Chemical kinetic modeling of ammonia oxidation with improved reaction mechanism for ammonia/air and ammonia/hydrogen/air combustion

To achieve comprehensive prediction of ammonia combustion in terms of flame speed and ignition delay time, an improved mechanism of ammonia oxidation was proposed in this work. The present model (UT-LCS) was based on a previous work [Song et al., 2016] and improved by relevant elementary reactions including NH₂, HNO, and N₂H₂. The model clearly explained reported values of laminar flame speed and ignition delay time in wide ranges of equivalence ratio and pressure. This suggests that NH₂, HNO, and N₂H₂ reactivities play a key role to improve the reaction mechanism of ammonia oxidation in the present model. The model was also applied to demonstrate NH₃/H₂/air combustion. The present model also appropriately predicted the laminar flame speed of NH₃/H₂/air combustion as a function of equivalence ratio. Using the model, we discussed the reduction of NO concentration downstream and H₂ formation via NH₃ decomposition in NH₃/H₂ fuel-rich combustion. The results provide suggestions for effective combustion of NH₃ for future applications.     

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.     

Studies on properties of laminar premixed hydrogen-added ammonia/air flames for hydrogen production

In order to evaluate the potential of burning and reforming ammonia as a carbon-free fuel in production of hydrogen, fundamental unstretched laminar burning velocities, and flame response to stretch (represented by the Markstein number) for laminar premixed hydrogen-added ammonia/air flames were studied both experimentally and computationally. Freely (outwardly)-propagating spherical laminar premixed flames at normal temperature and pressure were considered for a wide range of global fuel-equivalence ratios, flame stretch rates (represented by the Karlovitz number) and the extent of hydrogen substitution. Results show the substantial increase of laminar burning velocities with hydrogen substitution, particularly under fuel-rich conditions. Also, predicted flame structures show that the hydrogen substitution enhances nitrogen oxide (NO_x) and nitrous oxide (N₂O) formation. At fuel-rich conditions, however, the amount of NO_x and N₂O emissions and the extent of the increase with the hydrogen substitution are much lower than those under fuel-lean conditions. These observations support the potential of hydrogen as an additive for improving the burning performance with low NO_x and N₂O emissions in fuel-rich ammonia/air flames and hence the potential of using ammonia as a clean fuel. Increasing the amount of added hydrogen tends to enhance flame sensitivity to stretch.     

Laminar burning characteristics of ammonia/hydrogen/air mixtures with laser ignition

Ammonia, as a zero-carbon fuel, is drawing more and more attention. The major challenge of using ammonia as a fuel for the combustion engines lies in its low chemical reactivity, and therefore more fundamental researches on the combustion characteristics of ammonia are required to explore effective ways to burn ammonia in engines. In this study, the laminar burning characteristics of the premixed ammonia/hydrogen/air mixtures are investigated. In the experiment, the laser ignition was used to achieve stable ignition of the ammonia/air mixtures with an equivalence ratio range from 0.7 to 1.4. The propagating flame was recorded with the high-speed shadowgraphy. Three different processing methods were introduced to calculate the laminar burning velocity with a consideration of the flame structure characteristics induced by the laser ignition. The effects of initial pressure (0.1 MPa–0.5 MPa), equivalence ratio (0.7–1.4), hydrogen fraction (0–20%) on the laminar burning velocity were investigated under the initial ambient temperature of 360 K. The state-of-the-art kinetic models were used to calculate the laminar burning velocities in the CHEMKIN-pro software. Both the simulation and experimental results show that the laminar burning velocity of the ammonia mixtures increases at first, reaches the peak around ϕ of 1.1, and then decreases with the equivalence ratio increasing from 0.7 to 1.4. The peak laminar burning velocities of the ammonia mixture are lower than 9 cm/s and are remarkably lower than those of hydrocarbon fuels. The laminar burning velocity of the ammonia mixture decreases with the increase of the initial ambient pressure, and it can be drastically speeded up with the addition of hydrogen. While the models except for those by Miller and Bian can give reasonable predictions compared to the experimental results for the equivalence ratio from 0.7 to 1.1 in the ammonia (80%)/hydrogen (20%)/air mixtures, all the kinetic models overpredict the experiments for the richer mixtures, indicating further work necessary in this respect.     

