An experimental and kinetic modeling study of the oxidation of hexane isomers: Developing consistent reaction rate rules for alkanes

Zhang, Kuiwen; Banyon, Colin; Burke, Ultan; Kukkadapu, Goutham; Wagnon, Scott W.; Mehl, Marco; Curran, Henry J.; Westbrook, Charles K.; Pitz, William J.

doi:10.1016/j.combustflame.2019.04.011

Title: An experimental and kinetic modeling study of the oxidation of hexane isomers: Developing consistent reaction rate rules for alkanes

Full Record
Other Related Research

Abstract

Alkanes are key components in gasoline, jet and diesel fuels and considerably influence the combustion behavior of these fuels because of their wide range of reactivity. An improved understanding of their combustion behavior and the development of chemical kinetic models that can accurately simulate their combustion behavior are important for the development of next-generation internal-combustion and gas-turbine engines. The current work provides here improved insight into oxidation mechanisms of a representative family of hydrocarbon fuels, specifically the hexane isomers: n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane and 2,3-dimethylbutane. These isomers provide carbon “skeletons” ranging from straight-chained to highly-branched and provide a framework for the subsequent development of kinetic mechanisms for larger alkanes. New ignition delay times for the four branched hexane isomers were measured in a high-pressure shock tube and in a rapid compression machine, both at stoichiometric conditions (φ = 1), p = 15 bar and X_O2 = 21% over temperatures from 600 to1300 K. These data were combined with previously published measurements under the same conditions for the remaining n-hexane isomer to provide a complete body of experimental data for kinetic modeling analysis. In addition, very recent experimental measurements of individual intermediate chemical species concentrations from all five hexane isomers inmore »« less

Authors:

Zhang, Kuiwen ^[1]; Banyon, Colin ^[2]; Burke, Ultan ^[2]; Kukkadapu, Goutham ^[1]; Wagnon, Scott W. ^[1]; Mehl, Marco ^[3]; Curran, Henry J. ^[2]; Westbrook, Charles K. ^[1]; Pitz, William J. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
National Univ. of Ireland Galway (Ireland). Combustion Chemistry Centre. School of Chemistry. Ryan Inst.
Polytechnic Univ. of Milan (Italy)

Publication Date:: Thu May 09 00:00:00 EDT 2019

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); National Univ. of Ireland Galway (Ireland)

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); European Union (EU); Science Foundation Ireland

OSTI Identifier:: 1524732

Alternate Identifier(s):: OSTI ID: 1511757

Report Number(s):: LLNL-JRNL-764033
Journal ID: ISSN 0010-2180; 954052

Grant/Contract Number:: AC52-07NA27344; 607214; 15/IA/3177

Resource Type:: Accepted Manuscript

Journal Name:: Combustion and Flame

Additional Journal Information:: Journal Volume: 206; Journal ID: ISSN 0010-2180

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hexane isomers; detailed kinetic model; ignition delay time; reaction rate rules; rapid compression machine

Citation Formats


                    Zhang, Kuiwen, Banyon, Colin, Burke, Ultan, Kukkadapu, Goutham, Wagnon, Scott W., Mehl, Marco, Curran, Henry J., Westbrook, Charles K., and Pitz, William J. An experimental and kinetic modeling study of the oxidation of hexane isomers: Developing consistent reaction rate rules for alkanes.  United States: N. p., 2019. 
Web.  doi:10.1016/j.combustflame.2019.04.011.

Copy to clipboard


                    Zhang, Kuiwen, Banyon, Colin, Burke, Ultan, Kukkadapu, Goutham, Wagnon, Scott W., Mehl, Marco, Curran, Henry J., Westbrook, Charles K., & Pitz, William J. An experimental and kinetic modeling study of the oxidation of hexane isomers: Developing consistent reaction rate rules for alkanes.  United States.  https://doi.org/10.1016/j.combustflame.2019.04.011

Copy to clipboard


                    Zhang, Kuiwen, Banyon, Colin, Burke, Ultan, Kukkadapu, Goutham, Wagnon, Scott W., Mehl, Marco, Curran, Henry J., Westbrook, Charles K., and Pitz, William J. Thu .  
"An experimental and kinetic modeling study of the oxidation of hexane isomers: Developing consistent reaction rate rules for alkanes".  United States.  https://doi.org/10.1016/j.combustflame.2019.04.011.  https://www.osti.gov/servlets/purl/1524732.

