Lower flammability limit of hydrogen/air mixture under different electrode parameters,initial pressure and diluent gas

The investigation of the lower flammability limit (LFL) is essential to the security application of hydrogen. In the present work, the LFL of hydrogen under a variety of conditions is systematically measured. The effect of electrode gap length (2–4 mm), electrode shape (30°, 90°, and spherical) and initial pressure (40–200 kPa) on the LFL of hydrogen/air mixture are analyzed. It shows that the LFL of hydrogen/air mixture increases with the increase of initial pressure and decreases with the increase of electrode gap length. The LFL of 30° electrodes is higher than that of 90° and spherical electrodes at the initial pressure higher than 80 kPa. Besides, the LFL of hydrogen/air mixture diluted with inert gas (CO₂ and N₂) at different initial pressure (50 kPa, 100 kPa, and 150 kPa) is investigated. The LFL of H₂/air/CO₂ mixture increases with increasing CO₂ concentration, while the LFL of H₂/air/N₂ mixture is almost unchanged under different N₂ concentration.     

Calculation of the upper flammability limit of methane/hydrogen/air mixtures at elevated pressures and temperatures

The results of three different numerical methods to calculate flammability limits—namely (1) the calculation of planar flames with the inclusion of a (radiation) heat loss term in the energy conservation equation, and the application of (2) a limiting burning velocity and of (3) a limiting flame temperature—are compared with experimental data on the upper flammability limit (UFL) of methane/hydrogen/air mixtures with hydrogen fuel molar fractions of 20% and 40%, at initial pressures up to 10 bar and initial temperatures up to 200 °C. The application of a limiting burning velocity is found to predict the pressure dependence of the UFL well, while the application of a limiting flame temperature generally is found to slightly underestimate the temperature dependence of the UFL.     

Effect of ignition,initial pressure and temperature on the lower flammability limit of hydrogen/air mixture

In this research, the effect of ignition, initial pressure (50–250 kPa) and temperature (20–100 °C) on the lower flammability limit (LFL) of hydrogen/air mixture are investigated experimentally and numerically. The results show that with the ignition energy increases, the LFL of hydrogen decreases. When high voltage direct current power supply (HVDC) is used, the time for the flame to propagate to the edge of the window is much shorter than that of 15 kV high voltage transformer (15 kV HVT) ignition. As the initial pressure increases, the LFL of hydrogen increases. When HVDC is used, the time to reach the peak deflagration overpressure increases with the increase of initial pressure. However, when 15 kV HVT is used, the time to reach the peak deflagration overpressure is almost the same. As the initial temperature increases, the LFL of hydrogen decreases. The change of the LFL of hydrogen with 15 kV HVT ignition is greater than that of HVDC. Through the analysis of chemical kinetic factors, the effect of OH radical generation when the LFL of hydrogen increases with the increase of initial pressure is revealed.     

Micro-wrinkled palladium surface for hydrogen sensing and switched detection of lower flammability limit

We report the development and testing of a novel hydrogen sensor that shows a very peculiar response to hydrogen exposure, due to its micro-structured palladium surface. The fabrication of the wrinkled Pd surface is obtained using an innovative, fast and cheap technique based on the deposition of a thin Pd film on to a thermo-retractable polystyrene sheet that shrinks to 40% of its original size when heated. The buckling of the Pd surface induced by shrinking of the substrate produces nano and micro-wrinkles on the sensor surface. The micro-structured sensor surface is very stable even after repeated hydrogen sorption/desorption cycles. The hydrogen sensing mechanism is based on the transitory absorption of hydrogen atoms into the Pd layer, leading to the reversible change of its electrical resistance. Interestingly, depending on hydrogen concentration the proposed sensor shows the concurrent effect of both the usually described behaviors of increase or decrease of resistance, related to different phenomena occurring upon hydrogen exposure and formation of palladium hydride. The study reports and discusses evidences for an activation threshold of hydrogen concentration in air switching the behavior of sensor performances from, e.g., poor negative to large positive sensitivity and from slow to fast detection.     

