TY - GEN A1 - Shrestha, Krishna Prasad A1 - Giri, Binod Raj A1 - Elbaz, Ayman M. A1 - Issayev, Gani A1 - Roberts, William L. A1 - Seidel, Lars A1 - Mauß, Fabian A1 - Farooq, Aamir T1 - A detailed chemical insights into the kinetics of diethyl ether enhancing ammonia combustion and the importance of NOx recycling mechanism T2 - Fuel Communications N2 - In this work, we investigated the combustion characteristics of ammonia (NH3) by blending it with various proportions of diethyl ether (DEE). We measured laminar flame speed of various NH3/DEE blends (DEE, 10–40% by mole) using a constant volume spherical vessel at Ti = 298 K and Pi = 3 and 5 bar and Φ = 0.8–1.3. We developed a detailed kinetic model to describe the trends of the current and previously published experimental data. For the robustness of the model, we first developed a comprehensive diethyl ether kinetic mechanism to accurately characterize neat DEE oxidation behavior. We validated the kinetic model using a large pool of experimental data comprising shock tube, rapid compression machine, jet-stirred and flow reactors, freely propagating, and burner-stabilized premixed flames. The developed kinetic model performs remarkably in capturing the combustion behavior of pure DEE and NH3. Importantly, our model captures the experimental data of laminar flame speed and ignition delay times of various NH3/DEE blends over a wide range of conditions. We found that DEE is a promising candidate to promote the combustion characteristics of NH3. A small portion of DEE (10%) enhances the laminar flame speed of NH3 by a factor of 2 at Pi = 1 bar, Ti = 298 K, and Φ = 1.0. A further doubling of the DEE mole fraction to 20% did not enhance the laminar flame speed of NH3 with the same propensity. At low temperatures, adding 5% DEE in NH3 blend has significantly expedited the system reactivity by lowering the autoignition temperature. A further 5% increment of DEE (i.e., 10% DEE in NH3) lowers the autoignition temperature by ∼120 K to achieve the same ignition delay time. The “NOsingle bondNO2” looping mechanism predominantly drives such reactivity accelerating effect. Here, the reactions, NO + HO2 = NO2 + OH and NO2 + H = NO + OH, appear to enhance the reactive radical pool by generating OH radicals. We observed that the HNO path is favored more with increasing DEE content which eventually liberates NO. Other key reactions in “NOsingle bondNO2” looping mechanism are: CH3 + NO2 = CH3O + NO, CH3O2 + NO = CH3O + NO2, C2H5 + NO2 = C2H5O + NO, C2H5O2 + NO = C2H5O + NO2. In addition, CH3 + NH2(+M) = CH3NH2(+M) reaction is also one of the important cross-reactions which leads to the formation of HCN. Therefore, cross-reactions between the nitrogen and carbon family are crucial in accurately predicting autoignition timing. This work provides a detailed chemical insight into the NH3 and DEE interaction, which could be applied to other fuel blends of NH3. The kinetic model is also validated for several C1single bondC3 fuels including their interaction with NOx. KW - DEE KW - Ammonia KW - Kinetic Model KW - Laminar flame speed KW - Ignition delay time Y1 - 2022 U6 - https://doi.org/10.1016/j.jfueco.2022.100051 SN - 2666-0520 VL - 10 ER - TY - GEN A1 - Giri, Binod Raj A1 - Shrestha, Krishna Prasad A1 - Mai, Tam V.-T. A1 - Giri, Sushant A1 - Adil, Mohammad A1 - Naik, R. Thirumaleswara A1 - Mauß, Fabian A1 - Huynh, Lam Kim T1 - A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation T2 - Energies N2 - The reaction of NH2 radicals with C3H8 is crucial for understanding the combustion behavior of NH3/C3H8 blends. In this study, we investigated the temperature dependence of the rate coefficients for the hydrogen abstraction reactions of C3H8 by NH2 radicals using high-level theoretical approaches. The potential energy surface was constructed at the CCSD(T)/cc-pV(T, Q)//M06-2X/aug-cc-pVTZ level of theory, and the rate coefficients were computed using conventional transition state theory, incorporating the corrections for quantum tunneling and hindered internal rotors (HIR). The computed rate coefficients showed a strong curvature in the Arrhenius behavior, capturing the experimental literature data well at low temperatures. However, at T > 1500 K, the theory severely overpredicted the experimental data. The available theoretical studies did not align with the experiment at high temperatures, and the possible reasons for this discrepancy are discussed. At 300 K, the reaction of NH2 with C3H8 predominantly occurs at the secondary C-H site, which accounts for approximately 95% of the total reaction flux. However, the hydrogen abstraction reaction at the primary C-H site becomes the dominant reaction above 1700 K. A composite kinetic model was built, which incorporated the computed rate coefficients for NH2 + C3H8 reactions. The