Cool flame chemistry of diesel surrogate compounds: n-Decane, 2-methylnonane, 2,7-dimethyloctane, and n-butylcyclohexane

Wang, Zhandong; Hansen, Nils; Jasper, Ahren W.; Chen, Bingjie; Popolan-Vaida, Denisia M.; Yalamanchi, Kiran K.; Najjar, Ahmed; Dagaut, Philippe; Sarathy, S. Mani

doi:10.1016/j.combustflame.2020.06.003

Cool flame chemistry of diesel surrogate compounds: n-Decane, 2-methylnonane, 2,7-dimethyloctane, and n-butylcyclohexane

Journal Article · Tue Jun 23 00:00:00 EDT 2020 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2020.06.003· OSTI ID:1774404

Wang, Zhandong ^[1]; Hansen, Nils ^[2]; Jasper, Ahren W. ^[3]; ^[4]; Popolan-Vaida, Denisia M. ^[5]; Yalamanchi, Kiran K. ^[4]; Najjar, Ahmed ^[4]; Dagaut, Philippe ^[6]; Sarathy, S. Mani ^[4]

Univ. of Science and Technology of China, Hefei (China); King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Central Florida, Orlando, FL (United States)
Centre National de la Recherche Scientifique (CNRS), Orléans (France)

Elucidating the formation of combustion intermediates is crucial to validate reaction pathways, develop reaction mechanisms and examine kinetic modeling predictions. While high-temperature pyrolysis and oxidation intermediates of alkanes have been thoroughly studied, comprehensive analysis of cool flame intermediates from alkane autoxidation is lacking and challenging due to the complexity of intermediate species produced. Here, jet-stirred reactor autoxidation of four C₁₀ alkanes: n-decane, 2-methylnonane, 2,7-dimethyloctane, and n-butylcyclohexane, as model compounds of diesel fuel, was investigated from 500 to 630 K using synchrotron vacuum ultraviolet photoionization molecular beam mass spectrometry (SVUV-PIMS). Around 100 intermediates were detected for each fuel. The classes of molecular structures present during the autoxidation of the representative paraffinic functional groups in transport fuels, i.e., n-alkanes, branched alkanes, and cycloalkanes were established and were found to be similar from the oxidation of various alkanes. A theoretical approach was applied to estimate the photoionization cross sections of the intermediates with the same carbon skeleton as the reactants, e.g., alkene, alkenyl keto, cyclic ether, dione, keto-hydroperoxide, diketo-hydroperoxide, and keto-dihydroperoxide. These species are indicators of the first, second, and third O₂ addition reactions for the four C₁₀ hydrocarbons, as well as bimolecular reactions involving keto-hydroperoxides. Chemical kinetic models for the oxidation of these four fuels were examined by comparison against mole fraction of the reactants and final products obtained in additional experiments using gas chromatography analysis, as well as the detailed species pool and mole fractions of aforementioned seven types of intermediates measured by SVUV-PIMS. This works reveals that the models in the literature need to be improved, not only the prediction of the fuel reactivity and final products, but also the reaction network to predict the formation of many previous undetected intermediates.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China (NNSFC); King Abdullah Univ. of Science and Technology (KAUST); European Research Council (ERC)

Grant/Contract Number:: AC02-06CH11357; AC02-05CH11231; NA0003525

OSTI ID:: 1774404

Alternate ID(s):: OSTI ID: 1691881

Journal Information:: Combustion and Flame, Journal Name: Combustion and Flame Vol. 219; ISSN 0010-2180

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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