Experimental and Kinetic Modeling Study of 3-Methyl-2-butenol (Prenol) Oxidation

Lokachari, Nitin; Wagnon, Scott W.; Kukkadapu, Goutham; Pitz, William J.; Curran, Henry J.

doi:10.1021/acs.energyfuels.1c01530

Title: Experimental and Kinetic Modeling Study of 3-Methyl-2-butenol (Prenol) Oxidation

Journal Article · 19 August 2021 · Energy and Fuels

DOI: https://doi.org/10.1021/acs.energyfuels.1c01530 · OSTI ID:1825363

Lokachari, Nitin ^[1];

^[2]; Kukkadapu, Goutham ^[2];

^[2];

^[1]

National Univ. of Ireland, Galway (Ireland). Ryan Inst., MaREI
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Longer chain alcohols with 4–5 carbon atoms are attractive alternative fuels as they can be derived from biological sources and since their combustion leads to lower exhaust gas levels of NO_x and soot compared to commercial fossil fuels. The auto-ignition behavior of fuels that contain both a hydroxyl group and a C=C double bond in their molecular structure is not well established in the literature. Understanding the influence of these functional groups on the ignition behavior of fuels is critical in the development of tailor-made fuels for advanced combustion engines. In this study, ignition delay times of an unsaturated alcohol, 3-methyl-2-butenol (prenol), are measured using a high-pressure shock tube and a rapid compression machine at pressures of 15 and 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 in “air” in the temperature range 600–1400 K. Furthermore, a detailed kinetic model is developed and validated using the new experimental data in this study. In addition, speciation data in a jet-stirred reactor, ignition delay times, and laminar burning velocities available in the literature were also used to validate the new kinetic model. Fuel flux and sensitivity analyses are performed using this new model to determine the important fuel consumption pathways and critical reactions that affect the reactivity of prenol.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1825363

Report Number(s):: LLNL-JRNL--825434; 1039554

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 17 Vol. 35; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (43)

