An investigation of flammability limits of gaseous mixtures at reduced pressures

An experimental investigation of flammability limits of hydrogen, methane and propane in air and oxygen at reduced pressures was carried out. A slow influence of sizes of an experimental vessel of a diameter higher than 125 mm on the flammability limits was revealed, but an influence of a type of an oxidizer (air or oxygen) and an ignition energy is significant. Critical values of an initial pressure for a possibility of a flame propagation were determined. The limiting values of the ignition energy were determined, for which an elevation of this parameter does not influence the critical pressure and the flammability region. A qualitative interpretation of obtained experimental results is given, which is based on a peculiarities of a flame initiation.     

Combustion hazard of mixing ammonia with nitric oxide

Premixed ammonia/nitric oxide flame was simulated using the Lindstedt 1994 and Miller–Bowman 1989 reaction mechanisms in CHEMKIN. The predicted laminar burning velocities compared well with limited measured values in the literature. The effects of unburnt mixture temperature and pressure on laminar burning velocity, flammability limits, adiabatic flame temperature and species profiles were studied. The unburnt mixture temperature had a positive impact on both the laminar burning velocity and the adiabatic flame temperature, and it extended the ammonia-rich flammability limit. The pressure had a marginally negative influence on the laminar burning velocity, while it had a slightly positive effect on the adiabatic flame temperature.     

Flammability limits of binary mixtures of dimethyl ether with five diluent gases

Flammability limits of binary mixtures of dimethyl ether with five kinds of diluent gases were measured by ASHRAE method at room temperature. The five diluent gases are nitrogen, carbon dioxide, chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The experimental results were correlated with the extended Le Chatelier's formula. It was found that the experimental results were well reproduced by the formula. In addition, flammability limits of binary mixtures of dimethyl ether with nitrogen and carbon dioxide were compared with the estimated values based on the adiabatic flame temperature method. The experimental results were found to be in satisfactory agreement with the estimated values.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

低压下近熄灭极限区域纸火蔓延实验研究

对低压下的近熄灭极限区域水平纸火蔓延进行了实验研究。通过降低环境压力和氧气浓度,确定了水平纸火蔓延的着火极限,并得出了在极限氧气浓度条件下的火蔓延速度变化规律。在相同氧气浓度下(43%)进行了不同压力的水平纸火蔓延实验。结果表明,火蔓延速度在近熄灭极限区域内非线性增加,通过比较分析前人火蔓延速度实验结果,确定了火蔓延近熄灭极限区域和线性增长区域的分界压力值。此外,得出了压力分界处的火焰变化特征,并根据火焰图像与理论分析,得出了不同区域内的火蔓延传热机制。     

Experimental measurement and numerical analysis of binary hydrocarbon mixture flammability limits

The flammability limits of binary hydrocarbon mixtures in air were measured in a combustion apparatus using an innovative method developed for this apparatus. The experimental results were obtained at standard conditions (room temperature and ambient atmospheric pressure) with upward flame propagation. The experimentally determined flammability limits for pure hydrocarbons (methane and ethylene) were compared with existing data reported in the literature. Le Chatelier's Law was fit to all experimental data to obtain LFLs and UFLs for various two-component combinations of saturated and unsaturated hydrocarbons (methane, ethylene, acetylene, propane, propylene, and n-butane). A modification of this law was used if experimental observations showed large deviations from Le Chatelier's predictions. Also, experimentally measured flammability limit data of the binary hydrocarbon mixtures were analytically related to the stoichiometric concentrations.     

