Study of the severity of hybrid mixture explosions and comparison to pure dust-air and vapour-air explosions

The explosion behaviour of heterogeneous/homogeneous fuel-air (hybrid) mixtures is here analysed and compared to the explosion features of heterogeneous fuel-air and homogeneous fuel-air mixtures separately.Experiments are performed to measure the pressure history, deflagration index and flammability limits of nicotinic acid/acetone-air mixtures in a standard 20 L Siwek bomb adapted to vapour-air mixtures. Literature data are also used for comparison.The explosion tests performed on gas-air mixtures in the same conditions as explosion tests of dust-air mixtures, show that the increase in explosion severity of dust/gas-air mixtures has to be addressed to the role of initial level of turbulence prior to ignition.At a fixed value of the equivalence ratio, by substituting the dust to the flammable gas in a dust/gas-air mixture the explosion severity decreases. Furthermore, the most severe conditions of dust-gas/air mixtures is found during explosion of gas-air mixture at stoichiometric concentration.     

Determination of explosion limits – Criterion for ignition under non-atmospheric conditions

Many industrial processes are run at non-atmospheric conditions (elevated temperatures and pressures, other oxidizers than air). To judge whether and if yes to what extent explosive gas(vapor)/air mixtures will occur or may be generated during malfunction it is necessary to know the safety characteristic data at the respective conditions. Safety characteristic data like explosion limits, are depending on pressure, temperature and the oxidizer. Most of the determination methods are standardized for ambient conditions. In order to obtain determination methods for non-atmospheric conditions, particularly for higher initial pressures, reliable ignition criteria were investigated. Ignition tests at the explosion limits were carried out for mixtures of methane, propane, n-butane, n-hexane, hydrogen, ammonia and acetone in air at initial pressures up to 20 bar. The tests have been evaluated according to different ignition criteria: visual flame propagation, temperature and pressure rising. It could be shown that flame propagation and occasionally self-sustained combustion for several seconds occurred together with remarkable temperature rise, although the pressure rise was below 3%. The results showed that the combination of a pressure rise criterion of 2% and a temperature rise criterion of 100 K seems to be a suitable ignition criterion for the determination of explosion limits and limiting oxidizer concentration at higher initial pressures and elevated temperatures. The tests were carried out within the framework of a R&D project founded by the German Ministry of Economics and Technology.     

氢气爆炸特性研究

本文研究、总结了氢气与空气(氢气与氧气)的混合物的爆炸特性.即氢气在空气中,在比较低燃烧界限的情况下,只有向上的传播和非常少的超压可以观测得到.正因为氢气的这种特性,将氢应用于科技将极大地推进社会进步,氢燃料将成为一种主要的能源.然而,氢技术应用的成功与否主要取决于氢使用的安全性.所以,必须掌握实际使用时氢气燃烧的性能.本文在日本过去十年实验数据的基础上,通过实验研究了氢气与空气混合物的燃点.研究了氢气、氧气混合物经氮气稀释后,按化学当量比例将不同浓度的氢气与空气进行混合,并得出了低温下的爆炸压力特性.随后,分别讨论了在初始压力下一致的情况下,试管直径相同的状况下,氢气与空气混合浓度相同的情况下,这三种爆轰传播限制之间的关系.得出了在空气中直接点燃的发生爆轰的最小试管直径,最小的装药量之间的关系,进行了爆轰危险性分级.最后,文章概括比较了氢与其他燃料的燃烧特性,评估了氢气燃烧过程中的危险与安全因素.     

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.     

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.     

