Autoignition of methyl butanoate under engine relevant conditions

Kumar, Kamal; Sung, Chih-Jen

doi:10.1016/j.combustflame.2016.04.011

Title: Autoignition of methyl butanoate under engine relevant conditions

Journal Article · Thu Jun 16 00:00:00 EDT 2016 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2016.04.011· OSTI ID:1369808

^[1]; Sung, Chih-Jen ^[2]

Univ. of Idaho, Moscow, ID (United States)
Univ. of Connecticut, Storrs, CT (United States)

Here, this study reports the autoignition delay times of methyl butanoate in argon–air (i.e. Ar/O₂ = 3.76 by mole) mixtures under thermodynamic conditions relevant to compression ignition engines, using a rapid compression machine (RCM). The ignition delay times were obtained for the compressed temperature range of 833–1112 K and compressed pressures corresponding to 15, 30, 45, and 75 bar. In addition, the effect of fuel mole fraction on ignition delay times were experimentally studied by covering equivalence ratios corresponding to 0.25, 0.5, and 1.0 under realistic fuel loadings without additional dilution. For the range of conditions investigated, the ignition delay times exhibit an Arrhenius dependence on temperature and an inverse relationship with the compressed pressure. No evidence of two-stage ignition was observed in the current experiments, nor was a negative temperature coefficient trend seen in the ignition delay times. The experimental findings were compared to zero-dimensional simulations taking into account the full compression stroke and the heat loss characteristics of the RCM, using chemical kinetic models reported in the literature. The literature models were found to predict significantly higher reactivity when compared to the current experiments. Chemical kinetic analysis was then conducted to identify the reactions responsible for the mismatch between the experiments and the simulated results. Key reactions that could help obtain a better match between the experimental and simulated results were identified using both brute-force and global sensitivity analyses. In view of the large uncertainties associated with the low-temperature chemistry of methyl butanoate, additional studies are needed to update the kinetic parameters of the key reactions in order to improve the model comprehensiveness.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001198

OSTI ID:: 1369808

Alternate ID(s):: OSTI ID: 1334827

Journal Information:: Combustion and Flame, Vol. 171, Issue C; 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; ISSN 0010-2180

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 21 works

Citation information provided by
Web of Science

References (65)