importance of NH2 + C3H8 reactions in predicting the combustion behavior of NH3/C3H8 blends was demonstrated by kinetic modeling. Y1 - 2023 U6 - https://doi.org/10.3390/en16165943 SN - 1996-1073 VL - 16 IS - 16 ER - TY - GEN A1 - Elbaz, Ayman M. A1 - Giri, Binod Raj A1 - Shrestha, Krishna Prasad A1 - Arab, Omar Z. A1 - Farooq, Aamir A1 - Mauß, Fabian A1 - Roberts, William L. T1 - A comprehensive experimental and kinetic modeling study of laminar flame propagation of ammonia blended with propene T2 - Combustion and Flame N2 - Enhancement of ammonia reactivity is crucial for potential applications of ammonia as an engine and gas turbine fuel. A common strategy for improving ammonia's poor reactivity is blending it with more reactive fuels like hydrogen and methane. However, fundamental studies of ammonia combustion with higher hydrocarbons and key intermediate oxidation species of higher alkanes such as propene do not exist. Thus, this work presents an effort to study the laminar flame propagation of ammonia blended with propene. Laminar burning velocity (SL) of NH3/C3H6/air mixtures was measured at 298 K, pressures up to 5 bar, equivalence ratios of 0.7 to 1.3, and various propene to ammonia ratios (i.e.,% propene to ammonia mole fraction, xC3H6 = 10 to 50) in a high-pressure spherical propagating flame vessel. A kinetic model was developed based on our previous work to characterize the combustion behavior of NH3/C3H6/air mixture. The model reasonably agrees with the experimental data and follows the observed trends very well. The results showed that blending NH3 with C3H6 positively enhanced SL of NH3 by promoting the formation of key radicals e.g., O, OH, and H. Relative to a neat ammonia/air mixture, co-firing ammonia with propene leads to a reduced pressure dependence of the laminar burning velocity. However, the reaction H + O2(+M)=HO2(+M) leads to strong pressure dependency of lean NH3/C3H6 mixtures compared to rich mixtures. The model reveals that besides fuel-NO coming from NH3, prompt NO also actively contributes to NO formation. It is seen that N2O formation is significantly suppressed with increasing pressure or increasing C3H6 content in the fuel blend. In contrast to NO and N2O, NO2 concentration increases slightly with an increase in pressure. The reported experimental data and model will be useful in understanding the interaction between NH3 and alkenes. Y1 - 2023 U6 - https://doi.org/10.1016/j.combustflame.2023.112791 SN - 0010-2180 VL - 253 ER - TY - GEN A1 - Giri, Binod Raj A1 - Shrestha, Krishna Prasad A1 - Mai, Tam V.-T. A1 - Mauß, Fabian A1 - Huynh, Lam Kim T1 - A theoretical kinetic study of the reactions of NH2 radicals with methanol and ethanol and their implications in kinetic modeling T2 - International Journal of Chemical Kinetics N2 - 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. Y1 - 2023 U6 - https://doi.org/10.1002/kin.21609 SN - 0538-8066 VL - 55 IS - 1 SP - 3 EP - 14 ER - TY - GEN A1 - Shrestha, Krishna Prasad A1 - Eckart, Sven A1 - Drost, Simon A1 - Fritsche, Chris A1 - Schießl, Robert A1 - Seidel, Lars A1 - Maas, Ulrich A1 - Krause, Hartmut A1 - Mauß, Fabian T1 - A comprehensive kinetic modeling of oxymethylene ethers (OMEn, n= 1–3) oxidation-laminar flame speed and ignition delay time measurements T2 - Combustion and Flame N2 - This work reports on the development and experimental validation of a detailed reaction mechanism for the oxidation of polyoxymethylene dimethyl ethers (OMEn, n = 1–3). The validation is done by constant-volume chamber laminar flame speeds (393 K and 443 K, 1 to 5 bar, and equivalence ratio 0.8 to 1.6) and Rapid Compression Machine ignition delay times (550–680 K, 10 and 15 bar, equivalence ratios of 0.5–2.0) in OMEn/air mixtures. Using our new experimental and published data, the validation basis for the new kinetic model comprises the pyrolysis and oxidation of OMEn (n = 1–3) in freely propagating flames, auto-ignition in rapid compression machines and shock tubes, and speciation in jet-stirred and flow reactors as well as burner-stabilized premixed flames. The model provides a reasonable agreement with the experimental data for a broad range of conditions investigated. The performance of the developed model is compared against the recent literature models. OMEn (n = 1–3) all have the same laminar flame speed. The model suggests that the chemistry of OME0 (DME) and CH3OCHO (methyl formate) is the one that dictates the flame chemistry. Under the same pressure and equivalence ratio conditions, ignition delay times of OME2 and OME3 are similar for the investigated temperature range. This work helps to improve the understanding of OMEs chemistry. The model developed in this work will serve as the base mechanism for higher chain length OMEs (n>3). Y1 - 2022 U6 - https://doi.org/10.1016/j.combustflame.2022.112426 SN - 1556-2921 SN - 0010-2180 VL - 246 ER - TY - GEN A1 - Shrestha, Krishna Prasad A1 - Elbaz, Ayman M. A1 - Giri, Binod Raj A1 - Arab, Omar Z. A1 - Adil, Mohammad A1 - Seidel, Lars A1 - Roberts, William L. A1 - Farooq, Aamir A1 - Mauß, Fabian T1 - Experimental and Kinetic Modeling Study of 1, 3-Dioxolane Oxidation and Comparison with Dimethoxymethane T2 - Energy & Fuels N2 - 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. Y1 - 2022 U6 - https://doi.org/10.1021/acs.energyfuels.2c01132 SN - 1520-5029 SN - 0887-0624 VL - 36 IS - 14 SP - 7744 EP - 7754 ER - TY - GEN A1 - Rossi, Edoardo A1 - Bargende, Michael A1 - Kulzer, André Casal A1 - Chiodi, Marco A1 - Massoud, Ehab A1 - Shrestha, Krishna Prasad A1 - Mauß, Fabian T1 - Analysis of the applicability of Water Injection in Combination with an eFuel for Knock Mitigation and Improved Engine Efficiency T2 - SAE Technical Paper N2 - The development of future gasoline engines is dominated by the study of new technologies aimed at reducing the engine negative environmental impact and increase its thermal efficiency. One common trend is to develop smaller engines able to operate in stoichiometric conditions across the whole engine map for better efficiency, lower fuel consumption, and optimal conversion rate of the three-way catalyst (TWC). Water injection is one promising technique, as it significantly reduces the engine knock tendency and avoids fuel enrichment for exhaust temperature mitigation at high power operation. With the focus on reducing the carbon footprint of the automotive sector, another vital topic of research is the investigation of new alternative CO2-neutral fuels or so-called eFuels. Several studies have already shown how these new synthetic fuels can be produced by exploiting renewable energy sources and can significantly reduce engine emissions. This work is part of the FVV project number 1367, “Water Injection in Spark-Ignition Engines II”, which investigates the coexistence of two different engine technologies that heads towards the same direction of sustainability of the internal combustion engine: water injection and eFuels. The goal is to assess the advantages that the adoption of an eFuel in combination with water injection strategies can bring, with respect to the same strategies applied in combination with commercial gasoline. Several water injection strategies, including direct water injection, indirect water injection, injection timing, and pressure variations, are considered for a better understanding of the benefits brought by the combination of an eFuel with water injection. For this purpose, experimental tests and 3D-CFD engine simulations have been performed. The physical properties of the investigated eFuel have been experimentally measured for accurate modelling in the simulation environment, and the thermodynamic properties have been evaluated utilizing detailed chemistry calculations. Y1 - 2022 U6 - https://doi.org/10.4271/2022-37-0019 SN - 2688-3627 SN - 0148-7191 ER - TY - GEN A1 - Manna, Maria Virginia A1 - Sabia, Pino A1 - Shrestha, Krishna Prasad A1 - Seidel, Lars A1 - Ragucci, Raffaele A1 - Mauß, Fabian A1 - De Joannon, Mara T1 - NH3NO interaction at low-temperatures: an experimental and modeling study T2 - Proceedings of the Combustion Institute N2 - The present work provides new insight into NH3single bondNO interaction under low-temperature conditions. The oxidation process of neat NH3 and NH3 doped with NO (450, 800 ppm) was experimentally investigated in a Jet Stirred Flow Reactor at atmospheric pressure for the temperature range 900–1350 K. Results showed NO concentration is entirely controlled by DeNOx reactions in the temperature range 1100–1250 K, while NH3single bondNO interaction does not develop through a sensitizing NO effect, for these operating conditions. A detailed kinetic model was developed by systematically updating rate constants of controlling reactions and declaring new reactions for N2H2 isomers (cis and trans). The proposed mechanism well captures target species as NO and H2 profiles. For NH3single bondNO mixtures, NO profiles were properly reproduced through updated DeNOx chemistry, while NH2 recombination reactions were found to be essential for predicting the formation of H2. The role of ammonia as a third-body species is implemented in the updated mechanism, with remarkable effects on species predictions. For neat NH3 mixture, the reaction H+O2(+M)=HO2(+M) was crucial to predict NO formation via the reaction NH2+HO2double bondH2NO+OH. Y1 - 2023 U6 - https://doi.org/10.1016/j.proci.2022.09.027 SN - 1873-2704 VL - 39 IS - 1 SP - 775 EP - 784 ER - TY - GEN A1 - Mai, Tam V.