Electrostatic ignition of sensitive flammable mixtures: Is charge generation due to bubble bursting in aqueous solutions a credible hazard?

Experiments have been conducted to gain insight into the credibility of sparging aqueous solutions as an electrostatic ignition hazard for sensitive hydrogen/air or fuel/oxygen mixtures (Minimum Ignition Energies of ∼0.017 mJ and ∼0.002 mJ, respectively, compared to ∼0.25 mJ for hydrocarbon/air mixtures). Tests performed in a 0.5 m³ ullage produced electric field strengths between 125 and 560 V m⁻¹ for air flows of 5–60 l min⁻¹, respectively, comprised of 2–4 mm diameter bubbles. Field strength can be related to the space charge and fitting to an exponential accumulation curve enabled the charge generation rate from the air flows to be estimated. This was observed to be directly proportional to the air flow and its magnitude was consistent with literature data for bubble bursts. The charge accumulation observed at laboratory scale would not be a cause for concern. On the basis of a simple model, the charge accumulation in a 27 m³ ullage was predicted for a range of air flows. It is apparent from such calculations that ignition of hydrocarbon/air mixtures would not be expected. However, it would seem possible that field strengths might be sufficient to cause a risk of incendive spark or corona discharges in moderately sized vessels with sensitive flammable mixtures.     

Flammability of hydrocarbon and carbon dioxide mixtures

The effect of carbon dioxide (CO₂) concentration on the ignition behaviour of hydrocarbon and CO₂ gas mixtures is examined in both jets and confined explosions. Results from explosion tests are presented using a 20 l explosion sphere and an 8 m long section of 1.04 m diameter pipeline. Experiments to assess the flame stability and ignition probability in free-jets are reported for a range of different release velocities. An empirically-based flammability factor model for free-jets is also presented and results are compared to ignition probability measurements previously reported in the literature and those resulting from the present tests.The results help to understand how CO₂ changes the severity of fires and explosions resulting from hydrocarbon releases. They also demonstrate that it is possible to ignite gas mixtures when the mean concentration is outside the flammable range. This information may be useful for risk assessments of offshore platforms involved in carbon sequestration or enhanced oil recovery, or in assessing the hazards posed by poorly-inerted hydrocarbon processing plant.     

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.     

Modeling of detonation processes in chemically active bubble systems at normal and elevated initial pressures

The detonation processes in chemically active bubble liquids under elevated initial pressures are investigated theoretically. It is shown, that supersonic regimes of wave propagation can exist, if the initial pressure is relatively high and the volume fraction of the bubbles is relatively small. Characteristic values of the bubble detonation wave pressure at sub- and supersonic regimes differ by an order of magnitude.The principal possibility of detonation wave structure transformation in the case of propagation in the mixture with high initial pressure and longitudinal gradient of bubble volume fraction is predicted. The leading shock may transform into a smooth wave of compression.The Chapman-Jouguet conditions for self-sustaining supersonic bubble detonation wave is obtained.A model of shock induced single bubble dynamics and ignition taking into account the real properties of the liquid, inter-phase transition processes, mechanical mixing of phases, ignition delay and continuous shift of chemical equilibrium have been described. Calculations for the oxygen containing bubble in liquid cyclohexane have been performed.     

井喷失控点火时间与方位探讨

利用计算流体力学方法(CFD)对井喷失控后天然气扩散过程进行研究,在有限元基础上建立模型,采用κ-ε紊流模型求解得出井喷失控后可燃性蒸气云随时间、风速变化的影响情况,求出稳态以后易爆区域的蒸气云形状。取5.0%和15%作为甲烷的爆炸上、下限,在不同区域进行点火求解爆燃结果,通过比较给出推荐的点火时间和点火方位。该研究成果可对井喷失控蒸气云爆燃危害性进行预测,有助于指导井喷失控进行点火放喷工作,避免爆燃事故的发生。     

Explosions and deflagration-to-detonation transitions in epoxy propane/air mixtures

The explosion and deflagration-to-detonation transition (DDT) in epoxy propane (E.P.) vapor/air mixture clouds under weak ignition conditions has been studied in an experimental tube of diameter 199 mm and length 29.6 m. E.P. vapor clouds were formed by injecting liquid E.P. into the experimental tube and evaporating of the fine E.P. droplets. The dimension and the evaporating process of the E.P. droplet were measured and analyzed. The E.P. vapor/air mixture clouds were ignited by an electric spark with an ignition energy of 40 J. The characteristics and the stages of the DDT process in the E.P. vapor/air mixtures have been studied and analyzed. A self-sustained detonation wave formed, as was evident from the existence of a transverse wave and a cellular structure. Moreover, a retonation wave formed during the DDT process in the E.P. vapor/air mixture. The influence of the E.P. vapor concentration on the DDT process has been studied. The minimum E.P. vapor concentration for the occurrence of the DDT in the E.P. vapor/air mixture has been evaluated and the variation of DDT distance with E.P. vapor concentration has been analyzed.     

