Gasoline Surrogate Oxidation in a Motored Engine, a JSR, and an RCM: Characterization of Cool-Flame Products by High-Resolution Mass Spectrometry

Belhadj, Nesrine; Lailliau, Maxence; Dbouk, Zahraa; Benoit, Roland; Moreau, Bruno; Foucher, Fabrice; Dagaut, Philippe

doi:10.1021/acs.energyfuels.2c00259

Cited by 6 publications

(7 citation statements)

References 34 publications

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“…Exhaust chemical species dissolved in ACN were analyzed by reversed-phase ultrahigh-pressure liquid chromatography (RP-UHPLC) using a C 18 column (1.6 μm, 100 Å, 2.1 mm, 100 mm, Luna Omega from Phenomenex) under the following elution conditions: mobile phase (H 2 O + ACN), 5–90% of ACN; flow rate of 250 μL/min during 20 min. Additional flow injection analyzes (FIA) were performed as well as isotopic H/D exchange tests using D 2 O (Sigma-Aldrich) to probe the presence of OH and OOH groups in products, as employed previously, − ,, 300 μL of D 2 O was introduced into 1 mL of a DBE oxidation sample (reaction time 20 min at 20 °C). H/D exchange occurs only with labile hydrogen sites, whereas for nonexchangeable hydrogen atoms such as those in C–H groups, H/D exchange requires catalysis .…”

Section: Methodsmentioning

confidence: 99%

“…Recently, Belhadj et al 17 performed a characterization of the cool flame products of a 50/50 mixture of n-heptane and isooctane in a JSR, a RCM, and a motored HCCI engine. They collected exhaust gases through bubbling in cooled acetonitrile and analyzed the resulting solutions by ultrahigh-pressure liquid chromatography (UHPLC) coupled to high-resolution mass spectrometry (HRMS Orbitrap Q-Exactive).…”

Section: Introductionmentioning

confidence: 99%

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Low-Temperature Oxidation of Di-n-Butyl Ether in a Motored Homogeneous Charge Compression Ignition (HCCI) Engine: Comparison of Characteristic Products with RCM and JSR Speciation by Orbitrap

et al. 2022

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Previously, the oxidation of di-n-butyl ether (DBE) carried out in a jet-stirred reactor (JSR) and in a rapid compression machine (RCM) revealed that it proceeds similarly under both conditions (Belhadj et al, Combust. Flame 2020, 222, 133–144). Here, we extend that study to DBE oxidation in a motored homogeneous charge compression ignition engine, conditions under which this fuel has never been studied. Samples of exhaust gas were obtained by bubbling in acetonitrile maintained at 0 °C. The samples were analyzed using atmospheric pressure chemical ionization in positive and negative modes, high-resolution mass spectrometry (Orbitrap), and ultrahigh-pressure liquid chromatography. Flow injection analyses of samples before and after H/D exchange using D2O were also performed to verify the presence of isomeric products containing OH or OOH groups. Carbonyls were identified through derivatization with 2,4-dinitrophenylhydrazine. A large set of chemical products of the DBE cool flame were detected in the engine exhausts. They include hydroperoxides and diols (C8H18O3), unsaturated diols or unsaturated hydroperoxides (C8H16O3), keto hydroperoxides (C4H8O3 and C8H16O4), diketo ethers (C8H14O3), olefinic diketo ethers (C8H12O3), cyclic and keto ethers (C8H16O2), and olefinic cyclic and keto ethers (C8H14O2). Also, highly oxygenated chemicals, i.e., keto dihydroperoxides (C8H16O6) resulting from three O2 additions on radicals from the fuel, diketo hydroperoxides (C8H14O5) resulting from decomposition of keto dihydroperoxides (C8H16O6), in addition to other oxygenated intermediates i.e., hydroxy-DBE (C8H18O2) and organic peroxides ROOR′ (C16H34O4, C11H24O3, C11H22O3, and C10H22O3), were observed in the engine exhausts. The present speciation results of the engine exhausts were compared to those obtained for samples of the oxidation of DBE in an RCM and a JSR. Despite the significant differences in physical experimental conditions, the present study indicates thata common oxidation mechanism proceeds in JSR, RCM, and a motored engine, leading to the formation of products having the same chemical formulas and retention times.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Low-Temperature Oxidation of Di-n-Butyl Ether in a Motored Homogeneous Charge Compression Ignition (HCCI) Engine: Comparison of Characteristic Products with RCM and JSR Speciation by Orbitrap

et al. 2022

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“…A similar situation was observed in low-T oxidation of other linear alkanes, where 2-heptanone and 3-heptanone were the most abundant ketones in low-T oxidation of n-heptane by using the offline analysis. 16 With reference to the low-T oxidation mechanism of other linear alkanes, 14,16 Scheme 3 displays the potential formation pathways of 2-nonanone and 3-nonanone through different channels. Furthermore, GC × GC-TOF/MS also observed the signal of nonanal, which was a C 9 -aldehyde.…”

