Numerical analysis on influence of hydrogen peroxide (H2O2) addition on the combustion and emissions characteristics of NH3/CH4-air (O2/N2)/ H2O2 mixture

In this work, extensive chemical kinetic modeling is performed to analyze the combustion and emissions characteristics of premixed NH₃/CH₄–O₂/N₂/H₂O₂ mixtures at different replacement percentages of air with hydrogen peroxide (H₂O₂). This work is comprehensively discusses the ignition delay time, flame speed, heat release rate, and NOx & CO emissions of premixed NH₃/CH₄–O₂/N₂/H₂O₂ mixtures. Important intermediate crucial radicals such as OH, HO₂, HCO, and HNO effect on the above-mentioned parameters is also discussed in detail. Furthermore, correlations were obtained for the laminar flame speed, NO, and CO emissions with important radicals such as OH, HO₂, HCO, and HNO. The replacement of air with H₂O₂ increases flame speed and decreases the ignition delay time of the mixture significantly. Also, increases the CO and NOx concentration in the products. The CO and NOx emissions can be controlled by regulating the H₂O₂ concentration and equivalence ratios. Air replacement with H₂O₂ enhances the reactions rate and concentration of intermediate radicals such as O/H, HO₂, and HCO in the mixture. These intermediate radicals closely govern the combustion chemistry of the NH₃/CH₄– O₂/N₂/H₂O₂ mixture. A linear correlation is observed between the flame speed and peak mole fraction of OH + HO₂ radicals, and 2nd degree polynomial correlation is observed for the peak mole fraction of NO and CO with HNO + OH and HCO + OH radicals, respectively.     

Numerical investigation of the effects of H2/CO/syngas additions on laminar premixed combustion characteristics of NH3/air flame

Co-firing NH₃ with H₂/CO/syngas (SYN) is a promising method to overcome the low reactivity of NH₃/air flame. Hence, this study aims to systematically investigate the laminar premixed combustion characteristics of NH₃/air flame with various H₂/CO/SYN addition loadings (0–40%) using chemical kinetics simulation. The numerical results were obtained based on the Han mechanism which can provide accurate predictions of laminar burning velocities. Results showed that H₂ has the greatest effects on increasing laminar burning velocities and net heat release rates of NH₃/air flame, followed by SYN and CO. CO has the most significant effects on improving NH₃/air adiabatic flame temperatures. The H₂/CO/SYN additions can accelerate NH₃ decomposition rates and promote the generation of H and NH₂ radicals. Furthermore, there is an evident positive linear correlation between the laminar burning velocities and the peak mole fraction of H + NH₂ radicals. The reaction NH₂ + NH <=> N₂H₂ + H and NH₂ + NO <=> NNH + OH have remarkable positive effects on NH₃ combustion. The mole fraction of OH × NH₂ radicals positively affects the net heat release rates. Finally, it was discovered that H radicals play an important role in the generation of NO. The H₂/CO/SYN additions can reduce the hydrodynamic and diffusional-thermal instabilities of NH₃/air flame. The NH₃ reaction pathways for NH₃–H₂/CO/SYN-air flames can be categorized mainly into NH₃–NH₂–NH–N–N₂, NH₃–NH₂–HNO–NO(?N₂O)–N₂ and NH₃–NH₂(?N₂H₂)–NNH–N₂. CO has the greatest influence on the proportions of three NH₃ reaction routes.     

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.     

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 and numerical study of the laminar burning velocity of NH3/H2/air premixed flames at elevated pressure and temperature

Ammonia (NH₃) is a carbon-free fuel that shows great research prospects due to its ideal production and storage systems. The experimental data of the laminar burning velocity of NH₃/H₂/air flame at different hydrogen ratios (X_H2 = 0.1–0.5), equivalent ratios (φ = 0.8–1.3), initial pressures (P = 0.1–0.7 MPa), and initial temperatures (T = 298–493 K) were measured. The laminar burning velocity of the NH₃/H₂/air flame increased upon increasing the hydrogen ratios and temperature, but it decreased upon increasing the pressure. The equivalent ratio of the maximum laminar burning velocity was only affected by the proportion of reactants. The equivalence ratio value of the maximum laminar burning velocity was between 1.1 and 1.2 when X_H2 = 0.3. The chemical reaction kinetics of NH₃/H₂/air flame under four different initial conditions was analyzed. The less NO maximum mole fraction was produced during rich combustion (φ > 1). The results provide a new reference for ammonia as an alternative fuel for internal combustion engines.     

