An experimental and kinetic modeling study of methyl formate low-pressure flames

Dooley, S.; Dryer, F. L.; Yang, B.; Wang, J.; Cool, T. A.; Kasper, T.; Hansen, N.

doi:10.1016/j.combustflame.2010.11.003

An experimental and kinetic modeling study of methyl formate low-pressure flames

Journal Article · Fri Apr 01 04:00:00 EDT 2011 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2010.11.003· OSTI ID:1060395

Dooley, S. ^[1]; Dryer, F. L.; Yang, B.; Wang, J.; Cool, T. A.; Kasper, T.; Hansen, N.

Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551

The oxidation of methyl formate (CH3OCHO), the simplest methyl ester, is studied in a series of burner-stabilized laminar flames at pressures of 22-30 Torr and equivalence ratios ¦ from 1.0 to 1.8 for flame conditions of 25-35% fuel. Flame structures are determined by quantitative measurements of species mole fractions with flame-sampling molecular-beam synchrotron photoionization mass spectrometry (PIMS). Methyl formate is observed to be converted to methanol, formaldehyde and methane as major intermediate species of mechanistic relevance. Smaller amounts of ethylene and acetylene are also formed from methyl formate oxidation. Reactant, product and major intermediate species profiles are in good agreement with the computations of a recently developed kinetic model for methyl formate oxidation [S. Dooley, M.P. Burke, M. Chaos, Y. Stein, F.L. Dryer, V.P. Zhukov, O. Finch, J.M. Simmie, H.J. Curran, Int. J. Chem. Kinet. 42 (2010) 527-529] which shows that hydrogen abstraction reactions dominate fuel consumption under the tested flame conditions. Radical-radical reactions are shown to be significant in the formation of a number of small concentration intermediates, including the production of ethyl formate (C2H5OCHO), the subsequent decomposition of which is the major source of observed ethylene concentrations. The good agreement of model computations with this set of experimental data provides a further test of the predictive capabilities of the proposed mechanism of methyl formate oxidation. Other salient issues in the development of this model are discussed, including recent controversy regarding the methyl formate decomposition mechanism, and uncertainties in the experimental measurement and modeling of low-pressure flame-sampling experiments. Kinetic model computations show that worst-case disturbances to the measured temperature field, which may be caused by the insertion of the sampling cone into the flame, do not alter mechanistic conclusions provided by the kinetic model. However, such perturbations are shown to be responsible for disparities in species location between measurement and computation.

Research Organization:: Cornell Univ., Ithaca, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)

Sponsoring Organization:: USDOE

DOE Contract Number:: FG02-01ER15180

OSTI ID:: 1060395

Report Number(s):: DOE-ER15180-2

Journal Information:: Combustion and Flame, Journal Name: Combustion and Flame Journal Issue: 4 Vol. 158; ISSN 0010-2180

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

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