Theoretical evaluation of lower explosion limit of hybrid mixtures

Lower explosion limits of hybrid fuel mixtures are usually determined through time consuming and expensive experiments. Although, mathematical expressions like Le-Chatelier's Law and Bartknecht curve have been used by many researchers to predict the LEL of hybrid mixtures, significant deviations remain unexplained. This research work, presents a more sophisticated and general approach for the determination of LEL of hybrid mixtures.Assuming that the combustion kinetics of pure species are independent and unchanged by the presence of other combustible species, complete conversion of the reactants and no heat losses, a simple mathematical model has been derived from the enthalpy balance of the whole system. For the experimental validation of the modelled values, modified version of 20L sphere has been employed, following the European standard (EN 14034-3: 2011) as experimental protocol. Hybrid mixtures of three dusts with two gases were selected for the scope of this publication. By analyzing the modelled as well as the experimental values, it can be concluded that the LEL values of the individual components in the hybrid mixture set the upper and lower limit for the LEL of the hybrid mixture provided the total amount of fuel in the system is considered as the concentration of the hybrid mixture. Moreover, the amount of dust or gas required to render the hybrid mixture flammable mainly depends on the energy contribution upon combustion of the individual species to raise the temperature of the whole system from ambient to the flame temperature.Le-Chatelier's Law and Bartknecht curve are empirical relations, which might hold true for a first-order approximation of LEL of hybrid mixtures, but do not represent the most conservative values of LEL reported in literature. This implies that there is a non-zero probability of occurrence of an explosible mixture in the non-explosible concentrations ranges defined by these relations. Considering these arguments, the authors suggest to employ the model presented in this paper – which presents reasonably conservative values of LEL of hybrid mixtures – for theoretical calculation of LEL of hybrid mixtures, when no precise experimental data is available.     

Comparative study on standardized ignition sources used for explosion testing

For the determination of safety characteristics of gases, vapors and dusts different types of ignition sources are used in international standards and guidelines. The paper presents test results of a comparative calorimetric and visual study between four different types of ignition sources. The ignition procedures were analyzed visually with a high-speed camera and electric recordings. In addition to that, the influence of the electrode-orientation, -distance as well as ignition energy on the reproducibility of the exploding wire igniter was tested.The exploding wire is already in use for standardized determination of safety characteristics of gases, first tests on the suitability of the exploding wire igniter for dust testing have been carried out but are not standardized yet. Using the exploding wire, the ignition energy can be varied from 2 J to 10 000 J (2 x 5000 J) and thus it could be used for gases, vapors, dusts and hybrid mixtures. Moreover it can be used at high initial pressures and it is the only ignition source with an easily measurable ignition energy release. Furthermore, it does not introduce another chemical reaction into the system.Finally, a proposal for a standard ignition source for explosion tests on hybrid mixtures is derived from the test results.     

Experiment-based investigations of magnesium dust explosion characteristics

An experimental investigation was carried out on magnesium dust explosions. Tests of explosion severity, flammability limit and solid inerting were conducted thanks to the Siwek 20 L vessel and influences of dust concentration, particle size, ignition energy, initial pressure and added inertant were taken into account. That magnesium dust is more of an explosion hazard than coal dust is confirmed and quantified by contrastive investigation. The Chinese procedure GB/T 16425 is overly conservative for LEL determination while EN 14034-3 yields realistic LEL data. It is also suggested that 2000-5000 J is the most appropriate ignition energy to use in the LEL determination of magnesium dusts, using the 20 L vessel. It is essential to point out that the overdriving phenomenon usually occurs for carbonaceous and less volatile metal materials is not notable for magnesium dusts. Trends of faster burning velocity and more efficient and adiabatic flame propagation are associated with fuel-rich dust clouds, smaller particles and hyperbaric conditions. Moreover, Inerting effectiveness of CaCO₃ appears to be higher than KCl values on thermodynamics, whereas KCl represents higher effectiveness upon kinetics. Finer inertant shows better inerting effectiveness.     

Influence of different ignition delay times on the pressure rise rate in hybrid mixture explosions in the 20-L sphere

For the development of a standardized method for measuring the explosion safety characteristics of combustible hybrid dust/vapor mixtures, the influence of the ignition delay time needs to be investigated. The ignition delay time, defined as the time between the injection of dust and the activation of the ignition source, is related to the turbulence of the mixture and thus to the pressure rise rate. The ignition source for pure vapors, however, has to be activated in a quiescent atmosphere according to the standards. Nevertheless, when measuring the explosion safety characteristics of hybrid mixtures, it is important that the dust be in suspension around the igniter. Like pure dust/air mixtures, hybrid dust/vapor/air mixtures need to be ignited in a turbulent atmosphere to keep the dust in suspension.This work will therefore investigate the influence of ignition delay times on the severity of hybrid explosions. It was generally found that at shorter ignition delay times, (dp/dt)_ex increased due to higher turbulence and decreases as the dust sinks to the bottom of the 20 L-sphere. This effect is more pronounced for hybrid mixtures with higher vapor content compared to dust content.     

