NO mechanisms of syngas MILD combustion diluted with N2, CO2, and H2O

The NO mechanism under the moderate or intense low-oxygen dilution (MILD) combustion of syngas has not been systematically examined. This paper investigates the NO mechanism in the syngas MILD regime under the dilution of N₂, CO₂, and H₂O through counterflow combustion simulation. The syngas reaction mechanism and the counterflow combustion simulation are comprehensively validated under different CO/H₂ ratios and strain rates. The effects of oxygen volume fraction, CO/H₂ ratio, pressure, strain rate, and dilution atmosphere are systematically investigated. For all the MILD cases, the contribution of the prompt and NO-reburning routes to the overall NO emission is less than 0.1% due to the lack of CH₄ in fuel. At atmospheric pressure, the thermal route only accounts for less than 20% of the total NO emission because of the low reaction temperature. Moreover, at atmospheric pressure, the contribution of the NNH route to NO emission is always larger than 55% in the N₂ atmosphere. The N₂O-intermediate route is enhanced in CO₂ and H₂O atmospheres due to the increased third-body effects of CO₂ and H₂O through the reaction N₂ + O (+M) ? N₂O (+M). Especially in the H₂O atmosphere, the N₂O-intermediate route contributes to 60% NO at most. NO production is reduced with increasing CO/H₂ ratio or pressure, mainly due to decreased NO formation from the NNH route. Importantly, a high reaction temperature and low NO emission are simultaneously achieved at high pressure. To minimize NO emission, the reactions should be operated at high values of CO/H₂ ratios (i.e., >4) and pressures (e.g., P > 10 atm), low oxygen volume fractions (e.g., X_O2 < 15%), and using H₂O as a diluent. This study provides a new fundamental understanding of the NO mechanism of syngas MILD combustion in N₂, CO₂, and H₂O atmospheres.     

NO emission from non-premixed MILD combustion of biogas-syngas mixtures in opposed jet configuration

In this paper NO emission from MILD combustion of the mixture biogas-syngas is deeply elucidated, five NO routes were considered, specifically: thermal, prompt, NNH, N₂O and reburning. Several operating conditions are studied namely: fuel mixture composition, oxygen concentration in the oxidizer and injection velocity or strain rate. Biogas is modeled by a mixture of methane and carbon dioxide; while, syngas is considered to be composed by hydrogen and carbon monoxide, this gives a fuel mixture of CH₄/CO₂/H₂/CO. Volume of methane and hydrogen are varied alternatively from 0 to 50% in fuel mixture. Oxidizer is composed by O₂/N₂ mixture where oxygen volume is increased from 4 to 21%. Finally, injection strain rate is varied from apparition to vanishment of combustion. Atmospheric pressure is considered with constant fuel and oxidizer injection temperatures of 300 K and 1200 K respectively. Chemical kinetics of such complicated system is handled by a composed mechanism from the USC C₁–C₄ and the Gri 2.11 N-sub mechanism. It is found that under MILD regime, temperature intervals and levels are enhanced by hydrogen compared to methane. Furthermore, temperature levels keep relatively low which guarantees MILD regime. Contrariwise, when oxygen increases in oxidizer, temperature grows up rapidly and the MILD regime disappears. However, if strain rate augments, temperature shows a steep increase then reduces monotonically. It is observed that for low methane volume in the fuel mixture, NNH route dominates NO production. Whereas, when CH₄ increases, the prompt route is enhanced and exceeds NNH one at a methane volume of 12%. When hydrogen increases, prompt and NNH routes are enhanced with a domination of the prompt route until 44% of hydrogen volume. Oxygen increasing in the oxidizer improves thermal mechanism which surpasses prompt one at 17% of oxygen volume and governs NO production. Globally, the third most important route in NO production is the reburning one which is enhanced by all parameters except strain rate.     

