Scaling-effect of explosion in H2/CH4/air mixtures

The scaling-effect of mixture explosion is an unresolved issue in explosion science. In this work, we carry out experimental measurements of explosion characteristics using hydrogen/methane/air (H₂/CH₄/air) mixtures in two tubes with lengths of 1.5 m and 60 m. The explosion overpressure of the mixtures increases exponentially with hydrogen mole fractions in the small tube, as expected. In contrast, explosion overpressure increases rapidly, causing detonation when hydrogen is added to the mixtures. Comparing measurements in both tubes, the explosion overpressure exhibits a clear scaling-effect dependence on the tube size. The scaling-effect cannot be explained by the aspect ratio (AR) of the tube. The analysis of the hotspot size, which is correlated with the ignition delay time of mixtures, is the critical factor governing the scaling-effect of explosion seen in a large tube.     

Characteristics of hydrogen-assisted catalytic ignition of n-butane/air mixtures

External heating and hydrogen-assisted catalytic ignition characteristics of n-butane (n-C₄H₁₀) were studied experimentally in a Pt-coated monolith catalytic reactor. Special attention was paid to the chemical effect of hydrogen on hydrogen-assisted ignition. A comparison of the ignition temperature for these two ignition methods shows hydrogen can lower ignition temperature. Furthermore, the ignition experiment at low hydrogen mole fraction (1.5%) shows that hydrogen has a positive chemical effect on hydrogen-assisted ignition. At constant n-butane/air flow and within certain limits of hydrogen mole fraction of mixtures, the ignition temperature changes little, whereas the time required for ignition and the cumulative amount of hydrogen decrease substantially. Consequently, high hydrogen mole fraction is favorable to hydrogen-assisted ignition. Two startup methods and thermal insulation are discussed. The co-feed method (n-butane/air/hydrogen mixtures are fed into reactor) and thermal insulation were found to be beneficial to hydrogen-assisted ignition.     

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.     

Detonation wave propagation in semi-confined layers of hydrogen–air and hydrogen–oxygen mixtures

This paper presents results of an experimental investigation on detonation wave propagation in semi-confined geometries. Large scale experiments were performed in layers up to 0.6 m filled with uniform and non-uniform hydrogen–air mixtures in a rectangular channel (width 3 m; length 9 m) which is open from below. A semi confined driver section is used to accelerate hydrogen flames from weak ignition to detonation. The detonation propagation was observed in a 7 m long unobstructed part of the channel. Pressure measurements, ionization probes, soot-records and high speed imaging were used to observe the detonation propagation. Critical conditions for detonation propagation in different layer thicknesses are presented for uniform H₂/air-mixtures, as well as experiments with uniform H₂/O₂ mixtures in a down scaled transparent channel. Finally detail investigations on the detonation wave propagation in H₂/air-mixtures with concentration gradients are shown.     

Critical energy for direct initiation of spherical detonations in H2/N2O/Ar mixtures

Although the detonation phenomenon in hydrogen-nitrous oxide mixtures is a significant issue for nuclear waste storage facilities and development of propulsion materials, very limited amount of critical energy data for direct initiation - which provides a direct measure of detonability or sensitivity of an explosive mixture − is available in literature. In this study, the critical energies for direct blast initiation of spherical detonations in hydrogen-nitrous oxide-Ar mixtures obtained from laboratory experiments and theoretical predictions at different initial conditions (i.e., different initial pressure, equivalence ratio and amount of argon dilution) are reported. In the experiments, direct initiation is achieved via a spark discharge from a high voltage and low inductance capacitor and the initiation energy is estimated accordingly from the current output. Characteristic detonation cell sizes of hydrogen-nitrous oxide-Ar mixtures are estimated from chemical kinetics using a recently updated reaction mechanism. A correlation expression is developed as a function of initial pressure, argon dilution and equivalence ratio, which is fitted to provide good estimation of the experimental measured data. The direct link between cell size and critical energy for direct blast initiation is then analyzed. Good agreement is found between experimental results and theoretical predictions, which make use of the cell size estimation correlation and the semi-empirical surface energy model. The effects of the initial pressure, equivalence ratio and the amount of Ar dilution on the critical initiation energy H₂-N₂O-Ar mixtures are investigated. By comparing the critical energies with those of H₂-O₂-Ar mixtures, it is shown that H₂-N₂O mixtures are more detonation sensitive with smaller initiation energies than H₂-O₂ mixtures at the same initial pressure, equivalence ratio and amount of argon dilution, except for higher diluted condition with amount of argon in the mixture above 20%. Attempt is made to explain the critical energy variation and comparison between the two H₂-N₂O-Ar and H₂-O₂-Ar mixtures from the induction length analysis and detonation instability consideration.     

