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Title: Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model

Abstract

The oxidation of methyl formate (CH{sub 3}OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions: 1. A variable-pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K. 2. Shock tube ignition delays have been determined for CH{sub 3}OCHO/O{sub 2}/Ar mixtures at pressures of ≈ 2.7, 5.4, and 9.2 atm and temperatures of 1275–1935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0). 3. Laminar burning velocities of outwardly propagating spherical CH{sub 3}OCHO/air flames have been determined for stoichiometries ranging from 0.8–1.6, at atmospheric pressure using a pressure-release-type high-pressure chamber. A detailed chemical kinetic model has been constructed, validated against, and used to interpret these experimental data. The kinetic model shows that methyl formate oxidation proceeds through concerted elimination reactions, principally forming methanol and carbon monoxide as well as through bimolecular hydrogen abstraction reactions. The relative importance of elimination versus abstraction was found to dependmore » on the particular environment. In general, methyl formate is consumed exclusively through molecular decomposition in shock tube environments, while at flow reactor and freely propagating premixed flame conditions, there is significant competition between hydrogen abstraction and concerted elimination channels. It is suspected that in diffusion flame configurations the elimination channels contribute more significantly than in premixed environments.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
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:
1065134
DOE Contract Number:  
SC0001198
Resource Type:
Journal Article
Journal Name:
International Journal of Chemical Kinetics
Additional Journal Information:
Journal Volume: 42; Journal Issue: 9; 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 0538-8066
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., Burke, M. P., Chaos, M., Stein, Y., Dryer, F. L., Zhukov, V. P., Finch, O., Simmie, J. M., and Curran, H. J. Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model. United States: N. p., 2010. Web. doi:10.1002/kin.20512.
Dooley, S., Burke, M. P., Chaos, M., Stein, Y., Dryer, F. L., Zhukov, V. P., Finch, O., Simmie, J. M., & Curran, H. J. Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model. United States. doi:10.1002/kin.20512.
Dooley, S., Burke, M. P., Chaos, M., Stein, Y., Dryer, F. L., Zhukov, V. P., Finch, O., Simmie, J. M., and Curran, H. J. Fri . "Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model". United States. doi:10.1002/kin.20512.
@article{osti_1065134,
title = {Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model},
author = {Dooley, S. and Burke, M. P. and Chaos, M. and Stein, Y. and Dryer, F. L. and Zhukov, V. P. and Finch, O. and Simmie, J. M. and Curran, H. J.},
abstractNote = {The oxidation of methyl formate (CH{sub 3}OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions: 1. A variable-pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K. 2. Shock tube ignition delays have been determined for CH{sub 3}OCHO/O{sub 2}/Ar mixtures at pressures of ≈ 2.7, 5.4, and 9.2 atm and temperatures of 1275–1935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0). 3. Laminar burning velocities of outwardly propagating spherical CH{sub 3}OCHO/air flames have been determined for stoichiometries ranging from 0.8–1.6, at atmospheric pressure using a pressure-release-type high-pressure chamber. A detailed chemical kinetic model has been constructed, validated against, and used to interpret these experimental data. The kinetic model shows that methyl formate oxidation proceeds through concerted elimination reactions, principally forming methanol and carbon monoxide as well as through bimolecular hydrogen abstraction reactions. The relative importance of elimination versus abstraction was found to depend on the particular environment. In general, methyl formate is consumed exclusively through molecular decomposition in shock tube environments, while at flow reactor and freely propagating premixed flame conditions, there is significant competition between hydrogen abstraction and concerted elimination channels. It is suspected that in diffusion flame configurations the elimination channels contribute more significantly than in premixed environments.},
doi = {10.1002/kin.20512},
journal = {International Journal of Chemical Kinetics},
issn = {0538-8066},
number = 9,
volume = 42,
place = {United States},
year = {2010},
month = {7}
}