The regulation effect of methane and hydrogen on the emission characteristics of ammonia/air combustion in a model combustor

Ammonia, made up of 17.8% hydrogen, has attracted a lot of attention in combustion community due to its zero carbon emission as a fuel in gas turbines. However, ammonia combustion still faces some challenges including the weak combustion and sharp NOx emissions which discourage its application. It was demonstrated that the combustion intensity of ammonia/air flame can be enhanced through adding active fuels like methane and hydrogen, while the NOx emission issue will emerge in the meantime. This study investigates regulation effect of methane and hydrogen on the emission characteristics of ammonia/air flame in a gas turbine combustor. The instantaneous OH profile and global emissions at the combustion chamber outlet are measured with Planar Laser Induced Fluorescence (PLIF) technique and the Fourier Transform Infrared (FTIR), respectively. The flames are also simulated by large eddy simulation to further reveal physical and chemical processes of the emissions formation. Results show that for NH₃/air flames, the emissions behavior of the gas turbine combustor is similar to the calculated one-dimensional flames. Moreover, the NOx emissions and the unburned NH₃ can be simultaneously controlled to a proper value at the equivalence ratio (φ) of approximate 1.1. The variation of NO and NO₂ with φ for NH₃/H₂/air flames and NH₃/CH₄/air flames at blending ratio (Z_f) of 0.1 are similar to the NH₃/air flames, with the peak moving towards rich condition. This indicates that the NH₃/air flame can be regulated through adding a small amount of active fuels without increasing the NOx emission level. However, when Z_f = 0.3, we observe a clear large NOx emission and CO for NH₃/CH₄/air flames, indicating H₂ is a better choice on the emission control. The LES results show that NO and OH radicals exhibit a general positive correlation. And the temperature plays a secondary role in promoting NOx formation comparing with CH₄/air flame.     

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.     

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.     

Flame front evolution and laminar flame parameter evaluation of buoyancy-affected ammonia/air flames

For flames with very low burning speed, the flame propagation is affected by buoyancy. Flame front evolution and laminar flame parameter evaluation methods of buoyancy-affected flame have been proposed. The evolution and propagation process of a center ignited expanding ammonia/air flame has been analyzed by using the methods. The laminar flame parameters of ammonia/air mixture under different equivalence ratio (ER) and initial pressure have been studied. At barometric pressure, with the increase of ER, the laminar burning velocity (LBV) of ammonia/air mixture undergoes a first increase and then decrease process and reaches its maximum value of 7.17 cm/s at the ER of 1.1, while the Markstein length increases monotonously. For ammonia/air flames with ER less than unity, the flame velocity shows a decreasing trend with stretch rate, resulting in the propensity to flame instability, but no cellular structure was observed in the process of flame propagation. As the initial pressure increases, the LBV decreases monotonously as well as the Markstein length. The flame thicknesses of ammonia/air mixtures decrease with initial pressure and are much thicker than those of hydrogen flames, which makes a stronger stabilizing effect of curvature on the flame front. The most enhancement of LBV is contributed by the dehydrogenation reaction of NH₃ with OH. The NO concentration decreases significantly with the increase of ER.     

