A chemical kinetic study of the oxidation of dibutyl-ether in a jet-stirred reactor

Thion, Sébastien; Togbé, Casimir; Serinyel, Zeynep; Dayma, Guillaume; Dagaut, Philippe

doi:10.1016/j.combustflame.2017.06.019

Cited by 61 publications

(140 citation statements)

References 26 publications

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“…Note that Thion et al [22] have also observed two-NTC-zone behavior for DBE, a molecule satisfying both abovementioned criteria. They explained the first NTC zone by a difference in temperature dependence of formation/consumption reactions of a DBE-specific ketohydroperoxide, C3H7C(=O)OCH(OOH)C3H7, produced through the second O2 addition process, and propylhydroperoxide, C3H7OOH, produced via some subsequent steps in the ketohydroperoxide's decomposition.…”

Section: Model Development and Simulation Methodsmentioning

confidence: 84%

“…Rate coefficients of the second O2 addition forming the OOQOOH radicals were estimated based on the first O2 addition. Kinetic data of OOQOOH isomerization followed by a fast O-O β-scission to form ketohydroperoxides, and decomposition of the latter species were determined following Thion et al [22]. Indications from the present experiments (see Section 4) led us to consider new reaction classes for LT DEE oxidation illustrated in Figure 1.…”

Section: Model Development and Simulation Methodsmentioning

confidence: 91%

“…The order of magnitude of these rate coefficients is in the range of those proposed for DME and n-pentane chemistry (compare the core mechanism). The kinetic data of bimolecular reactions following this first step were estimated based on reactions proposed for LT oxidation of di-n-butyl ether (DBE) [22]. Note that the effect of ether function in DBE is quite similar to that in DEE, e.g., close bond dissociation energies of Cα-H (∼95 kcal mol −1 ) and Cα-O (∼87 kcal mol −1 ) bonds (Cα is the carbon bonded to O atom) [5,22].…”

Section: Model Development and Simulation Methodsmentioning

confidence: 99%

“…The kinetic data of bimolecular reactions following this first step were estimated based on reactions proposed for LT oxidation of di-n-butyl ether (DBE) [22]. Note that the effect of ether function in DBE is quite similar to that in DEE, e.g., close bond dissociation energies of Cα-H (∼95 kcal mol −1 ) and Cα-O (∼87 kcal mol −1 ) bonds (Cα is the carbon bonded to O atom) [5,22]. Kinetic data of ROO isomerization to hydroperoxyl-fuel radicals (QOOH) and of unimolecular reactions of these latter radicals were taken from calculations of Sakai et al [18].…”

Section: Model Development and Simulation Methodsmentioning

confidence: 99%

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Low-temperature gas-phase oxidation of diethyl ether: Fuel reactivity and fuel-specific products

Tran

Herbinet

et al. 2019

Proceedings of the Combustion Institute

144

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Diethyl ether (DEE) has been recently suggested as a potential biofuel for compression-ignition engines that are known to be significantly controlled by low-temperature (LT) chemistry. However, the LT oxidation of DEE has not fully been understood in term of the formation of LT fuel-specific products. We have thus studied the oxidation of DEE by examining detailed profiles of its oxidation products under LT conditions (400-1100 K). To this end, we have used a dedicated experimental setup including a nearly-atmospheric jet-stirred reactor (JSR) coupled to online gas chromatography (GC). The experiments were complemented by measurements made with a JSR coupled to tunable synchrotron vacuum ultraviolet (SVUV) photoionization (PI) molecular-beam mass spectrometry (MBMS) for a cross-validation of the identification of important LT species. Experimental results indicate that DEE is very reactive; it starts to react around 425 K. DEE exhibits an unusual oxidation behavior with two negative temperature coefficient (NTC) zones in the JSR study. Because of this two-NTC observation, additional experiments were performed with a plug flow reactor (PFR) combined with electron ionization (EI)-MBMS, confirming this behavior in the two types of reactor. Moreover, about 20 oxidation species in C1-C4 range were detected with several intermediates containing 2-3 O-atoms. Acetic acid is found to peak at 525 K with a very large amount, suggesting that it is a key species in the early stage of DEE's LT oxidation. Possible DEE-consumption paths leading to acetic acid formation could play an important role in the oxidation mechanism of DEE. A new model is proposed based on the present experimental observations to include new primary LT reaction paths. The model reproduces the experimental phenomena quite well and enhances the understanding of the two-NTC-zone occurrence and of intermediates containing 2-3 O-atoms during the LT oxidation of DEE.

