Exploring the oxidation chemistry of diisopropyl ether: Jet-stirred reactor experiments and kinetic modeling

Diisopropyl ether (DIPE) is considered as a promising gasoline additive due to the favorable blending Reid vapor pressure and the low water solubility. To get a good understanding of the DIPE oxidation chemistry, oxidation experiments of a stoichiometric mixture of DIPE/O₂/Ar/Kr were performed in a jet-stirred reactor (JSR) at atmospheric pressure over the temperature range of 525–900 K in this work. About 30 intermediates and products were identified and quantified using a photoionization molecular-beam mass spectrometer (PI-MBMS). Furthermore, a detailed kinetic model was proposed for DIPE oxidation, which showed satisfactory performances in predicting the species concentration profiles in this work as well as those in literature. For DIPE oxidation, the fuel consumption was observed only above 750 K, even though DIPE has two tertiary hydrogen atoms that are easy to be abstracted so that low-temperature oxidation reactivity is expected. The low oxidation reactivity at low temperature is because the formed OOQOOH radical mostly dissociates back to QOOH+O₂, instead of undergoing intramolecular isomerization which leads to the low-temperature chain-branching. At higher temperature, DIPE is mainly consumed by hydrogen abstraction reactions from the carbon atoms adjacent to the oxygen atom, producing dominantly the IC₃H₇OC(CH₃)₂ fuel radical, which then decomposes rapidly via CO bond β-scission instead of combining with O₂. In contrast, the minor fuel radical IC₃H₇OCH(CH₃)CH₂ tends to go through the O₂ addition reaction and the subsequent chain branching reactions, as confirmed by the detection of cyclic ether intermediates. Propylene and acetone are the most abundant intermediates in DIPE oxidation, both of which predominantly come from the initial fuel decomposition steps. Other intermediates are mainly formed via the consumption of these two species.     

An improved detailed chemical kinetic model for C3-C4 linear and iso-alcohols and their blends with gasoline at engine-relevant conditions

Propanol and butanol isomers have received significant research attention as promising fuel additives or neat biofuels. Robust chemical kinetic models are needed that can provide accurate and efficient predictions of combustion performance across a wide range of engine relevant conditions. This study seeks to improve the understanding of ignition and combustion behavior of pure C3-C4 linear and iso-alcohols, and their blends with gasoline at engine-relevant conditions. In this work, a kinetic model with improved thermochemistry and reaction kinetics was developed based on recent theoretical calculations of H-atom abstraction and peroxy radical reaction rates. Kinetic model validations are reported, and the current model reproduces the ignition delay times of the C3 and C4 alcohols well. Variations in reactivity over a wide range of temperatures and other operating conditions are also well predicted by the current model. Recent ignition delay time measurements from a rapid compression machine of neat iso-propanol and iso-butanol [Cheng et al., Proc. Combust Inst. (2020)] and blends with a research grade gasoline [Goldsborough et al., Proc. Combust Inst. (2020)] at elevated pressure (20–40 bar) and intermediate temperatures (780–950 K) were used to demonstrate the accuracy of the current kinetic model at conditions relevant to boosted spark-ignition engines. The effects of alcohol blending with gasoline on the autoignition behavior are discussed. The current model captures the suppression of reactivity in the low-temperature and negative-temperature-coefficient (NTC) region when either isopropanol and isobutanol are added to a research grade gasoline. Sensitivity and reaction flux analysis were performed to provide insights into the relevant fuel chemistry of the C3-C4 alcohols.     