Biofuel Combustion Chemistry: From Ethanol to Biodiesel Kohse-Höinghaus, Katharina; Oßwald, Patrick; Cool, Terrill A. Angewandte Chemie International Edition, Vol. 49, Issue 21 https://doi.org/10.1002/anie.200905335	journal	May 2010
Combustion chemical kinetics of biodiesel and related compounds (methyl and ethyl esters): Experiments and modeling – Advances and future refinements Coniglio, L.; Bennadji, H.; Glaude, P. A. Progress in Energy and Combustion Science, Vol. 39, Issue 4 https://doi.org/10.1016/j.pecs.2013.03.002	journal	August 2013
Pathways, kinetics and thermochemistry of methyl-ester peroxy radical decomposition in the low-temperature oxidation of methyl butanoate: A computational study of a biodiesel fuel surrogate Tao, Hairong; Lin, Kuang C. Combustion and Flame, Vol. 161, Issue 9 https://doi.org/10.1016/j.combustflame.2014.02.012	journal	September 2014
Development of a reduced biodiesel surrogate model for compression ignition engine modeling Liu, W.; Sivaramakrishnan, R.; Davis, Michael J. Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.05.090	journal	January 2013
Numerical study on spray and combustion characteristics of diesel and soy-based biodiesel in a CI engine Lee, Youngjae; Huh, Kang Y. Fuel, Vol. 113 https://doi.org/10.1016/j.fuel.2013.05.106	journal	November 2013
A comparative study of the chemical kinetic characteristics of small methyl esters in diffusion flame extinction Diévart, Pascal; Won, Sang Hee; Gong, Jing Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.06.180	journal	January 2013
Reaction Pathways for the Thermal Decomposition of Methyl Butanoate Akbar Ali, Mohamad; Violi, Angela The Journal of Organic Chemistry, Vol. 78, Issue 12 https://doi.org/10.1021/jo400569d	journal	May 2013
Experimental and kinetic modeling study of methyl butanoate and methyl butanoate/methanol flames at different equivalence ratios and C/O ratios Yu, Wu; Chen, Gen; Huang, Zuohua Combustion and Flame, Vol. 159, Issue 1 https://doi.org/10.1016/j.combustflame.2011.05.018	journal	January 2012
A wide range kinetic modeling study of pyrolysis and oxidation of methyl butanoate and methyl decanoate – Note II: Lumped kinetic model of decomposition and combustion of methyl esters up to methyl decanoate Grana, Roberto; Frassoldati, Alessio; Saggese, Chiara Combustion and Flame, Vol. 159, Issue 7 https://doi.org/10.1016/j.combustflame.2012.02.027	journal	July 2012
Chemical kinetic modeling of hydrocarbon combustion Westbrook, Charles K.; Dryer, Frederick L. Progress in Energy and Combustion Science, Vol. 10, Issue 1 https://doi.org/10.1016/0360-1285(84)90118-7	journal	January 1984
Autoignition measurements and a validated kinetic model for the biodiesel surrogate, methyl butanoate Dooley, S.; Curran, H. J.; Simmie, J. M. Combustion and Flame, Vol. 153, Issue 1-2 https://doi.org/10.1016/j.combustflame.2008.01.005	journal	April 2008
A study of the low temperature autoignition of methyl esters HadjAli, K.; Crochet, M.; Vanhove, G. Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.09.002	journal	January 2009
An experimental investigation of structural effects on the auto-ignition properties of two C5 esters Walton, S. M.; Wooldridge, M. S.; Westbrook, C. K. Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.06.208	journal	January 2009
Comparative Study of Methyl Butanoate and n -Heptane High Temperature Autoignition Akih-Kumgeh, Benjamin; Bergthorson, Jeffrey M. Energy & Fuels, Vol. 24, Issue 4 https://doi.org/10.1021/ef901489k	journal	March 2010
Ignition Delay Time Measurements of Normal Alkanes and Simple Oxygenates Davidson, D. F.; Ranganath, S. C.; Lam, K. -Y. Journal of Propulsion and Power, Vol. 26, Issue 2 https://doi.org/10.2514/1.44034	journal	March 2010
Oxidation of methyl and ethyl butanoates Hakka, M. H.; Bennadji, H.; Biet, J. International Journal of Chemical Kinetics, Vol. 42, Issue 4 https://doi.org/10.1002/kin.20473	journal	April 2010
Structure-reactivity trends of C1–C4 alkanoic acid methyl esters Akih-Kumgeh, Benjamin; Bergthorson, Jeffrey M. Combustion and Flame, Vol. 158, Issue 6 https://doi.org/10.1016/j.combustflame.2010.10.021	journal	June 2011
An experimental and computational study of methyl ester decomposition pathways using shock tubes Farooq, A.; Davidson, D. F.; Hanson, R. K. Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.06.084	journal	January 2009
Shock tube studies of methyl butanoate pyrolysis with relevance to biodiesel Farooq, Aamir; Ren, Wei; Lam, King Y. Combustion and Flame, Vol. 159, Issue 11 https://doi.org/10.1016/j.combustflame.2012.05.013	journal	November 2012
High-Temperature Measurements of the Reactions of OH with Small Methyl Esters: Methyl Formate, Methyl Acetate, Methyl Propanoate, and Methyl Butanoate Lam, King-Yiu; Davidson, David F.; Hanson, Ronald K. The Journal of Physical Chemistry A, Vol. 116, Issue 50 https://doi.org/10.1021/jp310256j	journal	December 2012
A comparison of saturated and unsaturated C4 fatty acid methyl esters in an opposed flow diffusion flame and a jet stirred reactor Sarathy, S. M.; Gaïl, S.; Syed, S. A. Proceedings of the Combustion Institute, Vol. 31, Issue 1 https://doi.org/10.1016/j.proci.2006.07.019	journal	January 2007
Experimental and chemical kinetic modeling study of small methyl esters oxidation: Methyl (E)-2-butenoate and methyl butanoate Gaïl, S.; Sarathy, S. M.; Thomson, M. J. Combustion and Flame, Vol. 155, Issue 4 https://doi.org/10.1016/j.combustflame.2008.04.007	journal	December 2008
