Determination of heterogeneous reaction mechanisms: A key milestone in dust explosion modelling

Reaction kinetics is fundamental for modelling the thermal oxidation of a solid phase, in processes such as dust explosions, combustion or gasification. The methodology followed in this study consists in i) the experimental identification of the reaction mechanisms involved in the explosion of organic powders, ii) the proposal of simplified mechanisms of pyrolysis and oxidation, iii) the implementation of the model to assess the explosion severity of organic dusts. Flash pyrolysis and combustion experiments were carried out on starch (22 μm) and cellulose (53 μm) at temperatures ranging from 973 K to 1173 K. The gases generated were collected and analyzed by gas chromatography. In this paper, a semi-global pyrolysis model was developed for reactive systems with low Damköhler number. It is in good agreement with the experimental data and shows that both carbon monoxide and hydrogen are mainly generated during the pyrolysis of the solid, the generation of the latter compound being greatly promoted at high temperature. A simplified combustion model was also proposed by adding two oxidation reactions of the pyrolysis products. In parallel, flame propagation tests were performed in a semi open tube in order to assess the burning velocity of such compounds. The laminar burning velocity of cellulose was determined to be 21 cm s⁻¹. Finally, this model will be integrated to a predictive model of dust explosions and its validation will be based on experimental data obtained using the 20 L explosion sphere. The explosion severity of cellulose was determined and will be used to develop and adjust the predictive model.     

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.     

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.     

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.     

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。     

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.     

Inerting effect of N2 on explosion of LDPE dust/ethylene hybrid mixtures

Explosion flame propagation characteristics and overpressure distribution of low density polyethylene (LDPE) dust and ethylene hybrid mixture were investigated under N₂ inerting conditions using a custom-designed 12 L cylindrical explosion tank. The results showed that a small amount of ethylene could promote the explosion characteristics of LDPE dust. N₂ inerting had different inhibitory effects on the explosion flame of LDPE dust and its mixture with ethylene. The explosion overpressure strength of the LDPE dust/ethylene hybrid mixture decreased with increasing N₂ concentration. The overall suppression effect of N₂ on the explosion overpressure of the LDPE dust was better than that of the LDPE dust/ethylene hybrid mixture explosion. As the ethylene concentration increased from 0% to 2.5%, the limiting oxygen concentration decreased by 13% oxygen. This small amount of ethylene restricted the traditional inerting process. The study conclusions can provide further scientific basis for the inerting and explosion proofing design of production process equipment involving LDPE dust.     

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.     

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.     

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.     

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%。     

管道内瓦斯煤尘共混爆炸温度特性

采用瞬态火焰传播实验系统,对7%,8%,9%,10%和11%的瓦斯体积浓度分别与不同浓度的长焰煤煤尘混合,并使用直径25 μm的Pt/Rh13-Pt微细热电偶测量温度,揭示受限空间内瓦斯与煤尘混合爆炸温度特性。结果表明:煤尘浓度一定时,随着瓦斯浓度的增加,爆炸温度先增加后减小;纯瓦斯浓度在10%时爆炸温度最高,加入煤尘后的混合体系中,瓦斯浓度为9%时爆炸温度最高;瓦斯浓度不变时,随着煤尘浓度的增加,爆炸温度一直减小;7%~11%瓦斯分别与130 g/m3煤尘混合爆炸后测得最高温度分别为1 333.6,1 475.4,1 511.4,1 455.6,1 396.4 ℃;与9%纯瓦斯爆炸相比,9%瓦斯与130,260,520,780 g/m3煤尘混合爆炸后测得最高温度分别降低7.2%,11.5%,15.0%和22.9%。结论得到的瓦斯煤尘共混爆炸温度数据可为煤矿灾害高温防护提供参考依据。     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

Thermo-kinetic modelling of dust explosions

The guidelines for protection and mitigation against hazard coming from dust explosion require the knowledge and then the evaluation either experimentally or theoretically of the thermo-kinetic parameters (i.e. K_St, P_max). We developed a numerical tool for the evaluation of the thermo-kinetic parameters of dust explosion. This model is based on the simulations of the combustion reaction by means of a detailed reaction mechanism assuming that the pyrolysis/devolatilization step is very fast and then gas combustion is controlling dust explosion. The model allows then the determination of the most conservative values of K_St, S_l, P_max. In the present paper we calculated the deflagration index and the laminar burning velocity for dusts utilized in various process industries (i.e. cornstarch, polyethylene, cellulose) as function of dust concentration. The obtained data were successfully compared with the available experimental results.     

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.     

