@misc{GiriShresthaMaietal., author = {Giri, Binod Raj and Shrestha, Krishna Prasad and Mai, Tam V.-T. and Giri, Sushant and Adil, Mohammad and Naik, R. Thirumaleswara and Mauß, Fabian and Huynh, Lam Kim}, title = {A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends' Oxidation}, series = {Energies}, volume = {16}, journal = {Energies}, number = {16}, issn = {1996-1073}, doi = {10.3390/en16165943}, abstract = {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.}, language = {en} } @misc{GiriMaiShresthaetal., author = {Giri, Binod Raj and Mai, Tam V.-T. and Shrestha, Krishna Prasad and Giri, Sushant and Naik, R. Thirumaleswara and Verma, Rakhi and Mauss, Fabian and Huynh, Lam K.}, title = {Theoretical kinetic study of NH₂ reactions with dimethyl ether and diethyl ether : implications for kinetic modeling}, series = {International journal of chemical kinetics}, volume = {57}, journal = {International journal of chemical kinetics}, number = {6}, publisher = {Wiley}, address = {Hoboken, NJ}, issn = {0538-8066}, doi = {10.1002/kin.21779}, pages = {353 -- 363}, abstract = {Ammonia (NH₃) and hydrogen (H₂) have emerged as promising carbon-free fuels to help mitigate global warming by reducing greenhouse gas emissions. Our ongoing research currently focuses on understanding the combustion characteristics of NH₃ blends with oxygenates and hydrocarbons, uncovering the critical role of carbon-nitrogen cross-reactions in accurately modeling their combustion behavior. Amino (NH₂) radicals, which are abundant in ammonia and nitrogen-rich environments, strongly influence the low-temperature reactivity of NH₃-hydrocarbon/oxygenate mixtures, affecting overall reactivity and emission characteristics. Recognizing the importance of NH₂ radicals, we investigated the reaction kinetics of NH₂ with dimethyl ether (DME, CH₃OCH₃) and diethyl ether (DEE, CH₃CH₂OCH₂CH₃) using appropriate high-level ab initio and statistical rate theory methods. We computed the potential energy profiles at the CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ level of theory, analyzing the reactivity of NH₂ radicals at various C─H sites of these diethers. Incorporating these newly derived rate parameters, our updated kinetic model successfully captures previous experimental data, addressing the modeling challenges encountered in our earlier studies. Our findings, including insights into the impact of NH₂ radicals, contribute to an understanding of ammonia combustion and its potential in achieving carbon-neutral energy systems.}, language = {en} } @misc{EckartShresthaGirietal., author = {Eckart, Sven and Shrestha, Krishna P and Giri, Binod R and Fang, Qilong and Li, Wei and Mauss, Fabian and Krause, Hartmut and Li, Yuyang}, title = {Insight into premixed diethoxymethane flames: Laminar burning velocities, temperatures, and emissions behaviour}, series = {Proceedings of the Combustion Institute}, volume = {40}, journal = {Proceedings of the Combustion Institute}, publisher = {Elsevier}, doi = {10.1016/j.proci.2024.105579}, pages = {1 -- 7}, abstract = {Diethoxymethane ((CH3CH2O)2CH2, DEM) is a promising carbon-neutral fuel. DEM is a diether or acetal with a molecular structure similar to oxymethylene ethers (CH3O-(CH2O)n-CH3, OMEn). Thus, DEM can be expected to have a similar combustion behavior to OMEs, reducing harmful emissions such as NOx and particulate matter (PM) in internal combustion engines. From both experimental and kinetic modeling, fundamental studies on DEM are scarce in the literature. More studies are required to gain a detailed insight into the oxidation kinetics of DEM. Laminar burning velocity (LBV) is a critical property that allows a detailed assessment of the potential application of DEM in combustion devices. Unfortunately, the literature on the LBV of DEM is limited. Therefore, in this study we have investigated the LBV of DEM using two reactors for the first time, namely a heat flux burner and a combustion chamber. The experimental data is reported for equivalence ratio between 0.7 and 1.7, initial temperatures of 368-423 K, and initial pressure of 1-5 bar. In addition, we developed a detailed kinetic model extending our recent work of Shrestha et al. (Combust. Flame. 246 (2022) 112,426) to characterize the combustion behavior of DEM utilizing the new experimental data from this work and the literature data. Our model performs remarkably well in capturing the newly measured LBV experimental data over various experimental conditions. We found that DEM and dimethoxy methane (DMM) have similar values of LBVs (within ±1.5 cm/s) for a given condition, which indicates that intermediate chemistry governs the flame chemistry. Despite DEM being a larger molecule that is expected to have slightly lower LBVs than DMM, its effect on the measured values of LBVs is negligible. Finally, we experimentally measured NOx formation in DEM flame for the first time. The stochiometric flame has the highest NOx formation. The proposed model predicted the equivalence ratio dependence of NOx nicely. However, it overestimates the NOx formation for stoichiometric DEM/air mixtures by ∼30 \%. The model suggests that the thermal NO formation route is favored at lean and stochiometric conditions. In contrast, the prompt NO formation route is enhanced for rich mixtures.