Construction of combustion models for rapeseed methyl ester bio-diesel fuel for internal combustion engine applications Golovitchev, Valeri I.; Yang, Junfeng Biotechnology Advances, Vol. 27, Issue 5 https://doi.org/10.1016/j.biotechadv.2009.04.024	journal	September 2009
Numerical Study on Combustion and Emission Characteristics of Homogeneous Charge Compression Ignition Engines Fueled with Biodiesel Um, Sukkee; Park, Sung Wook Energy & Fuels, Vol. 24, Issue 2 https://doi.org/10.1021/ef901092h	journal	December 2009
A comparison of injector flow and spray characteristics of biodiesel with petrodiesel Som, S.; Longman, D. E.; Ramírez, A. I. Fuel, Vol. 89, Issue 12 https://doi.org/10.1016/j.fuel.2010.05.004	journal	December 2010
A combustion model for IC engine combustion simulations with multi-component fuels Ra, Youngchul; Reitz, Rolf D. Combustion and Flame, Vol. 158, Issue 1 https://doi.org/10.1016/j.combustflame.2010.07.019	journal	January 2011
Numerical study on the combustion and emission characteristics in a direct-injection diesel engine with preheated biodiesel fuel Ren, Y.; Li, X-G Proceedings of the Institution of Mechanical Engineers, Part D: Journal of Automobile Engineering, Vol. 225, Issue 4 https://doi.org/10.1177/09544070JAUTO1593	journal	April 2011
Numerical Study Comparing the Combustion and Emission Characteristics of Biodiesel to Petrodiesel Som, S.; Longman, D. E. Energy & Fuels, Vol. 25, Issue 4 https://doi.org/10.1021/ef101438u	journal	April 2011
Comparison of Biodiesel Performance Based on HCCI Engine Simulation Using Detailed Mechanism with On-the-fly Reduction Zhang, Shuliang; Broadbelt, Linda J.; Androulakis, Ioannis P. Energy & Fuels, Vol. 26, Issue 2 https://doi.org/10.1021/ef2019512	journal	January 2012
NOx and soot emissions trends for RME, SME and PME fuels using engine and spray experiments in combination with simulations Johansson, Monica; Yang, Junfeng; Ochoterena, Raúl Fuel, Vol. 106 https://doi.org/10.1016/j.fuel.2012.11.078	journal	April 2013
Autoignition of binary fuel blends of n-heptane and C7 esters in a motored engine Zhang, Yu; Boehman, André L. Combustion and Flame, Vol. 159, Issue 4 https://doi.org/10.1016/j.combustflame.2011.11.019	journal	April 2012
Experimental study of the autoignition of C8H16O2 ethyl and methyl esters in a motored engine Zhang, Yu; Boehman, André L. Combustion and Flame, Vol. 157, Issue 3 https://doi.org/10.1016/j.combustflame.2009.09.003	journal	March 2010
Premixed ignition behavior of C9 fatty acid esters: A motored engine study Zhang, Yu; Yang, Yi; Boehman, André L. Combustion and Flame, Vol. 156, Issue 6 https://doi.org/10.1016/j.combustflame.2009.01.024	journal	June 2009
Premixed ignition behavior of alternative diesel fuel-relevant compounds in a motored engine experiment Szybist, James P.; Boehman, André L.; Haworth, Daniel C. Combustion and Flame, Vol. 149, Issue 1-2 https://doi.org/10.1016/j.combustflame.2006.12.011	journal	April 2007
Oxidation of small alkyl esters in flames Wang, Yang L.; Lee, Dong J.; Westbrook, Charles K. Combustion and Flame, Vol. 161, Issue 3 https://doi.org/10.1016/j.combustflame.2013.09.013	journal	March 2014
Fuel-specific influences on the composition of reaction intermediates in premixed flames of three C5H10O2 ester isomers Yang, Bin; Westbrook, Charles K.; Cool, Terrill A. Physical Chemistry Chemical Physics, Vol. 13, Issue 15 https://doi.org/10.1039/c0cp02065f	journal	January 2011
Studies of C4 and C10 methyl ester flames Wang, Yang L.; Feng, Qiyao; Egolfopoulos, Fokion N. Combustion and Flame, Vol. 158, Issue 8 https://doi.org/10.1016/j.combustflame.2010.12.032	journal	August 2011
Non-premixed ignition, laminar flame propagation, and mechanism reduction of n-butanol, iso-butanol, and methyl butanoate Liu, Wei; Kelley, Andrew P.; Law, Chung K. Proceedings of the Combustion Institute, Vol. 33, Issue 1 https://doi.org/10.1016/j.proci.2010.05.084	journal	January 2011
Absolute cross-sections for dissociative photoionization of some small esters Wang, Juan; Yang, Bin; Cool, Terrill A. International Journal of Mass Spectrometry, Vol. 292, Issue 1-3 https://doi.org/10.1016/j.ijms.2010.02.010	journal	May 2010
A detailed chemical kinetic reaction mechanism for oxidation of four small alkyl esters in laminar premixed flames Westbrook, C. K.; Pitz, W. J.; Westmoreland, P. R. Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.06.106	journal	January 2009
Methyl butanoate inhibition of n-heptane diffusion flames through an evaluation of transport and chemical kinetics Dooley, Stephen; Uddi, Mruthunjaya; Won, Sang Hee Combustion and Flame, Vol. 159, Issue 4 https://doi.org/10.1016/j.combustflame.2011.09.016	journal	April 2012
Sub-millimeter sized methyl butanoate droplet combustion: Microgravity experiments and detailed numerical modeling Farouk, T. I.; Liu, Y. C.; Savas, A. J. Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.07.074	journal	January 2013
Soot formation in flames of model biodiesel fuels Feng, Qiyao; Jalali, Aydin; Fincham, Adam M. Combustion and Flame, Vol. 159, Issue 5 https://doi.org/10.1016/j.combustflame.2012.01.003	journal	May 2012