Accident modeling of toxic gas-containing flammable gas release and explosion on an offshore platform

Toxic gas-containing flammable gas leak can lead to poisoning accidents as well as explosion accidents once the ignition source appears. Many attempts have been made to evaluate and mitigate the adverse effects of these accidents. All these efforts are instructive and valuable for risk assessment and risk management towards the poisoning effect and explosion effect. However, these analyses assessed the poisoning effect and explosion effect separately, ignoring that these two kinds of hazard effects may happen simultaneously. Accordingly, an integrated methodology is proposed to evaluate the consequences of toxic gas-containing flammable gas leakage and explosion accident, in which a risk-based concept and the grid-based concept are adopted to combine the effects. The approach is applied to a hypothetical accident scenario concerning an H₂S-containing natural gas leakage and explosion accident on an offshore platform. The dispersion behavior and accumulation characteristics of released gas as well as the subsequent vapor cloud explosion (VCE) are modeled by Computational Fluid Dynamics (CFD) code Flame Acceleration Simulator (FLACS). This approach is concise and efficient for practical engineering applications. And it helps to develop safety measures and improve the emergency response plan.     

圆柱形无约束气云爆炸高温效应研究

为了分析无约束可燃气云爆炸产生的高温伤害效应,建立了相应的数学模型,利用有限体积的离散方法,对无约束空间内甲烷浓度10％、高径比为1的圆柱形可燃气云爆炸的瞬态温度场进行了数值研究。研究结果表明,圆柱形可燃气云爆炸的温度场呈不对称性分布,靠近地面处足最危险区域,高温可能达到的最大怪直高度和最大水平距离分别约为圆柱体高的2倍和半径的3．2倍。对数值模拟结果的数据进行多项式拟合,得到了圆柱形可燃气云爆炸场最高温度随水平距离、初温及参与爆炸气云质量的函数关系式,给可燃气云爆炸灾害的预测及防护提供了科学依据。     

开敞空间可燃气云爆炸冲击波超压及灾害动力响应研究评述

为了进一步梳理和分析开敞空间可燃云爆炸冲击波超压传播规律及灾害动力响应方面的各项研究成果,推进可燃气体爆炸安全防控,减少人员伤亡和经济损失。在分析现有研究的基础上,总结开敞空间可燃气云爆炸冲击波超压传播规律及灾害动力响应研究等方面存在的不足,提出开敞空间多元混合气体爆炸冲击波超压传播规律研究、多影响参数下可燃气云爆炸冲击波超压传播规律定量分析、基于可燃气云爆炸冲击波超压作用下的承载体动力响应等未来研究的关键技术问题。     

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.     

20L近球形容器中甲醇喷雾液滴爆炸特性实验研究*

为了评估易燃液体喷雾的爆炸风险,借助喷雾粒度仪、高速相机以及喷雾爆炸实验系统,围绕2种粒径(表面积平均粒径:2.0 μm±0.5 μm;18.0 μm±0.5 μm)的甲醇喷雾,研究点火位置和延迟时间等因素对甲醇喷雾爆炸特性的影响。结果表明:甲醇喷雾粒径均随环境温度的增加而减小,当甲醇喷雾浓度较大时,环境温度对于甲醇喷雾粒径的影响更为显著;甲醇物料温度的改变对于其粒径的影响很小。随着点火延迟时间的增大,甲醇喷雾爆炸特性参数均呈现先增加后减小的趋势,在τ=120 ms时最大。受限空间内甲醇喷雾采用中心或上部点火方式,当甲醇喷雾浓度为356.4 g/m3(φ=1.8)时,甲醇喷雾爆炸特性参数均取得最大值;与上部位置点火相比,中心位置点火的甲醇喷雾爆炸特性参数值较大。     

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.     