Uncertainty quantification of the premixed combustion characteristics of NH3/H2/N2 fuel blends

Green ammonia is a candidate fuel to decarbonise shipping and other industries. However, ammonia features a lower reactivity compared to conventional fuels and is therefore difficult to burn. To resolve this issue, thermo-catalytic cracking of ammonia using waste heat is often employed to produce NH₃/H₂/N₂ blends as fuel. However, on-site operational variations in this process can become sources of uncertainty in the fuel composition, causing randomness of the flame's physicochemical properties and challenging flame stability. In the present work, a surrogate model is built using the polynomial chaos expansion (PCE) method to investigate the impact of fuel composition variability on combustion characteristics at different operating conditions. Impacts of 1.5% deviation in the fuel composition on the flame properties for different initial pressures (P_i) and unburnt fuel temperatures (T_u) are investigated for a wide range of equivalence ratios covering lean and rich mixtures. The uncertainty effects defined by the coefficient of variation (COV) fluctuate for equivalence ratios greater than 1.1, while no fluctuation is observed in COV for near stoichiometric combustion conditions. It is shown that H₂ variation in the fuel blend has the strongest effect (over 80%) on the uncertainty of all investigated physicochemical properties of the flame. The least affected property is the adiabatic flame temperature with variations of about 2.5% in richer fuel conditions. The results further show that preheating of the reactants can significantly reduce the COV of laminar flame speed. The consequences of these uncertainties upon different combustion technologies are then discussed and it is argued that moderate and intense low oxygen dilution (MILD) and colourless distributed combustion (CDC) technology may remain resilient.     

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.     

The decreasing effect of ammonia enrichment on the combustion emission of hydrogen,methane, and propane fuels

In the present study, non-premixed combustion and NOx emission of H₂, NH₃, C₃H₈, and CH₄ fuels have been studied in a combustion test unit under lean mixture conditions (λ = 4) at 8.6 kW thermal capacity. Furthermore, the combustion and NOx emission of the H₂, C₃H₈, and CH₄ fuels have been investigated for various NH₃ enrichment ratios (5, 10, 20, and 50%) and excess air coefficients (λ = 1.1, 2, 3, and 4) at the same thermal capacity. The obtained results have been compared for each fuel. Numerical simulation results show that H₂ emits intense energy through the reaction zone despite the lowest fuel consumption in mass, among others, due to its high calorific value. Therefore, it has a higher flame temperature than others. At the same time, C₃H₈ has the lowest flame temperature. Besides, NH₃ has the shortest flame length among others, while C₃H₈ has the most extended flame form. The highest level of NOx is released from the NH₃ flame in the combustion chamber, while the lowest NOx is released from the CH₄. However, the lowest NOx emission at the combustion chamber exit is obtained in NH₃ combustion, while the highest NOx emission is obtained with H₂ combustion. It results from the shortest flame length of NH₃, short residence time, and backward NOx reduction to N₂ for NH₃. As for H₂, high flame temperature and relatively long flame, and high residence time of the products trigger NOx formation and keep the NOx level high. On the other hand, excess air coefficient from 1.1 to 2 increases NOx for H₂, CH₄, and NH₃ due to their large flame diameters, unlike propane. Then, NOx emission levels decrease sharply as the excess air coefficient increases to 4 for each fuel. NH₃ fuel also emits minimum NOx in other excess air coefficients at the exit, while H₂ emits too much emission. With NH₃ enrichment, the NOx emissions of H₂, CH₄, and C₃H₈ fuels at the combustion chamber exit decrease gradually almost every excess air coefficient apart from λ = 1.1. As a general conclusion, like renewable fuels, H₂ appears to be a source of pollution in terms of NOx emissions in combustion applications. In contrast, NH₃ appears to be a relatively modest fuel with a low NOx level. In addition, the high amount of NOx emission released from H₂ and other fuels during the combustion can be remarkably reduced by NH₃ enrichment with an excess air combustion.     