Experimental investigation of premixed combustion limits of hydrogen and methane additives in ammonia

In this study, a specially designed premixed combustion chamber system for ammonia-hydrogen and methane-air laminar premixed flames is introduced and the combustion limits of ammonia-hydrogen and methane-air flames are explored. The measurements obtained the blow-out limits (mixed methane: 400–700 mL/min, mixed hydrogen: 200–700 mL/min), mixing gas lean limit characteristics (mixed methane: 0–82%, mixed hydrogen: 0–37%) and lean/rich combustion characteristics (mixed methane: ? = 0.6–1.9, mixed hydrogen: ? = 0.9–3.2) of the flames. The results show that the ammonia-hydrogen-air flame has a smaller lower blow-out limit, mixing gas ratio, lean combustion limit and higher rich combustion limit, thereby proving the advantages of hydrogen as an effective additive in the combustion performance of ammonia fuel. In addition, the experiments show that increasing the initial temperature of the premixed gas can expand the lean/rich combustion limits of both the ammonia-hydrogen and ammonia-methane flames.     

End-gas autoignition and knocking combustion of ammonia/hydrogen/air mixtures in a confined reactor

End-gas autoignition and detonation development in ammonia/hydrogen/air mixtures in a confined reactor is studied through detailed numerical simulations, to understand the knocking characteristics under IC engine relevant conditions. One-dimensional planar confined chamber filled with ammonia/hydrogen/air mixtures is considered. Various initial end-gas temperature and hydrogen concentration in the binary fuels are considered. Homogeneous ignition of stochiometric ammonia/hydrogen/air mixtures is firstly calculated. It is found that H₂ addition significantly promotes autoignition, even if the amount of addition is small. For ammonia/air mixtures and ammonia/hydrogen/air mixtures with low hydrogen mole ratios, it is found from chemical explosive mode analysis results that NH₂ and H₂NO are most important nitrogen-containing species, and R49 (NH₂+NO<=>N₂+H₂O) is a crucial reaction during thermal runaway process. When the hydrogen mole ratio is high, the nitrogen-containing species and reactions on chemical explosive mode becomes less important. Moreover, a series of one-dimensional simulations are carried out. Three end-gas autoignition and combustion modes are observed, which includes forcibly ignited flame propagation, autoignition (no detonation), and developing detonation. These modes are identified within wide ranges of hydrogen contents and initial end-gas temperatures. Furthermore, chemical kinetics at the reaction front and autoignition initiation locations are also studied with chemical explosive mode analysis. Finally, different thermochemical conditions on knocking intensity and timing are investigated. It is found that a higher initial temperature or a higher H₂ content does not always lead to a higher knocking intensity, and the knocking timing decreases with the reactivity of end-gas.     

Effects of O2 enrichment on NH3/air flame propagation and emissions

The potential utilization of ammonia as a carbon-free fuel under oxygen (O₂)-enriched condition is demonstrated, suggesting its practically appropriate burning conditions by measuring and predicting the combustion characteristics of outwardly-propagating spherical O₂-enriched NH₃/air premixed flames at normal temperature and pressure. Measured and computed laminar burning velocities and predicted flame structure exhibit that the O₂-enriched ammonia/air flames become thinner and propagate faster with O₂ enrichment. Observed flame morphologies and measured and computed Markstein numbers reveal that all the present O₂-enriched flames are stable in terms of the flamefront cellular instability due to preferential diffusion and the effects of O₂ enrichment on the instability are negligible. Volume-based 35–40% O₂ in the nonfuel mixtures demonstrates the proper burning intensity for practical applications, comparable to the typical hydrocarbon/air flames. In the present flame configuration, however, local nitrogen oxides emissions are found to be high, which should be substantially reduced in the practical systems.     