Evaluating the potential for overpressures from the ignition of an LNG vapor cloud during offloading

Ignition of natural gas (composed primarily of methane) is generally not considered to pose explosion hazards when in unconfined and low- or medium-congested areas, as most of the areas within LNG regasification facilities can typically be classified. However, as the degrees of confinement and/or congestion increase, the potential exists for the ignition of a methane cloud to result in damaging overpressures (as demonstrated by the recurring residential explosions due to natural gas leaks). Therefore, it is prudent to examine a proposed facility’s design to identify areas where vapor cloud explosions (VCEs) may cause damage, particularly if the damage may extend off site.An area of potential interest for VCEs is the dock, while an LNG carrier is being offloaded: the vessel hull provides one degree of confinement and the shoreline may provide another; some degree of congestion is provided by the dock and associated equipment.In this paper, the computational fluid dynamics (CFD) software FLACS is used to evaluate the consequences of the ignition of a flammable vapor cloud from an LNG spill during the LNG carrier offloading process. The simulations will demonstrate different approaches that can be taken to evaluate a vapor cloud explosion scenario in a partially confined and partially congested geometry.     

Modelling the mitigation of a hydrogen deflagration in a nuclear waste silo ullage with water fog

During the decommissioning of certain legacy nuclear waste storage plants it is possible that significant releases of hydrogen gas could occur. Such an event could result in the formation of a flammable mixture within the silo ullage and, hence, the potential risk of ignition and deflagration occurring, threatening the structural integrity of the silo. Very fine water mist fogs have been suggested as a possible method of mitigating the overpressure rise, should a hydrogen–air deflagration occur. In the work presented here, the FLACS CFD code has been used to predict the potential explosion overpressure reduction that might be achieved using water fog mitigation for a range of scenarios where a hydrogen–air mixture, of a pre-specified concentration (containing 800 L of hydrogen), uniformly fills a volume located in a model silo ullage space, and is ignited giving rise to a vented deflagration. The simulation results suggest that water fog could significantly reduce the peak explosion overpressure, in a silo ullage, for lower concentration hydrogen–air mixtures up to 20%, but would require very high fog densities to be achieved to mitigate 30% hydrogen–air mixtures.     

Effect of spark duration on explosion parameters of methane/air mixtures in closed vessels

The paper outlines an experimental study on influence of the spark duration and the vessel volume on explosion parameters of premixed methane–air mixtures in the closed explosion vessels. The main findings from these experiments are: For the weaker ignition the spark durations in the range from 6.5 μs to 40.6 μs had little impact on explosion parameters for premixed methane–air mixtures in the 5 L vessel or 20 L vessel; For the same ignitions and volume fractions of methane in air the explosion pressures and the flame temperatures in both vessels of 5 L and 20 L were approximately the same, but the rates of pressure rises in both vessels of 5 L and 20 L were different; The explosion indexes obtained from the measured pressure time histories for both vessels of 5 L and 20 L were approximately equal; For the weaker ignition with the fixed spark duration 45 μs the ignition energies in the range from 54 mJ to 430 mJ had little impact on the explosion parameters; For the same ignition and the volume fractions of methane in air, the vessel volumes had a significant impact on the flame temperatures near the vessel wall; The flame temperatures near the vessel wall decreased as the vessel volumes increased.     

Process of accidental explosions at a refuse derived fuel storage

Accidental gas explosions occurred at a refuse-derived-fuel (RDF) storage in Japan, and two fire fighters on duty were dead. The flammable gases, which caused the gas explosions generated during a RDF fire. It means that gas explosions could occur in the use of solid fuels under certain conditions. This study has been conducted for exploring the process to gas explosions in the RDF storage. The temperature at a part of the RDF pile in the storage was inferred to spontaneously increase, and the prediction of the temperature increase was attempted on the basis of the Frank-Kamenetskii theory. It was shown that the critical temperature of RDF for spontaneous temperature rise depends on the size of the pile. Larger the pile, lower the critical temperature. The possibility of accumulation of flammable gas in the space of the RDF storage is discussed. It is indicated that the spread rate of thermal wave is slow and a high temperature region likely established. After the RDF pile ignites, the oxygen concentration near the burning site becomes low and the flammable species components in the generated gas increases. Those species pass through surrounding low temperature region and come out into the space over the RDF pile without combustion. An explosion would occur when a fresh air comes into the storage, mixes with the flammable gas coming out from the pile to form a flammable mixture, and then the flammable mixture ignites. The most effective means to prevent accidental explosions is to avoid spontaneous ignition by cooling the heated RDF. If spontaneous ignition occurs, elimination of flammable gases from the storage should be strongly recommended.     