Numerical investigation of the effect of inlet mass flow rates on H2/air non-premixed rotating detonation wave

In this paper, a three dimensional numerical investigation was carried out to study the formation and propagation characteristics of non-premixed rotating detonation wave using H₂/air as reactive mixtures. At a constant global equivalence ratio, the effects of inlet mass flow rates of H₂ and air on various performance parameters of rotating detonation wave and based on it combustor were analyzed in detail. On this basis, the mode switching process of rotating detonation wave caused by transiently changing the inlet mass flow rates was also discussed. The numerical results showed that inlet mass flow rates of H₂ and air played a very critical role in the formation, propagation and mode switching of rotating detonation wave. With the increase of inlet mass flow rates, rotating detonation wave could be switched from single wave to double waves. The propagation direction of double waves depended on the changing process of inlet mass flow rates. Meanwhile, compared to the single wave, double waves or its based combustor had the obvious advantages in formation time, stability and thrust, but had disadvantage in pressure ratio. In addition, both fill characteristics and mixing quality of fresh reactive mixtures are the underlying important mechanisms to explain the effects of inlet mass flow rates on rotating detonation waves.     

Experimental investigation on the near detonation limits of propane/hydrogen/oxygen mixtures in a rectangular tube

In this paper, an experimental study on the near detonation limits for propane-hydrogen-oxygen is performed. Three mixtures (i.e., 8H₂–C₃H₈–9O₂, 4H₂–C₃H₈–7O₂ and 12H₂–C₃H₈–11O₂) are tested in a rectangular tube (52 mm × 32 mm). Photodiodes with regular intervals are mounted on the tube wall to measure the time of arrival of detonation waves, from which the detonation velocity is determined. Smoked foils are inserted into the tube to obtain the detonation cell pattern. The results indicate that well within the detonation limits, the detonation can propagate at a steady velocity. By reducing the initial pressure, the detonation velocity decreases gradually. Subsequently, the detonation fails as the initial pressure is below a critical pressure. The critical pressures for 8H₂–C₃H₈–9O₂, 4H₂–C₃H₈–7O₂ and 12H₂–C₃H₈–11O₂ mixtures are 4 kPa, 5 kPa and 6 kPa, and the corresponding detonation velocity deficits are 10%, 9%, 10%, respectively. The cellular detonation structures show that the cell size decreases with the decrease of the hydrogen concentration, and the cell structures are very irregular near the detonation limits.     

Physicochemical effects of varying fuel composition on knock characteristics of natural gas mixtures

The physicochemical origins of how changes in fuel composition affect autoignition of the end gas, leading to engine knock, are analyzed for a natural gas engine. Experiments in a lean-burn, high-speed medium-BMEP gas engine are performed using a reference natural gas with systematically varied fractions of admixed ethane, propane and hydrogen. Thermodynamic analysis of the measured non-knocking pressure histories shows that, in addition to the expected changes arising from changes in the heat capacity of the mixture, changes in the combustion duration relative to the compression cycle (the combustion “phasing”) caused by variations in burning velocity dominate the effects of fuel composition on the temperature (and pressure) of the end gas. Thus, despite the increase in the heat capacity of the fuel–air mixture with addition of ethane and propane, the change in combustion phasing is actually seen to increase the maximum end-gas temperature slightly for these fuel components. By the same token, the substantial change in combustion duration upon hydrogen addition strongly increases the end-gas temperature, beyond that caused by the decrease in mixture heat capacity. The impact of these variations in in-cylinder conditions on the knock tendency of the fuel have been assessed using autoignition delay times computed using SENKIN and a detailed chemical mechanism for the end gas under the conditions extant in the engine. The results show that the ignition-promoting effect of hydrogen is mainly the result of the increase in end-gas temperature and pressure, while addition of ethane and propane promotes ignition primarily by changing the chemical autoignition behavior of the fuel itself. Comparison of the computed end-gas autoignition delay time, based on the complete measured pressure history of each gas, with the measured Knock-Limited Spark Timing shows that the computed delay time accurately reflects the measured knock tendency of the fuels.     

Laminar burning velocities and flame instabilities of diluted H2/CO/air mixtures under different hydrogen fractions

An experimental study was conducted using outwardly propagating flame to evaluate the laminar burning velocity and flame intrinsic instability of diluted H₂/CO/air mixtures. The laminar burning velocity of H₂/CO/air mixtures diluted with CO₂ and N₂ was measured at lean equivalence ratios with different dilution fractions and hydrogen fractions at 0.1 MPa; two fitting formulas are proposed to express the laminar burning velocity in our experimental scope. The flame instability was evaluated for diluted H₂/CO/air mixtures under different hydrogen fractions at 0.3 MPa and room temperature. As the H₂ fraction in H₂/CO mixtures was more than 50%, the flame became more unstable with the decrease in equivalence ratio; however, the flame became more stable with the decrease in equivalence ratio when the hydrogen fraction was low. The flame instability of 70%H₂/30%CO premixed flames hardly changed with increasing dilution fraction. However, the flames became more stable with increasing dilution fraction for 30%H₂/70%CO premixed flames. The variation in cellular instability was analyzed, and the effects of hydrogen fraction, equivalence ratio, and dilution fraction on diffusive-thermal and hydrodynamic instabilities were discussed.     

