A detailed chemical insights into the kinetics of diethyl ether enhancing ammonia combustion and the importance of NOx recycling mechanism

Shrestha, Krishna Prasad; Giri, Binod Raj; Elbaz, Ayman M.; Issayev, Gani; Roberts, William L.; Seidel, Lars; Mauß, Fabian; Farooq, Aamir

doi:10.1016/j.jfueco.2022.100051

Cited by 79 publications

(44 citation statements)

References 59 publications

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“…As expected, both ethers show a decreasing trend of S L with the increase of initial pressure. Increasing the initial pressure enhances adiabatic flame temperature; this observation is consistent with our recent study . Increased pressure primarily improves the combustion intensity by increasing the mixture density and enhances the reaction rates of reactions that are weakly dependent or independent of the temperature .…”

Section: Results and Discussionsupporting

confidence: 91%

“…Our continuing effort is to develop a comprehensive kinetic model for C 1 –C 4 fuels, including the oxygenates (e.g., DEE, DME, DMM [7,13,14]) and their interaction with nitrogen-containing species, e.g., NH 3 and NO x . Our recent mechanism was validated for various C 1 –C 3 chemical systems, including nitrogen-containing species (see our previous studies). , …”

Section: Kinetic Modelingmentioning

confidence: 87%

“…The current model is an extension of our recent work, 7 which was developed to predict the oxidation behavior of diethyl ether (DEE) and its blend with ammonia (NH 3 ). Our continuing effort is to develop a comprehensive kinetic model for C 1 −C 4 fuels, including the oxygenates (e.g., DEE, DME, DMM [7,13,14]) and their interaction with nitrogen-containing species, e.g., NH 3 and NO x . Our recent mechanism 7 was validated for various C 1 −C 3 chemical systems, including nitrogen-containing species (see our previous studies).…”

Section: Kinetic Modelingmentioning

confidence: 99%

“…Our continuing effort is to develop a comprehensive kinetic model for C 1 −C 4 fuels, including the oxygenates (e.g., DEE, DME, DMM [7,13,14]) and their interaction with nitrogen-containing species, e.g., NH 3 and NO x . Our recent mechanism 7 was validated for various C 1 −C 3 chemical systems, including nitrogen-containing species (see our previous studies). 13,14 We adopted the 13DO submechanism from the recent work of Wildenberg et al 5 However, such simple adoption did not yield satisfactory results against the experimental data, especially IDTs and speciation data, mainly due to the different base chemistry and new reaction rate of the reaction 13DO (COCOC) = CH 3 CHO + CH 2 O in the kinetic models, which is discussed below.…”

Section: Kinetic Modelingmentioning

confidence: 99%

“…The knowledge of the 13DO kinetics is limited, and a comprehensive kinetic model of 13DO does not exist yet that can characterize its combustion behavior. The present work aims to add experimental targets by reporting the laminar flame speeds and IDTs of 13DO over a wide range of conditions and using the available experimental data to validate our updated kinetic model . This is an ongoing effort in developing a reliable and comprehensive kinetic model for C/H/N/O chemical systems.…”

Section: Introductionmentioning

confidence: 99%

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Experimental and Kinetic Modeling Study of 1,3-Dioxolane Oxidation and Comparison with Dimethoxymethane

et al. 2022

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This work reports laminar flame speeds and ignition delay times of 1,3-dioxolane/O2/inert gases over a wide range of conditions. Laminar flame speeds were determined experimentally at pressures of 1 and 3 bar, the temperature of 300 K, and equivalence ratios ranging from 0.7 to 1.4 using a constant-volume spherical chamber, whereas ignition delay times were measured in a shock tube at a pressure of 1 bar, the temperature range of 1000–1265 K, and equivalence ratios of 0.5 and 1.0. A detailed kinetic model is developed to predict the oxidation of 1,3-dioxolane utilizing our new experimental data and published datasets on the oxidation of 1,3-dioxolane in freely propagating flames, autoignition in rapid compression machines and shock tubes, and speciation in a jet-stirred reactor. Model predictions are in reasonable agreement with the experimental data. Laminar flame speeds and ignition delay times of 1,3-dioxolane (cyclic ether) are compared with those of dimethoxymethane (acyclic ether). It is found that 1,3-dioxolane has a higher laminar flame speed than that of dimethoxymethane, which may be attributed to the formation of C2H4, C2H2, and the H atom from 1,3-dioxolane. On the contrary, ignition delay times of 1,3-dioxolane are longer than those of dimethoxymethane below 1000 K and shorter above 1000 K for the same dilution level. The reaction ȮCHO = CO2 + H is critical for accurately predicting 1,3-dioxolane oxidation, and it significantly influences model predictions under low-pressure conditions. The model developed in this work will serve as the base mechanism for higher cyclic and acyclic ethers.

