Making hybrid mixture explosions a common case

Explosions of gas-dust hybrid mixtures have long been considered as particular cases encountered in specific industrial contexts. However, it should be reminded that during the explosion of an organic powder, the presence of a hybrid mixture composed of the dust itself and its pyrolysis gases is compulsory. On these premises, an experimental study to determine the role of cellulose pyrolysis products (gaseous, condensable and solid) on the global phenomenon is presented. Hybrid mixture explosion tests were exploited to carry out the investigation. The G-G furnace and the 20 L sphere were employed. Several experimental strategies were chosen to demonstrate the impact of pyrolysis reaction on the explosion of organic powders: i) the fuel equivalence ratio of the reactive mixture (case 1), or ii) the mass of reactants (case 2) were respectively kept constant, iii) the effects of water vapor, char and tar were tested. They were next compared to identify the most suitable one. The two first experimental approaches lead to significantly different results: only case 2 keeps the maximum explosion pressure almost constant, but maximum rate of pressure rises and deflagration index greatly decrease when the pyrolysis gases concentration decreases, which highlights the importance of the pyrolysis reaction on the explosion kinetics. It should also be stressed that the maximum explosion severity is not obtained for the pure gases but when a small dust content is added. The same evolution is observed when a small amount of char is introduced to pyrolysis gases, which underlines the influence of the radiative transfer. Adding small amounts of tar to cellulose tends to increase its explosion severity. However, this impact is less than that generated by the addition of pyrolysis gases.     

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.     

Influences of coal dust components on the explosibility of hybrid mixtures of methane and coal dust

In order to study the influences of coal dust components on the explosibility of hybrid mixture of methane and coal dust, four kinds of coal dust with different components were selected in this study. Using the standard 20 L sphere, the maximum explosion pressure, explosion index and lower explosion limits of methane/coal dust mixtures were measured. The results show that the addition of methane to different kinds of coal dust can all clearly increase their maximum explosion pressure and explosion index and decrease their minimum explosion concentration. However, the increase in the maximum explosion pressure and explosion index is more significant for coal dust with lower volatile content, while the decrease in the minimum explosion concentration is more significant for coal dust with higher volatile content. It is concluded that the influence of methane on the explosion severity is more pronounced for coal dust with lower volatile content, but on ignition sensitivity it is more pronounced for coal dust with higher volatile content. Bartknecht model for predicting the lower explosion limits of methane/coal dust mixture has better applicability than Le Chatelier model and Jiang model. Especially, it is more suitable for hybrid mixtures of methane and high volatile coal dust.     

Fast and tiny: A model for the flame propagation of nanopowders

To avoid the influence of external parameters, such as the vessel volume or the initial turbulence, the explosion severity should be determined from intrinsic properties of the fuel-air mixture. Therefore, the flame propagation of gaseous mixtures is often studied in order to estimate their laminar burning velocity, which is both independent of external factors and a useful input for CFD simulation. Experimentally, this parameter is difficult to evaluate when it comes to dust explosion, due to the inherent turbulence during the dispersion of the cloud. However, the low inertia of nanoparticles allows performing tests at very low turbulence without sedimentation. Knowledge on flame propagation concerning nanoparticles may then be modelled and, under certain conditions, extrapolated to microparticles, for which an experimental measurement is a delicate task. This work focuses on a nanocellulose with primary fiber dimensions of 3 nm width and 70 nm length. A one-dimensional model was developed to estimate the flame velocity of a nanocellulose explosion, based on an existing model already validated for hybrid mixtures of gas and carbonaceous nanopowders similar to soot. Assuming the fast devolatilization of organic nanopowders, the chemical reactions considered are limited to the combustion of the pyrolysis gases. The finite volume method was used to solve the mass and energy balances equations and mass reactions rates constituting the numerical system. Finally, the radiative heat transfer was also considered, highlighting the influence of the total surface area of the particles on the thermal radiation. Flame velocities of nanocellulose from 17.5 to 20.8 cm/s were obtained numerically depending on the radiative heat transfer, which proves a good agreement with the values around 21 cm/s measured experimentally by flame visualization and allows the validation of the model for nanoparticles.     

Investigations into the influence of dustiness on dust explosions

A new safety characteristic the “dustiness” according to VDI 2263 – part 9 (Verein Deutscher Ingenieure, 2008) is investigated. Dustiness means the tendency of a dust to form clouds. The paper deals with the influence of the dustiness on vented dust explosions. In order to look into the effects of the dustiness on dust cloud formation and explosion properties experiments and simulations in a vertical dust dispersion glass tube apparatus were carried out.Preliminary explosion experiments showed that the dustiness has an influence on the reduced explosion pressure in a vented 75 L test apparatus. Dusts with comparable p_max and K_St values and different dustiness were tested. Dusts with higher dustiness produced higher overpressures, despite comparable safety characteristics. In order to verify the results for applications in the process industries further tests with different settings are planned as well as industrial scale experiments. Characteristics of the dust such as particle size, density, specific surface area and particle shape, which influence the dispersibility, have been determined experimentally.The Euler/Lagrange and the Euler/Euler approaches are compared for simulating an exemplary dust/air mixture. Especially sedimentation and the ability of the approaches to simulate the tendency of dust to stay airborne were investigated. The Euler/Lagrange approach is better suited for simulating local dust concentrations, particle size distributions and particle forces. It could be used to point out regions of high dust concentrations in a vessel. With the Euler/Euler method it is possible to achieve fast solutions for one specified diameter, but the simulated dust/air mixtures are always more homogenous than in reality. ANSYS CFX version 13 was used in all simulations.     

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.     

