Effect of the ..beta..-Hydroxy Group on Ester Reactivity: Combustion Kinetics of Methyl Hexanoate and Methyl 3-Hydroxyhexanoate

Mohamed, Samah Y.; Naser, Nimal; Fioroni, Gina; Luecke, Jon; Kim, Yeonjoon; St. John, Peter C.; McCormick, Robert; Kim, Seonah

doi:10.1016/j.combustflame.2023.113071

Effect of the ..beta..-Hydroxy Group on Ester Reactivity: Combustion Kinetics of Methyl Hexanoate and Methyl 3-Hydroxyhexanoate

Journal Article · Fri Sep 29 04:00:00 EDT 2023 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2023.113071· OSTI ID:2204394

Mohamed, Samah Y.; ; ; ; Kim, Yeonjoon; ; ;

One of the major biofuels used today is biodiesel, composed of fatty acid methyl esters. The fats and oils feedstocks used to make biodiesel are in relatively short supply. To meet increasing global demand, engineered microorganisms have been developed to catalyze conversion of sugar to fatty acid esters that contain unique ..beta..-hydroxy-esters. This study investigated the effect of a hydroxyl group on the combustion characteristics of methyl esters by comparing the chemical behavior of methyl hexanoate (MHx) and methyl 3-hydroxyhexanoate (M3OHHx) - used as surrogates for diesel-boiling-range esters with longer fatty acid chains. The oxidation of these esters was studied experimentally in a flow reactor at 0.84 and 10 bar, 600 to 1,100 K, and stoichiometric conditions; and in a constant volume combustion chamber at 5 and 10 bar, 600 to 900 K, and equivalence ratios of 0.3 and 0.6. MHx was more reactive in the constant volume chamber at temperatures below 800 K at 10 bar and equivalence ratio of 0.6. MHx also exhibited a higher indicated cetane number (16.4) than M3OHHx (8.1). We investigated this reactivity trend using an updated MHx kinetic model and M3OHHx model developed as part of this work. The kinetic models predicted that radicals formed from MHx were consumed by low-temperature chemistry reactions, whereas the M3OHHx reactivity was significantly governed by the ..beta..-radical (on the same carbon as the OH group) chemistry which mainly terminated via the less reactive chain propagation pathway to methyl-3-oxohexanoate + HO2. This study extends our understanding of structural effects on ester reactivity, which will allow for accurate surrogate formulation and performance simulations.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: ExxonMobil Corporation

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 2204394

Report Number(s):: NREL/JA-5400-81703; MainId:82476; UUID:87543576-9bba-4483-b08b-48be7608f38d; MainAdminID:70980

Journal Information:: Combustion and Flame, Journal Name: Combustion and Flame Journal Issue: Part 2 Vol. 258

Country of Publication:: United States

Language:: English

References (48)

