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Title: An Experimental and Kinetic Modeling Study of Methyl Formate Low-Pressure Flames

Abstract

The oxidation of methyl formate (CH{sub 3}OCHO), the simplest methyl ester, is studied in a series of burner-stabilized laminar flames at pressures of 22–30 Torr and equivalence ratios (Φ) 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 (C{sub 2}H{sub 5}OCHO), the subsequent decomposition of which is the major source of observed ethylene concentrations. The good agreement of model computations with thismore » 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« less

Authors:
; ; ; ; ; ;
Research Org.:
Energy Frontier Research Centers (EFRC); Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1065132
DOE Contract Number:  
SC0001198
Resource Type:
Journal Article
Journal Name:
Combustion and Flame
Additional Journal Information:
Journal Volume: 158; Journal Issue: 4; Related Information: CEFRC partners with Princeton University (lead); Argonne National Laboratory; University of Connecticut; Cornell University; Massachusetts Institute of Technology; University of Minnesota; Sandia National Laboratories; University of Southern California; Stanford University; University of Wisconsin, Madison; Journal ID: ISSN 0010-2180
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biofuels (including algae and biomass), hydrogen and fuel cells, combustion, carbon capture

Citation Formats

Dooley, S., Dryer, F. L., Yang, B., Wang, J., Cool, T. A., Kasper, T., and Hansen, N. An Experimental and Kinetic Modeling Study of Methyl Formate Low-Pressure Flames. United States: N. p., Web. doi:10.1016/j.combustflame.2010.11.003.
Dooley, S., Dryer, F. L., Yang, B., Wang, J., Cool, T. A., Kasper, T., & Hansen, N. An Experimental and Kinetic Modeling Study of Methyl Formate Low-Pressure Flames. United States. doi:10.1016/j.combustflame.2010.11.003.
Dooley, S., Dryer, F. L., Yang, B., Wang, J., Cool, T. A., Kasper, T., and Hansen, N. . "An Experimental and Kinetic Modeling Study of Methyl Formate Low-Pressure Flames". United States. doi:10.1016/j.combustflame.2010.11.003.
@article{osti_1065132,
title = {An Experimental and Kinetic Modeling Study of Methyl Formate Low-Pressure Flames},
author = {Dooley, S. and Dryer, F. L. and Yang, B. and Wang, J. and Cool, T. A. and Kasper, T. and Hansen, N.},
abstractNote = {The oxidation of methyl formate (CH{sub 3}OCHO), the simplest methyl ester, is studied in a series of burner-stabilized laminar flames at pressures of 22–30 Torr and equivalence ratios (Φ) 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 (C{sub 2}H{sub 5}OCHO), 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},
doi = {10.1016/j.combustflame.2010.11.003},
journal = {Combustion and Flame},
issn = {0010-2180},
number = 4,
volume = 158,
place = {United States},
year = {},
month = {}
}