}, language = {en} } @misc{EckartShresthaGirietal., author = {Eckart, Sven and Shrestha, Krishna P and Giri, Binod R and Fang, Qilong and Chen, Chen and Li, Wei and Krause, Hartmut and Mauss, Fabian and Liu, Dong and Li, Yuyang}, title = {Chemical insights into ethyl acetate flames from experiment and kinetic modeling: Laminar burning velocity, speciation and NOx emission}, series = {Proceedings of the Combustion Institute}, volume = {40 (2024)}, journal = {Proceedings of the Combustion Institute}, publisher = {Elsevier}, doi = {10.1016/j.proci.2024.105487}, pages = {1 -- 7}, abstract = {Oxygenated fuels, such as alcohols, ethers, and esters, are promising alternatives to conventional fuels. These fuels can help reduce detrimental emissions like carbon monoxide and unburned hydrocarbons and enhance octane ratings. Among these oxygenates, ethyl acetate (EA), a small alkyl ester sourced from biomass, emerges as a clean, promising energy carrier. It serves as a surrogate fuel to facilitate investigations into the combustion behaviours of biodiesel. Despite its importance, the literature knowledge of EA combustion characteristics is limited. Therefore, this study aims to broaden the knowledge of the combustion behaviour of this type of oxygenated fuel compound. In this study, we measured the laminar burning velocities of EA by employing a heat flux burner and a closed combustion vessel over the equivalence ratios of 0.7 - 1.7, pressures of 1 - 10 bar and temperatures ranging from 353 - 423 K. Further, we also measured the NOx emissions in exhaust gas of the premixed flames fueled by EA/air for the first time over the equivalence ratio of 0.8 - 1.2. Additionally, we employed a non-premixed counterflow flame setup for extensive characterisation of species and their concentration under diverse conditions encompassing various strain rates and oxygen concentrations. Finally, we utilized these newly measured data to construct and validate a detailed kinetic model developed as part of this work. The newly developed model will help characterize the combustion properties of EA.}, language = {en} } @misc{UdaybhanuGiriLeeetal., author = {Udaybhanu, Gadi and Giri, Binod R. and Lee, Bok Jik and Shrestha, Krishna P. and Roberts, William L and Mauss, Fabian and Reddy, V. Mahendra}, title = {Investigation of staging techniques for hydrocarbon-assisted ammonia flames in a novel dual-stage combustor}, series = {Combustion and flame}, volume = {284}, journal = {Combustion and flame}, publisher = {Elsevier BV}, address = {Amsterdam}, issn = {0010-2180}, doi = {10.1016/j.combustflame.2025.114607}, pages = {1 -- 12}, abstract = {Ammonia presents itself as a high-hydrogen dense and carbon-free alternative for industrial heating, power generation, and transportation. Nevertheless, the challenges of its low flame speed and elevated NOx (nitrogen oxides) emissions pose significant challenges in combustor applications. This study investigates a novel two-stage burner employing a radial injection staging technique and explores various NOx reduction strategies for hydrocarbon-assisted ammonia flames. These strategies include premixing, fuel staging, balanced fuel staging, air staging, and sequential premixing. The focus is on LPG (liquid petroleum gas)-stabilized ammonia flames. The experiments are conducted at a constant thermal input of 20 kW (10 kW LPG + 10 kW NH3), with global equivalence ratios ranging from 0.7 to 1.4. This approach aims to provide valuable insights into the effectiveness of different staging strategies for NOx reduction in ammonia combustion. Experimental analysis is undertaken to ascertain the flame stabilization, flame temperature and its reaction zone, intermediate species and major emissions like NOx and NH3 of the burner. Staging configuration strongly influenced flame stabilization, heat release distribution, and thermal field, with downstream-shifted combustion zones lowering peak temperatures and NOx formation. Among the tested strategies, fuel staging and sequential premixing consistently achieved the greatest NOx reduction across the entire operating range compared to the premixed baseline, without compromising flame stability. Chemical kinetics analysis further reveals the dominant NO formation pathways, highlighting the key roles of HNO and NHi radicals. Additionally, this analysis helps identify dominant reaction routes and the role of intermediate species in NO formation and reduction processes. The combined experimental and kinetic insights provide a mechanistic basis for optimizing staged combustion of ammonia-hydrocarbon blends for lower NOx emissions.}, language = {en} }