玉米淀粉粉尘爆炸危险性研究

为研究玉米淀粉粉尘爆炸危险性,采用哈特曼管式爆炸测试装置和20 L球爆炸测试装置对200目(<75μm)以下的玉米淀粉粉尘爆炸危险性进行评估,基于静电火花和粉尘质量浓度对粉尘爆炸的影响,对玉米淀粉的静电火花最小点火能量、爆炸下限质量浓度、最大爆炸压力和爆炸指数进行了研究,根据试验结果对玉米淀粉爆炸危险性进行分级。试验结果表明:温度在25℃,喷粉压力为0.80 MPa,粉尘质量浓度在250～750 g/m3范围内,粉尘的最小点火能量随着粉尘质量浓度增加而降低,其最小点火能量在40～80 mJ之间;在点火能量为10 kJ时,粉尘爆炸下限质量浓度在50～60 g/m3之间;在粉尘质量浓度为750 g/m3时,爆炸压力达到最大,为0.66 MPa;在粉尘质量浓度为500 g/m3时,爆炸指数达到最大,为17.21 MPa.m/s,其粉尘爆炸危险性分级为Ⅰ级。     

Risk assessment method of polyethylene dust explosion based on explosion parameters

The explosion characteristic parameters of polyethylene dust were systematically investigated. The variations in the maximum explosion pressure (P_max), explosion index (K_st), minimum ignition energy (MIE), minimum ignition temperature (MIT), and minimum explosion concentration (MEC) of dust samples with different particle sizes were obtained. Using experimental data, a two-dimensional matrix analysis method was applied to classify the dust explosion severity based on P_max and K_st. Then, a three-dimensional matrix was used to categorize the dust explosion sensitivity based on three factors: MIE, MIT, and MEC. Finally, a two-dimensional matrix model of dust explosion risk assessment was established considering the severity and sensitivity. The model was used to evaluate the explosion risk of polyethylene dust samples with different particle sizes. It was found that the risk level of dust explosion increased with decreasing particle size, which was consistent with the actual results. The risk assessment method can provide a scientific basis for dust explosion prevention in the production of polyethylene.     

Experimental investigation and modelling of aluminum dusts explosions in the 20 L sphere

An experimental investigation was carried out on the influences of dust concentration, particle size distribution and humidity on aluminum dust explosion. Tests were mainly conducted thanks to a 20 L explosion sphere. The effect of humidity was studied by storing the aluminum particles at constant relative humidity until the sorption equilibrium or by introducing water vapour in the explosion vessel. The tested particles sizes ranged from a volume median diameter of 7 to 42 μm and the dust concentrations were up to 3000 g m^?3.Among other results, the strong influence of the particle size was pointed out, especially when the Sauter mean diameter is considered. These results stressed the predominance of the specific surface area on the mass median particle diameter.The effect of water on aluminum dust explosion was decoupled: on the one hand, when water adsorption occurs, hydrogen generation leads to an increase of the explosion severity; on the other hand, when the explosion of dried aluminum powder occurs in a humid atmosphere, the inhibiting effect of humidity is put forward.A model based on mass and heat balances, assuming a shrinking core model with chemical reaction limitation, leads to a satisfactory representation of the pressure evolution during the dust explosion.     

泄爆容器中粉尘爆炸的试验研究与数值模拟

为了解泄爆容器中粉尘爆炸的发展过程,采用试验和数值模拟相结合的方法对玉米淀粉在圆柱形容器内的泄爆过程进行研究。数值模型采用欧拉–拉格朗日方法模拟粉尘爆炸的两相流问题,通过求解非稳态的湍流两相反应流守恒方程对试验进行二维仿真。试验和模拟结果表明,点火位置对爆炸发展过程有明显影响,点火位置离泄爆口越远,容器中的最大泄爆压力Pred,max越高。在粉尘爆炸的安全防护设计中,应把点火位置作为重要影响因素之一加以考虑。     

Explosibility of cork dust in methane/air mixtures

Explosibility studies of hybrid methane/air/cork dust mixtures were carried out in a near-spherical 22.7 L explosibility test chamber, using 2500 J pyrotechnic ignitors. The suspension dust burned as methane/air/dust clouds and the uniformity of the cork dust dispersion inside the chamber was evaluated through optical dust probes and during the explosion the pressure and the temperature evolution inside the reactor were measured. Tested dust particles had mass median diameter of 71.3 μm and the covered dust cloud concentration was up to 550 g/m³. Measured explosions parameters included minimum explosion concentration, maximum explosion pressures and maximum rate of pressure rise. The cork dust explosion behavior in hybrid methane/air mixtures was studied for atmospheres with 1.98 and 3.5% (v/v) of methane. The effect of methane content on the explosions characteristic parameters was evaluated. The conclusion is that the risk and explosion danger rises with the increase of methane concentration characterized by the reduction of the minimum dust explosion concentration, as methane content increases in the atmosphere. The maximum explosion pressure is not very much sensitive to the methane content and only for the system with 3.5% (v/v) of methane it was observed an increase of maximum rate of pressure rise, when compared with the value obtained for the air/dust system.