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Section: Model Development and Simulation Methodsmentioning

confidence: 84%

Section: Model Development and Simulation Methodsmentioning

confidence: 91%

Section: Model Development and Simulation Methodsmentioning

confidence: 99%

Section: Model Development and Simulation Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Low-temperature gas-phase oxidation of diethyl ether: Fuel reactivity and fuel-specific products

Tran

Herbinet

et al. 2019

Proceedings of the Combustion Institute

144

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“…These authors developed the first kinetic model for the LT oxidation of this fuel using rate parameters of the primary reaction subset that were mainly determined by rate rules or by analogy to structurally similar species. Recently, Thion et al [15] investigated the oxidation of DBE in a jet-stirred reactor (JSR) in the 470-1250 K temperature range and at 1 and 10 atm. Reactants, main species, and about 18 C1-C5 intermediate species were quantified using gas chromatography.…”

Section: Introductionmentioning

confidence: 99%

Probing the low-temperature chemistry of di-n-butyl ether: Detection of previously unobserved intermediates

Tran

Wullenkord

et al. 2019

Combustion and Flame

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Din -butyl ether (DBE, C8H18O) has been proposed as a promising biofuel for diesel engines, but details of its low-temperature (LT) oxidation chemistry are not well understood. This paper reports new speciation data obtained in the temperature range of 400-1100 K at ϕ=1 and nearly-atmospheric pressure, using a plug flow reactor (PFR) combined with electron ionization (EI) molecular-beam mass spectrometry (MBMS) and two different jet-stirred reactors (JSRs) coupled with either online gas chromatography (GC) or tunable synchrotron vacuum ultraviolet (SVUV) photoionization (PI)-MBMS. The experimental results confirm that DBE is very reactive and exhibits two negativetemperature coefficient (NTC) zones around 500-550 K and 650-750 K. Speciation data with about 40 C0-C8 species are presented, including about 20 LT species not reported previously. Among those, fuel-specific C8H16O2 cyclic ethers were quantified. Also, butanoic acid, which is present in highest amounts among the detected LT intermediates, and C8H14O3 diones, were found to peak already near 500 K, suggesting their importance in the LT chemistry of DBE. Signals of several highly oxygenated peroxides (e.g., C8H14O5 and C8H16O6) were detected, indicating third O2 addition steps. Respective reaction pathways are suggested and discussed based on these experimental results. To better understand the LT chemistry of DBE, the present data were compared to two recent DBE models [L. Cai et al. Combust. Flame. 161 (2014) 798-809 and S. Thion et al. Combust. Flame 185 (2017) 4-15]. Significant discrepancies between the experimental data and both models were found for important LT intermediates, of which many were not included in the respective mechanisms. The results reported in the present study thus provide new opportunities for refining DBE kinetic models.

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Automatic mechanism generation for the combustion of advanced biofuels: A case study for diethyl ether

Michelbach,

Tomlin

2023

Int J of Chemical Kinetics

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Advanced biofuels have the potential to supplant significant fractions of conventional liquid fossil fuels. However, the range of potential compounds could be wide depending on selected feedstocks and production processes. Not enough is known about the engine relevant behavior of many of these fuels, particularly when used within complex blends. Simulation tools may help to explore the combustion behavior of such blends but rely on robust chemical mechanisms providing accurate predictions of performance targets over large regions of thermochemical space. Tools such as automatic mechanism generation (AMG) may facilitate the generation of suitable mechanisms. Such tools have been commonly applied for the generation of mechanisms describing the oxidation of non‐oxygenated, non‐aromatic hydrocarbons, but the emergence of biofuels adds new challenges due to the presence of functional groups containing oxygen. This study investigates the capabilities of the AMG tool Reaction Mechanism Generator for such a task, using diethyl ether (DEE) as a case study. A methodology for the generation of advanced biofuel mechanisms is proposed and the resultant mechanism is evaluated against literature sourced experimental measurements for ignition delay times, jet‐stirred reactor species concentrations, and flame speeds, over conditions covering φ = 0.5–2.0, P = 1–100 bar, and T = 298–1850 K. The results suggest that AMG tools are capable of rapidly producing accurate models for advanced biofuel components, although considerable upfront input was required. High‐quality fuel specific reaction rates and thermochemistry for oxygenated species were required, as well as a seed mechanism, a thermochemistry library, and an expansion of the reaction family database to include training data for oxygenated compounds. The final DEE mechanism contains 146 species and 4392 reactions and in general, provides more accurate or comparable predictions when compared to literature sourced mechanisms across the investigated target data. The generation of combustion mechanisms for other potential advanced biofuel components could easily capitalize on these database updates reducing the need for future user interventions.

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A chemical kinetic study of the oxidation of dibutyl-ether in a jet-stirred reactor

Cited by 61 publications

References 26 publications

Low-temperature gas-phase oxidation of diethyl ether: Fuel reactivity and fuel-specific products

Low-temperature gas-phase oxidation of diethyl ether: Fuel reactivity and fuel-specific products

Probing the low-temperature chemistry of di-n-butyl ether: Detection of previously unobserved intermediates

Automatic mechanism generation for the combustion of advanced biofuels: A case study for diethyl ether

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