Chemistry A, Vol. 110, Issue 15 https://doi.org/10.1021/jp0575456	journal	April 2006
Sampling Probe Influences on Temperature and Species Concentrations in Molecular Beam Mass Spectroscopic Investigations of Flat Premixed Low-pressure Flames Struckmeier, Ulf; Oßwald, Patrick; Kasper, Tina Zeitschrift für Physikalische Chemie, Vol. 223, Issue 4-5 https://doi.org/10.1524/zpch.2009.6049	journal	May 2009
Modeling the combustion of toluene-butane blends Klotz, Stephen D.; Brezinsky, Kenneth; Glassman, Irvin Symposium (International) on Combustion, Vol. 27, Issue 1 https://doi.org/10.1016/S0082-0784(98)80421-9	journal	January 1998
Investigation of the reaction of toluene with molecular oxygen in shock-heated gases Oehlschlaeger, Matthew A.; Davidson, David F.; Hanson, Ronald K. Combustion and Flame, Vol. 147, Issue 3 https://doi.org/10.1016/j.combustflame.2006.08.006	journal	November 2006
Oxidation of small alkenes at high temperature Heyberger, Barbara; Belmekki, Najib; Conraud, Val�rie International Journal of Chemical Kinetics, Vol. 34, Issue 12 https://doi.org/10.1002/kin.10092	journal	January 2002
Experimental Study of a Fuel-Rich Premixed Toluene Flame at Low Pressure Li, Yuyang; Zhang, Lidong; Tian, Zhenyu Energy & Fuels, Vol. 23, Issue 3 https://doi.org/10.1021/ef800902t	journal	March 2009
A modelling study of aromatic soot precursors formation in laminar methane and ethene flames Slavinskaya, N. A.; Frank, P. Combustion and Flame, Vol. 156, Issue 9 https://doi.org/10.1016/j.combustflame.2009.04.013	journal	September 2009
Toluene Combustion: Reaction Paths, Thermochemical Properties, and Kinetic Analysis for the Methylphenyl Radical + O ₂ Reaction da Silva, Gabriel; Chen, Chiung-Chu; Bozzelli, Joseph W. The Journal of Physical Chemistry A, Vol. 111, Issue 35 https://doi.org/10.1021/jp068640x	journal	September 2007
The Formation of Naphthalene, Azulene, and Fulvalene from Cyclic C ₅ Species in Combustion: An Ab Initio/RRKM Study of 9-H-Fulvalenyl (C ₅ H ₅ −C ₅ H ₄ ) Radical Rearrangements ^† Kislov, V. V.; Mebel, A. M. The Journal of Physical Chemistry A, Vol. 111, Issue 38 https://doi.org/10.1021/jp0732099	journal	September 2007
Oxidation, ignition and combustion of toluene: Experimental and detailed chemical kinetic modelingElectronic supplementary information (ESI) available: Arrhenius parameters for reactions. See http://www.rsc.org/suppdata/cp/b1/b110282f/ Dagaut, P.; Pengloan, G.; Ristori, A. Physical Chemistry Chemical Physics, Vol. 4, Issue 10 https://doi.org/10.1039/b110282f	journal	April 2002
Thermal decomposition of toluene: Overall rate and branching ratio Oehlschlaeger, Matthew A.; Davidson, David F.; Hanson, Ronald K. Proceedings of the Combustion Institute, Vol. 31, Issue 1 https://doi.org/10.1016/j.proci.2006.07.002	journal	January 2007
Experimental and modeling study of the oxidation of toluene Bounaceur, R.; Da Costa, I.; Fournet, R. International Journal of Chemical Kinetics, Vol. 37, Issue 1 https://doi.org/10.1002/kin.20047	journal	January 2004
A high pressure model for the oxidation of toluene Sivaramakrishnan, R.; Tranter, R. S.; Brezinsky, K. Proceedings of the Combustion Institute, Vol. 30, Issue 1 https://doi.org/10.1016/j.proci.2004.08.128	journal	January 2005
Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry Hansen, Nils; Cool, Terrill A.; Westmoreland, Phillip R. Progress in Energy and Combustion Science, Vol. 35, Issue 2 https://doi.org/10.1016/j.pecs.2008.10.001	journal	April 2009
Fuel-rich flame chemistry in low-pressure cyclopentene flames Lamprecht, A.; Atakan, B.; Kohse-Höinghaus, K. Proceedings of the Combustion Institute, Vol. 28, Issue 2 https://doi.org/10.1016/S0082-0784(00)80584-6	journal	January 2000

Similar Records

The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings

Journal Article · Tue Jan 27 23:00:00 EST 2015 · Journal of Chemical Physics · OSTI ID:22416049

An experimental and theoretical study of toluene pyrolysis with tunable synchrotron VUV photoionization and molecular-beam mass spectrometry

Journal Article · Sat Nov 14 23:00:00 EST 2009 · Combustion and Flame · OSTI ID:21235975

Exploring old and new benzene formation pathways in low-pressure premixed flames of aliphatic fuels

Conference · Tue Dec 12 23:00:00 EST 2000 · OSTI ID:751237

Related Subjects

30 DIRECT ENERGY CONVERSION
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANTHRACENE
AROMATICS
BENZENE
BENZYL RADICALS
CHRYSENE
COMBUSTION
FLAMES
FLOW RATE
KINETICS
LAMINAR FLAMES
MASS SPECTROSCOPY
MOLECULAR BEAMS
OXIDATION
OXYGEN
PHENANTHRENE
PHOTOIONIZATION
PYRENE
RADICALS
SENSITIVITY ANALYSIS
TOLUENE

A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

Citation Formats

References (26)

Similar Records

Related Subjects