Experimental studies on syngas catalytic combustion on Pt/Al2O3 in a microreactor

Synthesis gas (a mixture of CO and H₂) oxidation is studied over a supported Pt/Al₂O₃ catalyst in a novel microreactor fabricated for studying the intrinsic chemical kinetics of highly exothermic reactions. CO was found to significantly inhibit H₂ oxidation. In contrast, H₂ addition promotes CO oxidation at low mole fractions but has a small promoting effect at high hydrogen mole fractions. As a result, the apparent reaction order of H₂ changes from positive to zero. The change in hydrogen reaction order is associated with hysteresis. Possible mechanisms for the observed behavior are discussed.     

Experimental and numerical study on the effect of composition on laminar burning velocities of H2/CO/N2/CO2/air mixtures

Experimental and numerical study on laminar burning velocity of H₂/CO/N₂/CO₂/air mixtures was conducted by using a constant volume bomb and Chemkin package. Good agreement between experimental measurements and numerical calculations by using USCII Mech is achieved. Diffusional-thermal instability is enhanced but hydrodynamic instability is insensitive to the increase of hydrogen fraction in fuel mixtures. For mixtures with different hydrogen fractions, the adiabatic flame temperature is not the dominant influencing factor while high thermal diffusivity of hydrogen obviously enhances the laminar burning velocity. Laminar burning velocities increase with increasing hydrogen fraction and equivalence ratio (0.4–1.0). This is mainly due to the high reactivity of H₂ leading to high production rate of H and OH radicals. Reactions  and  play the dominant role in the production of H radical for mixtures with high hydrogen fraction, and reaction R31 plays the dominant role for mixtures with low hydrogen fraction.     

Comparative study on the effect of CO2 and H2O dilution on laminar burning characteristics of CO/H2/air mixtures

A study on the effect of CO₂ and H₂O dilution on the laminar burning characteristics of CO/H₂/air mixtures was conducted at elevated pressures using spherically expanding flames and CHEMKIN package. Experimental conditions for the CO₂ and H₂O diluted CO/H₂/air/mixtures of hydrogen fraction in syngas from 0.2 to 0.8 are the pressures from 0.1 to 0.3 MPa, initial temperature of 373 K, with CO₂ or H₂O dilution ratios from 0 to 0.15. Laminar burning velocities of the CO₂ and H₂O diluted CO/H₂/air/mixtures were measured and calculated using the mechanism of Davis et al. and the mechanism of Li et al. Results show that the discrepancy exists between the measured values and the simulated ones using both Davis and Li mechanisms. The discrepancy shows different trends under CO₂ and H₂O dilution. Chemical kinetics analysis indicates that the elementary reaction corresponding to peak ROP of OH consumption for mixtures with CO/H₂ ratio of 20/80 changes from reaction R3 (OH + H₂ = H + H₂O) to R16 (HO₂+H = OH + OH) when CO₂ and H₂O are added. Sensitivity analysis was conducted to find out the dominant reaction when CO₂ and H₂O are added. Laminar burning velocities and kinetics analysis indicate that CO₂ has a stronger chemical effect than H₂O. The intrinsic flame instability is promoted at atmospheric pressure and is suppressed at elevated pressure for the CO₂ and H₂O diluted mixtures. This phenomenon was interpreted with the parameters of the effective Lewis number, thermal expansion ratio, flame thickness and linear theory.     

One-dimensional turbulence model simulations of autoignition of hydrogen/carbon monoxide fuel mixtures in a turbulent jet

The autoignition of hydrogen/carbon monoxide in a turbulent jet with preheated co-flow air is studied using the one-dimensional turbulence (ODT) model. The simulations are performed at atmospheric pressure based on varying the jet Reynolds number and the oxidizer preheat temperature for two compositions corresponding to varying the ratios of H₂ and CO in the fuel stream. Moreover, simulations for homogeneous autoignition are implemented for similar mixture conditions for comparison with the turbulent jet results. The results identify the key effects of differential diffusion and turbulence on the onset and eventual progress of autoignition in the turbulent jets. The differential diffusion of hydrogen fuels results in a reduction of the ignition delay relative to similar conditions of homogeneous autoignition. Turbulence may play an important role in delaying ignition at high-turbulence conditions, a process countered by the differential diffusion of hydrogen relative to carbon monoxide; however, when ignition is established, turbulence enhances the overall rates of combustion of the non-premixed flame downstream of the ignition point.     