Theoretical investigation of the combustion performance of ammonia/hydrogen mixtures on a marine diesel engine

Ammonia is a good hydrogen carrier and can be well combined with hydrogen for combustion. The combustion performance of the mixtures of ammonia and hydrogen in a medium-speed marine diesel engine was investigated theoretically. The HCCI combustion mode was selected for reducing thermal-NO_x production. The start fire characteristic of the NH₃–H₂ mixtures was studied under different equivalence ratio, hydrogen-doped ratio, and intake air temperature and pressure. Then, the combustion performance of the NH₃–H₂ mixtures (doping 30% hydrogen) was analyzed at a typical operation condition of engine. The addition hydrogen improved the laminar flame velocity of ammonia, and affected the NO_x emission. For the medium-speed marine engine fueled with NH₃–H₂, reducing combustion temperature, introducing EGR and combining with post-treatment technology would be a feasible scheme to reduce NO_x emission.     

The characteristics of flame propagation in hydrogen/oxygen mixtures

The extreme explosiveness and high flame velocity of hydrogen challenge its application. Overcoming these challenges requires improving the fundamental flame characteristics of H₂/O₂ mixtures. In this study, the propagation characteristics of H₂/O₂ flames are investigated. The laminar burning velocity (LBV) is evaluated using nonlinear extrapolation. The empirical relations of LBV are given with the equivalence ratio (ER) and initial mixture pressure (IMP). The LBV increases first and then decreases as the ER increases and reaches its maximum value at the ER slightly higher than 1.0 (φ = 1.1–1.2). The LBV increases monotonically with increasing IMP. The critical instability radius and Markstein length increase as the ER increases, while decreasing with the IMP increase. The flame thickness decreases significantly with increasing IMP. The flame remains stable and smooth throughout the propagation process for all examined ERs only at the lower IMPs of 0.1 atm and 0.3 atm.     

Properties of premixed hydrogen/propane/air flame in ceramic granular beds

This study investigated how various H₂ concentrations of fuel mixed with a ceramic granular bed (CGB) affect the propagation characteristics of a premixed C₃H₈/air flame. The results showed that at low firing rates (Γ < 1.5 kJ/s), as Γ increased, adding H₂ exerted little effect on the flame temperature and absolute flame front velocity (S_ab); however, at high Γ (Γ > 1.5 kJ/s), as Γ increased, adding H₂ caused a significant decrease in the flame temperature and a substantial increase in S_ab. Thus, heat transfer was not obvious, and the flame reaction zone was relatively broad. Although adding H₂ moved the flame reaction zone upstream, the heat transfer mechanism reduced the effect that resulted from adding H₂ under low Γ conditions. Because of the characteristics of H₂, the flame reaction zones moved upstream, causing the flame thickness and heat loss to increase. Adding H₂ decreased the flame temperature and increased S_ab.     

Premixed ammonia/hydrogen swirl combustion under rich fuel conditions for gas turbines operation

Energy storage is one of the highest priority challenges in transitioning to a low-carbon economy. Fluctuating, intermittent primary renewable sources such as wind and solar require low-carbon storage options to enable effective load matching, ensuring security of supply. Chemical storage is one such option, with low or zero carbon fuels such as hydrogen, alcohols and ammonia having been proposed. Ammonia provides zero-carbon hydrogen storage whilst offering liquefaction at relatively low pressures and atmospheric temperatures, enabling ease of transportation in a pre-existing infrastructure. Ammonia can also be used directly as a fuel in power plants such as gas turbines to avoid complete conversion back to hydrogen. It is a relatively unreactive fuel, and so it is of interest to explore the potential utilisation of ammonia/hydrogen mixtures. Hence, the goal of this paper is to provide a first assessment of the suitability of a chosen 70%NH₃30%H₂ (%vol) blend for utilisation within a gas turbine environment, based on primary combustion diagnostics including combustion stability – via OH chemiluminescence - and emissions (NO_x and NH₃). An established optical generic swirl-burner enabled studies of the influence of equivalence ratio (φ > 1), ambient temperature (<484 ± 10 K) and bypass air, with a focus on NO_x reduction, one of the main challenges for ammonia combustion. A numerical GT cycle model is developed alongside the experimental investigation. The results demonstrate that the blend has considerable potential as a fuel substitute with reasonable combustion stability and significant reduction of emissions for the cases without bypass air, due to increased chemical reactivity of unburned ammonia. However, emissions are still above those recommended for gas turbine cycles, with a theoretical cycle that still produces low efficiencies compared to DLN methane, highlighting the requirement for new injection techniques to reduce NO_x/unburned NH₃ in the flue gases whilst ensuring increased power outputs.     