Numerical modeling for structure and NOx formation characteristics of oxygen-enriched syngas turbulent non-premixed jet flames

The present study numerically investigated the effect of oxygen enrichment on the precise structure and NO_x formation characteristics of turbulent syngas non-premixed flames. The turbulence-chemistry interactions were represented by a Lagrangian flamelet model. In context with the Lagrangian flamelet model, the NO concentration was obtained directly from the flamelet calculation based on full NO_x chemistry, with radiative heat loss being accounted for through the flamelet energy equation. Computations were performed for three different syngas compositions with a designated nitrogen dilution level. Numerical results indicated that, for the CO-rich composition with the lowest LHV yielding the highest scalar dissipation rate and shortest flight time, the flame structure was dominantly influenced by turbulence-chemistry interactions. On the other hand, with regard to the H₂-rich composition with the highest LHV yielding the lowest injection velocity and longest flight time, the flame structure was strongly influenced by radiative cooling. The peak NO level was remarkably elevated by increased oxygen level due to the elevated temperature of the oxygen-enriched flame. In the enhanced oxygen level (30%), the H₂-rich case produced the highest NO level due to a higher temperature and longer residence time within the hot flame zone, while the CO-rich case yielded the lowest NO level due to a lower temperature and shorter residence time. It was also found that, by enhancing the oxygen level, contributions of NNH and N₂O to total NO emission rapidly decreased while the contributions of the thermal NO path were progressively dominant for all cases.     

Computed NOx emission characteristics of opposed-jet syngas diffusion flames

This paper reported a numerical study on the NO_x emission characteristics of opposed-jet syngas diffusion flames. A narrowband radiation model was coupled to the OPPDIF program, which used detailed chemical kinetics and thermal and transport properties to enable the study of 1-D counterflow syngas diffusion flames with flame radiation. The effects of syngas composition, pressure and dilution gases on the NO_x emission of H₂/CO synthetic mixture flames were examined. The analyses of detailed flame structures, chemical kinetics, and nitrogen reaction pathways indicate NO_x are formed through Zeldovich (or thermal), NNH and N₂O routes both in the hydrogen-lean and hydrogen-rich syngas flames at normal pressure. Zeldovich route is the main NO formation route. Therefore, the hydrogen-rich syngas flames produce more NO due to higher flame temperatures compared to that for hydrogen-lean syngas flames. Although NNH and N₂O routes also are the primary NO formation paths, a large amount of N₂ will be reformed from NNH and N₂O species. For hydrogen-rich syngas flames, the NO formation from NNH and N₂O routes are lesser, where NO can be dissipated through the reactions of NH + NO → N₂ + OH and NH + NO → N₂O + H more actively. At a rather low pressure (0.01 atm), NNH-intermediate route is the only formation path of NO. Increasing pressure then enhances NO formation reactions, especially through Zeldovich mechanisms. However, at higher pressures (5–10 atm), NO is then converted back to N₂ through reversed N₂O route for hydrogen-lean syngas flames, and through NNH as well for hydrogen-rich syngas flames. In addition, the dilution effects from CO₂, H₂O, and N₂ on NO emissions for H₂/CO syngas flames were studied. The hydrogen-lean syngas flames with H₂O dilution have the lowest NO production rate among them, due to a reduced reaction rate of NNH + O → NH + NO. But for hydrogen-rich syngas flames with CO₂ dilution, the flame temperatures decrease significantly, which leads to a reduction of NO formation from Zeldovich route.     

Numerical and experimental analysis of NO emissions from a lab-scale burner fed with hydrogen-enriched fuels and operating in MILD combustion

An experimental and computational investigation of a lab-scale burner, which can operate in both flame and MILD combustion conditions and is fed with methane and a methane/hydrogen mixture (hydrogen content of 60% by vol.), is carried out. The modelling results indicate the need of a proper turbulence/chemistry interaction treatment and rather detailed kinetic mechanisms to capture MILD combustion features, especially in presence of hydrogen. Despite these difficulties, Computational Fluid Dynamics results to be very useful, as for instance it allows evaluating the internal recirculation degree in the burner, a parameter which is otherwise difficult to be determined. Moreover the model helps interpreting experimental evidences: for instance the modelling results indicate that in presence of hydrogen the NNH and N₂O intermediate routes are the dominant formation pathways for the MILD combustion conditions investigated.     