Kinetics of propyl acetate oxidation: Experiments in a jet-stirred reactor, ab initio calculations, and rate constant determination Dayma, Guillaume; Thion, Sébastien; Lailliau, Maxence Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.05.178	journal	January 2019
Reaction Mechanism Generator v3.0: Advances in Automatic Mechanism Generation Liu, Mengjie; Grinberg Dana, Alon; Johnson, Matthew S. Journal of Chemical Information and Modeling, Vol. 61, Issue 6 https://doi.org/10.1021/acs.jcim.0c01480	journal	May 2021
The potential of sustainable algal biofuel production using wastewater resources Pittman, Jon K.; Dean, Andrew P.; Osundeko, Olumayowa Bioresource Technology, Vol. 102, Issue 1 https://doi.org/10.1016/j.biortech.2010.06.035	journal	January 2011
Biodiesel production by in situ transesterification of municipal primary and secondary sludges Mondala, Andro; Liang, Kaiwen; Toghiani, Hossein Bioresource Technology, Vol. 100, Issue 3 https://doi.org/10.1016/j.biortech.2008.08.020	journal	February 2009
Comprehensive H2/O2 kinetic model for high-pressure combustion Burke, Michael P.; Chaos, Marcos; Ju, Yiguang International Journal of Chemical Kinetics, Vol. 44, Issue 7 https://doi.org/10.1002/kin.20603	journal	December 2011
Influence of functional groups on low-temperature combustion chemistry of biofuels Rotavera, Brandon; Taatjes, Craig A. Progress in Energy and Combustion Science, Vol. 86 https://doi.org/10.1016/j.pecs.2021.100925	journal	September 2021
High-Pressure Rate Rules for Alkyl + O ₂ Reactions. 2. The Isomerization, Cyclic Ether Formation, and β-Scission Reactions of Hydroperoxy Alkyl Radicals Villano, Stephanie M.; Huynh, Lam K.; Carstensen, Hans-Heinrich The Journal of Physical Chemistry A, Vol. 116, Issue 21 https://doi.org/10.1021/jp3023887	journal	May 2012
Experimental and Kinetic Modeling Study of the Oxidation of Methyl Hexanoate Dayma, Guillaume; Gaïl, Sandro; Dagaut, Philippe Energy & Fuels, Vol. 22, Issue 3 https://doi.org/10.1021/ef700695j	journal	April 2008
Alcohol combustion chemistry Sarathy, S. Mani; Oßwald, Patrick; Hansen, Nils Progress in Energy and Combustion Science, Vol. 44 https://doi.org/10.1016/j.pecs.2014.04.003	journal	October 2014
Modeling of the oxidation of methyl esters—Validation for methyl hexanoate, methyl heptanoate, and methyl decanoate in a jet-stirred reactor Glaude, Pierre Alexandre; Herbinet, Olivier; Bax, Sarah Combustion and Flame, Vol. 157, Issue 11 https://doi.org/10.1016/j.combustflame.2010.03.012	journal	November 2010
Experimental and kinetic modeling study of trans-methyl-3-hexenoate oxidation in JSR and the role of CC double bond Zhang, Kuiwen; Togbé, Casimir; Dayma, Guillaume Combustion and Flame, Vol. 161, Issue 3 https://doi.org/10.1016/j.combustflame.2013.10.022	journal	March 2014
Prediction of organic homolytic bond dissociation enthalpies at near chemical accuracy with sub-second computational cost St. John, Peter C.; Guan, Yanfei; Kim, Yeonjoon Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16201-z	journal	May 2020
Methyl-3-hexenoate combustion chemistry: Experimental study and numerical kinetic simulation Gerasimov, Ilya E.; Knyazkov, Denis A.; Bolshova, Tatyana A. Combustion and Flame, Vol. 222 https://doi.org/10.1016/j.combustflame.2020.08.028	journal	December 2020
Extraction of Lipids from Municipal Wastewater Plant Microorganisms for Production of Biodiesel Dufreche, Stephen; Hernandez, R.; French, T. Journal of the American Oil Chemists' Society, Vol. 84, Issue 2 https://doi.org/10.1007/s11746-006-1022-4	journal	January 2007
Combustion chemistry of alkenes and alkadienes Zhou, Chong-Wen; Farooq, Aamir; Yang, Lijun Progress in Energy and Combustion Science, Vol. 90 https://doi.org/10.1016/j.pecs.2021.100983	journal	May 2022