Numerical studies on minimum ignition energies in methane/air and iso-octane/air mixtures

In this study, the dependence of minimum ignition energies (MIE) on ignition geometry, ignition source radius and mixture composition is investigated numerically for methane/air and iso-octane/air mixtures. Methane and iso-octane are both important hydrocarbon fuels, but differ strongly with respect to their Lewis numbers. Lean iso-octane air mixtures have particularly large Lewis numbers. The results show that within the flammability limits, the MIE for both mixtures stays almost constant, and increases rapidly at the limits. The MIEs for both fuels are also similar within the flammability limits. Furthermore, the MIEs of iso-octane/air mixtures with a small spherical ignition source increase rapidly for lean mixtures. Here the Lewis number is above unity, and thus, the flame may quench because of flame curvature effects. The observations show a distinct difference between ignition and flame propagation for iso-octane. The minimum energy required for initiating a successful flame propagation can be considerably higher than that required for initiating an ignition in the ignition volume. For iso-octane with a small spherical ignition source, this effect was observed at all equivalence ratios. For iso-octane with cylindrical ignition sources, the phenomenon appeared at lower equivalence ratios only, where the mixture's Lewis number is large. For methane fuel, the effect was negligible. The results highlight the significance of molecular transport properties on the decision whether or not an ignitable mixture can evolve into a propagating flame.     

Distinction between the upper explosion limit and the lower cool flame limit in determination of flammability limit at elevated conditions

Previous research showed that at certain conditions, close to the flammability range exists a regime where cool flame may develop either due to elevated temperature or it may be initiated by an ignition source. Propagation of the cool flame in a closed test vessel may double the initial pressure. Such pressure increase exceeds recommended ignition criteria for explosion limit determination that are based on 5 or 7% of pressure rise leading to inaccurate classification of the oxidation phenomena, i.e. cool flame propagation may be classified as hot flame propagation.Two mixtures were tested: n-butane-oxygen (extensively) and C1–C2–oxygen (in limited range), which represent a typical composition in ethylene oxide production, at elevated conditions at their upper explosion limits. Flame development was analysed by flame emission spectroscopy and the post-oxidation mixture was analysed by gas chromatography (GC) to characterise the oxidation mechanism of the flame. Additionally explosion pressure rise, flame temperature, and maximum rate of pressure rise were measured. In all experiments with the pressure rise ratio below two the low temperature oxidation mechanism assisted the flame propagation.     

甲烷/空气混合气燃爆特性的实验研究

对不同初始压力和温度条件下的甲烷/空气混合气的爆炸极限进行实验研究,利用最大-最小准则来确定爆炸极限.分析了温度和压力对甲烷/空气混合气燃爆特性的影响.采用氮气作为惰性气体,对其防爆抑爆效果进行了实验研究.     

Effects of N2 and CO2 on the flammability of 2,3,3,3-tetrafluoropropene at elevated temperatures

The flammability characteristics of refrigerants are affected by environmental factors, making them prone to flammability and explosion accidents in cooling systems. In this paper, the flammability characteristics of R1234yf–air mixtures with N₂ and CO₂ were investigated comparatively at temperatures between 20 and 50 °C at 80% relative humidity. The lower and upper flammability limits of R1234yf were measured. The limiting oxygen concentration (LOC), critical flammable ratio (CFR), and critical flammable concentration (CFC) of the R1234yf–air mixtures with inert gases were investigated. The paper developed a linear formula between the flammability limit of R1234yf and the temperature. The changes in CFC with different temperatures were negligible for R1234yf. Furthermore, the mixed refrigerant had both non-flammability and the lowest vapor pressure when the CFR of the R1234yf/CO₂ mixture was 2.9. The experimental results were used to propose a new prediction model to estimate the flammability limits of R1234yf. Finally, molecular simulation explained the effect of inert gases on the flammability of R1234yf from a microscopic point of view. The research aimed to provide valid evidence and data for preventing flammable and explosive refrigerant incidents.     