Oxidation of ethyl methyl ether: Jet-stirred reactor experiments and kinetic modeling

Larger ethers such as diethyl ether (DEE) and di-n-propyl ether (DPE) have different oxidation behavior (double-NTC behavior) compared to the simplest dimethyl ether (DME). Such phenomena are interpreted with different reactions and processes in different ether kinetic models, which also predict different formation pathways of oxidation intermediates such as acids. To gain further insights into the oxidation kinetics of linear ethers, ethyl methyl ether (EME), which has a nonsymmetrical structure, was studied in this work. Oxidation experiments of 1% of EME were performed in a jet-stirred reactor at 1 atm, a residence time of 2 s, an equivalence ratio of 1, and over a temperature range of 375–850 K. The intermediates were analyzed with photoionization molecular-beam mass spectrometry. To explain the oxidation behavior of EME, a detailed kinetic model was also constructed. The oxidation of EME spans a wider temperature range than DME, but no obvious double-NTC behavior was observed as DEE. Based on the model analysis and profiles of critical intermediates such as ketohydroperoxides (KHPs) and CH₃O₂H, the low-temperature oxidation behavior of EME was explained by the chain-branching reactions of the fuel itself and the oxidation intermediates. Abundant species such as aldehydes, acids, esters, and fuel-specific dione species were detected and could be well reproduced by the current model. In particular, acids are produced by the decomposition of KHPs and subsequent reactions of the intermediate CH₃CHO. Esters and dione species are mainly formed via fuel-related pathways.     

Ethanol ignition in a high-pressure shock tube: Ignition delay time and high-repetition-rate imaging measurements

Ethanol is known to be prone to pre-ignition in internal combustion engines under high-load conditions and its ignition shows large deviations from ideal, spatially, and temporally-homogeneous ignition in shock tubes at moderate temperatures (800–950 K). In this context, the ignition of stoichiometric ethanol/O₂ mixtures with various levels of inert gas dilution was investigated in a high-pressure shock tube at ?20 bar between 800 and 1250 K. Ignition delay times were determined from spatially integral detection of chemiluminescence emission. Additionally, high-repetition-rate color imaging enabled the differentiation of the luminescence in time, space, and spectral range between various ignition modes. In the low-temperature range (800–860 K), different inhomogeneous ignition modes were identified. The addition of small amounts of helium into the undiluted fuel/air mixture was found to be efficient to mitigate pre-ignition, attributed to a variation in heat transfer and thus suppression of the build-up of local temperature inhomogeneities. The experiments in case of spatially homogeneous ignition show very good agreement with the predictions based on three detailed kinetics mechanisms (Zhang et al., CNF 190 (2018) 74, Frassoldati et al., CNF 159 (2012) 2295, and Zhou et al. CNF 197 (2018) 423), inhomogeneities, however, resulted in a shortening of the ignition delay times up to a factor of 2.6.     

Chemical structure of atmospheric pressure premixed laminar formic acid/hydrogen flames

The work presents an experimental and kinetic modeling study of laminar premixed formic acid [HC(O)OH]/H₂/O₂/Ar flames at different equivalence ratios (φ=0.85, 1.1 and 1.3) stabilized on a flat burner at atmospheric pressure, as well as laminar flame speed of HC(O)OH/O₂/Ar flames (φ=0.5–1.5) at 1 atm. Flame structure as well as laminar flame speed were simulated using three different detailed chemical kinetic mechanisms proposed for formic acid oxidation. The components in the fuel blends show different consumption profiles, namely, hydrogen is consumed slower than formic acid. According to kinetic analysis, the reason of the observed phenomenon is that the studied flames have hydrogen as a fuel but also as an intermediate product formed from HC(O)OH decomposition. Comparison of the measured and simulated flame structure shows that all the mechanisms satisfactorily predict the mole fraction profiles of the reactants, main products, and intermediates. It is noteworthy that the mechanisms proposed by Glarborg et al., Konnov et al. and the updated AramcoMech2.0 adequately predict the spatial variations in the mole fractions of free radicals, such as H, OH O and HO₂. However, some drawbacks of the mechanisms used were identified; in particular, they predict different concentrations of CH₂O. As for laminar flame speed simulations, the Konnov et al. mechanism predicts around two times higher values than in experiment, while the Glarborg et al. and updated AramcoMech2.0 show good agreement with the experimental data.     