Laminar flame speed of H2/CH4/air mixtures with CO2 and N2 dilution

The laminar flame speeds of H₂/CH₄/air mixtures with CO₂ and N₂ dilution were systematic investigated experimentally and numerically over a wide range of H₂ blending ratios (0–75 vol%) with CO₂ (0–67 vol%) and N₂ (0–67 vol%) dilution in the fuels. The experimental measurements were conducted via the Bunsen flame method incorporating the Schlieren technique under the condition of equivalence ratios from 0.8 to 2.0. To gain an insightful understanding of the experimental observations, detailed numerical simulation was carried out using Chemkin-Pro with GRI3.0-Mech. The experimental measurements were also used to validate the corresponding performance of a semiempirical correlation derived through asymptotic analysis method coupled with the reduced chemistry mechanism. The results showed that at lower H₂ fraction (x_H2 ≤ 0.5), the laminar flame speeds of H₂/CH₄/air mixtures displayed great linearly increase with the growth of H₂ fractions. The combustion of mixtures with low H₂ contents was dominated by CH₄ conversion which was mainly controlled by the increasing OH radicals produced from the key oxidation reactions of H + O₂ = O + OH. With the further increase of H₂ fractions, the methane-dominated combustion gradually transformed into the methane-inhibited hydrogen combustion, resulting to the growth of laminar flame speeds was dramatical and non-linear. Due to the larger heat capacity and chemical kinetic effect, CO₂ presented a stronger dilution effect on reducing the laminar flame speeds than N₂. With the addition of CO₂, the increasing stronger competition for H radical through CO + OH = CO₂ + H with H + O₂ = O + OH due to the significant reduction of H mole fractions, leading to the larger decrease of laminar flame speeds of mixtures. Besides, although the contribution of thermal effect of CO₂ decreased near the equivalence ratio, the thermal effect of CO₂ still preformed the dominated contribution to the total dilution effect. A comparison between the experimental data and estimated results using the semiempirical correlation showed that, the correlation using new modified coefficients provided the satisfactorily accuracy predictions on the laminar flame speeds of diluted H₂/CH₄/air mixtures at lower x_H2 (x_H2 ≤ 0.5) and lower x_dilution (x_dilution = 0.25). The estimated results were generally located within a deviation range of ±20% errors except for two unsatisfactory eases occurred at conditions of x_H2 = 0.75 and x_CO2 = 0.67. The considerably poor predictions were attributed to the significantly variation of the chemical kinetics under high H₂ content and large CO₂ dilution conditions.     

The flammability limits of H2–CO–CH4 mixtures in air at elevated temperatures

The present contribution reports experimentally obtained values of the flammability limits of some fuel mixtures made up of H₂, CO, and CH₄ in air at different initial mixture temperatures of up to 300 °C. The potential catalytic effects of the surface of the test apparatus when the fuel–air mixtures were allowed to reside within the test apparatus at elevated temperatures for different time periods prior to ignition were also considered. Both stainless steel and quartz flame tubes of identical design and size were employed in the investigation.     

Flammability limits of NH3–H2–N2–air mixtures at elevated initial temperatures

Experiments investigating the flammability of hydrogen and ammonia in air and of mixtures of these two fuels in air were performed in a 12.6-liter combustion vessel at an initial pressure of 1 atm and initial temperatures up to 600 °C. Flammability maps based on the limiting fuel concentration as a function of the initial temperature for the various mixtures were constructed. The flammability limit data obtained for both hydrogen and ammonia agreed well with data in the literature. The flammability limits for both hydrogen–air and ammonia–air were found to widen linearly with increased initial temperature. The lower flammability limits of hydrogen–ammonia–air mixtures at various initial temperatures were found to follow closely the Le Chatelier flammability limit mixing rule. Ammonia readily dissociates to hydrogen and nitrogen. The flammability limits of ammonia dissociation products mixed with pure ammonia and air were also measured at initial temperatures of 400, 500, and 600 °C. At each temperature it was found that as the mixture fraction consisting of dissociated ammonia increases the flammability envelope based on the volume fraction of air in the mixture also increases. The flammability limits for these mixtures were largely unchanged for temperatures between 400 and 600 °C except for the fuel-rich flammability limit which decreased significantly at 600 °C. This can be attributed to the slow reaction of the mixture during the vessel fill process before ignition. For experiments at 500 and 600 °C it was found that mixtures with a large fraction of dissociated ammonia autoignited upon injection into the test vessel. The range of mixtures that autoignited was larger at 600 °C than at 500 °C. For mixtures with a large fraction of dissociated ammonia, autoignition of the mixture prevented the measurement of the fuel-rich flammability limit.     