Influence of concentration distribution of hydrogen in air on measured flammability limits

There is a clear difference between exiting data on the measured flammability limits of hydrogen-air mixture. The non-uniformity of concentration distribution of hydrogen in air is a contributor to deviations of the upper flammability limit (UFL) and the lower flammability limit (LFL) measured in different experiments. This paper presents a numerical model to simulate the gas mixing process from start to stability, to predict the concentration distribution, and to research the influence of concentration distribution of hydrogen in air on measured UFLs and LFLs. The commercial software package Fluent was used to carry out the numerical simulation for the concentration distribution of hydrogen in air in the vessels with length-to-diameter ratios (L: D) of 1:1, 3:1, 5:1 and 7:1 respectively. Based on the numerical simulation and analysis, the influence of concentration distribution on measured flammability limits was demonstrated for hydrogen in air in the vessel. It is found that the deviations of measured flammability limits of hydrogen in air are the minimum in the vessel with length-to-diameter ratio of 1:1, and augment with the augmentation of vessel length-to-diameter ratio. Moreover, it is presented that the deviations of measured flammability limits of hydrogen in the center of the vessel are lower than that in the top and the bottom.     

Prediction of flammability limits of fuel-air and fuel-air-inert mixtures from explosivity parameters in closed vessels

Flammability limits of fuel-air and fuel-air-inert gaseous mixtures, especially at non-atmospheric conditions, are essential properties required for establishing safety operating conditions for handling and processing flammable gases. For pure fuels, an important data pool exists, formed by the flammability limits of fuel-air and fuel-air-inert gaseous mixtures at ambient initial conditions measured by standard methods. Such methods can be used for experimental determination of flammability limits for multi-fuels mixed with air, with or without additives, under non-atmospheric conditions. Their use is however a time- and material-consuming process; in addition, the flammability limits obtained by various standard methods may be scattered as a result of different choices in the operating parameters, for each standard method. It appears that a preliminary estimation of the flammability limits for fuel-air and fuel-air-inert gaseous mixtures can minimize the effort of measuring them in specific initial conditions.The present paper describes a new method for estimating the flammability range of fuel-oxidizer gaseous mixtures based on measurements of explosivity properties e.g. the peak explosion pressure and maximum rate of pressure rise recorded during closed vessel laminar explosions of fuel-oxidizer mixtures far from limits. Data obtained for several hydrocarbon-air gaseous mixtures with or without inert gas addition are used to examine the accuracy of estimated flammability limits (LFL – the lower and UFL – the upper flammability limit) as well as of the Limiting Oxygen Concentration (LOC) and the Minimum Inert Concentration (MIC). The predictive ability of the proposed method is examined against the predictive ability of other recently described methods.     

Experimental investigation on the lower flammability limits of diethyl ether/ n-pentane/epoxypropane-air mixtures

Diethyl ether (DEE), epoxypropane (PO) and n-pentane have excellent ignition and combustion performance; hence, they have a wide variety of applications in industry and advanced aviation propulsion systems. As these fuels are flammable at normal temperature and pressure, their explosive characteristics need to be explored. In this study, the lower flammability limits (LFLs) of vapor mixtures of DEE/PO/n-pentane in air were measured in 20 L, closed, stainless steel spherical vessels. Experimental results were obtained at ambient atmospheric pressure and an initial temperature of 40 °C. The experimental results show that the LFLs of DEE-air, n-pentane -air, and PO-air are 1.81 vol%, 1.41 vol% and 2.44 vol%, respectively. The LFLs of binary/ternary fuel mixtures under different compositions were tested, and the experimental results are compared with the classical Le Chatelier's formula. The results show that, for the binary fuels (i.e., DEE/PO, DEE/n-pentane, PO/n-pentane)-air mixtures, the maximum difference of the LFLs between Le Chatelier's formula and the experimental results is 6.10%. For the ternary fuels (i.e., DEE/PO/n-pentane)-air mixtures, the maximum difference of the LFLs between the two results is 6.33%. Due to the adiabatic flame temperature of each single fuel mixture being close, the Le Chatelier's formula is applicable for an estimation of the LFL for DEE/PO/n-pentane-air mixtures.     