NO formation of opposed-jet syngas diffusion flames: Strain rate and dilution effects

The NO formation characteristics and reaction pathways of opposed-jet H₂/CO syngas diffusion flames were analyzed with a revised OPPDIF program which coupled a narrowband radiation model with detailed chemical kinetics in this work. The effects of strain rates ranging from 0.1 to 1000 s^?1 and diluents including CO₂, H₂O and N₂ on NO production rates were investigated for three typical syngas compositions. The numerical results demonstrated that NO is produced primary through NNH-intermediate route and thermal route at high strain rates, where the reaction of NH + O = NO + H (R51) also become more active. Near the strain rate of 10 s^?1, the flame temperature is the highest and thermal route is the dominant NO formation route, but NO would be consumed by reburn route where NO is converted to NH through HNO, especially for H₂-rich syngas. At low strain rates, radiative heat loss results in a lower flame temperature and further reduce NO formation, while the reaction of N + CO₂ = NO + CO (R140) become more important, especially for CO-rich syngas. With the diluents, NO production rates decreased with increasing dilution percentages. When the flame temperature is very high as the thermal route is dominant near strain rate of 10 s^?1, CO₂ dilution makes flame temperature and NO production rate the lowest. Toward both lower and higher strain rates, adding H₂O is more effective in reducing NO because R140 and NNH-intermediate route are suppressed the most by H₂O dilution respectively.     

MILD combustion of hydrogenated biogas under several operating conditions in an opposed jet configuration

MILD combustion of biogas takes its importance firstly from the combustion process that diminishes significantly fuel consumption and reduces emissions and secondly from the use of biogas which is a renewable fuel. In this paper, the influence of several operating conditions (namely biogas composition, hydrogen enrichment and oxidizer dilution) is studied on flame structure and emissions. The investigation is conducted in MILD regime with a special focus on chemical effects of CO₂ in the oxidizer. Opposed jet diffusion combustion configuration is adopted. The combustion kinetics is described by the Gri 3.0 mechanism and the Chemkin code is used to solve the problem.It is found that oxygen reduction has a significant effect on flame temperature and emissions while less sensitivity corresponds to hydrogen enrichment in MILD combustion regime. Temperature and species are considerably reduced by oxygen decrease in the oxidizer and augmented by hydrogen addition to the fuel. The maximum values of temperature and species are not influenced by the composition of the biogas in MILD regime. Blending biogas with hydrogen can be used to sustain MILD combustion at very low oxygen concentration in the fuel.In MILD combustion regime, the chemical effect of CO₂ in the oxidizer stream reduces considerably the flame temperature and species production, except CO which is enhanced. For high amounts of CO₂ in the oxidizer, the chemical effect of CO₂ becomes negligible.     

NO formation in counterflow partially premixed flames

An experimental and computational study of NO formation in low-strain-rate partially premixed methane counterflow flames is reported. For progressive fuel-side partial premixing the peak NO concentration increased and the NO distribution along the stagnation streamline broadened. New temperature-dependent emissivity data for a SiO₂-coated Pt thermocouple was used to estimate the radiation correction for the thermocouple, thus improving the accuracy of the reported flame temperature. Flame structure computations with GRIMech 3.00 showed good agreement between measured and computed concentration distributions of NO and OH radical. With progressive partial premixing the contribution of the thermal NO pathway to NO formation increases. The emission index of NO (EINO) first increased and then decreased, reaching its peak value for the level of partial premixing that corresponds to location of the nonpremixed reaction zone at the stagnation plane. The observation of a maximum in EINO at a level of partial premixing corresponding to the nonpremixed reaction zone at the stagnation plane seems to be a consistent feature of low (<20 s⁻¹)-strain-rate counterflow flames.     

Detailed investigation of NO mechanism in non-premixed oxy-fuel jet flames with CH4/H2 fuel blends

This study systematically investigates the detailed mechanism of nitrogen oxides (NO_x) in CH₄ and CH₄/H₂ jet flames with O₂/CO₂ hot coflow. After comprehensive validation of the modeling by experiments of Dally et al. [Proc. Combust. Inst. 29 (2002) 1147–1154]; the effects of CO₂ replacement of N₂, mass fraction of oxygen in the coflow (Y_O2), and mass fraction of hydrogen in the fuel jet (Y_H2) on NO formation and destruction are investigated in detail. For methane oxy-fuel combustion, the NNH route is found to control the NO formation at Y_O2 ≤ 3%, while both NNH and N₂O-intermediate routes dominate the NO production at 3% < Y_O2 < 10%. When Y_O2 ≥ 10%, NO is obtained mainly from thermal mechanism. Moreover, in the oxy-combustion of methane and hydrogen fuel blends with Y_O2 = 3%, with hydrogen addition the contribution of the NNH and prompt routes increases, while that of the N₂O-intermediate route decreases. Furthermore, the chemical effect of CO₂ is significant in reducing NO in both oxy-combustion of methane with Y_O2 ≤ 3% and combustion of methane and hydrogen fuel blends with Y_H2 ≤ 10%.     