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.     

Effects of ignition energy on fire and explosion characteristics of dilute hybrid fuel in ventilation air methane

Deflagration explosions of coal dust clouds and flammable gases are a major safety concern in coal mining industry. Accidental fire and explosion caused by coal dust cloud can impose substantial losses and damages to people and properties in underground coal mines. Hybrid mixtures of methane and coal dust have the potential to reduce the minimum activation energy of a combustion reaction. In this study the Minimum Explosion Concentration (MEC), Over Pressure Rise (OPR), deflagration index for gas and dust hybrid mixtures (K_st) and explosive region of hybrid fuel mixtures present in Ventilation Air Methane (VAM) were investigated. Experiments were carried out according to the ASTM E1226-12 guideline utilising a 20 L spherical shape apparatus specifically designed for this purpose.Resultsobtained from this study have shown that the presence of methane significantly affects explosion characteristics of coal dust clouds. Dilute concentrations of methane, 0.75–1.25%, resulted in coal dust clouds OPR increasing from 0.3 bar to 2.2 bar and boosting the K_st value from 10 bar m s⁻¹ to 25 bar m s⁻¹. The explosion characteristics were also affected by the ignitors’ energy; for instance, for a coal dust cloud concentration of 50 g m⁻³ the OPR recorded was 0.09 bar when a 1 kJ chemical ignitor was used, while, 0.75 bar (OPR) was recorded when a 10 kJ chemical ignitor was used.For the first time, new explosion regions were identified for diluted methane-coal dust cloud mixtures when using 1, 5 and 10 kJ ignitors. Finally, the Le-Chatelier mixing rule was modified to predict the lower explosion limit of methane-coal dust cloud hybrid mixtures considering the energy of the ignitors.     

A theoretical model for the prediction of the minimum ignition energy of dust clouds

In this study, a physical model of the dust cloud ignition process is developed for both cylindrical coordinates with a straight-line shaped ignition source and spherical coordinates with a point shaped ignition source. Using this model, a numerical algorithm for the calculation of the minimum ignition energy (MIE) is established and validated. This algorithm can evaluate MIEs of dusts and their mixtures with different dust concentrations and particle sizes. Although the average calculated cylindrical MIE (MIE_cylindrical) of the studied dusts only amounts to 63.9% of the average experimental MIE value due to reasons including high idealization of the numerical model and possible energy losses in the experimental tests, the algorithm with cylindrical coordinates correctly predicts the experimental MIE variation trends against particle diameter and dust concentration. There is a power function relationship between the MIE and particle diameter of the type MIE ∝ d_p^k with k being approximately 2 for cylindrical coordinates and 3 for spherical coordinates. Moreover, as dust concentration increases MIE(conc) first drops because of the decreasing average distance between particles and, at fuel-lean concentrations the increasing dust cloud combustion heat; however, after the dust concentration rises beyond a certain value, MIE(conc) starts to increase as a result of the increasingly significant heat sink effect from the particles and, at fuel-rich concentrations the no longer increasing dust cloud combustion heat.     

A review on hybrid mixture explosions: Safety parameters,explosion regimes and criteria,flame characteristics

The hybrid mixture of combustible dusts and flammable gases/vapours widely exist in various industries, including mining, petrochemical, metallurgical, textile and pharmaceutical. It may pose a higher explosion risk than gas/vapor or dust/mist explosions since the hybrid explosions can still be initiated even though both the gas and the dust concentration are lower than their lower explosion limit (LEL) values. Understanding the explosion threat of hybrid mixtures not only contributes to the inherent safety and sustainability of industrial process design, but promotes the efficiency of loss prevention and mitigation. To date, however, there is no test standard with reliable explosion criteria available to determine the safety parameters of all types of hybrid mixture explosions, nor the flame propagation and quenching mechanism or theoretical explanation behind these parameters. This review presents a state-of-the-art overview of the comprehensive understanding of hybrid mixture explosions mainly in an experimental study level; thereby, the main limitations and challenges to be faced are explored. The discussed main contents include the experimental measurement for the safety parameters of hybrid mixtures (i.e., explosion sensitivity and severity parameters) via typical test apparatuses, explosion regime and criterion of hybrid mixtures, the detailed flame propagation/quenching characteristics behind the explosion severities/sensitivities of hybrid mixtures. This work aims to summarize the essential basics of experimental studies, and to provide the perspectives based on the current research gaps to understand the explosion hazards of hybrid mixtures in-depth.     