Strong flame interaction-induced collective dynamics of multi-element lean-premixed hydrogen flames

Multi-element injector configurations, typically comprising numerous small-scale jet nozzles, will be required to enable reliable lean-premixed gas turbine combustion operating with pure hydrogen or high hydrogen content fuels. The integration of large numbers of millimeter-scale injectors in tightly clustered arrays is highly likely to produce peculiar topological states determined by the collective dynamics of strongly interacting premixed hydrogen flames. To understand the influence of inter-element flame interactions in a multi-element nozzle environment, here we experimentally investigate the combustion dynamics of two different pure hydrogen flame ensembles, one relatively coarse array of 293 round jet nozzles, and the other a dense array of 421 nozzles. Measurements of self-induced instability were conducted for both configurations under 60–130 thermal power conditions, in conjunction with phase-synchronized OH PLIF and high-speed OH1 chemiluminescence emission measurements. We demonstrate that for both cases the characteristic dimension of a single injector element is the main determinant of the fundamental frequency of self-induced pressure oscillations, and that the oscillations are primarily driven by the combination of coherent structure-related flame surface rollup and local extinction/pinch-off. Whereas the coarse injector arrangement exhibits well-organized parallel propagation and deformation of isolated vortical structures, the dense array case manifests strong repulsive interactions between adjacent coherent structures, naturally creating lateral flame surface modulations as well as limited streamwise oscillations. Importantly, collision-induced lateral flame dynamics play a mechanistic role in the substantial growth of higher harmonics in the frequency range of 1–2 kHz, leading to the creation of multiple frequency excitation states of commensurate amplitude, which uniquely define the thermoacoustic state of clustered lean-premixed hydrogen flames.     

Study on the mechanism of the ignition process of ammonia/hydrogen mixture under high-pressure direct-injection engine conditions

As environmental problems and energy crisis become more serious, ammonia is one of the potential alternative fuels. In order to better use ammonia as fuel in power equipment, the ignition process was studied under high-pressure direct-injection engine condition. In the paper, the Homogeneous model in Chemkin package was selected for numerical calculation. In the six cases with different hydrogen mixing ratios, the effect of initial temperature, pressure, equivalence ratio and hydrogen mixing ratio on ignition delay time (IDT) were studied. It conducted that IDT could be effectively reduced when adding 10–50% hydrogen to ammonia. Then, after sensitivity analysis of NH₃/H₂ mixtures, the key equations and free radicals affecting combustion characteristics were found. The rate of production (ROP) of the key radicals were carried out. It was found that the hydrogen provided the initial concentration of H radical before the start fire, which greatly improved the ROP of OH radical of R1(H + O₂=O + OH) compared to the original H needed to break the N–H chemical bond in pure ammonia. And the OH radical was related to the consumption of NH₃ by R31(NH₃+OH=NH₂+H₂O).     