Burning syngas in a high swirl burner: Effects of fuel composition

Flame characteristics of swirling non-premixed H₂/CO syngas fuel mixtures have been simulated using large eddy simulation and detailed chemistry. The selected combustor configuration is the TECFLAM burner which has been used for extensive experimental investigations for natural gas combustion. The large eddy simulation (LES) solves the governing equations on a structured Cartesian grid using a finite volume method, with turbulence and combustion modelling based on the localised dynamic Smagorinsky model and the steady laminar flamelet model respectively. The predictions for H₂-rich and CO-rich flames show considerable differences between them for velocity and scalar fields and this demonstrates the effects of fuel variability on the flame characteristics in swirling environment. In general, the higher diffusivity of hydrogen in H₂-rich fuel is largely responsible for forming a much thicker flame with a larger vortex breakdown bubble (VBB) in a swirling flame compare to the H₂-lean but CO-rich syngas flames.     

Hydrogen turbulent nonpremixed flames blended with spray or prevapourised biofuels

The low radiant intensity of hydrogen flames may be enhanced by adding biofuels with a high sooting propensity. This paper reports the effect of biofuel concentration and phase on the combustion characteristics of turbulent nonpremixed hydrogen-based flames. The 0.2 and 1 mol% vapourised/spray biofuel surrogates blended flames exhibit limited soot loading, except for 1 mol% spray toluene and anisole blends where soot starts to form. Spray additives benefit the formation of soot by creating localised fuel-rich conditions. Blending 3.5 and 4 mol% vapourised toluene attains a sooting flame and significantly enhances the luminosity and radiant fraction. The global NO_x emissions increase with prevapourised/spray biofuel surrogates due to the enhanced NO formation via thermal and prompt routes. Reducing the hydrogen concentration from 9:1 to 7:3 in H₂/N₂ (by mole) leads to large increases in luminosity and radiant fraction by 34 times and 135%, respectively, and a reduction in NO_x emissions by 68%.     

Hydrogen addition effect on NO formation in methane/air lean-premixed flames at elevated pressure

The present study investigates freely propagating methane/hydrogen lean-premixed laminar flames at elevated pressures to understand the hydrogen addition effect of natural gas on the NO formation under the conditions of industrial gas turbine combustors. The detailed chemical kinetic model which was used in the previous study on the NO formation in high pressure methane/air premixed flames was adopted for the present study to analyze NO formation of methane/hydrogen premixed flames. The present mechanism shows good agreement with experimental data for methane/hydrogen mixtures, including ignition delay times, laminar burning velocities, and NO concentration in premixed flames. Hydrogen addition to methane/air mixtures with maintaining methane content leads to the increase of NO concentration in laminar premixed flames due to the higher flame temperature. Methane/hydrogen/argon/air premixed flames are simulated to avoid the flame temperature effect on NO formation over a pressure range of 1–20atm and equivalence ratio of 0.55. Kinetic analyses shows that the N₂O mechanism is important on NO formation for lean flames between the reaction zone and postflame region, and thermal NO is dominant in the postflame zone. The hydrogen addition leads to the increase of NO formation from prompt NO and NNH mechanisms, while NO formation from thermal and N₂O mechanisms are decreased. Additionally, the NO formation in the postflame zone has positive pressure dependencies for thermal NO with an exponent of 0.5. Sensitivity analysis results identify that the initiation reaction step for the thermal NO and the N₂O mechanism related reactions are sensitive to NO formation near the reaction zone.     

Combustion characteristics of H2/N2 and H2/CO syngas nonpremixed flames

Turbulent nonpremixed H₂/N₂ and H₂/CO syngas flames were simulated using 3D large eddy simulations coupled with a laminar flamelet combustion model. Four different syngas fuel mixtures varying from H₂-rich to CO-rich including N₂ have been modelled. The computations solved the Large Eddy Simulation governing equations on a structured non-uniform Cartesian grid using the finite volume method, where the Smagorinsky eddy viscosity model with the localised dynamic procedure is used to model the sub-grid scale turbulence. Non-premixed combustion has been incorporated using the steady laminar flamelet model. Both instantaneous and time-averaged quantities are analysed and data were also compared to experimental data for one of the four H₂-rich flames. Results show significant differences in both unsteady and steady flame temperature and major combustion products depending on the ratio of H₂/N₂ and H₂/CO in syngas fuel mixture.     