Effects of ammonia substitution on hydrogen/air flame propagation and emissions

In order to evaluate the potential of partial ammonia substitution to improve the safety of hydrogen use and the effects on the performance of internal combustion engines, the propagation, development of surface cellular instability and nitrogen oxide (NO_x) and nitrous oxide (N₂O) emissions of spark-ignited spherical laminar premixed ammonia/hydrogen/air flames were studied experimentally and computationally. With ammonia being the substituent, the fundamental unstretched laminar burning velocities and Markstein numbers, the propensity of cell formation and the associated flame structure were determined. Results show substantial reduction of laminar burning velocities with ammonia substitution in hydrogen/air flames, similar to hydrocarbon (e.g., methane with a similar molecular weight to ammonia) substitution. In all cases, ammonia substitution enhances the NO_x and N₂O formation. At fuel-rich conditions, however, the amount of NO_x emissions increases and then decreases with ammonia substitution and the increased amount of NO_x and N₂O emissions with ammonia substitution is much lower than that under fuel-lean conditions. These observations support the potential of ammonia as a carbon-free, clean additive for improving the safety of hydrogen use with low NO_x and N₂O emissions in fuel-rich hydrogen/air flames. The potential of ammonia as a suppressant of both preferential-diffusional and hydrodynamic cellular instabilities in hydrogen/air flames was also found particularly for fuel-lean conditions, different from methane substitution. However, it should be noted that the use of ammonia also imposes considerable technological challenges and public concerns, particularly those associated with toxicity and the specific properties such as high reactivity with container materials and water, which should be completely resolved.     

Comparison of the combustion and emission characteristics of NH3/NH4NO2 and NH3/H2 in a two-stroke low speed marine engine

As a marine engine fuel of great concern, ammonia needs to be mixed with another high reactive fuel to improve its combustion performance. In this work, the combustion performance of NH₃/NH₄NO₂ and NH₃/H₂ was compared under different boundary conditions (excess air coefficient, initial temperature, pressure and mixing ratio). The numerical simulation of compression combustion is carried out under different power loads. The addition of ammonium nitrite decreases the ignition requirement of ammonia and shortens the ignition delay time of the mixture fuel. The boundary conditions of compression ignition can be reduced by mixing hydrogen and mixing ammonium nitrite, but it is not enough to achieve compression ignition under NH₃/H₂ mode. The addition of 30% ammonium nitrite can reduce the intake temperature to 300–360 K, which makes the compression ignition of the mixed fuel feasible. Meanwhile, in order to reduce the high in-cylinder combustion pressure and improve the combustion performance of the mixed fuel, the fuel injection strategy was proposed to achieve constant combustion pressure of 30 MPa under the premise of less power loss, which is a potential solution for the combustion of ammonia fuel.     

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).     

Chemical structure and laminar burning velocity of atmospheric pressure premixed ammonia/hydrogen flames

This paper presents experimental data on the flame structure of laminar premixed ammonia and ammonia/hydrogen flames at different equivalence ratios (φ = 0.8, 1.0 and 1.2) and the laminar flame speed of ammonia/hydrogen flames (φ = 0.7–1.5) at 1 atm. Experimental data were compared with modeling results obtained using four detailed chemical-kinetic mechanisms of ammonia oxidation. In general, all models adequately predict the flame structure. However, for the laminar burning velocity, this is not so. The main nitrogen-containing species present in the post-flame zone in significant concentrations are N₂ and NO. Experimental data and numerical simulations show that the transition to slightly rich conditions enables to reduce NO concentration. Numerical simulation indicate that increasing the pressure rise also results into reduction of NO formation. However, when using ammonia as a fuel, additional technologies should be employed to reduce NO formation.     

Burning velocity and flame structure of CH4/NH3/air turbulent premixed flames at high pressure

Ammonia is one of the most promising alternative fuels. In particular, ammonia combustion for gas turbine combustors for power generation is expected. To shift the fuel for a gas turbine combustor to ammonia step-by-step, the partial replacement of natural gas by ammonia is considered. To reveal the turbulent combustion characteristics, CH₄/NH₃/air turbulent premixed flame at 0.5 MPa was experimentally investigated. The ammonia ratio based on the mole fraction and lower heating value was varied from 0 to 0.2. The results showed that the ratio of the turbulent burning velocity and unstretched laminar burning velocity decreased with an increase in the ammonia ratio. The reason for this variation is that the flame area decreased with an increase in the ammonia ratio as the flame surface density decreased and the fractal inner cutoff increased. The volume fractions in the turbulent flame region were almost the same with ammonia addition, indicating that combustion oscillation can be handled in a manner similar to that for the case of natural gas for CH₄/NH₃/air flames.     