Detailed chemical kinetic modeling of the effects of CC double bonds on the ignition of biodiesel fuels Westbrook, C. K.; Pitz, W. J.; Sarathy, S. M. Proceedings of the Combustion Institute, Vol. 34, Issue 2 https://doi.org/10.1016/j.proci.2012.05.025	journal	January 2013
High-Pressure Limit Rate Rules for α-H Isomerization of Hydroperoxyalkylperoxy Radicals Mohamed, Samah Y.; Davis, Alexander C.; Al Rashidi, Mariam J. The Journal of Physical Chemistry A, Vol. 122, Issue 14 https://doi.org/10.1021/acs.jpca.7b11955	journal	March 2018
Kinetics of the C–C bond beta scission reactions in alkyl radicals Ratkiewicz, Artur Physical Chemistry Chemical Physics, Vol. 13, Issue 33 https://doi.org/10.1039/c1cp21229j	journal	January 2011
Engineering Escherichia coli for Biodiesel Production Utilizing a Bacterial Fatty Acid Methyltransferase Nawabi, Parwez; Bauer, Stefan; Kyrpides, Nikos Applied and Environmental Microbiology, Vol. 77, Issue 22 https://doi.org/10.1128/AEM.05046-11	journal	September 2011
Experimental and Modeling Study of Methyl trans -3-Hexenoate Autoignition Wagnon, Scott W.; Karwat, Darshan M. A.; Wooldridge, Margaret S. Energy & Fuels, Vol. 28, Issue 11 https://doi.org/10.1021/ef501806s	journal	October 2014
Theoretical Study on Abstraction and Addition Reaction Kinetics for a Medium-Size Unsaturated Methyl Ester: Methyl-3-hexenoate + H/OH Radicals Liu, Bo; Zhou, Zihao; Zhang, Zhenpeng The Journal of Physical Chemistry A, Vol. 126, Issue 50 https://doi.org/10.1021/acs.jpca.2c06249	journal	December 2022
Oxidation and pyrolysis of methyl propyl ether Johnson, Matthew S.; Nimlos, Mark R.; Ninnemann, Erik International Journal of Chemical Kinetics, Vol. 53, Issue 8 https://doi.org/10.1002/kin.21489	journal	May 2021
Biodiesel combustion: Advances in chemical kinetic modeling Lai, Jason Y. W.; Lin, Kuang C.; Violi, Angela Progress in Energy and Combustion Science, Vol. 37, Issue 1 https://doi.org/10.1016/j.pecs.2010.03.001	journal	February 2011
Kinetic barriers, rate constants and branching ratios for unimolecular reactions of methyl octanoate peroxy radicals: A computational study of a mid-sized biodiesel fuel surrogate Tao, Hairong; Lin, Kuang C. Combustion and Flame, Vol. 180 https://doi.org/10.1016/j.combustflame.2017.02.034	journal	June 2017
Microbial production of advanced biofuels Keasling, Jay; Garcia Martin, Hector; Lee, Taek Soon Nature Reviews Microbiology, Vol. 19, Issue 11 https://doi.org/10.1038/s41579-021-00577-w	journal	June 2021
Microbial production of fatty-acid-derived fuels and chemicals from plant biomass Steen, Eric J.; Kang, Yisheng; Bokinsky, Gregory Nature, Vol. 463, Issue 7280, p. 559-562 https://doi.org/10.1038/nature08721	journal	January 2010
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
Polyhydroxyalkanoates as a source of chemicals, polymers, and biofuels Gao, Xue; Chen, Jin-Chun; Wu, Qiong Current Opinion in Biotechnology, Vol. 22, Issue 6 https://doi.org/10.1016/j.copbio.2011.06.005	journal	December 2011
Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms Gao, Connie W.; Allen, Joshua W.; Green, William H. Computer Physics Communications, Vol. 203 https://doi.org/10.1016/j.cpc.2016.02.013	journal	June 2016
An experimental and chemical kinetic modeling study of 1,3-butadiene combustion: Ignition delay time and laminar flame speed measurements Zhou, Chong-Wen; Li, Yang; Burke, Ultan Combustion and Flame, Vol. 197 https://doi.org/10.1016/j.combustflame.2018.08.006	journal	November 2018
Small ester combustion chemistry: Computational kinetics and experimental study of methyl acetate and ethyl acetate Ahmed, Ahfaz; Pitz, William J.; Cavallotti, Carlo Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.06.178	journal	January 2019
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
Decarbonising ships, planes and trucks: An analysis of suitable low-carbon fuels for the maritime, aviation and haulage sectors Gray, Nathan; McDonagh, Shane; O'Shea, Richard Advances in Applied Energy, Vol. 1 https://doi.org/10.1016/j.adapen.2021.100008	journal	February 2021