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Section: Results and Discussionsupporting

confidence: 91%

Section: Kinetic Modelingmentioning

confidence: 87%

Section: Kinetic Modelingmentioning

confidence: 99%

Section: Kinetic Modelingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Experimental and Kinetic Modeling Study of 1,3-Dioxolane Oxidation and Comparison with Dimethoxymethane

et al. 2022

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A theoretical kinetic study of the reactions of NH₂ radicals with methanol and ethanol and their implications in kinetic modeling

Giri

Shrestha

V.‐T.

et al. 2022

Int J of Chemical Kinetics

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Amino (NH2) radicals play a central role in the pyrolysis and oxidation of ammonia. Several reports in the literature highlight the importance of the reactions of NH2 radicals with fuel in NH3‐dual‐fuel combustion. Therefore, we investigated the reactions of NH2 radicals with methanol (CH3OH) and ethanol (C2H5OH) theoretically. We explored the various reaction pathways by exploiting CCSD(T)/cc‐pV(T, Q)Z//M06‐2X/aug‐cc‐pVTZ level of theory. The reaction proceeds via complex formation at the entrance and exit channels in an overall exothermic process. We used canonical transition state theory to obtain the high‐pressure limiting rate coefficients for various channels over the temperature range of 300–2000 K. We discerned the role of various channels in the potential energy surface (PES) of NH2 + CH3OH/C2H5OH reactions. For both reactions, the hydrogen abstraction pathway at the OH‐site of alcohols plays a minor role in the entire T‐range investigated. By including the title reactions into an extensive kinetic model, we demonstrated that the reaction of NH2 radicals with alcohols plays a paramount role in accurately predicting the low‐temperature oxidation kinetics of NH3‐alcohols dual fuel systems (e.g., shortening the ignition delay time). On the contrary, these reactions have negligible importance for high‐temperature oxidation kinetics of NH3‐alcohol blends (e.g., not affecting the laminar flame speed). In addition, we calculated the rate coefficients for NH2 + CH4 = CH3 + NH3 reaction that are in excellent agreement with the experimental data.

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A quantum chemical and kinetics study on the unimolecular reactions of fuel radicals formed during the oxidation of n‐propylamine

Sone

Miyazaki

Sakai

2023

Int J of Quantum Chemistry

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The major intermediate product under co‐combustion conditions of hydrocarbon fuels with ammonia are amines. Herein, we have theoretically investigated the unimolecular reactions of fuel radicals formed during the oxidation of n‐propylamine. Quantum chemical calculations were performed to obtain the optimized structures and vibrational frequencies of reactants, products, and transition states at the B3LYP/aug‐cc‐pVTZ theory level. CCSD(T) single point energy calculations with the basis sets of aug‐cc‐pVDZ and aug‐cc‐pVTZ were further performed against the optimized structures, and the energies were extrapolated into infinite basis limit. Pressure‐dependent rate constants were calculated using Rice–Ramsperger–Kassel–Marcus/master equation analysis. The major reaction pathways for the fuel radicals were found to be β‐scission reactions at CC or CN bonds, and minor pathways were internal hydrogen shift and β‐scission reactions at CH or NH bonds. The calculated reaction rate constant trends were attributed to the decrease in CC and CN bond dissociation energies due to substitution effects from the amino group.

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A detailed chemical insights into the kinetics of diethyl ether enhancing ammonia combustion and the importance of NOx recycling mechanism

Cited by 79 publications

References 59 publications

Experimental and Kinetic Modeling Study of 1,3-Dioxolane Oxidation and Comparison with Dimethoxymethane

Experimental and Kinetic Modeling Study of 1,3-Dioxolane Oxidation and Comparison with Dimethoxymethane

A theoretical kinetic study of the reactions of NH₂ radicals with methanol and ethanol and their implications in kinetic modeling

A quantum chemical and kinetics study on the unimolecular reactions of fuel radicals formed during the oxidation of n‐propylamine

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A detailed chemical insights into the kinetics of diethyl ether enhancing ammonia combustion and the importance of NOx recycling mechanism

Cited by 79 publications

References 59 publications

Experimental and Kinetic Modeling Study of 1,3-Dioxolane Oxidation and Comparison with Dimethoxymethane

Experimental and Kinetic Modeling Study of 1,3-Dioxolane Oxidation and Comparison with Dimethoxymethane

A theoretical kinetic study of the reactions of NH2 radicals with methanol and ethanol and their implications in kinetic modeling

A quantum chemical and kinetics study on the unimolecular reactions of fuel radicals formed during the oxidation of n‐propylamine

Contact Info

Product

Resources

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A theoretical kinetic study of the reactions of NH₂ radicals with methanol and ethanol and their implications in kinetic modeling