Effects of hydrogen addition on combustion and flame propagation characteristics of laser ignited methane/air mixtures

In this study, effects of hydrogen addition on combustion and flame propagation characteristics of methane/air mixtures were investigated in a constant volume combustion chamber. Tested gas mixtures are 100% CH₄, 05% H₂ – 95% CH₄, 10% H₂ – 90% CH₄ and 15% H₂ – 85% CH₄, and such mixtures were ignited using a passively Q-switched Nd:YAG laser ignitor which has a pulse energy of 12.3 mJ, pulse duration of 2.4 ns and wave length of 1064 nm. A Schlieren setup coupled with a high-speed camera enabled evaluating flame propagation behavior, while pressure curve analysis provided necessary data for characterization of combustion properties. Additionally, lean flammability limits of gas mixtures were also determined at the test conditions. The unique properties of hydrogen (such as low density, high reactivity, high diffusivity etc) widened lean flammability limit. Rate of pressure rise and measured pressure values increased with hydrogen addition, regardless of the air-fuel equivalence ratio (λ). Lastly, hydrogen addition uniformly affected flame propagation characteristics and flame luminosity. Combustion process became more stable with hydrogen addition.     

In-line adsorption system for reducing cold-start ammonia emissions from engines fueled with ammonia and hydrogen

Ammonia-free emissions from an engine system fueled with ammonia and hydrogen during cold-start and warm-up periods are demonstrated. The fuels are supplied into a single-cylinder test engine under constant-speed conditions. The exhaust system consists of a redox catalyst followed by an in-line adsorber, the latter of which stores the ammonia that flows through the former. The results show that all adsorbers, H-ZSM-5, Cu-ZSM-5, and Pt-ZSM-5, can adsorb ammonia during cold-start conditions although the engine should be operated with retarded spark timing and a high hydrogen ratio because of low combustion efficiency at low coolant temperatures. Cu-ZSM-5 and Pt-ZSM-5 are regenerated after adsorption through their catalytic reactions without ammonia slip. Cu-ZSM-5, which has the largest adsorption capacity among the tested adsorbers, favors lean burn operation for regeneration. Pt-ZSM-5 has the advantage of simple regeneration control.     

Three-dimensional simulation of a rotating detonation engine in ammonia/hydrogen mixtures and oxygen-enriched air

Rotating detonation using ammonia as fuel may be a potential carbon free combustion technology for gas turbine. The detonation wave structure and flow field of a rotating detonation annular combustor are investigated by three-dimensional simulation with detailed chemistry of ammonia/hydrogen-air. The detonation properties, propagation mode, combustor performance and emission characteristics are studied by varying the equivalence ratios and hydrogen concentrations. Both the increases of the combustor pressure and the hydrogen concentration promote the chemical reaction rate of the ammonia burn and the detonation wave velocity gradually increases with increasing hydrogen proportion based on one-dimensional simulation. A stable single-rotating waves resulting in ammonia/hydrogen combustor are observed for a wide range of equivalent ratios only when the hydrogen concentration is at least 0.2. The steady run of the single rotating detonation had an optimal cycle efficiency when the hydrogen concentration is increased to a critical value of 0.3. NOx emissions are more dependent on equivalent ratios than hydrogen concentration in equivalence ratios ranging from 0.70 to 1.40.     

Effect of hydrogen enrichment and electric field on lean CH4/air flame propagation at elevated pressure

Electric assisted combustion for hydrogen enriched hydrocarbons may even extend the lean burn limit and provide the further improvement on combustion stability. This study investigates the effect of hydrogen enrichment and DC electric field on lean CH₄/air flame propagation. Electric field inside the chamber was generated by mesh and needle electrodes. Effect of hydrogen enrichment on the ion mole fraction in the flame was discussed based on reaction mechanism included neutral and ion reactions. The flame propagation images, flame displacement speed were used to evaluate the combined influences of hydrogen enrichment and electric field on propagating flame. Results showed that the hydrogen addition would increase positive ions mole fraction and the peak value is mainly determined by H₃O⁺. This would be due to that CH increases with hydrogen fraction, which is the main species in the initial reaction for the ion reactions. Electric field effect about flame propagation was suppressed with hydrogen addition due to the competition between the increment in ion mole fraction and the decrement in flame time. Electric assisted combustion is more evident at leaner conditions and elevated pressure. The ratio of ionic wind velocity to flow velocity may be the determined factor to predict the electric field effect about propagating flame. The tendency based on this ratio is in accordance with the experimental results for various hydrogen fraction and equivalence ratio at elevated pressure.     

