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.     

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.     

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.     

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.     

密闭空间内天然气混合及爆炸传播规律研究

为研究密闭容器内甲烷-空气不均匀分布对混合气体燃烧的影响,将数值模拟和实验相结合,发现在重力作用下混合气体浓度分布不均匀,长径比越大的容器,混合气体浓度分布梯度越大。混合气体浓度分布影响气体火焰传播规律。宏观浓度为5%的甲烷与空气混合后,容器上部甲烷浓度高于5%,在该处点火时非均匀混合甲烷-空气火焰传播较快,非均匀混合气体的爆炸压力比均匀混合气体压力上升快,且分层混合气体的超压峰值高于均匀混合气体的值。由于浓度分布不均匀,点火位置影响甲烷/空气火焰传播的规律。     

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.     

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.     

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.     

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.     

Flammability limit measurements for dusts in 20-L and 1-m3 vessels

Two types of flammability limits have been measured for various dusts in the Fike 1-m³ (1000-L) chamber and in the Pittsburgh Research Laboratory (PRL) 20-L chamber. The first limit is the minimum explosible concentration (MEC), which was measured at several ignition energies. In addition to the three dusts studied previously (bituminous coal, anthracite coal, and gilsonite), this work continues the effort by adding three additional dusts: RoRo93, lycopodium, and iron powder. These materials were chosen to extend the testing to non-coal materials as well as to a metallic dust. The new MEC data corroborate the previous observations that very strong ignitors can overdrive the ignition in the smaller 20-L chamber. Recommendations are given in regard to appropriate ignition energies to be used in the two chambers. The study also considered the other limiting component, oxygen. Limiting oxygen concentration (LOC) testing was performed in the same 20-L and 1-m³ vessels for gilsonite, bituminous coal, RoRo93, and aluminum dusts. The objective was to establish the protocol for testing at different volumes. A limited investigation was made into overdriving in the 20-L vessel. The LOC results tended to show slightly lower results for the smaller test volume. The results indicated that overdriving could occur and that ignition energies of 2.5 kJ in the 20-L vessel would yield comparable results to those in the 1-m³ vessel using 10.0 kJ. The studies also illustrate the importance of dust concentration on LOC determinations.     

Fast flame speeds and rates of pressure rise in the initial period of gas explosions in large L/D cylindrical enclosures

Flame speeds and rates of pressure rise for gaseous explosions in a 76 mm diameter closed cylindrical vessel of large length to diameter ratio (L/D = 21.6), were quantitatively investigated. Methane, propane, ethylene and hydrogen mixtures with air were studied across their respective flammability ranges. Ignition was affected at one end of the vessel. Very fast flame speeds corresponding to high rates of pressure rise were measured in the initial 5–10% of the total explosion time. During this period 20–35% of the maximum explosion pressure was produced, and over half of the flame propagation distance was completed. Previous work has concentrated on the later stages of this type of explosion; the development of tulip flames, pressure wave effects and transition to turbulence. The initial fast phase is very important and should dominate considerations in pressure relief vent design for vessels of large L/D.     

Influence of the ignition source location on the determination of the explosion pressure at elevated initial pressures

Explosion pressures are determined for rich methane–air mixtures at initial pressures up to 30 bar and at ambient temperature. The experiments are performed in a closed spherical vessel with an internal diameter of 20 cm. Four different igniter positions were used along the vertical axis of the spherical vessel, namely at 1, 6, 11 and 18 cm from the bottom of the vessel. At high initial pressures and central ignition a sharp decrease in explosion pressures is found upon enriching the mixture, leading to a concentration range with seemingly low explosion pressures. It is found that lowering the ignition source substantially increases the explosion pressure for mixtures inside this concentration range, thereby implying that central ignition is unsuitable to determine the explosion pressure for mixtures approaching the flammability limits.     

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.     

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.     

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.     