Experimental and numerical studies of the effects of hydrogen addition on the structure of a laminar methane–nitrogen jet in hot coflow under MILD conditions

In this work we investigate the effects of hydrogen addition on the flame structure of MILD combustion both experimentally and numerically using a laminar-jet-in-hot-coflow (LJHC) geometry. The addition of hydrogen appreciably decreases the flame height (∼25%), however only modestly affects the maximal flame temperature and the thickness of combustion zone. The NO distribution is dominated by mixing of the NO formed in the coflow with the reaction products of the diluted fuel, with negligible NO formation from the fuel in all flames studied. The numerical data are in reasonably good agreement with the measurements.     

Numerical study of the effect of hydrogen addition on methane–air mixtures combustion

The stoichiometric methane–hydrogen–air freely propagated laminar premixed flames at normal temperature and pressure were calculated by using PREMIX code of CHEMKIN II program with GRI-Mech 3.0 mechanism. The mole fraction profiles and the rate of production of the dominant reactions contributing to the major species and some selected intermediate species in the flames of methane–hydrogen–air were obtained. The rate of production analysis was conducted and the effect of hydrogen addition on the reactions of methane–air mixtures combustion was analyzed by the dominant elementary reactions for specific species. The results showed that the mole fractions of major species CH₄, CO and CO₂ were decreased while their normalized values were increased as hydrogen is added. The rate of production of the dominant reactions contributing to CH₄, CO and CO₂ shows a remarkable increase as hydrogen is added. The role of H₂ in the flame will change from an intermediate species to a reactant when hydrogen fraction in the blends exceeds 20%. The enhancement of combustion with hydrogen addition can be ascribed to the significant increase of H, O and OH in the flame as hydrogen is presented. The decrease of the mole fractions of CH₂O and CH₃CHO with hydrogen addition suggests a potential in the reduction of aldehydes emissions of methane combustion as hydrogen is added. The methane oxidation reaction pathways will move toward the lower carbon reaction pathways when hydrogen is available and this has the potential in reducing the soot formation. Chemical kinetics effect of hydrogen addition has a little influence on NO formation for methane combustion with hydrogen addition.     

Laminar burning velocities and flame characteristics of CO–H2–CO2–O2 mixtures

Laminar burning velocities of CO–H₂–CO₂–O₂ flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO₂ on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H₂–CO₂–O₂ mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO₂ fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO₂ fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO₂ fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO₂ fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO₂ in the flame. The CO₂ acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O₂ = O + OH, CO + OH = CO₂ + H and H + O₂(+M) = HO₂(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO₂ fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.     

A multiscale combustion model formulation for NOx predictions in hydrogen enriched jet flames

The present paper investigates the role of combustion models and kinetic mechanisms on the prediction of NO_x emissions in a turbulent combustion system where conventional and unconventional routes are equally important for NO_x formation. To this end, a lab-scale combustion system working in Moderate and Intense Low-oxygen Dilution (MILD) conditions, namely the Adelaide Jet in Hot Co-flow (JHC) burner, is targeted. The Eddy Dissipation Concept (EDC) and the Partially-Stirred Reactor (PaSR) models are used for turbulence-chemistry interactions. The KEE and GRI2.11 chemical mechanisms are employed. The results show that the choice of the combustion model has a higher impact than the selection of the kinetic mechanism for the investigated cases, indicating that biases in the turbulent reactive flow closure are as important, if not more, as the level of the accuracy of the chemical scheme employed. Moreover, the sensitivity of the NO emissions to the uncertain kinetic parameters of the rate-limiting reactions of the NNH pathway is found to be significant when a detailed kinetic mechanism is used. An engineering modification of the PaSR combustion model is proposed to account for the different chemical time scales of fuel oxidation reactions and NO_x formation pathways. It shows an equivalent impact on the emissions of NO than the uncertainty in the NNH pathway kinetics. At the cost of introducing a negligible mass imbalance, the adjustment leads to improved predictions of NO. The investigation establishes a possibility for the engineering modeling of NO formation in turbulent flames with a finite-rate chemistry combustion model that can incorporate a detailed mechanism at an affordable computational cost.     