Key Chemical Kinetic Steps in Reaction Mechanisms for Fuels from Biomass: A Perspective Westbrook, Charles; Heufer, Karl Alexander; Wildenberg, Alina Energy & Fuels, Vol. 35, Issue 19 https://doi.org/10.1021/acs.energyfuels.1c02210	journal	September 2021
Oxidation of C₅ esters: Influence of the position of the ester function Dayma, Guillaume; Thion, Sébastien; Lailliau, Maxence International Journal of Chemical Kinetics, Vol. 53, Issue 10 https://doi.org/10.1002/kin.21519	journal	June 2021
Advances in predictive chemistry enable a multi-scale rational design approach for biofuels with advantaged properties Lockwood, Katherine S.; Ahmed, Sheikh F.; Huq, Nabila A. Sustainable Energy & Fuels, Vol. 6, Issue 23 https://doi.org/10.1039/D2SE00773H	journal	January 2022
An Experimental and Kinetic Modeling Study of Premixed Laminar Flames of Methyl Pentanoate and Methyl Hexanoate Korobeinichev, Oleg P.; Gerasimov, Ilya E.; Knyazkov, Denis A. Zeitschrift für Physikalische Chemie, Vol. 229, Issue 5 https://doi.org/10.1515/zpch-2014-0596	journal	December 2014
Properties of a new gasoline oxygenate blend component: 3-Hydroxybutyrate methyl ester produced from bacterial poly-3-hydroxybutyrate Wang, Shen Yu; Wang, Zhen; Liu, Ming Ming Biomass and Bioenergy, Vol. 34, Issue 8 https://doi.org/10.1016/j.biombioe.2010.03.020	journal	August 2010
Renewable fuels from algae: An answer to debatable land based fuels Singh, Anoop; Nigam, Poonam Singh; Murphy, Jerry D. Bioresource Technology, Vol. 102, Issue 1 https://doi.org/10.1016/j.biortech.2010.06.032	journal	January 2011
Relative Reactivity of Oxygenated Fuels: Alcohols, Aldehydes, Ketones, and Methyl Esters Pelucchi, Matteo; Cavallotti, Carlo; Ranzi, Eliseo Energy & Fuels, Vol. 30, Issue 10 https://doi.org/10.1021/acs.energyfuels.6b01171	journal	September 2016
Probing the low-temperature chemistry of methyl hexanoate: Insights from oxygenate intermediates Rogers, Cory O.; Kaczmarek, Dennis; Kasper, Tina Proceedings of the Combustion Institute, Vol. 38, Issue 1 https://doi.org/10.1016/j.proci.2020.07.056	journal	January 2021
Experimental and numerical investigation of the Advanced Fuel Ignition Delay Analyzer (AFIDA) constant-volume combustion chamber as a research platform for fuel chemical kinetic mechanism validation Luecke, Jon; Rahimi, Mohammad J.; Zigler, Bradley T. Fuel, Vol. 265 https://doi.org/10.1016/j.fuel.2019.116929	journal	April 2020
Isomeric effects on the reactivity of branched alkenes: An experimental and kinetic modeling study of methylbutenes Song, Hwasup; Kang, Dongil; Fioroni, Gina Combustion and Flame, Vol. 254 https://doi.org/10.1016/j.combustflame.2023.112849	journal	August 2023
Calculation of Flame Ionization Detector Relative Response Factors Using the Effective Carbon Number Concept Scanlon, J. T.; Willis, D. E. Journal of Chromatographic Science, Vol. 23, Issue 8 https://doi.org/10.1093/chromsci/23.8.333	journal	August 1985
Kinetics of the C–C Bond Beta Scission Reactions in Alkyl Radical Reaction Class Ratkiewicz, Artur; Truong, Thanh N. The Journal of Physical Chemistry A, Vol. 116, Issue 25 https://doi.org/10.1021/jp3018265	journal	June 2012
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
Production and characterization of biodiesel from trap grease Park, Ji-Yeon; Lee, Jin-Suk; Wang, Zhong-Ming Korean Journal of Chemical Engineering, Vol. 27, Issue 6 https://doi.org/10.1007/s11814-010-0297-1	journal	September 2010
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

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Effect of the ..beta..-Hydroxy Group on Ester Reactivity: Combustion Kinetics of Methyl Hexanoate and Methyl 3-Hydroxyhexanoate

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