Capturing pressure-dependence in automated mechanism generation: Reactions through cycloalkyl intermediates Matheu, David M.; Green, William H.; Grenda, Jeffrey M. International Journal of Chemical Kinetics, Vol. 35, Issue 3 https://doi.org/10.1002/kin.10106	journal	January 2003
THERM: Thermodynamic property estimation for gas phase radicals and molecules Ritter, Edward R.; Bozzelli, Joseph W. International Journal of Chemical Kinetics, Vol. 23, Issue 9 https://doi.org/10.1002/kin.550230903	journal	September 1991
Rapid Compression Machines: Heat Transfer and Suppression of Corner Vortex Lee, Daeyup; Hochgreb, Simone Combustion and Flame, Vol. 114, Issue 3-4 https://doi.org/10.1016/S0010-2180(97)00327-1	journal	August 1998
Gas-phase oxidation of butene-2: The role of acetaldehyde in the reaction Ray, D. J. M.; Ruiz Diaz, R.; Waddington, D. J. Symposium (International) on Combustion, Vol. 14, Issue 1 https://doi.org/10.1016/S0082-0784(73)80026-8	journal	January 1973
Ethanol?diesel fuel blends ?? a review Hansen, A. Bioresource Technology, Vol. 96, Issue 3 https://doi.org/10.1016/j.biortech.2004.04.007	journal	February 2005
Genesys: Kinetic model construction using chemo-informatics Vandewiele, Nick M.; Van Geem, Kevin M.; Reyniers, Marie-Françoise Chemical Engineering Journal, Vol. 207-208 https://doi.org/10.1016/j.cej.2012.07.014	journal	October 2012
A rapid compression machine study of the oxidation of propane in the negative temperature coefficient regime Gallagher, S. M.; Curran, H. J.; Metcalfe, W. K. Combustion and Flame, Vol. 153, Issue 1-2 https://doi.org/10.1016/j.combustflame.2007.09.004	journal	April 2008
An experimental and modeling study of shock tube and rapid compression machine ignition of n-butylbenzene/air mixtures Nakamura, Hisashi; Darcy, Daniel; Mehl, Marco Combustion and Flame, Vol. 161, Issue 1 https://doi.org/10.1016/j.combustflame.2013.08.002	journal	January 2014
Autoignition of ethanol in a rapid compression machine Mittal, Gaurav; Burke, Sinéad M.; Davies, Varun A. Combustion and Flame, Vol. 161, Issue 5 https://doi.org/10.1016/j.combustflame.2013.11.005	journal	May 2014
Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol De Bruycker, Ruben; Herbinet, Olivier; Carstensen, Hans-Heinrich Combustion and Flame, Vol. 171 https://doi.org/10.1016/j.combustflame.2016.06.009	journal	September 2016
Autoignition behavior of gasoline/ethanol blends at engine-relevant conditions Cheng, Song; Kang, Dongil; Fridlyand, Aleksandr Combustion and Flame, Vol. 216 https://doi.org/10.1016/j.combustflame.2020.02.032	journal	June 2020
An experimental and kinetic modeling study of cyclopentane and dimethyl ether blends Lokachari, Nitin; Wagnon, Scott W.; Kukkadapu, Goutham Combustion and Flame, Vol. 225 https://doi.org/10.1016/j.combustflame.2020.10.017	journal	March 2021
Investigation of biofuels from microorganism metabolism for use as anti-knock additives Mack, J. Hunter; Rapp, Vi H.; Broeckelmann, Malte Fuel, Vol. 117 https://doi.org/10.1016/j.fuel.2013.10.024	journal	January 2014
Discovery of novel octane hyperboosting phenomenon in prenol biofuel/gasoline blends Monroe, Eric; Gladden, John; Albrecht, Karl O. Fuel, Vol. 239 https://doi.org/10.1016/j.fuel.2018.11.046	journal	March 2019
Co-optima fuels combustion: A comprehensive experimental investigation of prenol isomers Ninnemann, Erik; Kim, Gihun; Laich, Andrew Fuel, Vol. 254 https://doi.org/10.1016/j.fuel.2019.115630	journal	October 2019
Progress and recent trends in biofuels Demirbas, A. Progress in Energy and Combustion Science, Vol. 33, Issue 1 https://doi.org/10.1016/j.pecs.2006.06.001	journal	February 2007
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
Knocking combustion in spark-ignition engines Wang, Zhi; Liu, Hui; Reitz, Rolf D. Progress in Energy and Combustion Science, Vol. 61 https://doi.org/10.1016/j.pecs.2017.03.004	journal	July 2017
Theoretical rate coefficients for allyl+HO2 and allyloxy decomposition Goldsmith, C. Franklin; Klippenstein, Stephen J.; Green, William H. Proceedings of the Combustion Institute, Vol. 33, Issue 1 https://doi.org/10.1016/j.proci.2010.05.054	journal	January 2011
Pressure-dependent branching in the reaction of 1 CH 2 with C 2 H 4 and other reactions on the C 3 H 6 potential energy surface Ye, Lili; Georgievskii, Yuri; Klippenstein, Stephen J. Proceedings of the Combustion Institute, Vol. 35, Issue 1 https://doi.org/10.1016/j.proci.2014.05.097	journal	January 2015
Faster solvers for large kinetic mechanisms using adaptive preconditioners McNenly, Matthew J.; Whitesides, Russell A.; Flowers, Daniel L. Proceedings of the Combustion Institute, Vol. 35, Issue 1 https://doi.org/10.1016/j.proci.2014.05.113	journal	January 2015
The oxidation of 2-butene: A high pressure ignition delay, kinetic modeling study and reactivity comparison with isobutene and 1-butene Li, Yang; Zhou, Chong-Wen; Somers, Kieran P. Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.05.052	journal	January 2017
A Comprehensive Experimental and Simulation Study of Ignition Delay Time Characteristics of Single Fuel C ₁ –C ₂ Hydrocarbons over a Wide Range of Temperatures, Pressures, Equivalence Ratios, and Dilutions Baigmohammadi, Mohammadreza; Patel, Vaibhav; Martinez, Sergio Energy & Fuels, Vol. 34, Issue 3 https://doi.org/10.1021/acs.energyfuels.9b04139	journal	February 2020
Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by ³ O ₂ ; Implications for Combustion Modeling and Simulation Zhou, Chong-Wen; Simmie, John M.; Somers, Kieran P. The Journal of Physical Chemistry A, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpca.6b12144	journal	February 2017
Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ ₄ H ₇ Potential Energy Surface Li, Yang; Klippenstein, Stephen J.; Zhou, Chong-Wen The Journal of Physical Chemistry A, Vol. 121, Issue 40 https://doi.org/10.1021/acs.jpca.7b05996	journal	September 2017