Emission characteristics and heat release rate surrogates for ammonia premixed laminar flames

Ammonia is a carbon-free fuel that has the potential to meet increasing energy demand and to reduce CO₂ emissions. In the present work, the characteristics of pollutant emissions in ammonia premixed laminar flames are investigated using one-dimensional simulations, and heat release rate (HRR) surrogates for ammonia combustion are proposed. Both atmospheric and high-pressure conditions were considered, and four representative mechanisms for ammonia combustion were employed. It is shown that the total emission of NO and NH₃ achieves a minimum around an equivalence ratio (?) of 1.1 under atmospheric conditions, and there is no noticeable emission of NO and NH₃ for ? = 1.1 ~ 1.5 under high-pressure conditions. Three HRR surrogates, [NH₃][OH], [NH₂][O], and [NH₂][H], were proposed based on the analysis of HRR and elementary reaction profiles. The performance of HRR surrogates was found to vary with equivalence ratios. For example, with the Miller mechanism, [NH₃][OH], [NH₂][O], and [NH₂][H] have the best performance under atmospheric conditions at ? = 1.15, 0.95 and 1.05, respectively, and under high-pressure conditions at ? = 1.11, 0.87 and 0.96, respectively. Similar conclusions can also be drawn with other mechanisms. These findings provide valuable insights into emission control and flame identification of ammonia combustion.     

Effects of diluents on the ignition of premixed H2/air mixtures

A computational study is performed to investigate the effects of diluents on the ignition of premixed H₂/air mixtures. The ignition processes for fuel lean, stoichiometric, and fuel rich H₂/air mixed with different diluents (He, Ar, N₂, and CO₂) are simulated with detailed chemistry and variable thermodynamic and transport properties. The minimum ignition energies (MIE) for different diluents at different dilution ratios are obtained. It is found that the change of the MIE with the dilution ratio consists of two regimes: in the first regime with a small value of dilution ratio, diluent addition has little effect on the MIE and in the second regime with dilution ratio above a certain value, the MIE increases exponentially with the dilution ratio. The kinetic and radiation effects of dilution are assessed by conducting sensitivity analysis and using the optically thin model, respectively. The thermal and flame-dynamic effects of dilution, characterized by the adiabatic flame temperature and Markstein length, respectively, are also discussed. Moreover, the dilution limits for H₂/air mixtures at different equivalence ratios are obtained. The dilution limits predicted by present ignition calculation are found to agree well with those based on laminar flame speed measurements at micro-gravity conditions. The ranking in terms of the effectiveness on ignition inhibition for stoichiometric H₂/air is shown to be in the order of Ar, N₂, He, and CO₂. The dilution limit is of practical interest since it is a measure of the efficiency of the diluent in fire prevention and suppression.     

Laminar flame speeds and kinetic modeling of hydrogen/chlorine combustion

In this study, laminar flame speeds at atmospheric pressure are accurately measured for H₂/Cl₂/N₂ mixtures at different equivalence ratios and N₂ mole fractions by the counterflow flame technique. A kinetic mechanism based on recently published and evaluated rate constants is developed to model these measured laminar flame speeds as well as the literature data on the concentrations of H₂, Cl₂, and HCl species in flat-burner flames and the ignition delay times from shock tube experiments. The kinetic model yields satisfactory comparison with these experimental data, and suggests that the reactions involving excited HCl(v) species and energy branching are not of substantial significance in combustion situations, and that the use of accurate elementary rate constants is instead crucial to the accuracy of the reaction mechanism.