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Title: Small ester combustion chemistry: Computational kinetics and experimental study of methyl acetate and ethyl acetate

Abstract

Small esters represent an important class of high octane biofuels for advanced spark ignition engines. They qualify for stringent fuel screening standards and could be synthesized through various pathways. In this work, we performed a detailed investigation of the combustion of two small esters, MA (methyl acetate) and EA (ethyl acetate), including quantum chemistry calculations, experimental studies of combustion characteristics and kinetic model development. The quantum chemistry calculations were performed to obtain rates for H-atom abstraction reactions involved in the oxidation chemistry of these fuels. The series of experiments include: a shock tube study to measure ignition delays at 15 and 30 bar, 1000-1450 K and equivalence ratios of 0.5, 1.0 and 2.0; laminar burning velocity measurements in a heat flux burner over a range of equivalence ratios [0.7-1.4] at atmospheric pressure and temperatures of 298 and 338 K; and speciation measurements during oxidation in a jet-stirred reactor at 800-1100 K for MA and 650-1000 K for EA at equivalence ratios of 0.5, 1.0 and at atmospheric pressure. The developed chemical kinetic mechanism for MA and EA incorporates reaction rates and pathways from recent studies along with rates calculated in this work. The new mechanism shows generally good agreement inmore » predicting experimental data across the broad range of experimental conditions. As a result, the experimental data, along with the developed kinetic model, provides a solid groundwork towards improving the understanding the combustion chemistry of smaller esters.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [2]; ORCiD logo [4];  [5]; ORCiD logo [1]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [6]; ORCiD logo [4]; ORCiD logo [7];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Politecnico di Milano (Italy)
  4. National Univ. of Ireland, Galway (Ireland)
  5. Lund Univ. (Sweden)
  6. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  7. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1464915
Alternate Identifier(s):
OSTI ID: 1694202
Report Number(s):
NREL/JA-2700-72197
Journal ID: ISSN 1540-7489
Grant/Contract Number:  
AC36-08GO28308; AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the Combustion Institute
Additional Journal Information:
Journal Volume: 37; Journal Issue: 1; Journal ID: ISSN 1540-7489
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; esters; ignition; laminar burning velocity; jet stirred reactor; kinetic mechanism

Citation Formats

Ahmed, Ahfaz, Pitz, William J., Cavallotti, Carlo, Mehl, Marco, Lokachari, Nitin, Nilsson, Elna J. K., Wang, Jui-Yang, Konnov, Alexander A., Wagnon, Scott W., Chen, Bingjie, Wang, Zhandong, Kim, Seonah, Curran, Henry J., Klippenstein, Stephen J., Roberts, William L., and Sarathy, S. Mani. Small ester combustion chemistry: Computational kinetics and experimental study of methyl acetate and ethyl acetate. United States: N. p., 2018. Web. doi:10.1016/j.proci.2018.06.178.
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Ahmed, Ahfaz, Pitz, William J., Cavallotti, Carlo, Mehl, Marco, Lokachari, Nitin, Nilsson, Elna J. K., Wang, Jui-Yang, Konnov, Alexander A., Wagnon, Scott W., Chen, Bingjie, Wang, Zhandong, Kim, Seonah, Curran, Henry J., Klippenstein, Stephen J., Roberts, William L., & Sarathy, S. Mani. Small ester combustion chemistry: Computational kinetics and experimental study of methyl acetate and ethyl acetate. United States. https://doi.org/10.1016/j.proci.2018.06.178
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Ahmed, Ahfaz, Pitz, William J., Cavallotti, Carlo, Mehl, Marco, Lokachari, Nitin, Nilsson, Elna J. K., Wang, Jui-Yang, Konnov, Alexander A., Wagnon, Scott W., Chen, Bingjie, Wang, Zhandong, Kim, Seonah, Curran, Henry J., Klippenstein, Stephen J., Roberts, William L., and Sarathy, S. Mani. Tue . "Small ester combustion chemistry: Computational kinetics and experimental study of methyl acetate and ethyl acetate". United States. https://doi.org/10.1016/j.proci.2018.06.178. https://www.osti.gov/servlets/purl/1464915.
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@article{osti_1464915,
title = {Small ester combustion chemistry: Computational kinetics and experimental study of methyl acetate and ethyl acetate},
author = {Ahmed, Ahfaz and Pitz, William J. and Cavallotti, Carlo and Mehl, Marco and Lokachari, Nitin and Nilsson, Elna J. K. and Wang, Jui-Yang and Konnov, Alexander A. and Wagnon, Scott W. and Chen, Bingjie and Wang, Zhandong and Kim, Seonah and Curran, Henry J. and Klippenstein, Stephen J. and Roberts, William L. and Sarathy, S. Mani},
abstractNote = {Small esters represent an important class of high octane biofuels for advanced spark ignition engines. They qualify for stringent fuel screening standards and could be synthesized through various pathways. In this work, we performed a detailed investigation of the combustion of two small esters, MA (methyl acetate) and EA (ethyl acetate), including quantum chemistry calculations, experimental studies of combustion characteristics and kinetic model development. The quantum chemistry calculations were performed to obtain rates for H-atom abstraction reactions involved in the oxidation chemistry of these fuels. The series of experiments include: a shock tube study to measure ignition delays at 15 and 30 bar, 1000-1450 K and equivalence ratios of 0.5, 1.0 and 2.0; laminar burning velocity measurements in a heat flux burner over a range of equivalence ratios [0.7-1.4] at atmospheric pressure and temperatures of 298 and 338 K; and speciation measurements during oxidation in a jet-stirred reactor at 800-1100 K for MA and 650-1000 K for EA at equivalence ratios of 0.5, 1.0 and at atmospheric pressure. The developed chemical kinetic mechanism for MA and EA incorporates reaction rates and pathways from recent studies along with rates calculated in this work. The new mechanism shows generally good agreement in predicting experimental data across the broad range of experimental conditions. As a result, the experimental data, along with the developed kinetic model, provides a solid groundwork towards improving the understanding the combustion chemistry of smaller esters.},
doi = {10.1016/j.proci.2018.06.178},
journal = {Proceedings of the Combustion Institute},
number = 1,
volume = 37,
place = {United States},
year = {Tue Jul 17 00:00:00 EDT 2018},
month = {Tue Jul 17 00:00:00 EDT 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.proci.2018.06.178
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Cited by: 30 works
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Figures / Tables:

Fig.1 Fig.1: Comparison between literature rate constants [14, 19, 21, 22] for the CH3COOCH3 + ȮH reaction and those computed in this work at different levels of theory.
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    Works referencing / citing this record:

    Benchmarking dual-level MS-Tor and DLPNO-CCSD(T) methods for H-abstraction from methyl pentanoate by an OH radical
    journal, January 2019

    • Shang, Yanlei; Ning, Hongbo; Shi, Jinchun
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 37
    • DOI: 10.1039/c9cp03832a
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