Oxidation of linear and branched ethers: A comparative flow reactor study of OME2 and trimethoxymethane

Oxidation processes of a linear and a branched ether, oxymethylene ether 2 (OME₂) and trimethoxymethane, also known as trimethyl orthoformate (TMOF), were investigated in two complementary atmospheric flow reactor setups coupled to electron ionization molecular-beam mass spectrometer (EI-MBMS). One with high mass resolution to measure speciation data and the second with photoionization MBMS (i²PEPICO) to gain isomer distribution. It can be shown that both ethers have different reactivity with trimethoxymethane reacting at lower temperatures. Furthermore, fuel decomposition and intermediate profiles can be analyzed by combining the results of isomer fractionation using i²PEPICO combined with the quantitative species profiles of EI-MBMS. The results show a huge number of oxygenated species. While the obtained species pool is similar, measured mole fractions differ. Isomers, as for example ethanol and dimethyl ether, are separated and quantified. Direct comparison of the oxidation intermediates of the linear and branched ether clarifies the different reactivity due to their given fuel structures.     

The oxidation characteristics of furan derivatives and binary TPGME blends under engine relevant conditions

Furan and its derivatives have been receiving attention as next generation alternative fuels, related to advanced bio-oil production. However, the ignition quality of furans allows their use only as an additive to diesel fuel in CI engines, which potentially requires the continued use of a fossil-derived base fuel. This study first adopts tri-propylene glycol mono-methyl ether (TPGME) as a substitute for diesel fuel with addition of furan and furan derivatives, including 2-methylfuran, 2,5-dimethylfuran, and furfural, thereby removing fossil-derived fuels from the mixture. With this motivation, gas-phase ignition characteristics of furans were investigated in a modified CFR motored engine, displaying an absence of low temperature heat release (LTHR), while n-heptane as a reference fuel shows a strong two-stage ignition characteristic under the same condition. The structural impact of furans is represented as global oxidation reactivities that are as follows: furan?<?2-methylfuran?<?2,5-dimethylfuran?<?furfural?<?n-heptane. The ranking of individual furans is supported by bond dissociation energies of each fuel's functional group substituent on the furan-ring. Ignition characteristics of TPGME display a strong low-temperature oxidation reactivity; however, its reactivity rapidly diminishes with increasing amounts of furan, shutting down low-temperature oxidation paths. The structural impact of furan and methyl-substituted furans on reactivity is significantly muted when blended with TPGME, as observed in a motored CFR engine and a constant volume spray combustion chamber.     

Experimental and modeling study on the auto-ignition properties of ammonia/methane mixtures at elevated pressures

Ammonia (NH₃) is considered as a promising carbon free energy carrier for energy and transportation systems. However, its low flammability and high NO_x emission potential inhibit the implementation of pure NH₃ in these systems. On the other hand, methane is a favorable low emission fuel that can be used as a co-firing fuel in ammonia combustion to promote the reactivity and control the emission levels. However, knowledge of the ignition properties of NH₃/CH₄ mixtures at intermediate temperatures and elevated pressures is still scarce. This study reports ignition delay times of NH₃/CH₄/O₂ mixtures diluted in Ar or Ar/N₂ over a temperature range of 900–1100 K, pressures of 20 and 40 bar, and equivalence ratios of 0.5, 1.0, and 2.0. The results demonstrate that a higher CH₄ mole fraction in the fuel mixture increases its reactivity, and that the reactivity decreases with increasing the fuel-oxygen equivalence ratio. The most recent mechanisms of Glarborg et al. (2018) and Li et al. (2019) were compared against the experimental data for validation purposes. Both mechanisms can predict the measurements fairly well, and key elementary reactions applied in both mechanisms were compared. A modified mechanism is provided, which can reproduce the measurements with smaller discrepancies in most cases. Detailed modeling for emissions indicated that adding CH₄ to the fuel mixture increases the emission of NO_x.     

