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.     

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.     

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.     

A correlation of the lower flammability limit for hybrid mixtures

Hybrid mixtures are widely encountered in industries such as coal mines, paint factories, pharmaceutical industries, or grain elevators. Hybrid mixtures explosions involving dust and gas can cause great loss of lives and properties. The lower flammability limit (LFL) is a critical parameter when conducting a hazard assessment or developing mitigation methods for processes involving hybrid mixtures. Unlike unitary dust or gas explosions, which have been widely studied in past decades, only minimal research focuses on hybrid mixtures, and data concerning hybrid mixtures can rarely be found. Although methods to predict the LFL have been developed by using either Le Chatelier's Law, which was initially proposed for homogeneous gas mixtures, or the Bartknecht curve, which was adopted for only certain hybrid mixtures, significant deviations still remain. A more accurate correlation to predict an LFL for a hybrid mixtures explosion is necessary for risk assessment. This work focuses on the study of hybrid mixtures explosions in a 36 L dust explosion apparatus including mixtures of methane/niacin, methane/cornstarch, ethane/niacin and ethylene/niacin in air. By utilizing basic characteristics of unitary dust or gas explosions, a new formula is proposed to improve the prediction of the LFL of the mixture. The new formula is consistent with Le Chatelier's Law.     

Lower flammability limits of flammable ternary organic mixtures: Synergistic behavior

Organic flammable liquids and their mixtures, which possess high risk of combustion and explosion, are widely used as raw materials and solvents in chemical and pharmaceutical industries. Lower flammability limits (LFL) is one of the most important parameters to characterize the combustion and explosion hazards of combustible gases and liquid vapors. The LFL of various ternary organic mixtures consist of ketone (acetone and butanone), ester (ethyl acetate) and alcohol (ethanol and isopropanol) were tested at 25 °C and atmospheric pressure. The results showed that resulted LFL values of the experiment were always lower than those calculated by volume fraction weighting method when the volume fraction of alcohol was less than 20 vol% but more than 10 vol%. The co-existence of alcohol and ethyl acetate had synergistic effect on reducing the LFL values of ternary organic mixtures and thus increased their explosive risk. The mechanism of synergistic effect was analyzed, and the results showed that the OH· and H· radicals produced by the oxidation decomposition of alcohols and esters accelerated the oxidation process of ternary organic mixtures, which led to the decrease of experimental LFL values and thus corresponding increased of their explosive risk. This study would be expected to provide some guidance for designing or choosing safer and more suitable ternary organic mixtures prior to their applications for engineering.     

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.     

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.     

Explosion hazards related to hydrogen releases in nuclear facilities

Hydrogen explosion risk needs to be carefully assessed and evaluated in nuclear facilities because of the potential catastrophic consequences: breakdown of safety equipments, failure of containment, dissemination of radioactive materials in the environment.When studying an indoor release, one possible simplification is to assume a perfect gas mixing inside the room. This assumption is effectively often used to evaluate toxic risks in the environment outside a building (Mastellone, Ponte, & Arena, 2003). However, perfect gas mixing assumption is only a rough approximation, as indoor concentrations can largely differ from mean values, due to buoyancy, recirculation zones or obstacles for example.In order to better evaluate the risk of explosion in case of an accidental release of hydrogen, IRSN conducted a numerical study using FLACS CFD software. Several parameters have been studied to identify dangerous situations and draw a representative picture of the risk: room size, position and direction of hydrogen leak, ventilation characteristics. Hydrogen release flow rates used for numerical simulations have been chosen as the highest leak rate which, by applying the assumption of perfect mixing, produces an average concentration in the room equal to hydrogen lower flammability limit (LFL).Simulation results indicate that in some particular configurations, especially for impinging hydrogen jets, hydrogen concentrations can locally be above LFL and then create explosive atmospheres with significant volumes.     

Experimental investigation of the lower flammability limit of volatile liquid fuel-aluminum powder mixtures in air

Aluminum powder was always chosen as an additive to improve the explosive performance. In this work, experiments were performed to investigate the lower flammability limit (LFL) of volatile liquid fuel-aluminum powder mixtures using a 20 L closed spherical stainless steel vessel at a temperature of 20 °C (293 K) and 40 °C (313 K). The volatile liquid fuels tested in the work were diethyl ether (DEE), epoxypropane (PO), n-pentane and n-hexane. DEE, PO and n-pentane are in the liquid phase at room temperature and can easily transition to the gas phase at 40 °C (313 K). Through a series of experiments carried out, it was found that the change in phase would affect the interaction between the components. Aluminum powder always has an inhibitory effect on the flammability of the mixtures when it is mixed with gas-phase fuels. The inhibition effect was most obvious when the aluminum powder concentration reached 200 g/m³. While the interaction between aluminum powder and liquid-phase volatile fuels was promotion and was influenced by the component proportion and the type of the volatile fuels.     