Copy to clipboard


                    
@article{osti_1524732,

  title        = {An experimental and kinetic modeling study of the oxidation of hexane isomers: Developing consistent reaction rate rules for alkanes},

  author       = {Zhang, Kuiwen and Banyon, Colin and Burke, Ultan and Kukkadapu, Goutham and Wagnon, Scott W. and Mehl, Marco and Curran, Henry J. and Westbrook, Charles K. and Pitz, William J.},

  abstractNote = {Alkanes are key components in gasoline, jet and diesel fuels and considerably influence the combustion behavior of these fuels because of their wide range of reactivity. An improved understanding of their combustion behavior and the development of chemical kinetic models that can accurately simulate their combustion behavior are important for the development of next-generation internal-combustion and gas-turbine engines. The current work provides here improved insight into oxidation mechanisms of a representative family of hydrocarbon fuels, specifically the hexane isomers: n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane and 2,3-dimethylbutane. These isomers provide carbon “skeletons” ranging from straight-chained to highly-branched and provide a framework for the subsequent development of kinetic mechanisms for larger alkanes. New ignition delay times for the four branched hexane isomers were measured in a high-pressure shock tube and in a rapid compression machine, both at stoichiometric conditions (φ = 1), p = 15 bar and XO2 = 21% over temperatures from 600 to1300 K. These data were combined with previously published measurements under the same conditions for the remaining n-hexane isomer to provide a complete body of experimental data for kinetic modeling analysis. In addition, very recent experimental measurements of individual intermediate chemical species concentrations from all five hexane isomers in a jet-stirred reactor are also included and provide another family of data for further assessment of hexane isomer reactivity. Different reactivities were observed for each hexane isomer in each experimental facility, resulting from differences in their molecular structures. Consistent reaction rate rules have been applied to develop a combined detailed chemical kinetic model for all five hexane isomers. Kinetic model validation studies are reported to show that the current model reproduces well the ignition delay times of all five alkane isomers, as well as their variations in reactivity over a wide range of temperatures and other operating conditions. Equally important, these results show that it is not necessary to have a separate, different kinetic model for each isomer of a family of alkane fuels and that a single, coherent, integrated set of reaction rate classes and rules is sufficient to accurately describe combustion rates of combustion of straight-chain n-alkanes and branched-chain alkane fuels. This suggests strongly that a single set of reaction classes and rate rules should be sufficient to describe combustion kinetics of alkane fuels of any size and degree of branching.},

  doi          = {10.1016/j.combustflame.2019.04.011},

  journal      = {Combustion and Flame},

  number       = ,

  volume       = 206,

  place        = {United States},

  year         = {Thu May 09 00:00:00 EDT 2019},

  month        = {Thu May 09 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.combustflame.2019.04.011

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 34 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

A comprehensive combustion chemistry study of 2,5-dimethylhexane

Journal Article Sarathy, S. Mani ; Javed, Tamour ; Karsenty, Florent ; ... - Combustion and Flame

Iso-paraffinic molecular structures larger than seven carbon atoms in chain length are commonly found in conventional petroleum, Fischer–Tropsch (FT), and other alternative hydrocarbon fuels, but little research has been done on their combustion behavior. Recent studies have focused on either mono-methylated alkanes and/or highly branched compounds (e.g., 2,2,4-trimethylpentane). In order to better understand the combustion characteristics of real fuels, this study presents new experimental data for the oxidation of 2,5-dimethylhexane under a wide variety of temperature, pressure, and equivalence ratio conditions. This new dataset includes jet stirred reactor speciation, shock tube ignition delay, and rapid compression machine ignition delay, whichmore »« less
https://doi.org/10.1016/j.combustflame.2013.12.010

Full Text Available
An experimental and modeling study of the autoignition of 3-methylheptane

Journal Article Wang, Weijing ; Li, Zhenhua ; Oehlschlaeger, Matthew A. ; ... - Proceedings of the Combustion Institute

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negativemore »« less
Cited by 29
https://doi.org/10.1016/j.proci.2012.06.001

Full Text Available
A 4 U laser heterodyne radiometer for methane (CH ₄ ) and carbon dioxide (CO ₂ ) measurements from an occultation-viewing CubeSat

Journal Article Wilson, Emily L. ; DiGregorio, A. J. ; Riot, Vincent J. ; ... - Measurement Science and Technology

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negativemore »« less
Cited by 15
https://doi.org/10.1088/1361-6501/aa5440

Full Text Available
The protolysis of hexanes over a USHY zeolite

Journal Article Bassir, M ; Wojciechowski, B W - Journal of Catalysis

Detailed information gathered on the cracking of five hexane isomers has revealed major differences in the mechanisms of cracking in the individual isomers and suggests the possibility that synergistic effects play a role in the cracking of mixtures of hydrocarbons. The authors find that both n-hexane and 2,2-dimethylbutane do not crack via the chain process to any significant extent, presumably due to the absence of tertiary hydrogens in both molecules. On the other hand, 2,3-dimethylbutane, with two tertiary hydrogens, cracks readily via a chain process. The two monomethyl pentanes illustrate the fact that tertiary hydrogens are not all the samemore »« less
https://doi.org/10.1006/jcat.1994.1317
High-temperature reaction rates for five- and six-carbon saturated alkanes

Technical Report Tamura, T M

High-temperature reaction rates for five- and six-carbon saturated alkanes were estimated for use in combustion modelling. The isomers investigated included n-hexane, 2-methylbutane, 2-methylpentane, 3-methylpentane, 2,2-dimethylpropane, 2,2-dimethylbutane, and 2,3-dimethylbutane. A total of 43 new species and 446 reactions were added to the existing data file (CDAT). 19 refs.

Similar Records