Hybrid H2/Al dust explosions in Siwek sphere

Explosion indices and explosion behaviour of Al dust/H₂/air mixtures were studied using standard 20 l sphere. The study was motivated by an explosion hazard occurring at some accidental scenarios considered now in ITER design (International Thermonuclear Experimental Reactor). During Loss-of-Vacuum or Loss-of-Coolant Accidents (LOCA/LOVA) it is possible to form inside the ITER vacuum vessel an explosible atmosphere containing fine Be or W dusts and hydrogen. To approach the Be/H₂ explosion problem, Be dust is substituted in this study by aluminium, because of high toxicity of Be dusts. The tested dust concentrations were 100, 200, 400, 800, and 1200 g/m3; hydrogen concentrations varied from 8 to 20 vol. % with 2% step. The mixtures were ignited by a weak electric spark. Pressure evolutions were recorded during the mixture explosions. In addition, the gaseous compositions of the combustion products were measured by a quadruple mass-spectrometer. The dust was involved in the explosion process at all hydrogen and dust concentrations even at the combination ‘8%/100 g/m3’. In all the other tests the explosion overpressures and the pressure rise rates were noticeably higher than those relevant to pure H₂/air mixtures and pure Al dust/air mixtures. At lower hybrid fuel concentrations the mixture exploded in two steps: first hydrogen explosion followed by a clearly separated Al dust explosion. With rising concentrations, the two-phase explosion regime transits to a single-phase regime where the two fuel components exploded together as a single fuel. In this regime both the hybrid explosion pressures and pressure rise rates are higher than either H₂ or Al ones. The two fuels compete for the oxygen; the higher the dust concentration, the more part of O2 it consumes (and the more H₂ remains in the combustion products). The test results are used to support DUST3D CFD code developed at KIT to model LOCA or LOVA scenarios in ITER.     

Experiment-based investigations on the effect of ignition energy on dust explosion behaviors

Explosion behaviors of typical light metal and carbonaceous dusts induced by different ignition energies were investigated based on systematic experiments in a Siwek 20 L vessel. Comparative analysis reveals that the explosion mechanism of carbonaceous dust is the volatile combustion, whereas the mechanism for light metal dust mainly features the surface heterogeneous oxidation. Influences of ignition energy on severity and flammability limit are much more significant for carbonaceous dust than light metal, especially for the powder with less volatile. An innovative approach was introduced to derive flame thickness from the pressure–time trace. The relation between explosion induction time and combustion duration of ignitor was also analyzed. Results show inappropriate ignition energy will cause under-/over-driving in the thermodynamic/kinetic characteristic measurements. In this way, a dimensionless parameter pressure ratio was introduced to evaluate the under-driving, while two methods by using flame thickness and induction time respectively, were proposed to evaluate over-driving. To improve the accuracy of dust explosion tests, authors advocate that explosion severity determination should be conducted at the critical ignition energy. Moreover, a comparison between the European and Chinese flammability limit determination procedures was also conducted, indicating that EN 14034-3 is suitable for light metal but not for carbonaceous, while GB/T 16425 appears to be slightly conservative for both carbonaceous and light metal dusts.     

Minimum ignition energy of LDPE dust/ethylene hybrid mixture

An experimental device for evaluating the minimum ignition energy (MIE) of LDPE dust/ethylene hybrid mixture was built with the innovative mixing mode. The MIE of the hybrid mixture that contained ethylene below its lower explosive limit (LEL) was studied. The result indicated that adding a small amount of ethylene significantly reduced the MIE of the original dust cloud. All the MIEs with five different particle sizes were found to show similar trends of exponential attenuation with the increase of ethylene concentration; such attenuating effect grew as the dust particle size rose. When ethylene concentration increased and approached to its LEL, the reaction mechanism dominated by combustible dust turned into one dominated by combustible gas. The MIE decreased first and then increased with the dust mass and increased with the dust particle size. A multifactor mathematical correlation model of the MIE with the dust particle size and ethylene concentration was developed.     