基于绝热火焰温度多元混合气体可燃性极限的理论预测

为了预测多元混合气体可燃性极限,通过化学平衡计算软件分析确定了气体在可燃性下限（LFL）和可燃性上限（UFL）的燃烧产物及计算绝热火焰温度（CAFT）,基于能量平衡方程和简化反应模型,分别建立了混合气体LFL和UFL预测模型。应用该预测模型对CH4、C2H4、C3H8、C3H6和CO组成的不同比例混合气体可燃性极限进行预测。结果表明:简化反应模型对于LFL和UFL预测值与文献中实验值的平均相对误差分别为2.76%和5.45%,相关系数分别为0.995和0.950;同时发现两步简化模型对含有C2H4和CO混合组分预测结果误差较大,但对于平均碳原子数大于2的混合气体,预测结果一致性较好。     

Explosion limits of mixtures relevant to the production of 1,2-dichloroethane (ethylene dichloride)

A simple method exists to estimate the limiting oxygen concentration (LOC) based upon the lower explosion limit (LEL) by assuming (1) that the LOC lies at the apex of the explosion area, (2) that the LEL is unaffected by nitrogen addition and (3) that the apex of the explosion area lies on the stoichiometric line. This estimation method is assessed for mixtures relevant to the production of 1,2-dichloroethane. To this end, the explosion areas of ethylene/hydrogen/nitrogen/air, ethylene/nitrogen/air and ethylene/1,2-dichloroethane/hydrogen chloride/nitrogen/air mixtures are determined at typical process conditions. The experiments are performed in a closed spherical 8 l vessel. The mixtures are ignited by fusing a coiled tungsten wire, placed at the centre of the vessel. A 5% pressure rise criterion is used to determine the explosion limits. The experimental procedure is based upon EN 14756. It is found that a safe estimate of the LOC of ethylene/hydrogen/nitrogen/air mixtures can be found based upon the LEL of these mixtures.     

Validation of a new formula for predicting the lower flammability limit of hybrid mixtures

A correlation of the lower flammability limit for hybrid mixtures was recently proposed by us. The experimental conditions including ignition energy and turbulence which play a primary role in a gas or dust explosion were at fixed values. The sensitivity of such experimental conditions to the accuracy of the proposed formula was not thoroughly discussed in the previous work. Therefore, this work studied the effect of varying the ignition energy and turbulence intensity to the formula proposed in our previous paper. For ignition energy effect, results from methane/niacin mixture demonstrated that the MEC and LFL will not be affected by changing ignition energy. There is no distinguishable difference among gas explosion index (K_G) and dust explosion index (K_St) derived from tests with every ignition energy (2.5 kJ, 5 kJ and 10 kJ) in a 36 L vessel. The proposed formula is independent of ignition energy. For turbulence effect, the proposed formula can have a good prediction of the explosion and non-explosion zone if the ignition delay time is within a certain range. The formula prediction is good as the ignition delay time increases up to 100 ms in this work. Propane/niacin and propane/cornstarch mixtures are also tested to validate the proposed formula. It has been confirmed that the proposed formula predicts the explosion and non-explosion zone boundary of such mixtures.     

Explosion of lycopodium-nicotinic acid–methane complex hybrid mixtures

With the terms “complex hybrid mixtures”, we mean mixtures made of two or more combustible dusts mixed with flammable gas or vapors in air (or another comburent).In this work, the flammability and explosion behavior of selected complex hybrid mixtures was studied. In particular, we investigated mixtures of nicotinic acid, lycopodium and methane. We performed explosion tests in the 20-L explosion vessel at different overall (nicotinic plus lycopodium) dust concentrations, nicotinic acid/lycopodium ratios, and methane concentrations.An exceptional behavior (in terms of unexpected values of rate of pressure rise and pressure) was found for the complex hybrid mixtures containing lycopodium and nicotinic acid in equal amounts. This mixture was found to be much more reactive than all the other dust mixtures, whatever the dust concentration and the methane content.     