Experimental and kinetic modeling studies on the auto-ignition of methyl crotonate at high pressures and intermediate temperatures

Biofuels, including biodiesel have the potential to partially replace the conventional diesel fuels for low-temperature combustion engine applications to reduce the CO₂ emission. Due to the long chain lengths and high molecular weights of the biodiesel components, it is quite challenging to study the biodiesel combustion experimentally and computationally. Methyl crotonate, a short unsaturated fatty acid methyl ester (FAME) is chosen for this chemical kinetic study as it is considered as a model biodiesel fuel. Auto-ignition experiments were performed in a rapid compression machine (RCM) at pressures of 20 and 40 bar under diluted conditions over a temperature range between 900 and 1074 K, and at different equivalence ratios (? = 0.25, 0.5 and 1.0). A chemical kinetic mechanism is chosen from literature (Gaïl et al. 2008) and is modified to incorporate the low-temperature pathways. The mechanism is validated against existing shock tube data (Bennadji et al. 2009) and the present RCM data. The updated mechanism shows satisfactory agreement with the experimental data with significant improvements in low-temperature ignition behavior. The key reactions at various combustion conditions and the improved reactivity of the modified mechanism are analyzed by performing sensitivity and path flux analysis. This study depicts the importance of low-temperature pathways in predicting the ignition behavior of methyl crotonate at intermediate and low temperatures.     

Corrigendum to “Constraints on operator ordering from third quantization” [Ann. Phys. 365 (2016) 54–65]

In our previous paper Ohkuwa et al. (2016) corrigendum was found in Eqs. (3.4) and (3.6). However, conclusions of our previous paper are not changed.     

Corrigendum to “Constraints on operator ordering from third quantization” [Ann. Phys. 365 (2016) 54–65]

In our previous paper (Ohkuwa et al., 2016) corrigendum was found in Eqs. (3.4) and (3.6). However, conclusions of our previous paper are not changed.     

A high temperature and atmospheric pressure experimental and detailed chemical kinetic modelling study of 2-methyl furan oxidation

An experimental ignition delay time study for the promising biofuel 2-methyl furan (2MF) was performed at equivalence ratios of 0.5, 1.0 and 2.0 for mixtures of 1% fuel in argon in the temperature range 1200–1800 K at atmospheric pressure. Laminar burning velocities were determined using the heat-flux method for mixtures of 2MF in air at equivalence ratios of 0.55–1.65, initial temperatures of 298–398 K and atmospheric pressure. A detailed chemical kinetic mechanism consisting of 2059 reactions and 391 species has been constructed to describe the oxidation of 2MF and is used to simulate experiment. Accurate reproduction of the experimental data has been obtained over all conditions with the developed mechanism. Rate of production and sensitivity analyses have been carried out to identify important consumption pathways of the fuel and key kinetic parameters under these conditions. The reactions of hydrogen atom with the fuel are highlighted as important under all experimental conditions studied, with abstraction by the hydrogen atom promoting reactivity and hydrogen atom addition to the furan ring inhibiting reactivity. This work, to the authors knowledge, is the first to combine theoretical and experimental work to describe the oxidation of any of the alkylated furans. The mechanism developed herein to describe 2MF combustion should also function as a sub-mechanism to describe the oxidation of 2,5-dimethyl furan whilst also providing key insights into the oxidation of this similar biofuel candidate.     

A pyrolysis study on C4–C8 symmetric ethers

Pyrolysis of diethyl (C₄), di-n-propyl (C₆), di-isopropyl (C₆) and di-n-butyl (C₈) ethers were studied in a jet-stirred reactor between 720 and 1140 K, at 10 atm with an initial ether mole fraction of 0.1%. Major common pyrolysis products were observed to be CO, CH₄, H₂, and C₂H₄. All ethers produced the n/2 alcohol and olefin as products of molecular reaction to a small extent. Under pyrolysis conditions at 10 atm, hydrogen abstraction reactions by H atoms and CH₃ radicals were found to be important. Acetylene and benzene were formed for all ethers when T > 1000 K. A kinetic mechanism is used to represent these results. This study shows that there is need of systematic studies in determining site specific rate constants of important fuel related reactions of ethers.     