Applications of dust explosion hazard and disaster prevention technology

Powdered materials are widely used in industrial processes, chemical processing, and nanoscience. Because most flammable powders and chemicals are not pure substances, their flammability and self-heating characteristics cannot be accurately identified using safety data sheets. Therefore, site staff can easily underestimate the risks they pose. Flammable dust accidents are frequent and force industrial process managers to pay attention to the characteristics of flammable powders and create inherently safer designs.This study verified that although the flammable powders used by petrochemical plants have been tested, some powders have different minimum ignition energies (MIEs) before and after drying, whereas some of the powders are released of flammable gases. These hazard characteristics are usually neglected, leading to the neglect of preventive parameters for fires and explosions, such as dust particle size specified by NFPA-654, MIE, the minimum ignition temperature of the dust cloud, the minimum ignition temperature of the dust layer, and limiting oxygen concentration. Unless these parameters are fully integrated into process hazard analysis and process safety management, the risks cannot be fully identified, and the reliability of process hazard analysis cannot be improved to facilitate the development of appropriate countermeasures. Preventing the underestimation of process risk severity due to the fire and explosion parameters of unknown flammable dusts and overestimation of existing safety measures is crucial for effective accident prevention.     

Study of the explosion parameters of vapor–liquid diethyl ether/air mixtures

The knowledge of the vapor–liquid two-phase diethyl ether (DEE)/air mixtures (mist) on the explosion parameters was an important basis of accident prevention. Two sets of vapor–liquid two-phase DEE/air mixtures of various concentrations were obtained with Sauter mean diameters of 12.89 and 22.90 μm. Experiments were conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at an ignition energy of 40.32 J and at an initial room temperature and pressure of 21 °C and 0.10 MPa, respectively. The effects of the concentration and particle size of DEE on the explosion pressure, the explosion temperature, and the lower and upper flammability limits were analyzed. Finally, a series of experiments was conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at various ignition energies. The minimum ignition energies were determined, and the results were discussed. The results were also compared against our previous work on the explosion characteristics of vapor–liquid two-phase n-hexane/air mixtures.     

Effect of bubble generation on hot zone formation in tank fires

Boilover is a phenomenon that both stakeholders and fire-fighters in the petrochemical industry try to avoid. This phenomenon results in an explosion of liquid hydrocarbon materials (e.g., crude oil) due to prolonged oil tank fires. The elevated temperature provides energy to vaporize the water sub-layer, which commonly resides at bottom of storage tanks, leading to tremendous fire enlargement as fuel tends to spill over around the tank. Boilover follows the formation of an isothermal layer called ‘hot zone’, and is typically accompanied by continuing bubble appearance in the hot zone. Previous studies have suggested that bubble generation could be a driving force for boilover, as it accelerates heat mixing. However, the effect of bubble generation on the mechanism of hot zone formation has not yet been systematically studied. This work investigates the effect of bubble formation on hot zone formation by installing a metal mesh in a burning fuel container. The size of the mesh grid and the position of the mesh are varied to generate bubbles with different volumes from different depths from the fuel surface. Experimental results demonstrate that the metal mesh definitely increases the volume of bubbles, and significantly reduces the time to form a hot zone. The mesh with small grids generates more bubbles than that with large grids. Additionally, bubbles start to generate earlier when the mesh is fixed nearer the fuel surface. Experimental results provide direct evidence of the bubble effect on hot zone formation.     

Ignitability assessment of shredder dusts of refrigerator and the prevention of the dust explosion

Explosibility of polyurethane dusts produced in the recycling process of refrigerator and the ways to prevent the dust explosion were studied. In recent years, cyclopentane is often used as the foaming agent and this produces explosive atmosphere in the shredding process. The minimum explosive concentration of polyurethane dust, influence of coexisting cyclopentane gas on the explosibility, effect of relative humidity on the minimum explosive concentration of polyurethane dusts, the minimum ignition energy, influence of cyclopentane mixture on the explosion severity, etc. were investigated.The minimum explosive dust concentration decreased with the increase of cyclopentane concentration and increased with the increase of relative humidity. The minimum ignition energy was about 11 mJ. The ignition energy decreased with the increase of the cyclopentane gas concentration. The cyclopentane gas concentration up to about 5300 ppm did not influence too much on the explosion index (K_st) and maximum explosion pressure. From these, it would be a good way to increase the relative humidity and to regulate the cyclopentane concentration in the shredding process to prevent the dust explosion hazard.