Extensive Theoretical Study of the Thermochemical Properties of Unsaturated Hydrocarbons and Allylic and Super-Allylic Radicals: The Development and Optimization of Group Additivity Values Li, Yang; Curran, Henry J. The Journal of Physical Chemistry A, Vol. 122, Issue 20 https://doi.org/10.1021/acs.jpca.8b02912	journal	May 2018
Thermochemical Property, Pathway and Kinetic Analysis on the Reactions of Allylic Isobutenyl Radical with O ₂ : an Elementary Reaction Mechanism for Isobutene Oxidation Chen, Chiung-Ju; Bozzelli, Joseph W. The Journal of Physical Chemistry A, Vol. 104, Issue 43 https://doi.org/10.1021/jp001060u	journal	November 2000
Experimental and Theoretical Studies of Rate Coefficients for the Reaction O( ³ P) + C ₂ H ₅ OH at High Temperatures Wu, Chih-Wei; Lee, Yuan-Pern; Xu, Shucheng The Journal of Physical Chemistry A, Vol. 111, Issue 29 https://doi.org/10.1021/jp068977z	journal	May 2007
Thermochemical and Kinetic Analysis on the Reactions of O ₂ with Products from OH Addition to Isobutene, 2-Hydroxy-1,1-dimethylethyl, and 2-Hydroxy-2-methylpropyl Radicals: HO ₂ Formation from Oxidation of Neopentane, Part II Sun, Hongyan; Bozzelli, Joseph W.; Law, Chung K. The Journal of Physical Chemistry A, Vol. 111, Issue 23 https://doi.org/10.1021/jp070072d	journal	June 2007
Pressure-Dependent OH Yields in Alkene + HO ₂ Reactions: A Theoretical Study Zádor, Judit; Klippenstein, Stephen J.; Miller, James A. The Journal of Physical Chemistry A, Vol. 115, Issue 36 https://doi.org/10.1021/jp2059276	journal	September 2011
Ethanol Oxidation: Kinetics of the α-Hydroxyethyl Radical + O ₂ Reaction da Silva, Gabriel; Bozzelli, Joseph W.; Liang, Long The Journal of Physical Chemistry A, Vol. 113, Issue 31 https://doi.org/10.1021/jp903210a	journal	August 2009
Relevance of the Channel Leading to Formaldehyde + Triplet Ethylidene in the O( ³ P) + Propene Reaction under Combustion Conditions Cavallotti, Carlo; Leonori, Francesca; Balucani, Nadia The Journal of Physical Chemistry Letters, Vol. 5, Issue 23 https://doi.org/10.1021/jz502236y	journal	November 2014
Non-fermentative pathways for synthesis of branched-chain higher alcohols as biofuels Atsumi, Shota; Hanai, Taizo; Liao, James C. Nature, Vol. 451, Issue 7174, p. 86-89 https://doi.org/10.1038/nature06450	journal	January 2008
Metabolic engineering for the high-yield production of isoprenoid-based C5 alcohols in E. coli George, Kevin W.; Thompson, Mitchell G.; Kang, Aram Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep11128	journal	June 2015
Critical Evaluation of Thermochemical Properties of C ₁ –C ₄ Species: Updated Group-Contributions to Estimate Thermochemical Properties Burke, S. M.; Simmie, J. M.; Curran, H. J. Journal of Physical and Chemical Reference Data, Vol. 44, Issue 1 https://doi.org/10.1063/1.4902535	journal	March 2015
Chemical Kinetic Data Base for Combustion Chemistry. Part I. Methane and Related Compounds Tsang, W.; Hampson, R. F. Journal of Physical and Chemical Reference Data, Vol. 15, Issue 3 https://doi.org/10.1063/1.555759	journal	July 1986
Chemical Kinetic Data Base for Combustion Chemistry Part V. Propene Tsang, Wing Journal of Physical and Chemical Reference Data, Vol. 20, Issue 2 https://doi.org/10.1063/1.555880	journal	March 1991
A facility for gas- and condensed-phase measurements behind shock waves Petersen, Eric L.; Rickard, Matthew J. A.; Crofton, Mark W. Measurement Science and Technology, Vol. 16, Issue 9 https://doi.org/10.1088/0957-0233/16/9/003	journal	July 2005
Synthetic Pathway for Production of Five-Carbon Alcohols from Isopentenyl Diphosphate Chou, Howard H.; Keasling, Jay D. Applied and Environmental Microbiology, Vol. 78, Issue 22 https://doi.org/10.1128/AEM.01175-12	journal	August 2012
Metabolic engineering of Escherichia coli for high-specificity production of isoprenol and prenol as next generation of biofuels Zheng, Yanning; Liu, Qiang; Li, Lingling Biotechnology for Biofuels, Vol. 6, Article No. 57 https://doi.org/10.1186/1754-6834-6-57	journal	January 2013
Co-Optimization of Fuels & Engines: Fuel Blendstocks with the Potential to Optimize Future Gasoline Engine Performance; Identification of Five Chemical Families for Detailed Evaluation Farrell, John T.; Holladay, John; Wagner, Robert https://doi.org/10.2172/1434413	report	April 2018
Top Ten Blendstocks For Turbocharged Gasoline Engines: Bioblendstocks With Potential to Deliver the for Highest Engine Efficiency Gaspar, Daniel; West, Brian https://doi.org/10.2172/1567705	report	September 2019
Fuel Anti-Knock Quality - Part I. Engine Studies Kalghatgi, G. T. SAE International Fall Fuels & Lubricants Meeting & Exhibition, SAE Technical Paper Series https://doi.org/10.4271/2001-01-3584	conference	September 2001

Similar Records

Co-optima fuels combustion: A comprehensive experimental investigation of prenol isomers

Journal Article · 2019 · Fuel · OSTI ID:1575864

Ninnemann, Erik; Kim, Gihun; Laich, Andrew; +8 more

A comprehensive iso-octane combustion model with improved thermochemistry and chemical kinetics

Journal Article · 2017 · Combustion and Flame · OSTI ID:1361588

Atef, Nour; Kukkadapu, Goutham; Mohamed, Samah Y.; +14 more

Investigating the kinetic effect of prenol on iso-octane auto-ignition by means of an experimental and modeling study

Journal Article · 2022 · Fuel · OSTI ID:2007281

Mergulhão, Carolina S.; Fenard, Yann; Kukkadapu, Goutham; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Fossil fuels
Kinetic modeling
Mixtures
Organic reactions
Reactivity

Title: Experimental and Kinetic Modeling Study of 3-Methyl-2-butenol (Prenol) Oxidation

Citation Formats

References (43)

Similar Records

Related Subjects