Theoretical estimation of the lower flammability limit of fuel-air mixtures at elevated temperatures and pressures

We present an approach for predicting the lower flammability limits of combustible gas in air. The influence of initial pressure and temperature on lower flammability limit has been examined in this study. The lower flammability limits of methane, ethylene and propane in air are estimated numerically at the pressure from one to 100 bar and the temperature from ambient to 1200 K. It was found that the predicted LFLs of methane, ethylene and propane decrease slightly with the elevated pressure at the high temperature. The LFLs variation for methane-air mixture is 0.17, 0.18, 0.18 volume% with the initial pressure from one to 100  bar at the initial temperature of 800 K, 1000 K and 1200 K respectively, which is significantly higher than that at lower temperature. And the LFL of methane-air mixture at 1200 K and 100 bar reaches 1.03 volume% which is much lower than that at 1 bar and ambient temperature. On the other hand, the LFLs variation is 0.11–0.12 volume% for ethylene-air mixture and 0.06–0.07 volume% for propane-air mixture with the initial temperature from 800 K to 1200 K at the same range of pressure. The LFL values at high temperatures and pressures represent higher risk of explosion.     

Flow and flame visualization near the upper flammability limits of methane/air and propane/air mixtures at elevated pressures

In this study, direct visualization of flow and flame from the ignition of methane/air and propane/air mixtures near the UFL at elevated pressures of up to 2.0 MPa were obtained with a test cell comprised of double-sided plexiglass and a containment vessel with double-sided glass. These visualizations allowed direct observations of ignition and flame near UFL at elevated pressures. Two distinctive features were observed in ignition at elevated pressures that differ from those under ambient pressure: the hot igniter formed a convective plume, rather than a convection cell; and the flame initiated from the top of the test cell and propagated downwards, rather than directly from the igniter. Both these distinctive features are characteristics of convection at high Rayleigh number accompanied with increased gas density at elevated pressures. Our study also shows that visualization of the formation of planar flame provides the most objective criterion for defining flammability limits at elevated pressures.     

An influence of oxygen content in an oxidizing atmosphere on inhibitive action of fluorinated agents on a hydrogen flame

An experimental investigation of the influence of inhibitors of various chemical natures on flammability limits in mixtures H₂+oxidizer (O₂+N₂)–suppressant (C₂HF₅; CHF₃; C₄F₁₀; inhibitor AKM, which is a mixture of olefins) was carried out. Compositions of N₂ and O₂ with elevated (25 vol%) and reduced (15 vol%) oxygen concentrations and air were used as oxidizing atmospheres. Experiments were done at room temperature and atmospheric pressure. Flammability limits were determined in a closed vessel of volume of 4.2 dm³ (internal diameter 20 cm). Mixtures were prepared immediately in the preliminary evacuated reaction vessel by partial pressures. The mixtures were ignited by an electrical spark of energy near 1 J in the center of the reaction vessel. A flame propagation was detected by a pressure transducer. Twelve flammability curves were measured, which allowed to compare effectiveness of the inhibitors at various oxygen contents in the atmosphere. A qualitative analysis of the obtained results was done, which showed an important role of an inhibitor regeneration.     

Determination of the performance limits of flame arresters at increased oxygen concentrations

This investigation shows how an increased oxygen concentration influences the performance limits of crimped ribbon deflagration flame arresters at elevated pressures. An evaluation of the maximum experimental safe gap (MESG) as reliable criterion for describing the performance limits under non-atmospheric conditions is given. Measurements of MESGs and flame arrester performance tests were performed. Various fuel/oxygen/air mixtures containing ethylene and propane were used as testing gases. Former studies on the pressure dependence and the influence of oxygen on the MESG were initially confirmed. Furthermore, performance tests using a commercial deflagration flame arrester revealed that such a flame arrester may prevent flame transmission also at non-atmospheric conditions within a limited range. For various oxygen concentrations the performance limits were reached at the same MESG. Hence, it can be assumed that a flame arrester possesses a device- and fuel-specific maximum experimental safe gap for a specific gas mixture in different concentrations and at different pressures. This performance-related maximum safe gap can be used as a parameter for estimating and describing the performance limits of a flame arrester. It offers an attempt to simplify the testing and qualification of deflagration flame arresters for non-atmospheric conditions.     