Characterisation of hydrogen jet flames under different pressures with varying coflow oxygen concentrations

The elevated temperature of hydrogen combustion increases the formation of thermal NO_x. Moderate or intense low oxygen dilution (MILD) combustion is known to reduce NO_x emissions and increase thermal efficiency. Pressure is often also used for increasing thermal efficiency. The impact that pressure has on fluid dynamics and chemical kinetics is especially relevant in MILD combustion conditions. Hydrogen jet flames issuing into a hot and vitiated coflow were imaged using OH¹ chemiluminescence at different pressures (1–7 bar) and oxygen levels (3–9% by vol.). Laminar flame simulations complemented the experiments. The observed mean radial OH¹ width increased with increased pressure, but only at O₂ content less than 9%, suggesting that pressure has greater influence on kinetics when oxygen is reduced. The integrated OH¹ signal strength remained constant at 3% coflow O₂, despite an apparent increase in flame width, suggesting a spatial broadening of the flame with pressure. Numerical results indicate that at 3–6% O₂, conditions for MILD combustion of H₂ are met across a wide range of strains and pressures, supporting the experimental observations for 3% O₂.     

A detailed numerical study of NOx kinetics in low calorific value H2/CO syngas flames

The present study provides an extensive and detailed numerical analysis of NO_x chemical kinetics in low calorific value H₂/CO syngas flames utilizing predictions by five chemical kinetic mechanisms available out of which four deal with H₂/CO while the fifth mechanism (GRI 3.0) additionally accounts for hydrocarbon chemistry. Comparison of predicted axial NO profiles in premixed flat flames with measurements at 1 bar, 3.05 bar and 9.15 bar shows considerably large quantitative differences among the various mechanisms. However, at each pressure, the quantitative reaction path diagrams show similar NO formation pathways for most of the mechanisms. Interestingly, in counterflow diffusion flames, the quantitative reaction path diagrams and sensitivity analyses using the various mechanisms reveal major differences in the NO formation pathways and reaction rates of important reactions. The NNH and N₂O intermediate pathways are found to be the major contributors for NO formation in all the reaction mechanisms except GRI 3.0 in syngas diffusion flames. The GRI 3.0 mechanism is observed to predict prompt NO pathway as the major contributing pathway to NO formation. This is attributed to prediction of a large concentration of CH radical by the GRI 3.0 as opposed to a relatively negligible value predicted by all other mechanisms. Also, the back-conversion of NNH into N₂O at lower pressures (2–4 bar) was uniquely observed for one of the five mechanisms. The net reaction rates and peak flame temperatures are used to correlate and explain the differences observed in the peak [NO] at different pressures. This study identifies key reactions needing assessment and also highlights the need for experimental data in syngas diffusion flames in order to assess and optimize H₂/CO and nitrogen chemistry.     

Effects of ammonia substitution on extinction limits and structure of counterflow nonpremixed hydrogen/air flames

The potential of partial ammonia substitution to improve the safety of hydrogen use was evaluated computationally, using counterflow nonpremixed ammonia/hydrogen/air flames at normal temperature and pressure. The ammonia-substituted hydrogen/air flames were considered using a recent kinetic mechanism and a statistical narrow-band radiation model for a wide range of flame strain rates and the extent of ammonia substitution. The effects of ammonia substitution on the extinction limits and structure, including nitrogen oxide (NO_x) and nitrous oxide (N₂O) emissions, of nonpremixed hydrogen/air flames were investigated. Results show reduction of the high-stretch extinction (i.e., blow-off) limits, the maximum flame temperature and the concentration of light radicals (e.g., H and OH) with ammonia substitution in hydrogen/air flames, supporting the potential of ammonia as a carbon-free, clean additive for improving the safety of hydrogen use in nonpremixed hydrogen/air flames. For high-stretched flames, however, NO_x and N₂O emissions substantially increase with ammonia substitution even though ammonia substitution reduces flame temperature, implying that chemical effects (rather than thermal effects) of ammonia substitution on flame structure are dominant. Radiation effects on the extinction limits and flame structure are not remarkable particularly for high-stretched flames.