When solids meet solids: A glimpse into dust mixture explosions

Mixing an inert solid or a less flammable compound with a combustible dust can be regarded as a direct application of the inherent safety principle of moderation. An experimental investigation was carried out to determine the evolution of the ignition sensitivity and the explosion severity of such various mixtures as a function of their compositions. It demonstrates that the introduction of small amounts of highly combustible powders (such as sulphur or nicotinic acid) to a less flammable dust (such as microcrystalline cellulose or carbon black) can strongly influence the ignition sensitivity as well as the explosion severity.It has notably been shown that the ignition sensitivity of solid/solid mixtures significantly rises up when only 10–5%wt. of highly flammable dust is introduced. Simple models can often be applied to estimate the minimum ignition energy, minimum ignition temperature and minimum explosive concentration of such mixtures. Concerning the dust explosivity, three cases have been studied: mixtures of combustibles dusts without reaction, dusts with reactions between the powders, combustible dusts with inert solid. If the evolution of the maximum explosion pressure can be estimated by using thermodynamic calculations, the maximum rate of pressure rise is more difficult to predict with simple models, and both combustion kinetics and hydrodynamics of the dust clouds should be taken into account. These results were also extended to flammable dust/solid inertant mixture. They clearly show that the concentration of solid inertant at which the ignition is not observed anymore could reach 95%wt. As a consequence, the common recommendation of solid inertant introduction up to 50–80%wt. to prevent dust explosion/ignition should be reconsidered.     

Explosibility of fine graphite and tungsten dusts and their mixtures

To evaluate the explosion hazard of ITER-relevant dusts, a standard method of 20-l-sphere was used to measure the explosion indices of fine graphite and tungsten dusts and their mixtures. The effect of dust particle size was studied on the maximum overpressures, maximum rates of pressure rise, and lower explosive concentrations of graphite dusts in the range 4 μm to 45 μm. The explosion indices of 1 μm tungsten dust and its mixtures with 4 μm graphite dust were measured. The explosibility of these dusts and mixtures were evaluated. The dusts tested were ranked as St1 class. Dust particle size was shown to be very important for explosion properties. The finest graphite dust appeared to have the lowest minimum explosion concentration and be able to explode with 2 kJ ignition energy.     

Minimum ignition energy of mixtures of combustible dusts

Most industrial powder processes handle mixtures of various flammable powders. Consequently, hazard evaluation leads to a reduction of the disaster damage that arises from dust explosions. Determining the minimum ignition energy (MIE) of flammable mixtures is critical for identifying possibility of accidental hazard in industry. The aim of this work is to measure the critical ignition energy of different kinds of pure dusts with various particle sizes as well as mixtures thereof.The results show that even the addition of a modest amount of a highly flammable powder to a less combustible powder has a significant impact on the MIE. The MIE varies considerably when the fraction of the highly flammable powder exceeds 20%. For dust mixtures consisting of combustible dusts, the relationship between the ignition energy of the mixture and the minimum ignition energy of the components follows the so-called harmonic model based upon the volume fraction of the pure dusts in the mixture. This correlation provides results which show satisfactory agreement with the experimental values.     

EVA树脂粉尘/甲烷/空气杂混物爆炸特性

在20 L爆炸实验装置中,开展了3种不同中值粒径的EVA树脂粉尘/甲烷/空气所组成的杂混物爆炸特性研究,探究了甲烷浓度对粉尘爆炸下限、最大爆炸压力的影响。结果表明,尽管添加的甲烷气体浓度低于爆炸下限,仍使得粉尘爆炸下限得以降低,粒径较大的EVA III粉尘,当甲烷体积分数为1%时,爆炸下限降低约25%;粒径较小的EVA I粉尘,当混入甲烷体积分数为4%时,爆炸下限则降低80%;甲烷体积分数每增加1%,可燃粉尘最大爆炸压力上升约10%,但对于粒径较小的EVA I粉尘,当甲烷体积分数为4%时,最大爆炸压力的上升呈现突变趋势,上升近50%。     

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.     

Differences and similarities of gas and dust explosions: A critical evaluation of the European ‘ATEX’ directives in relation to dusts

Explosive gas mixtures and explosive dust clouds, once existing, exhibit similar ignition and combustion features. However, there are two basic differences between dusts and gases which are of substantially greater significance in design of safety standards than these similarities. Firstly, the physics of generation and up-keeping of dust clouds and premixed gas/vapour clouds are substantially different. This means that in most situations where accidental explosive gas clouds may be produced quite readily, generation of explosive dust clouds would be highly unlikely. Secondly, contrary to premixed gas flame propagation, the propagation of flames in dust/air mixtures is not limited only to the flammable dust concentration range of dynamic clouds. The state of stagnant layers/deposits offers an additional discrete possibility of flame propagation.