Evaluation of limits for effective flame acceleration in hydrogen mixtures

Results of experiments and data analysis on turbulent flame propagation in obstructed channels are presented. The data cover a wide range of mixtures: H₂/air, H₂/air/steam (from lean to rich) at normal and elevated initial temperatures (from 298 to 650 K) and pressures (from 1 to 3 bar); and stoichiometric H₂/O₂ mixtures diluted with N₂, Ar, He and CO₂ at normal initial conditions. The dataset chosen also covers a wide range of scales exceeding two orders of magnitude. It is shown that basic flame parameters, such as mixture expansion ratio σ, Zeldovich number β and Lewis number Le, can be used to estimate a priori a potential for effective flame acceleration for a given mixture. Critical conditions for effective flame acceleration are suggested in the form of correlations of critical expansion ratio σ^* versus dimensionless effective activation energy. On this basis, limits for effective flame acceleration for hydrogen combustibles can be estimated. Uncertainties in determination of critical σ^* values are discussed.     

Effect of scale on freely propagating flames in aluminum dust clouds

The majority of experimental tests done on combustible dusts are performed in constant volume vessels that have limited or no optical access. Over the years, McGill University has been developing alternative experimental techniques based on direct observation of dust flames, yielding reliable fundamental parameters such as flame burning velocity, temperature and structure. The present work describes two new experimental set-ups allowing direct observation of isobaric and freely propagating dust flames at two sufficiently different scales to test the influence of scale on dust flame phenomena. In the laboratory-scale experiments, a few grams of aluminum powder are dispersed in transparent, 30 cm diameter latex balloons that allow for full visualization of the spherical flame propagation. In the field experiments, about 1 kg of aluminum powder is dispersed by a short pulse of air, forming a conical dust cloud with a total volume of about 5 m³. High-speed digital imaging is used to record the particle dispersal and flame propagation in both configurations. In the small-scale laboratory tests, the measured flame speed is found to be about 2.0 ± 0.2 m/s in fuel-rich aluminium clouds. The burning velocity, calculated by dividing the measured flame speed by the expansion factor deduced from thermodynamic equilibrium calculations, correlates well with the previously measured burning velocity of about 22–24 cm/s from Bunsen dust flames. Flame speeds observed in field experiments with large-scale clouds, however, are found to be much higher, in the range of 12 ± 2 m/s. Estimations are presented that show that the presumably greater role of radiative heat transfer in larger-scale aluminium flames is insufficient to explain the six-fold increase in flame speed. The role of residual large-eddy turbulence, as well as the frozen-turbulence effect leading to large-scale dust concentration fluctuations that cause flame folding, are discussed as two possible sources for the greater flame speed.     

Experimental study on the influence of flame retardants on the flammability of R1234yf

As an alternative refrigerant, R1234yf shows great environmental friendliness. However, the flammability has a negative impact on its use and promotion. To lower the combustible risk, it's a proper way to mix with nonflammable refrigerants in applications, but the research on the flammability of these blends is still limited. Therefore, the influence of three typical nonflammable refrigerants CO₂, R1336mzz(E) and R1233zd(E) as flame retardants on the flammability of R1234yf was experimentally studied in this paper. With the measurements of flammable limits of R1234yf/CO₂, R1234yf/R1336mzz(E) and R1234yf/R1233zd(E) at different concentrations, the parameters of regression equations for their flammable limits were obtained. The critical suppression concentrations of retardant were determined as 0.575, 0.35 and 0.6, respectively. The results showed that their suppression abilities could be ranked as R1336mzz(E)>CO₂>R1233zd(E). Then the inhibition mechanisms were analyzed, and the differences in flame colors at flammable limits were compared. With the establishment of estimation model for calculating critical suppression concentrations of ternary blends, the critical suppression lines of CO₂/R1234yf/R1336mzz(E) and CO₂/R1234yf/R1233zd(E) were obtained, by which the nonflammable zones of them were preliminarily determined. The results will provide practical guidance for the applications utilizing R1234yf and its blends in safety.