Detailed chemical kinetic mechanisms of ethyl methyl, methyl tert-butyl and ethyl tert-butyl ethers: The importance of uni-molecular elimination reactions

Yasunaga, Kōjirō; Simmie, John M.; Curran, Henry J.; Koike, Takao; Takahashi, Osamu; Kuraguchi, Yuma; Hidaka, Yoshiaki

doi:10.1016/j.combustflame.2010.10.012

Cited by 69 publications

(54 citation statements)

References 32 publications

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“…Brocard et al [17], Dot-dash line is from Yasunaga et al [10] and the dashed curve is from Chen and Bozzelli [16].…”

Section: Figure 5: Rate Constants For the 4-centered Elimination Reacmentioning

confidence: 99%

“…The Yasunaga et al [10] rate constant plotted in Fig. 5 includes fall-off but because of the large number of additional vibration modes in TPGME compared to MTBE, TPGME is not expected to exhibit significant fall-off for the temperature and pressure range of the this study.…”

Section: Figure 5: Rate Constants For the 4-centered Elimination Reacmentioning

confidence: 99%

“…It contains both the alcoholic and ether moiety, with secondary C-H bonds adjacent to the alcoholic functional group and primary, secondary and tertiary C-H bonds adjacent to the ether moieties distributed throughout the molecule. Most other oxygenated fuels investigated previously in the literature (methanol [6], iso-butanol [7], dimethyl ether [8,9] and methyl tert-butyl ether [10] etc.) are much smaller than TPGME in molecular size and are either lightly-branched or straight-chained in their skeletal structure.…”

Section: Figure 2: Isomer 3a Chosen To Represent Tpgme Mixture For Momentioning

confidence: 99%

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Experimental and kinetic modeling study of the shock tube ignition of a large oxygenated fuel: Tri-propylene glycol mono-methyl ether

Burke

Pitz

Curran

2015

Combustion and Flame

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“…Brocard et al [17], Dot-dash line is from Yasunaga et al [10] and the dashed curve is from Chen and Bozzelli [16].…”

Section: Figure 5: Rate Constants For the 4-centered Elimination Reacmentioning

confidence: 99%

Section: Figure 5: Rate Constants For the 4-centered Elimination Reacmentioning

confidence: 99%

Section: Figure 2: Isomer 3a Chosen To Represent Tpgme Mixture For Momentioning

confidence: 99%

See 1 more Smart Citation

Experimental and kinetic modeling study of the shock tube ignition of a large oxygenated fuel: Tri-propylene glycol mono-methyl ether

Burke

Pitz

Curran

2015

Combustion and Flame

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“…Satisfactory agreement was achieved with substantial low temperature chemical reaction additions to the comprehensive DEE sub-mechanism, as discussed below. Yasunaga et al [37,38] presented a DEE chemical kinetic model for high temperature pyrolysis and oxidation conditions. Werler et al [39] later validated the model against high temperature shock tube measurements and made modifications to rates of hydrogen abstraction by HO 2 radicals to better predict their data.…”

Section: Chemical Kineticsmentioning

confidence: 99%

“…The DEE model was not validated under lower temperature conditions of relevance to CI engine ignition. Therefore, we started with the high temperature kinetic model from Yasunaga et al [37,38] with the modifications suggested by Werler et al [39]. The low temperature reaction classes and related rate constants were added by analogy to the comprehensive di-butyl ether (DBE) kinetic model developed by Cai et al [40].…”

Section: Chemical Kineticsmentioning

confidence: 99%

Experimental and Numerical Investigation of Ethanol/Diethyl Ether Mixtures in a CI Engine