QSPR在混合物典型燃爆特性预测中的研究进展

为全面了解定量结构-性质关系（QSPR）方法在混合物燃爆特性预测中的研究现状,展望其发展趋势,综述其在混合物闪点、爆炸极限与自燃温度预测中的国内外研究进展,分析预测目标参数的选择、数据收集、描述符计算和筛选以及模型建立和验证等方面的不足与研究方向。结果表明:QSPR在混合物燃爆特性预测中尚处于起步阶段,当前研究的首要限制是混合物燃爆特性参数实验数据样本不足,关键点及难点是混合物结构的准确表征,未来研究应关注的重点是大量数据源统一的数据样本的获取方法、非加和性混合物分子描述符的计算方法以及机器学习等非线性建模方法。     

The explosion parameters of methanol under variable pressures and 423 K

The high-temperature and high-pressure methanol one-step oxidation has been the primary process for the mass production of dimethoxymethane. However, the risk of explosion for this process is still not properly defined. This paper presents new results from the experimental study on the explosion characteristics, including the explosion pressure and the explosion limits for methanol/air mixtures with a variable oxygen level, under an initial pressure between 0.3 MPa and 0.75 MPa and at the initial temperature of 423 K. The upper explosive limits were found to increase along with the initial pressure. If the limits for normal air are known, the oxygen effect on flammability is predictable from the thermal balance method. With a correlation for the pressure effect and a method for the oxygen effect, we can have the flammable range predictable.     

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.     

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.     

Flammability of gas mixtures containing volatile organic compounds and hydrogen

An experimental program was conducted to evaluate the accuracy of some current methods for predicting the flammability of gas mixtures containing hydrogen and flammable or nonflammable volatile organic compounds (VOCs) in air. The specific VOCs tested were toluene, 1,2-dichloroethane, 2-butanone, and carbon tetrachloride. The lower flammability limits (LFLs) of gas mixtures containing equal molar quantities of the components were determined in a 19.4-l laboratory flammability chamber using a strong spark ignition source and a pressure criterion for flammability. All but one of the LFL values for the individual components were in agreement with earlier literature values. However, the LFL of 1,2-dichloroethane was found to be significantly lower than the range of values reported for previous determinations in smaller chambers. Two methods for calculating the LFL of mixtures were considered. The Group Factor (atomic) Contribution Method was determined to be generally more accurate than the LeChatelier Method for estimating the LFL of the gas mixtures reported here, although the LeChatelier Method was usually more conservative. The Group Factor Method predicted higher values (nonconservative) for the LFLs of several mixtures than were experimentally measured. For the case of a mixture of hydrogen and carbon tetrachloride, the Group Method estimation of the LFL was seriously in error.     

Experimental flammability limits and associated theoretical flame temperatures as a tool for predicting the temperature dependence of these limits

The utility and limitations of adiabatic flame temperature calculations and minimum mixture energies in predicting the temperature dependence of flammability limits are explored. The limiting flame temperatures at constant pressure (1 bar) are calculated using a standard widely-used thermodynamic computer program. The computation is based on the calculated limiting flame temperature value at the reference initial temperature and the experimental limit concentration. The values recently determined in large chambers for the lower and upper flammability limits of a variety of simple organic and inorganic gases (methane, ethylene, dimethy lether, and carbon monoxide) are used as the basis for the predictions of the limiting flame temperature concept. Such thermodynamic calculations are compared with more traditional ones based on a limiting mixture energy and a constant average heat capacity of the reactant mixture. The advantages and limitations of the methods are discussed in this paper.     

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.     

Effects of initial temperature and pressure on explosion characteristics of propane–diluent–air mixtures

The explosion characteristics of propane–diluent–air mixtures under various temperatures and pressures were investigated using a 20-L apparatus. The explosion limits of propane diluted with nitrogen or carbon dioxide were measured at high temperatures from 25 to 120 °C. The results showed that the upper explosion limit (UEL) increased, and the lower explosion limit (LEL) decreased with the rising temperature. The explosion limits of propane diluted with nitrogen or carbon dioxide were also measured at high pressures from 0.10 to 0.16 MPa. The results showed that the UEL increased, and the LEL almost remainedunchanged along with increased pressure. Under the same initial operating conditions, the concentration of nitrogen required to reach the minimum inerting concentration (MIC) point was higher than the concentration of carbon dioxide. Finally, the study investigated the limiting oxygen concentration (LOC) of propane under various initial temperatures, initial pressures, and inert gases. The LOC of propane decreased approximately linearly with increased temperature or pressure, and the LOC of propane dilution with carbon dioxide was greater than dilution with nitrogen from 25 to 120 °C or from 0.10 to 0.16 MPa, which indicated that the dilution effect of carbon dioxide was better than that of nitrogen.     