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.     

Detonation cellular structure in NO2/N2O4-fuel gaseous mixtures

Experimental and numerical studies of the detonation in NO₂-N₂O₄/fuel (H₂, CH₄, and C₂H₆) gaseous mixtures show that for equivalence ratio Φ>0.8-1, (1) the detonation has a double cellular structure, the ratio between the cell size of each net being at least one order of magnitude; (2) inside the detonation reaction zone the chemical energy is released in two successive exothermic steps. Their chemical induction lengths, defined between the leading shock front and each local maximum heat release rate associated with each step, differ by at least one order of magnitude. The chemical reaction NO₂ + H → NO + OH is mainly responsible for the first exothermic step (fast kinetics), NO being the oxidizer on the second one (slow kinetics). Existence of correlations between calculated induction lengths and corresponding cell sizes strengthen the assumption that the cellular structure originates from local strong gradients of chemical heat release inside the detonation reaction zone.     

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.     

Detonation limits in methane-hydrogen-oxygen mixtures: Dominant effect of induction length

New-concept detonation combustors, for example, rotating detonation engines (RDEs), motivate investigations of the phenomena and theory relevant to detonation limits. Because CH₄–H₂ binary fuel mixtures have excellent combustion performance in engines, it is interesting to investigate the application possibilities of such mixtures in advanced detonation engines. Therefore, the detonation characteristics (e.g., initiation, propagation and failure) and their mechanisms for methane-hydrogen mixtures under different thermodynamic conditions need further study. In this work, the physical connection between detonation limits and induction length (Δ_I) of detonation structures for CH₄–H₂–O₂ mixtures is investigated; the dominant effect of induction length on the detonation limits is examined. The results show that a single-headed spinning structure is a unique feature of detonation limits; hence, the detonation limits can be qualitatively estimated by this phenomenon. The relation between λ and Δ_I is proportional, and the proportionality factor is 34.62; this relation is applicable in methane/hydrogen and oxygen mixtures with various fuel contents. By scaling the critical pressure p_c with Δ_I near the detonation limits, the relation between them is shown to be an exponential function: Δ_I = 201.2·(1+p_c)^−2.1.     

Noncatalytic hydrothermolysis of ammonia borane

Hydrolysis of ammonia borane (AB) is attractive as a chemical method for hydrogen storage. The use of catalysts is, however, usually required. In the present paper, two new methods for releasing hydrogen from AB and water are investigated which do not involve any catalyst. One method is based on combustion of AB mixtures with nanoscale aluminum powder and gelled water. It is shown experimentally that these mixtures, upon ignition, exhibit self-sustained combustion with hydrogen release from both AB and water. The other method involves external heating of aqueous AB solutions to temperatures 120 °C or higher, under argon pressure to avoid water boiling. To clarify the reaction mechanism, isotopic experiments using D₂O instead of H₂O were conducted. It is shown that heating AB/D₂O solution to temperatures 117–170 °C releases 3 equiv. of hydrogen per mole AB, where 2–2.1 equiv. originate from AB and 0.9–1 equiv. from water. The prospects of both methods for hydrogen storage are discussed.     

Database of thermophysical properties of H2/CO2/CO/CH4/H2O mixtures

As a potential alternative to fossil fuel, hydrogen has attracted much attention due to its renewable and environmentally friendly properties. Systems built for hydrogen-production and hydrogen-application tend to be larger, more integrated and more complex. In order to more efficiently design the vital components of hydrogen energy systems, accurate estimations of the thermodynamic and thermophysical properties of hydrogen-containing mixtures involved is essential. In this study, we introduced methods typically for calculating the thermodynamic and thermophysical properties of H₂/CO₂/CO/CH₄/H₂O mixtures, and established the technical database covering a wide range of mole fractions, pressures and temperatures. Moreover, a user-friendly software integrating all the calculation methods called H2MixThermoDatabase is compiled, whose code has been made available on the GitHub page for other researchers to effectually facilitate the further developments of hydrogen energy system.     

The autoignition in air of some binary fuel mixtures containing hydrogen

A predictive model for the autoignition and combustion of fuel–air mixtures employing detailed full chemical schemes was used to examine the autoignition and combustion characteristics in air of hydrogen in the presence of a range of common fuels. These included the gaseous fuels: methane, carbon monoxide and the higher hydrocarbon fuel n-heptane. A wide range of relative concentrations of the fuel components in the binary mixtures with hydrogen for different values of initial mixture temperature and pressure were considered under constant volume adiabatic conditions. It is shown that the presence of hydrogen in turn with these fuels can bring about complex changes to the autoignition behaviour of the fuel mixtures that show hydrogen may behave as an accelerant or retardant depending on the fuel, initial temperature, pressure and equivalence ratio considered.