Physical and chemical comparison of soot in hydrocarbon and biodiesel fuel diffusion flames: A study of model and commercial fuels Matti Maricq, M. Combustion and Flame, Vol. 158, Issue 1 https://doi.org/10.1016/j.combustflame.2010.07.022	journal	January 2011
Enthalpies of Formation, Bond Dissociation Energies and Reaction Paths for the Decomposition of Model Biofuels: Ethyl Propanoate and Methyl Butanoate ^† El-Nahas, Ahmed M.; Navarro, Maria V.; Simmie, John M. The Journal of Physical Chemistry A, Vol. 111, Issue 19 https://doi.org/10.1021/jp067413s	journal	May 2007
Thermal Decomposition of Methyl Butanoate: Ab Initio Study of a Biodiesel Fuel Surrogate Huynh, Lam K.; Violi, Angela The Journal of Organic Chemistry, Vol. 73, Issue 1 https://doi.org/10.1021/jo701824n	journal	January 2008
Thermochemistry of CO, (CO)O, and (CO)C bond breaking in fatty acid methyl esters Osmont, Antoine; Yahyaoui, Mohammed; Catoire, Laurent Combustion and Flame, Vol. 155, Issue 1-2 https://doi.org/10.1016/j.combustflame.2008.06.007	journal	October 2008
Exploring the oxidative decompositions of methyl esters: Methyl butanoate and methyl pentanoate as model compounds for biodiesel Hayes, C. J.; Burgess, D. R. Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.05.075	journal	January 2009
Theoretical and Kinetic Study of the Hydrogen Atom Abstraction Reactions of Esters with HȮ ₂ Radicals Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J. The Journal of Physical Chemistry A, Vol. 117, Issue 51 https://doi.org/10.1021/jp409133x	journal	December 2013
Two-line thermometry and H2O measurement for reactive mixtures in rapid compression machine near 7.6μm Das, Apurba Kumar; Uddi, Mruthunjaya; Sung, Chih-Jen Combustion and Flame, Vol. 159, Issue 12 https://doi.org/10.1016/j.combustflame.2012.06.020	journal	December 2012
A Rapid Compression Machine for Chemical Kinetics Studies at Elevated Pressures and Temperatures Mittal, Gaurav; Sung*, Chih-Jen Combustion Science and Technology, Vol. 179, Issue 3 https://doi.org/10.1080/00102200600671898	journal	March 2007
Autoignition of n-decane under elevated pressure and low-to-intermediate temperature conditions Kumar, Kamal; Mittal, Gaurav; Sung, Chih-Jen Combustion and Flame, Vol. 156, Issue 6 https://doi.org/10.1016/j.combustflame.2009.01.009	journal	June 2009
Detailed chemical kinetic mechanisms for combustion of oxygenated fuels Fisher, E. M.; Pitz, W. J.; Curran, H. J. Proceedings of the Combustion Institute, Vol. 28, Issue 2 https://doi.org/10.1016/S0082-0784(00)80555-X	journal	January 2000
A wide-ranging kinetic modeling study of methyl butanoate combustion Gaïl, S.; Thomson, M. J.; Sarathy, S. M. Proceedings of the Combustion Institute, Vol. 31, Issue 1 https://doi.org/10.1016/j.proci.2006.08.051	journal	January 2007
A kinetic model for methyl decanoate combustion Diévart, Pascal; Won, Sang Hee; Dooley, Stephen Combustion and Flame, Vol. 159, Issue 5 https://doi.org/10.1016/j.combustflame.2012.01.002	journal	May 2012
Speciation studies of methyl butanoate ignition Walton, Stephen M.; Karwat, Darshan M.; Teini, Paul D. Fuel, Vol. 90, Issue 5 https://doi.org/10.1016/j.fuel.2011.01.028	journal	May 2011
Study of the sensitivity of coupled reaction systems to uncertainties in rate coefficients. I Theory Cukier, R. I.; Fortuin, C. M.; Shuler, K. E. The Journal of Chemical Physics, Vol. 59, Issue 8 https://doi.org/10.1063/1.1680571	journal	October 1973
Study of the sensitivity of coupled reaction systems to uncertainties in rate coefficients. II Applications Schaibly, John H.; Shuler, Kurt E. The Journal of Chemical Physics, Vol. 59, Issue 8 https://doi.org/10.1063/1.1680572	journal	October 1973
Global sensitivity analysis—a computational implementation of the Fourier Amplitude Sensitivity Test (FAST) McRae, Gregory J.; Tilden, James W.; Seinfeld, John H. Computers & Chemical Engineering, Vol. 6, Issue 1 https://doi.org/10.1016/0098-1354(82)80003-3	journal	January 1982
A Quantitative Model-Independent Method for Global Sensitivity Analysis of Model Output Saltelli, A.; Tarantola, S.; Chan, K. P. -S. Technometrics, Vol. 41, Issue 1 https://doi.org/10.1080/00401706.1999.10485594	journal	February 1999
Evaluated Kinetic Data for Combustion Modeling: Supplement II Baulch, D. L.; Bowman, C. T.; Cobos, C. J. Journal of Physical and Chemical Reference Data, Vol. 34, Issue 3 https://doi.org/10.1063/1.1748524	journal	September 2005
Rate Constants for OH with Selected Large Alkanes: Shock-Tube Measurements and an Improved Group Scheme Sivaramakrishnan, R.; Michael, J. V. The Journal of Physical Chemistry A, Vol. 113, Issue 17 https://doi.org/10.1021/jp810987u	journal	April 2009
Rate constants for the H abstraction from alkanes (R–H) by R′O2 radicals: A systematic study on the impact of R and R′ Carstensen, Hans-Heinrich; Dean, Anthony M.; Deutschmann, Olaf Proceedings of the Combustion Institute, Vol. 31, Issue 1 https://doi.org/10.1016/j.proci.2006.08.091	journal	January 2007
Experimental and Modeling Study of Methyl Cyclohexane Pyrolysis and Oxidation Orme, J. P.; Curran, H. J.; Simmie, J. M. The Journal of Physical Chemistry A, Vol. 110, Issue 1 https://doi.org/10.1021/jp0543678	journal	January 2006
Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate Herbinet, Olivier; Pitz, William J.; Westbrook, Charles K. Combustion and Flame, Vol. 154, Issue 3 https://doi.org/10.1016/j.combustflame.2008.03.003	journal	August 2008