Flammability envelopes for methanol,ethanol, acetonitrile and toluene

The flammability envelope was experimentally determined up to the point of vapor saturation for four flammable liquids: methanol, ethanol, acetonitrile, and toluene. The experimental apparatus consisted of a 20-L spherical chamber with a centrally located 10 J fuse wire igniter. The liquid was injected and vaporized into the chamber via a septum and a precision syringe. Nitrogen and oxygen were mixed from pure components using a precision pressure gauge. Pressure versus time data were measured for each ignition test. Flammability was defined as any ignition resulting in an increase in pressure of 7% over the initial pressure, as per ASTM E 918–83. All data were obtained at an initial temperature of 298 K and 1 atm. The experimental values of the LFL agreed well with published values. Limiting oxygen concentrations (LOC) were also determined—although these were somewhat lower than published values.The calculated adiabatic flame temperature (CAFT) method was used to model the data using a threshold temperature of 1200 K. A reasonable fit of the flammability envelope was obtained, although this could be improved with a higher threshold 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.     

Development of machine learning based prediction models for hazardous properties of chemical mixtures

Lower flammability limit (LFL), upper flammability limit (UFL), auto-ignition temperature (AIT) and flash point (FP) are crucial hazardous properties for fire and explosion hazards assessment and consequence analysis. In this study, a comprehensive prediction model set was constructed by using expanded chemical mixture databases of chemical mixture hazardous properties. Machine learning based gradient boosting quantitative structure-property relationship (GB-QSPR) method is implemented for the first time to improve the model performance and prediction accuracy. The result shows that all developed models have significantly higher accuracy than other regular QSPR models, with the 5-fold cross-validation RMSE of LFL, UFL, AIT, and FP models being 1.06, 1.14, 1.08, and 1.17, respectively. All developed QSPR models can be used to estimate reliable chemical mixture hazardous properties and provide useful guidance in chemical mixture hazard assessment and consequence analysis.     

Effect of admixture of solid inertant on fire hazard of dust layers oriented at varying degrees of inclination

Unlike metallic dust layers, the layer flammability levels (LFL) of non-metallic dust layers exhibit a wide range from Class 1 (No self-sustained combustion) to Class 6 (explosive combustion). However, determinations of layer flammability have not considered the effect of inclination angle, thereby potentially underestimating fire hazard of combustible dust layers in many industrial situations. In this research, inclined dust layers showed greater fire hazard than did horizontally oriented dust layers. For example, LFL of wood dust jumped from class 3 to class 5 when layers were positioned with an incline. Flame spread rate of PMMA dust layers increased from 1.8 to 3.6 mm/s when the angle of inclination increased from 0 to 40°. Even small amounts of solid inertant significantly decreased surface layer fires. The required amount of inertant to completely inert layer fires was far less than that for smoldering layer fires or dust explosions.     

The hazards and risks of hydrogen

An analysis was completed of the hazards and risks of hydrogen, compared to the traditional fuel sources of gasoline and natural gas (methane). The study was based entirely on the physical properties of these fuels, and not on any process used to store and extract the energy. The study was motivated by the increased interest in hydrogen as a fuel source for automobiles.The results show that, for flammability hazards, hydrogen has an increased flammability range, a lower ignition energy and a higher deflagration index. For both gasoline and natural gas (methane) the heat of combustion is higher (on a mole basis). Thus, hydrogen has a somewhat higher flammability hazard.The risk is based on probability and consequence. The probability of a fire or explosion is based on the flammability range, the auto-ignition temperature and the minimum ignition energy. In this case, hydrogen has a larger flammability zone and a lower minimum ignition energy—thus the probability of a fire or explosion is higher. The consequence of a fire or explosion is based on the heat of combustion, the maximum pressure during combustion, and the deflagration index. Hydrogen has an increased consequence due to the large value of the deflagration index while gasoline and natural gas (methane) have a higher heat of combustion. Thus, based on physical properties alone, hydrogen poses an increase risk, primarily due to the increased probability of ignition.This study was unable to assess the effects of the increased buoyancy of hydrogen—which might change the probability depending on the actual physical situation.A complete hazard and risk analysis must be completed once the actual equipment for hydrogen storage and energy extraction is specified. This paper discusses the required procedure.     

Effect of self-inhibition at a flame propagation in rich gaseous mixtures of combustible–air–diluent

An analysis of published experimental data characterizing the influence of diluents of various chemical nature (both halogenated and chemically inert) on upper flammability limits of flammable gases in air (methane and hydrogen have been considered as examples) has been done. Dependences of critical oxygen concentration and critical fuel equivalence ratio _cr for mixtures combustible–air–diluent at upper flammability limits on diluent concentration were determined. The obtained data were interpreted on the basis of the concept of self-inhibition at combustion of rich mixtures of organic combustibles in air. A method for evaluation of relative effectiveness of various inhibitors and for determination of availability of self-inhibitive properties of a combustible gas has been proposed.