Experimental investigations on laminar burning velocity variation of CH4+H2+air mixtures at elevated temperatures

The present work reports experimental investigations on laminar burning velocity variation of CH₄+H₂+air mixtures at elevated temperatures (300–650 K) using an externally heated diverging-channel method. The effect of mixture equivalence ratio (? = 0.7–1.3) and H₂ fraction (0–50% by volume) on burning velocity have been reported at elevated temperatures. The experimental measurements are compared with numerical simulations using GRI Mech 3.0 and FFCM-1 kinetic models. The obtained results exhibit an increase in the laminar burning velocity with H₂ fraction due to the formation of H-atom as an intermediate. The temperature dependency is established through a power-law correlation. The temperature-exponent shows a parabolic variation with a minimum value at ? = 1.1. Reaction pathway diagram interprets the major oxidation paths followed by reactants for higher carbon-consumption with varying H₂ fraction. The P2 pathway involving ethane breakdown plays a major role in enhancing the burning velocity at rich mixture conditions.     

Numerical investigation on effects of high initial temperatures and pressures on flame behavior of CO/H2/Air mixtures near the dilution limit

This study investigates effects of initial temperatures and pressures on dilution limits of CO/H₂/air mixtures by numerical simulation of one-dimensional laminar premixed flames of CO/H₂/air mixtures (50%CO–50%H₂). Maximum flame temperatures, laminar flame speeds, mass burning rates and flame thickness near the dilution limits are analyzed. Results reveal that the dilution limits are extended at the elevated initial temperatures. The laminar flame speeds and mass burning rates at the dilution limits increase with the elevation of initial temperature, however, the flame thickness at the dilution limits decreases with increasing pressures and increases slightly with elevated initial temperature. The decreased flame thickness renders the flamelet modeling more favorable for turbulent combustion at elevated pressure conditions. The ratio of the flame thickness to the reaction thickness and the Zeldovich number increase first and then decrease with increasing pressure, but the non-monotonic trend of ratio of flame thickness to reaction thickness with the increasing pressures is unnoticeable. Sensitivity analysis suggested that the non-monotonic trend of the Zeldovich number could be caused by the combined effects of following elementary reactions: H + O₂ + M → HO₂ + M, 2HO₂ → H₂O₂ + O₂ and H₂O₂ + M → 2OH + M.     

Macrovoid-free high performance polybenzimidazole hollow fiber membranes for elevated temperature H2/CO2 separations

Thermally robust membranes are required for H₂ production and carbon capture from hydrocarbon fuel derived synthesis (syn) gas. Polybenzimidaole (PBI) materials have exceptional thermal, chemical and mechanical characteristics and high H₂ perm-selectivity for efficient syngas separations at process relevant conditions. The large gas volumes processed mandate the use of a high-throughput, small footprint hollow fiber membrane (HFM) platform. In this work, an industrially attractive spinning protocol is developed to fabricate PBI HFMs with unprecedented H₂/CO₂ separation performance. A unique dope composition incorporating an acetonitrile diluent is discovered enabling asymmetric macro-void free PBI HFM fabrication using a water coagulant. The influences of dope viscosity, coagulant chemistry, and air gap on HFM morphology are evaluated. Elevated temperature (up to 350 °C) H₂ permeances of 400 GPU with H₂/CO₂ selectivities > 20 are achieved. This unprecedented separation performance is a ground breaking achievement at temperatures traditionally considered out-of-reach for polymeric membranes.     