Section: Decomposition and Bimolecular Of Roomentioning

confidence: 99%

Oxidation of n-Nonane: Measurements of Low-Temperature Products in Jet-Stirred Reactors

Zhai,

Wang,

Samaras

et al. 2023

Energy Fuels

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n-Nonane is a medium-chain n-alkane representative of the light-end components found in jet and diesel fuels. In this work, low-temperature (low-T) oxidation of n-nonane was investigated in jet-stirred reactors at near-atmospheric pressure, fuel-lean conditions (ϕ = 0.5), an initial fuel concentration of 5000 ppm, a mean residence time of 2 s, and over a temperature range of 500–770 K. Reactants, intermediates, and products were detected and identified by chromatography and mass spectrometry. Gas-phase samples were analyzed by using synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Liquid-phase samples were analyzed by two-dimensional gas chromatography coupled with time-of-flight MS (GC × GC-TOF/MS) through flow injection. Besides stable species, some other low-T oxidation species, which are the main first and second O2 addition products, were observed. Through the combination of theoretical, chromatographic, and mass spectrometric results, clarification was achieved regarding various isomers and their formation mechanisms during the low-T oxidation of n-nonane. In addition, simulations were performed using a literature kinetic model to predict the reactivity of n-nonane and the formation of crucial compounds, indicating that improvements are needed to better describe the low-T oxidation of n-nonane under the present conditions. The results of this study provide deep insight into the low-T oxidation of n-nonane and contribute to the development of kinetic models for n-nonane and larger-chain alkane oxidation.

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“…7 Fuel surrogates and derivate motor fuels can be used to decrease the influence of gasoline engines on the environment. 8 Various scenarios can be used to decrease the ecological influence of gasoline engine operation. 9 Among the scenarios, introducing olefinic and isoolefinic hydrocarbons can be one scenario by making them feed for the methoxylation process.…”

Section: Introductionmentioning

confidence: 99%

“…Fuel surrogates and derivate motor fuels can be used to decrease the influence of gasoline engines on the environment . Various scenarios can be used to decrease the ecological influence of gasoline engine operation .…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Superior Role of Characterizing Methyl Ester of Isohexene as an Innovative High-Octane Gasoline Mixing Component

et al. 2022

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High concentrations of isoolefinic hydrocarbons can adversely affect the physical, chemical, mechanical, and ecological characteristics of gasoline fuels. One of the solutions to reduce olefin contents is the utilization of the methoxylation process. The current paper declares a perspective toward a gasoline-component-first technique, revealing an innovative highoctane additive on the basis of isoolefinic components, like isohexene. The olefin content of isohexene was 94% volumetrically. This affected the chemical oxidation under atmospheric conditions. Several gasoline fuels and experimental facilities that match European and Russian requirements were used to execute the recent work. The objective of the methoxylation process is to enhance the chemical oxidation fuels to raise the portion of aliphatic hydrocarbon isomers, to decrease unwanted olefin content, as well as to generate high-octane motor ethers as gasoline octane boosters. The product can be defined as methyl ester of isohexene (MEIH). Various MEIH blends have been measured with other gasoline octane boosters and refinery products. The results proved that antidetonation properties of MEIH were higher than those of base gasolines, tertiary amyl methyl ether (TAME), and isohexene and approximately equal to that of methyl tertiary butyl ether (MTBE). Additionally, the results of the calculated MEIH mixing octane rating were from 104.3 to 131.5 for the research method and from 87.5 to 120.0 for the motor method. Likewise, the olefin content of MEIH was 74.2% when the methoxylation process was applied for isohexene. The oxygen content of MEIH was 3.3 wt %, with no oxygen content in the sample of isohexene. Those have been done thanks to the utilization of the methoxylation process of isohexene. Finally, MEIH provided an individual perspective as a liquid transportation fuel with merits over isohexene, in terms of antidetonation properties, olefin contents, as well as a distillation characteristic range.

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Gasoline Surrogate Oxidation in a Motored Engine, a JSR, and an RCM: Characterization of Cool-Flame Products by High-Resolution Mass Spectrometry

Cited by 6 publications

References 34 publications

Low-Temperature Oxidation of Di-n-Butyl Ether in a Motored Homogeneous Charge Compression Ignition (HCCI) Engine: Comparison of Characteristic Products with RCM and JSR Speciation by Orbitrap

Low-Temperature Oxidation of Di-n-Butyl Ether in a Motored Homogeneous Charge Compression Ignition (HCCI) Engine: Comparison of Characteristic Products with RCM and JSR Speciation by Orbitrap

Oxidation of n-Nonane: Measurements of Low-Temperature Products in Jet-Stirred Reactors

Unraveling the Superior Role of Characterizing Methyl Ester of Isohexene as an Innovative High-Octane Gasoline Mixing Component

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