Vedharaj¹,

Vallinayagam²,

Ali³

et al. 2016

SAE Technical Paper Series

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The auto-ignition characteristics of diethyl ether (DEE)/ethanol mixtures are investigated in compression ignition (CI) engines both numerically and experimentally. While DEE has a higher derived cetane number (DCN) of 139, ethanol exhibits poor ignition characteristics with a DCN of 8. DEE was used as an ignition promoter for the operation of ethanol in a CI engine. Mixtures of DEE and ethanol (DE), i.e., DE75 (75% DEE + 25% ethanol), DE50 (50% DEE + 50% ethanol) and DE25 (25% DEE + 75% ethanol), were tested in a CI engine. While DE75 and DE50 auto-ignited at an inlet air pressure of 1.5 bar, DE25 failed to auto-ignite even at boosted pressure of 2 bar. The peak in-cylinder pressure for diesel and DE75 were comparable, while DE50 showed reduced peak in-cylinder pressure with delayed start of combustion (SOC). Numerical simulations were conducted to study the engine combustion characteristics of DE mixture. A comprehensive detailed chemical kinetic model was created to represent the combustion of DE mixtures. The detailed mechanism was then reduced using standard direct relation graph (DRG-X) method and coupled with 3D CFD code, CONVERGE, to simulate the experimental data. The simulation results showed that the effects of physical properties on DE50 combustion are negligible. Simulations of DE50 mixture revealed that the combustion is nearly homogenous, while diesel (n-heptane used as a surrogate) and DE75 showed similar combustion behavior with flame liftoff and diffusion controlled combustion. Diesel exhibited auto-ignition at an equivalence ratio of 2, while DE75 and DE50 showed auto-ignition in the equivalence ratio range of 1-1.5 and 0-1, respectively. The experiments and numerical simulations demonstrate how the high reactivity of DEE supports the auto-ignition of ethanol, while ethanol acts as a radical scavenger.

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Shock tube investigation of methyl tert butyl ether and methyl tetrahydrofuran high‐temperature kinetics

Jouzdani

Zheng

Zhou

et al. 2019

Int J of Chemical Kinetics

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The autoignition and pyrolysis of two C5 ethers, methyl tert butyl ether (MTBE) and 2‐methyltetrahydrofuran (2‐MTHF), are investigated using the shock tube reactor. The experiments are carried out at pressures of 3.5 and 12 atm at temperatures above 1000 K with argon as a diluent gas. By means of direct laser absorption, carbon monoxide time histories and associated chemical kinetic timescales are also determined. It is observed that the competition between ignition and pyrolysis times depends on the temperature and equivalence ratio of the ignition mixture, such that there is a temperature above which pyrolysis predominates oxidative kinetics. This crossover temperature shifts toward higher temperatures for reactive systems with a fixed fuel concentration but higher oxygen content. The resulting experimental observations are also compared with predictions of existing chemical kinetic models from the literature. The results point to differences in chemical reactivity, such that in pyrolysis conditions, the reactivity of the cyclic ether, 2‐MTHF, is generally higher than that of the aliphatic ether, MTBE. While agreement between experimental observations and model predictions is observed under certain conditions, significant variance between observations and predictions is observed under other conditions. With respect to prediction of the pyrolysis time used to capture the global kinetics of pyrolysis, it is observed that the relation of this time to the time needed to attain 90% of the equilibrium CO concentration varies greatly with the result that the models used in this work generally predict a faster initial formation of CO but a much slower approach to the equilibrium concentration. This is thought to arise from the slow transformation of intermediate CH2O and CH2CO to CO. The chemical kinetic models considered in this work are therefore not capable of predicting the CO time histories during pyrolysis.

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Detailed chemical kinetic mechanisms of ethyl methyl, methyl tert-butyl and ethyl tert-butyl ethers: The importance of uni-molecular elimination reactions

Cited by 69 publications

References 32 publications

Experimental and kinetic modeling study of the shock tube ignition of a large oxygenated fuel: Tri-propylene glycol mono-methyl ether

Experimental and kinetic modeling study of the shock tube ignition of a large oxygenated fuel: Tri-propylene glycol mono-methyl ether

Experimental and Numerical Investigation of Ethanol/Diethyl Ether Mixtures in a CI Engine

Shock tube investigation of methyl tert butyl ether and methyl tetrahydrofuran high‐temperature kinetics

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