Combustion performances of premixed ammonia/hydrogen/air laminar and swirling flames for a wide range of equivalence ratios

Ammonia, a carbon-free source of hydrogen has recently gained considerable attention as energy solution towards a green future. Previous works have shown that adding 30_VOL.% hydrogen with ammonia can eradicate the drawbacks of pure ammonia combustion but no study in the literature has investigated this blend across a wide range of equivalence ratios. The present work investigates 70/30_VOL.% NH₃/H₂ blend from 0.55 ≤ Φ ≤ 1.4 for both premixed laminar spherically expanding flames and turbulent swirling flames at atmospheric conditions. A detailed chemistry analysis has been conducted in Ansys CHEMKIN-PRO platform using a chemical reactor network (CRN) model to simulate the swirling turbulent flames. NO and NO₂ emissions have followed similar bell-shaped trends, peaking at around Φ = 0.8, while N₂O emission rises at lean conditions (Φ ≤ 0.7). The results indicate that Φ = 1.2 is the optimum equivalence ratio with reduced NO_X emissions and some ammonia slip.     

Effects of hydrogen addition on the structure and pollutant emissions of a turbulent unconfined swirling flame

This article aims at investigating the effect of hydrogen addition on the temperature and pollutant emissions of turbulent unconfined swirling methane/air flame. A computational approach utilizing the steady laminar flamelet and the realizable k–ε combustion and turbulence models, respectively, has been used. The turbulence–combustion interaction has been modeled by a β-shaped presumed probability density function. The percentage of hydrogen in the fuel stream is modeled at a wide range from 0% to 50% of the fuel volume flow rate. Results show that with the increase of volumetric hydrogen percentage in the fuel stream the flame structure changes considerably. The size of maximum temperature region decreases significantly to a small region at flame tip and peak temperature rises which leads to increase in NO emission levels. The flame with 10% hydrogen is observed to be slightly of the general trend. This is deemed to be due to the change in flow field as a result of change in fuel density, while the amount of hydrogen is not effective enough to change the combustion characteristics of the flame.     

Effect of the initial pressures on evolution of intrinsically unstable hydrogen/air premixed flame fronts

Laminar premixed flame front may be wrinkled due to the hydrodynamic and diffusive-thermal instabilities. This may lead to the occurrence of the cellular structure and the self-acceleration. The lean unstable hydrogen/air premixed flame at various initial pressures are studied to clarify the effect of the initial pressure on the evolution of the unstable laminar flame. Linear and nonlinear development stages of the unstable flame are simulated and investigated separately. In the linear stage, the initial sinusoidal wave disturbance on the flame front will still keep its initial configuration. The growth rate increases firstly and then decreases with the increase of the wavenumbers. The effect of the self-acceleration on the unstable flame front will be stronger in the linear stage at the higher initial pressure, since there are larger thermal expansion and constant Lewis number for hydrogen/air premixed flame at higher pressure. There are little discrepancies for the calculated growth rates with those predicted by the revised dispersion relation. The nonlinear stage of the unstable flame propagation could be divided into two stages, the transitional and the stable nonlinear stages. In the transitional stage, the flame front cells splits, merges and moves all the time and the initial wavenumber has a great influence on the cell evolution process. With the evolution of the cell on the flame front, the cellular structure on the flame front will not change greatly with the initial wavenumbers in the stable nonlinear stage. The effect of self-acceleration due to the wrinkling of the flame front at this stage is weakened with the increase of the initial pressure. At the higher pressure, more wrinkled structures with smaller mean curvature are distributed on the flame front. At last, results show that the flame front will propagate faster for the larger computation domain. Based on the fractal theory, the fractal dimension of lean hydrogen/air premixed flame with the equivalence ratio of 0.6 at 0.5 MPa in the 2D domain is obtained and around 1.26.