Role of CH2O moiety on laminar burning velocities of oxymethylene ethers (OMEn): A case study of dimethyl ether,OME1 and OME2

Oxymethylene ethers (OME_n) are an important family of e-fuels that can be produced sustainably from carbon dioxide and hydrogen via renewable electricity. In this work, laminar flame propagation of dimethyl ether (DME, which can be deemed as OME₀), dimethoxymethane (OME₁) and methoxy(methoxymethoxy)methane (OME₂) was investigated in a constant-volume cylindrical combustion vessel. Laminar burning velocities (LBVs) of the three fuels were derived at 423 K, 1–10 atm and equivalence ratios of 0.7–1.5. A kinetic model for the high-temperature oxidation of the three fuels was developed with the isomerization and decomposition reactions of OME₂ radicals theoretically calculated. Reasonable predictions can be achieved by the present model during the validation against the new data in this work and previous data in literature. Based on the modeling analysis, fuel-specific flame chemistry of the three fuels was analyzed, especially for the key formation pathways of major intermediates including formaldehyde, methyl formate and CH₃. Special attentions were paid on the role of CH₂O moiety, which is demonstrated by the variation of LBV and flame chemistry with the ratio (α) of CH₂O moiety to the rest moiety in the fuel molecule (α = 1, 2 and 3 for DME, OME₁ and OME₂). It is observed from the experimental and simulated results that as α increases, the LBV profile has close peak values and peaks towards rich conditions, which results in the crossings of profiles and ascending LBV values under the richest conditions. Reactions involving fuel-specific radicals HCO and CH₃ result in the peak shift of H profile and different LBV values, especially under the richest conditions. Furthermore, extended α values at 0 and ∞ by using methane and formaldehyde respectively were also explored with kinetic modeling to provide more insight into the effects of fuel molecular structures.     

Blending effect of methanol on the formation of polycyclic aromatic hydrocarbons in the oxidation of toluene

Methanol has been considered as a potential renewable liquid fuel and blending it with gasoline and diesel is an effective way to reduce greenhouse gas emissions from the transport sector. To understand the mixing effect of methanol on the formation of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs), the fuel-rich oxidation of toluene with and without methanol was studied using a flow reactor at atmospheric pressure, temperatures from 1050 to 1350 K, equivalence ratio of 9.0, and residence time of 1.2 s. The blending ratio of methanol was varied as 0% and 50% on a molar basis. Gas chromatograph mass spectrometer was employed to identify and quantify PAHs and OPAHs in gaseous products. A kinetic model on PAH growth up to five ring structures was used to investigate the blending effect on PAH and OPAH formation. Both experiment and modeling showed that PAH and OPAH production at lower temperatures was unexpectedly promoted in toluene/methanol oxidation compared with toluene oxidation, while their production in toluene oxidation was identical with or larger than that in toluene/methanol oxidation at elevated temperatures. In methanol oxidation, no PAHs were produced under the current experimental conditions. Kinetic analysis indicated that high methanol reactivity produced several radicals, such as OH, H, and HO₂, which promoted toluene reactivity at lower temperatures, resulting in the enlargement of PAH and OPAH formation in toluene/methanol oxidation compared to neat toluene oxidation. When the temperature was increased, the effect of methanol blending was diminished based on the kinetic analysis. These results suggest that oxygenated fuels do not necessarily reduce PAH production, but promote it under some conditions.     

High pressure organic chemistry; XV. Non-catalyzed cleavage reaction of ethers with acyl halides

Abstract

A variety of cyclic and acyclic ethers are efficiently reacted with acyl chlorides or acyl bromides to afford the ether-cleaved compounds of ω-chloro-or ω-bromoesters under high pressure conditions. The reactivity of ethers is found to be roughly depend on the basicity of the ether oxygen atom.     

Laminar flame propagation of acetone and 2-butanone at normal to high pressures: Insight into fuel molecular structure effects of ketones