甲烷煤尘燃烧爆炸试验研究

为揭示甲烷煤尘空气混合物爆炸波的传播规律,采用试验分析的方法,建立甲烷煤尘空气混合物燃烧爆炸的3种试验方案,分析不同体积分数的甲烷和不同质量浓度的煤尘消耗不同体积空气时的爆压和爆速等参数的发展趋势,探究爆轰波传播的稳定性,阐明了甲烷煤尘燃烧爆炸的基本特征。试验结果表明,在最优配比条件下,与单一甲烷空气、煤尘空气混合物相比,甲烷煤尘空气混合物的爆压、爆速明显增加。甲烷煤尘空气混合物爆轰比单一的气相、固相混合物爆轰的爆炸压力、爆速明显增加、爆轰更稳定。     

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.     

Explosibility of hydrogen–graphite dust hybrid mixtures

To evaluate the hazard of combined hydrogen/dust explosions under severe accident conditions in International Thermonuclear Experimental Reactor (ITER), standard method of 20-L-sphere was used to measure the explosion indices of 4-μm fine graphite dust in lean hydrogen/air mixtures. The mixtures were ignited by a weak electric spark. The tested fuel concentrations were 8–18 vol% H₂ and 25–250 g/m³ dust. If the hydrogen content is higher than 10 vol%, the dust constituent can be induced to explode by the hydrogen explosion initiated by a weak electric spark. Depending on the fuel component concentrations, the explosions proceed in either one or two stages. In two-stage explosions occurring at low hydrogen and dust concentrations, the mixture ignition initiates first a fast hydrogen explosion followed by a slower phase of the dust explosion. With increasing dust concentration, the dust explodes faster and can overlap the hydrogen-explosion stage. At higher hydrogen concentrations, the hybrid mixtures explode in one stage, with hydrogen and dust reacting at the same time scale. Maximum overpressures of hybrid explosions are higher than those observed with hydrogen alone; maximum rates of pressure rise are lower in two-phase explosions and, generally, higher in one-stage explosions, than those characteristic of the corresponding H₂/air mixtures.     

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.     

Explosion of lycopodium-nicotinic acid–methane complex hybrid mixtures

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

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.     

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.     

Effects of ignitors and turbulence on dust explosions

The aim of this work is in an attempt to increase the understanding of the acting behaviour of pyrotechnic ignitors and their effects on confined dust explosions. Flame visualization has shown that pyrotechnic ignitors can initiate an explosion by instantaneous jet-like volumetric and/or multipoint ignition. Hence, the rate of pressure rise and also the apparent burning velocity will be increased to some extent, depending on the ignitor energy and the reactivity of the mixtures. The ignitor effect is more important for the early stages of flame propagation and would be more significant in small explosion chambers. Thus, for dust explosion tests with various purposes, use of pyrotechnic ignitors should be made carefully, and the ignitor effect must be accounted for in the data interpretation. Turbulence induced by dust dispersion is a dominant factor in affecting dust explosions. At different ignition delays, however, the turbulence influence will be coupled with that of ignitors. This complicates further the interpretation of explosion data measured under turbulent conditions.     

A correlation of the lower flammability limit for hybrid mixtures

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

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.     

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.     

硬脂酸粉尘爆炸特性试验研究

为研究硬脂酸粉尘的爆炸特性,采用20 L球型爆炸仪对4个粒径范围的硬脂酸粉尘进行粉尘爆炸试验研究。结果表明:一定浓度范围内增大粉尘浓度能够提升硬脂酸粉尘的爆炸能量和燃烧速率。增大粉尘浓度,爆炸猛烈度先增强后减弱;减小粉尘粒径,能增强爆炸猛烈度和敏感度。粒径小于58 μm粉尘的爆炸猛烈度和敏感度最大,浓度500 g/m3时,该粉尘有最大爆炸压力1.12 MPa和最大升压速率142.00 MPa/s。     

Influence of dustiness on small-scale vented dust explosions

A new safety characteristic the “dustiness” according to VDI 2263 – part 9 (Verein Deutscher Ingenieure, 2008) is investigated. Dustiness means the tendency of a dust to form clouds. The paper deals with the physical reasons for the different behavior of dusts, even if they have similar properties such as particle size and density and the influence of the dustiness on dust explosions. In order to study the effects of the dustiness on dust cloud formation for different dispersion methods experiments in a vertical dust dispersion glass tube apparatus were carried out. Furthermore vented dust explosion experiments were done for two different dispersion methods and two static activation pressures.Experiments show that particle size and density are not the only factors which influence dispersibility. Particle shape, specific surface area, flow and dispersion method have an influence which can outweigh size and density. Preliminary explosion experiments showed that the dustiness has an influence on the reduced explosion pressure and flame speed in a vented 75 L test apparatus. In order to verify the results for applications in the process industries further tests with industrial scale experiments are planned.     

Measuring the violence of dust explosions with the “20 l sphere” and with the standard “ISO 1 m vessel”: Systematic comparison and analysis of the discrepancies

On the basis of a systematic testwork with a number of different dusts, the explosion indices as determined within the 20 l sphere and with the ISO-VDI 1 m³ vessel have been compared. The repeatability has been assessed and since some systematic deviations appear a refined physical analysis of the explosion processes is developed. It appears in particular that the cube root law supposed to link both vessels is not verified. A striking illustration of this appears when a dust with a significant explosion severity inside the 20 l sphere is not even explosible in the larger vessel. It is strongly suggested that the ignition energy is forcing very significantly the explosion in the smaller vessel inducing several tens of Celsius degrees of preheating. It is shown also that the inner level of turbulence is decreasing very fast in the 20 l sphere during the flame development so that difficult-to-ignite mixtures would tend to burn at a lower combustion rate. It is further demonstrated that the major bias between the chambers can be explained and quantified with these elements. A correlation with the standard 1 m³ vessel and a grid of interpretation of the data is proposed.