Cited By (1)

Benchmarking dual-level MS-Tor and DLPNO-CCSD(T) methods for H-abstraction from methyl pentanoate by an OH radical Shang, Yanlei; Ning, Hongbo; Shi, Jinchun Physical Chemistry Chemical Physics, Vol. 21, Issue 37 https://doi.org/10.1039/c9cp03832a	journal	January 2019

Similar Records

Autoignition measurements and a validated kinetic model for the biodiesel surrogate, methyl butanoate

Journal Article · Tue Apr 15 00:00:00 EDT 2008 · Combustion and Flame · OSTI ID:1369808

Dooley, S; Curran, H J; Simmie, J M

Autoignition study of iso-cetane/tetralin blends at low temperature

Journal Article · Tue Mar 02 00:00:00 EST 2021 · Combustion and Flame · OSTI ID:1369808

Wang, Mengyuan; Kukkadapu, Goutham; Fang, Ruozhou; +2 more

An experimental investigation of flame and autoignition behavior of propane

Journal Article · Fri Dec 18 00:00:00 EST 2020 · Combustion and Flame · OSTI ID:1369808

Burnett, Miles A.; Wooldridge, Margaret S.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Methyl butanoate
Autoignition
Rapid compression machine
Bio-diesel
Surrogate fuel

Title: Autoignition of methyl butanoate under engine relevant conditions

Citation Formats

References (65)

Cited By (1)

Similar Records

Related Subjects