This work reports an experimental and kinetic modeling investigation on the laminar flame propagation of acetone and 2-butanone at normal to high pressures. The experiments were performed in a high-pressure constant-volume cylindrical combustion vessel at 1–10 atm, 423 K and equivalence ratios of 0.7–1.5. A kinetic model of acetone and 2-butanone combustion was developed from our recent pentanone model [Li et al., Proc. Combust. Inst. 38 (2021) 2135–2142] and validated against experimental data in this work and in literature. Together with our recently reported data of 3-pentanone, remarkable fuel molecular structure effects were observed in the laminar flame propagation of the three C₃C₅ ketones. The laminar burning velocity increases in the order of acetone, 2-butanone and 3-pentanone, while the pressure effects in laminar burning velocity reduces in the same order. Modeling analysis was performed to provide insight into the key pathways in flames of acetone and 2-butanone. The differences in radical pools are concluded to be responsible for the observed fuel molecular structure effects on laminar burning velocity. The favored formation of methyl in acetone flames inhibits its reactivity and leads to the slowest laminar flame propagation, while the easiest formation of ethyl in 3-pentanone flames results in the highest reactivity and fastest laminar flame propagation. Furthermore, the LBVs of acetone and 3-pentanone exhibit the strongest and weakest pressure effects respectively, which can be attributed to the influence of fuel molecular structures through two crucial pressure-dependent reactions CH₃ + H (+M) = CH₄ (+M) and C₂H₄ + H (+M) = C₂H₅ (+M).     

On the sudden reversal of soot formation by oxygen addition in DME flames

Dimethyl ether (DME) is a non-toxic and renewable fuel known for its soot emissions reduction tendencies. In laminar co-flow DME diffusion flames, adding oxygen to the fuel stream increases the sooting tendency until a critical point is reached, at which point the trend suddenly reverses. This work unravels the mechanisms behind this reversal process, and characterizes their contribution to controlling soot production. A series of experimental measurements using diffuse-light line-of-sight attenuation and two-colour pyrometry were performed to measure soot volume fraction and soot temperature considering a fixed mass flow rate of DME and variable addition of oxygen. Soot volume fraction increases from 0.095 ppm in the pure DME flame to 0.32 ppm when the added oxygen concentration reaches 33%. When the oxygen concentration is slightly increased to 35%, soot volume fraction is reduced by 60%. To explain the reasons behind the reversal, a series of numerical simulations were performed, which successfully demonstrated the same trend. Results show that the chemical effects of adding oxygen to the fuel stream are exceedingly more important than the thermal and dilution effects. It was found that the reversal occurred when nearly all DME disassociated before exiting the fuel tube, indicating a sudden transition from a partially premixed DME flame, to one which primarily burns C1 fuel fragments. An analysis of soot formation and oxidation rates showed that near the reversal, soot inception is the least affected process; furthermore, soot precursor availability is not significantly affected in magnitude, rather they appear further upstream. It is concluded that the favourable conditions for rapid DME decomposition into soot precursors enhances soot inception while depleting the necessary species for further soot mass growth, dramatically reducing soot concentration.     

Separation of long-lived radionuclides from high active nuclear waste

The management of vitrified high activity waste issued from the reprocessing of spent nuclear fuel is often made questionable by the presence within this waste of long-lived radionuclides (LLRNs). New management scenarios of this waste are under study at the CEA since the beginning of the 1990s, involving the development of separation processes for some LLRNs. Six LLRNs are the targets of these studies; they are: (i) the minor actinides: neptunium, americium and curium; (ii) the fission products: technetium, iodine and caesium. The present paper highlights the main achievements of the research performed at the CEA in this field. To cite this article: C. Madic et al., C. R. Physique 3 (2002) 797–811.     

Experimental and modelling study of gasoline surrogate mixtures oxidation in jet stirred reactor and shock tube

The oxidation of several mixtures of surrogate for gasoline was studied using a jet stirred reactor and a shock tube. One representative of each classes constituting gasoline was selected: iso-octane, toluene, 1-hexene and ethyl tert-butyl ether (ETBE). The experiments were carried out in the 800-1880 K temperature range, for two different initial pressures (0.2 and 1 MPa), with an initial fuel molar fraction of 0.001. The equivalence ratio varied from 0.5 to 1.5. Each hydrocarbon sub-mechanism was validated using shock tube data. The full mechanism describing the surrogate fuel oxidation is constituted of the sub-mechanisms for each fuel components and by adding interaction reactions between different hydrocarbon fragments. Good agreement between the experimental results and the computations was observed under JSR and shock tube conditions.