-T. A1 - Bui, Thanh Q. A1 - Nhung, Nguyen Thi Ai A1 - Quy, Phan Tu A1 - Shrestha, Krishna Prasad A1 - Mauß, Fabian A1 - Giri, Binod Raj A1 - Huynh, Lam Kim T1 - An Ab Initio RRKM-Based Master Equation Study for Kinetics of OH-Initiated Oxidation of 2-Methyltetrahydrofuran and Its Implications in Kinetic Modeling T2 - Energies N2 - Cyclic ethers (CEs) can be promising future biofuel candidates. Most CEs possess physico-chemical and combustion indicators comparable to conventional fuels, making them suitable for internal combustion engines. This work computationally investigates the kinetic behaviors of hydrogen abstraction from 2-methyl tetrahydrofuran (2MTHF), one of the promising CEs, by hydroxyl radicals under combustion and atmospheric relevant conditions. The various reaction pathways were explored using the CCSD(T)/cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory. The Rice–Ramsperger–Kassel–Marcus-based master equation (RRKM-ME) rate model, including treatments for hindered internal rotation and tunneling, was employed to describe time-dependent species profiles and pressure and temperature-dependent rate coefficients. Our kinetic model revealed that the H-abstraction proceeds via an addition-elimination mechanism forming reaction complexes at both the entrance and exit channels. Eight different reaction channels yielding five radical products were located. The reaction exhibited complex kinetics yielding a U-shaped Arrhenius behavior. An unusual occurrence of negative temperature dependence was observed at low temperatures, owing to the negative barrier height for the hydrogen abstraction reaction from the C-H bond at the vicinity of the O-atom. A shift in the reaction mechanism was observed with the dominance of the abstraction at Cα-H of 2MTHF ring (causing negative-T dependence) and at CH3 (positive-T dependence) at low and high temperatures, respectively. Interestingly, the pressure effect was observed at low temperatures, revealing the kinetic significance of the pre-reaction complex. Under atmospheric pressure, our theoretical rate coefficients showed excellent agreement with the available literature data. Our model nicely captured the negative temperature-dependent behaviors at low temperatures. Our predicted global rate coefficients can be expressed as k (T, 760 Torr) = 3.55 × 101 × T−4.72 × exp [−340.0 K/T] + 8.21 × 10−23 × T3.49 × exp [918.8 K/T] (cm3/molecule/s). Our work provides a detailed kinetic picture of the OH-initiated oxidation kinetics of 2MTHF. Hence, this information is useful for building a kinetic me chanism for methylated cyclic ethers. KW - ab initio KW - RRKM-ME calculations KW - 2-methyl tetrahydrofuran KW - OH radicals KW - kinetic modeling Y1 - 2023 U6 - https://doi.org/10.3390/en16093730 SN - 1996-1073 VL - 16 IS - 9 ER - TY - GEN A1 - Giri, Binod Raj A1 - Palacios, Manuel Monge A1 - Thangaraj, Ravikumar A1 - Shrestha, Krishna Prasad A1 - Viskolcz, Béla A1 - Mauss, Fabian A1 - Szőri, Milán T1 - An Ab initio based OH initiated oxidation kinetics of glycerol carbonate: A promising biofuel component T2 - Proceedings of the Combustion Institute N2 - The global energy demand is steadily increasing because of the population explosion and economic growth. Fossil fuels supply around 85 % of global primary energy demand. On one hand, fulfilling the increasing energy demands is a big challenge for the next few decades. On the other hand, the continued burning of fossil fuels leads to higher CO2 emissions, severely impacting global warming. Therefore, the policymakers vow to shift from conventional fuels to renewable resources for economic, environmental, and future energy security reasons. In this context, biofuels from lignocellulosic biomass and/or carbon-neutral fuels produced in the sustainable carbon cycle can close the carbon cycle and reach net zero-carbon emission. Recently, glycerol carbonate has been proposed as a promising fuel or fuel additive for future sustainability. Therefore, we investigated the hydrogen abstraction reactions of glycerol carbonate (GC) by OH radicals using high-level ab initio and variational transition state theory calculations. We mapped out the potential energy surface using the CCSD(T)/cc-pV(D, T)Z//MP2/cc-pVTZ level of theory. We used the ab initio parameters to obtain the site-specific rate coefficients by employing the variational transition state theory. We observed that every hydrogen atom in GC displays a unique reactivity with OH radicals. We derived branching ratio of each channel that are difficult to access experimentally. The overall rate coefficients exhibit a strong non-Arrhenius behaviour, which can be represented as: This is the first reported rate data for the glycerol carbonate and OH radicals reaction. Y1 - 2024 UR - https://www.sciencedirect.com/science/article/abs/pii/S1540748924004760 U6 - https://doi.org/10.1016/j.proci.2024.105668 VL - 40 SP - 1 EP - 8 PB - Elsevier ER -