Non-monotonic behaviors of laminar burning velocities of H2/O2/He mixtures at elevated pressures and temperatures

Both experimental and calculated laminar burning velocities of H₂/O₂/He mixtures were obtained, with equivalence ratios of 0.6–4.0, initial pressures of 0.1 MPa–0.5 MPa, initial temperature of 373 K, and dilution ratio of 7.0. Laminar burning velocities changed non-monotonically with the increasing initial pressures at equivalence ratios of 1.0–3.0. The decrease of overall reaction orders can explain the non-monotonic relationship between the laminar burning velocities and initial pressures. Consumption and production of both H and HO₂ radicals were also obtained to explain the decrease of overall reaction order. The competition of H and HO₂ radical between elemental reactions were also discussed. The three body reaction R15 (H + O₂(+M) = HO₂(+M)) gained more H radical in the competition with R1 (H + O₂ = O + OH), producing more HO₂ radical. Through the reaction pathway analysis, the restraint in production of both OH and H leaded to a reducing radical pool. The poorer reaction pool would restrain the overall reaction and lead to the reduction of overall reaction order and the non-monotonic behavior of the laminar burning velocity.     

Effects of CO2 and N2 dilution on the characteristics and NOX emission of H2/CH4/CO/air partially premixed flame

For the combustion of the mixture of blast furnace gas, natural gas, and coke oven gas in industrial burners, how to improve combustion efficiency and reduce pollutant emission are of significance. To accomplish this, an industrial partially premixed burner with a combustion diagnostic system is used to experimentally reveal the characteristics and NO_X emission of H₂/CH₄/CO/air flame under CO₂, N₂, and CO₂/N₂ (replacing half of N₂ with CO₂) dilution. NO_X emission and flame length, temperature profile, along with CO, CH₄, and CO₂ concentration profiles are analyzed with the three diluents in the fuel stream under different dilution rates (0–32% by volume). Experimental results show that for lean H₂/CH₄/CO combustion, greater proportions of CO₂ in the diluent affect flame characteristics in various ways. These effects include longer flame length, lower highest flame temperature, the highest flame temperature being located farther away from the nozzle, and the highest CO₂ concentration being located nearer the nozzle. Furthermore, results of CO, CH₄, and CO₂ concentrations indicate that chemical reactions in the flame are significantly affected by CO₂ owing to the series reaction CH₄?CH₃→CO?CO₂. Finally, increasing diluents or the ratio of CO₂ in diluents has the benefit of reducing NO_X emission.     

A review on mixing laws of laminar flame speed and their applications on H2/CH4/CO/air mixtures

As one of the most promising environmentally-friendly and renewable energies, biomass derived gas (BDG) has a great application prospect in the future energy system. Due to complex diversity of BDG components, the prediction of the important parameters, such as laminar flame speed, from the individual component will be realistic and reasonable than those from the direct measurement or calculation in some circumstances. In this study, existing mixing models are evaluated to predict the laminar flame speed of BDG. In addition, one-dimensional laminar premixed flame propagations are simulated to analyze flame temperatures and sensitivity coefficients of the laminar flame speed. For BDG with main components of CH₄, H₂ and CO, we employ the strategy that CH₄ and H₂ are mixed first and then wet CO is added into CH₄/H₂ mixture. For CH₄/H₂ blended fuels, flame-temperature-based and Le Chaterlier's models have the best fits for the laminar flame speed estimations of CH₄/H₂/air mixtures with lower and higher Z_H2, respectively. Sensitivity analysis shows there are large discrepancy in chemical pathways for BDG with higher or lower Z_CO and the laminar flame speed prediction of BDG will be conducted in two different circumstances. When CO ratio is lower than 0.85, Spalding rule and energy fraction method could predict the laminar flame speed best. For BDG with CO ratio larger than 0.85, Spalding rule and Chen's model are the best choices to predict the laminar flame speed of BDG.     