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.     

Flammability of kerosene in civil and military aviation

The investigation of the ignition conditions of kerosene vapors in the air contained in an aircraft fuel tank contributes to the definition of onboard safety requirements. Civil and military kerosene are characterized by specification. The specification of civil aviation kerosene is based upon usage requirements and property limits. while military kerosene is primarily controlled by specific chemical composition. Characterization of the flammability properties is a first step for the establishment of aircraft safety conditions. Flash point, vapor pressure, gas chromatography analysis, and flammability properties of the kerosene used by the French Military aviation (F-34 and F-35 kerosene) are compared with the flammability properties of civil kerosene. The empirical law established by the Federal Aviation Administration (FAA) in 1998, expressing the ignition energy in terms of fuel, temperature, flash point and altitude is modified and expressed in terms of fuel temperature, flash point and pressure.     

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.     

Effect of inert species on the laminar burning velocity of hydrogen and ethylene

The maximum laminar burning velocity (LBV) of a fuel-air mixture is an important input parameter to vapor cloud explosion (VCE) blast load prediction methods. In particular, the LBV value has a significant impact on the predicted blast loads for high reactivity fuels with the propensity to undergo a deflagration-to-detonation transition (DDT). Published data are available for the maximum LBV of many pure fuel-air mixtures. However, little test data are available for mixtures of fuels, particularly for mixtures of fuels and inert species. Such mixtures are common in the petroleum refining and chemical processing industries. It is therefore of interest to be able to calculate the maximum LBV of a fuel/inert mixture based on the mixture composition and maximum LBV of each component.This paper presents measured test data for the maximum LBV of H₂/inert and C₂H₄/inert mixtures, with both nitrogen and carbon dioxide as the inert species. The LBV values were determined using a constant-volume vessel and the pressure rise method. This paper also provides a comparison of the measured LBV values with simplified LBV prediction methods.     

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.     

Parametric study of the explosivity of graphite-metals mixtures

The explosivity of dust clouds is greatly influenced by several parameters which depend on the operating conditions, such as the initial turbulence, temperature or ignition energy, but obviously also on the materials composition. In the peculiar case of a mixture of two combustible powders, the physical and chemical properties of both dusts have an impact on the cloud flammability and on its explosivity. Nevertheless, no satisfactory ‘mixing laws’ predicting the mixture behavior are currently available and the composition variable to be considered for such models greatly depend on the safety parameters which have to be determined: from volume ratios for some thermal exchanges and ignition phenomena, to surface proportions for some heterogeneous reactions and molar contents for chemical reactions. This study is mainly focused on graphite/magnesium mixtures as they are encountered during the decommissioning activities of UNGG reactors (Natural Uranium Graphite Gas). Due to the different nature and reactivity of both powders, these mixtures offer a wide range of interests. Firstly, the rate-limiting steps for the combustion of graphite are distinct from those of metals (oxygen diffusion or metal vaporization). Secondly, the flame can be thickened by the presence of radiation during metal combustion, whereas this phenomenon is negligible for pure graphite. Finally, the turbulence of the initial dust cloud is modified by the addition of a second powder. In order to assess the explosivity of graphite/magnesium clouds, a parametric study of the effects of storage humidity, particle size distribution, ignition energy, and initial turbulence has been carried out. In particular, it was clearly demonstrated that the turbulence significantly influences the explosion severity by speeding up the rate of heat release on the one hand and the oxygen diffusion through the boundary layer surrounding particles on the other hand. Moreover, it modifies the mean particle size and the spatial dust distribution in the test vessel, impacting the uniformity of the dust cloud. Thus, the present work demonstrates that the procedures developed for standard tests are not sufficient to assess the dust explosivity in industrial conditions and that an extensive parametric study is relevant to figure out the explosive behavior of solid/solid mixtures subjected to variations of operating conditions.     

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.