The two European Directives 94/9/EC (1994) and 1999/92/EC (1999) primarily address gases/vapours, whereas the particular properties of dusts are not addressed adequately. Some recent IEC and European dust standards resulting from this deficiency are discussed, and the need for revising the two directives accordingly is emphasized.     

Experimental study on the minimum explosion concentration of anthracite dust: The roles of O2 mole fraction,inert gas and CH4 addition

The explosion characteristics of anthracite coal dust with/without small amount of CH₄ (1.14 vol %) were investigated by using a 20 L spherical explosion apparatus with an emphasis on the roles of oxygen mole fraction and inert gas. Two methods based on overpressure and combustion duration time were used to determine the minimum explosion concentration (MEC) or the lower explosion limit (LEL) of the pure anthracite coal dust and the hybrid coal-methane mixtures, respectively. The experiment results showed that increasing oxygen mole fraction increases the explosion risk of coal dust: with increasing oxygen mole fraction, the explosion pressure (P_ex) and the rate of explosion pressure rise ((dp/dt)_ex)) increase, while MEC decreases. The explosion risk of anthracite dust was found to be lower after replacing N₂ with CO₂, suggesting that CO₂ has a better inhibition effect on explosion mainly due to its higher specific heat. However, the addition of 1.14% CH₄ moderates the inhibition effect of CO₂ and the promotion effect of O₂ on anthracite dust explosion for some extent, increasing explosion severity and reducing the MEC of anthracite dust. For hybrid anthracite/CH₄ mixture explosions, Barknecht's curve was found to be more accurate and conservative than Chatelier's line, but neither are sufficient from the safety considerations. The experimental results provide a certain help for the explosion prevention and suppression in carbonaceous dust industries.     

Dust explosion risk moderation for flocculent dusts

The research presented in this paper is focused on dust explosions of coarse and fine flocculent (or fibrous) samples of wood and polyethylene. Hybrid mixtures of fibrous polyethylene and admixed ethylene were also studied. Experimentation was conducted by following standardized test procedures and using standardized apparatus for determination of maximum explosion pressure, size-normalized maximum rate of pressure rise, minimum explosible concentration, minimum ignition energy, and minimum ignition temperature. A general trend was observed of enhanced explosion likelihood and consequence severity with a decrease in material diameter, as well as enhanced consequence severity with admixture of a flammable gas to the combustion atmosphere. The same phenomena are well-established for dusts composed of spherical particles; this highlights the importance of inherently safer design and the principle of moderation in avoiding the generation of fine sizes of flocculent dusts and hybrid mixtures of such materials with flammable gases.In addition to presenting experimental findings, the paper describes phenomenological modelling efforts for the flocculent polyethylene using four geometric equivalence models: radial equivalence, volumetric equivalence, surface area equivalence, and specific surface area equivalence. The surface area equivalence model was found to yield the best estimates of maximum rate of pressure rise for the flocculent polyethylene samples investigated experimentally.     

Experimental investigation of the complex deflagration phenomena of hybrid mixtures of activated carbon dust/hydrogen/air

This paper aims to develop quantitative insights based on measured deflagration parameters of hybrid mixtures of activated carbon (AC) dust and hydrogen (H₂) gas in air. The generated experimental evidence is used to reject the claim of the null hypothesis (H₀) that severity of deflagrations of H₂/air mixtures always bound the severity of deflagrations of heterogenous combustible mixtures of AC dust/H₂/air containing the same H₂ concentrations as in the H₂/air binaries. The core insights of this investigation show that the maximum deflagration pressure rise (ΔP_MAX) and maximum rate of pressure rise ((dP/dt)_MAX) of this hybrid mixture are greater than those corresponding to deflagrations of H₂/air mixtures for all the dust and H₂ concentrations being examined. The deflagration severity indices (K_St and ES) of the hybrid mixture containing 29 mol% H₂ are found to be greater than those of the H₂/air mixture containing 29 mol% H₂. Also, the minimum explosible concentration (MEC) of the hybrid mixture is lower than that of the AC dust in air only. The insights gained should lead to better realization of the severity of a postulated safety-significant accident scenario associated with on-board cryoadsorption H₂ storage systems for fuel-cell (FC) powered light-duty vehicles. The identified insights could also be relevant to other industrial processes where combustible dusts are generated in the vicinity of solvent vapors. Moreover, these insights should be useful for supporting quantitative risk assessment (QRA) of on-board H₂ storage systems, designing improved safety measures for cryoadsorption H₂ storage tanks, and guiding H₂ safety standards and transportation regulations.