Large eddy simulation of hydrogen piloted CH4/air premixed combustion with CO2 dilution

Large eddy simulation (LES) of constant adiabatic temperature, hydrogen-piloted, turbulent lean premixed methane/air jet flames with varying amounts of CO₂ addition are reported. Constant adiabatic temperature is achieved by increasing the fuel flow rate slightly to account for the higher specific heat of CO₂ compared to N₂. Such flames are relevant to low NOx gas turbines with high hydrogen content fuels and Exhaust Gas Recirculation (EGR). A newly designed burner called Piloted Axisymmetric Reactor Assisted Turbulent (PARAT) flame burner was utilized. The operating conditions in the experiment were selected to highlight the kinetic effects of CO₂ addition by matching the Reynolds numbers, Lewis numbers and adiabatic flame temperatures. The LES simulations utilize a finite rate chemistry solver with DRM19 combustion mechanism with adaptive zoning and a dynamic structure turbulence model. A five-level adaptive mesh refinement (AMR) improves the velocity and temperature gradient resolution. The LES predicts the experimentally observed increase in flame length with CO₂ levels caused by a decrease in the turbulent flame speed. The computational results also capture the experimentally observed departure from the thin flame limit and a collapse of the root mean square (RMS) versus mean temperature profiles for the three levels of CO₂. The flame structure analysis showed super-equilibrium CO concentrations because of non-equilibrium chemistry effects caused by the external addition of CO₂.     

Effects of mesh aluminium alloy and aluminium velvet on the explosion of H2/air,CH4/air and C2H2/air mixtures

MAA (mesh aluminium alloy) is one of the most widely used explosion suppression materials in military and civilian applications. To systematically research the effect of MAA on the explosion reactions of flammable gases, we investigated the effect of MAA and AV (aluminium velvet) on the explosion of hydrogen-air, methane-air and acetylene-air mixtures. The results indicated that MAA and AV suppress the methane-air mixture explosion but significantly promote the explosions of the hydrogen-air mixture and the acetylene-air mixture. MAA and AV have the dual effect of promoting and suppressing an explosion. In addition, with an increase in filling density, the promotion of MAA and AV first strengthens and then weakens. The results of this study show that the properties of flammable gas, not the shapes of the explosion suppression materials, determine whether the dominant effect of explosion suppression material is promotion or suppression. Use of explosion suppression materials is not suitable for all flammable gases, especially highly reactive chemical fuels. Applying explosion suppression materials blindly may greatly increase safety risk.     

Effects of steam dilution on laminar flame speeds of H2/air/H2O mixtures at atmospheric and elevated pressures

The laminar flame speeds of H₂/air with steam dilution (up to 33 vol%) were measured over a wide range of equivalence ratio (0.9–3.0) at atmospheric and elevated pressures (up to 5 atm) by an improved Bunsen burner method. Burke, Sun, HP (High Pressure H₂/O₂ mechanism), and Davis mechanisms were employed to calculate the laminar flame speeds and analyze different effects of steam addition. Four studied mechanisms all underestimated the laminar flame speeds of H₂/air/H₂O mixtures at medium equivalence ratios while the Burke mechanism provided the best estimates. When the steam concentration was lower than 12%, increasing pressure first increased and then decreased the laminar flame speed, the inflection point appeared at 2.5 atm. When the steam concentration was greater than 12%, increasing the pressure monotonously decrease the laminar flame speed. The chemical effect was amplified by elevated pressure and it played an important role for the inhibiting effect of the pressure on laminar flame speed. The fluctuations of the chemical effect at 1 atm were mainly caused by three-body reactions, while the turn at 5 atm was mainly caused by the direct reaction effect. Elevated pressure and steam addition amplified the influences of uncertainties in the rate constants for elementary reactions, which might leaded to the disagreement between experimental and simulation results.     

Determination of the laminar burning velocities for mixtures of ethanol and air at elevated temperatures

Experimental test for premixed laminar combustion of ethanol–air mixtures has been conducted in a constant volume combustion bomb. The laminar burning velocities of ethanol–air mixtures are determined over a wide range of equivalence ratio at elevated temperatures, by means of the measurements of spherically expanding flames using schlieren photography technique. The effect of flame stretch imposed at the flame front has been discussed and the Markstein lengths are deduced to characterize the stretch effect on flame propagation. Following a linear relation between flame speed and flame stretch, the unstretched laminar burning velocities of ethanol–air flames have been derived. Over the ranges studied, a power law correlation has been suggested for the unstretched laminar burning velocities as a function of initial temperature and equivalence ratio. The empirical correlation is also compared with those data available in the literature, and it is found that the discrepancies are acceptable.