Safety parameters for oxygen-enriched flames

The utilization of low-quality gaseous fuel from biomass gasification and the abundance of oxygen-rich streams obtained as a by-product of nitrogen-air separation by membrane technology has incentivized the development of sustainable oxygen-enriched combustion technologies in the last decades. However, a dearth of experimental and numerical analysis addressing the reactivity and safety aspects of these mixtures at initial low temperatures can be observed in the current literature.In this work, the heat flux burner was adopted for the measurement of the laminar burning velocity of methane in oxygen enriched air at different equivalence ratios. Results were compared with numerical data obtained by means of detailed kinetic mechanisms developed at the University of Bologna and the Gas Research Institute (GriMech3.0). Simplified correlations for the estimation of the laminar burning velocity with respect to the oxygen content at any equivalence ratio were developed, tested and evaluated.An elemental reaction-based function was found appropriate for the estimation of the overall reactivity of the investigated mixtures. Besides, numerical analyses were performed to characterize the flame structures in terms of temperature and product distribution under several initial conditions. These results gave further insights into the reaction mechanisms of gaseous fuels in the case of oxygen-enriched air, highlighting potential bottlenecks for kinetic model refinements. Eventually, relevant safety parameters were estimated, in particular the flammability range of the fuel/oxidant mixture, in terms of lower and upper flammability limits.     

Theoretical and experimental study of the inhibition and inert effect of HFC125, HFC227ea and HFC13I1 on the flammability of HFC32

HFC32 is a potential alternative refrigerant with excellent thermal performance, but the flammability is a main obstacle for its applications. The group contribution method is utilized to analyze the inhibition efficiency of nonflammable refrigerants in binary mixtures. Furthermore, a novel equation of predicting the minimum inerting concentration of nonflammable refrigerants has been proposed by analyzing the variation of the flame propagation velocity and the flammable refrigerant concentration. Experimental studies of the explosion limits of HFC125/HFC32, HFC227ea/HFC32 and HFC13I1/HFC32 were carried out and the ranges of explosion limits were obtained. At the same time, the relationship between the maximum charge of the flammable refrigerants and lower flammability limit (LFL) was analyzed. The result demonstrates that the proposed novel theoretical equation can effectively predict the minimum inerting concentration of nonflammable refrigerants to flammable refrigerants, and the theoretical results have significance on the security application of the binary mixtures.     

CFD simulations of dust dispersion in the 20 L vessel: Effect of nominal dust concentration

Measurements of flammability and explosion parameters for dust/air mixtures require uniform dispersion of the dust cloud inside the test vessel. In a previous work, we showed that, in the standard 20 L sphere, the dust injection system does not allow generation of a uniform cloud, but rather high gradients of dust concentration are established. In this work, we used a previously validated three-dimensional CFD model to simulate the dust dispersion inside the 20 L sphere at different dust nominal concentrations (and fixed dust diameter). Results of numerical simulations have shown that, as the dust nominal concentration is increased, sedimentation prevails and, thus, when ignition is provided, the dust is mainly concentrated at the vessel walls.     

Effect of the concentration distribution on the gaseous deflagration propagation in the case of H2/O2 mixture

The investigation of flame propagation accompanying the explosions of unconfined gaseous reactive clouds which are diluted in atmosphere ambient is a fundamental interest in the analysis of industrial risk assessment.Following the previous work [Sochet, I., Guelon, F., Gillard, P. (2002). Deflagrations of non-uniform mixtures: A first experimental approach, Journal of physics, 12, 7–273, 7–280], an experimental study is conducted on a deflagration of a hydrogen/oxygen gaseous cloud which is released in air. The burning velocity is directly or indirectly measured. The flammability limits of the non homogeneous cloud has been as well investigated.     

球形压力容器中甲烷-氢气-空气爆炸过程数值模拟及实验研究

为研究受限空间内甲烷-氢气-空气混合气体爆炸特性参数分布规律,在20 L球形压力容器装置内开展甲烷-氢气-空气混合气体爆炸实验,探究掺氢比变化对当量比为1的甲烷-氢气-空气混合气体爆炸过程的影响;运用Fluent数值模拟软件,采用标准k-ε湍流模型,结合层流有限速率燃烧模型,探究混合气体爆炸过程中燃烧特性(爆炸温度、压力、密度等)与反应时间的变化规律。研究结果表明：爆炸过程中,添加一定氢气时爆炸压力峰值、爆炸压力上升速率峰值增大,而到达峰值时间缩短;反应初期,中心点火处密度下降,反应釜各处密度持续上升;距离点火点越远,密度变化越大,反应釜中压力分布基本相同。研究结果可为甲烷-氢气-空气混合燃料的安全使用提供相关参考。