The hazards and risks of hydrogen

An analysis was completed of the hazards and risks of hydrogen, compared to the traditional fuel sources of gasoline and natural gas (methane). The study was based entirely on the physical properties of these fuels, and not on any process used to store and extract the energy. The study was motivated by the increased interest in hydrogen as a fuel source for automobiles.The results show that, for flammability hazards, hydrogen has an increased flammability range, a lower ignition energy and a higher deflagration index. For both gasoline and natural gas (methane) the heat of combustion is higher (on a mole basis). Thus, hydrogen has a somewhat higher flammability hazard.The risk is based on probability and consequence. The probability of a fire or explosion is based on the flammability range, the auto-ignition temperature and the minimum ignition energy. In this case, hydrogen has a larger flammability zone and a lower minimum ignition energy—thus the probability of a fire or explosion is higher. The consequence of a fire or explosion is based on the heat of combustion, the maximum pressure during combustion, and the deflagration index. Hydrogen has an increased consequence due to the large value of the deflagration index while gasoline and natural gas (methane) have a higher heat of combustion. Thus, based on physical properties alone, hydrogen poses an increase risk, primarily due to the increased probability of ignition.This study was unable to assess the effects of the increased buoyancy of hydrogen—which might change the probability depending on the actual physical situation.A complete hazard and risk analysis must be completed once the actual equipment for hydrogen storage and energy extraction is specified. This paper discusses the required procedure.     

彩虹粉引燃危险性实验研究

为了研究彩虹粉引燃危险性,应用固体燃烧速率试验仪初步甄别了彩虹粉传播燃烧能力,发现堆垛状彩虹粉固体火焰传播危险性较低;采用粉尘爆炸筛选装置,判定彩虹粉具有爆炸性;应用最小点火能测定装置测定彩虹粉粉尘云的最小点火能在24~60 mJ之间,最优爆炸浓度为1 167 g/m3;应用快速筛选量热仪测试,彩虹粉在227℃开始分解;固体自燃点测试仪显示彩虹粉在250℃附近会发生自燃。向彩虹粉内添加不同比例相近粒径分布的食用盐粉体进行抑爆研究,结果证明食用盐对彩虹粉具有明显的抑爆效果。     

Experimental investigation of the influence of inert solids on ignition sensitivity of organic powders

This work presents the results of the experimental characterization of the ignition sensitivity of solid inertant/combustible powders mixtures. Three inert solids (alumina, Kieselguhr, aerosil) and eleven organic powders have been considered and the following parameters have been determined: (1) the minimum ignition energy, (2) the minimum ignition temperature in cloud and (3) the minimum ignition temperature in 5 mm layer. The effects of the addition of inert solids are described and a simple model is proposed to represent the experimental results.Generally, increasing inert solid content in a powder leads to a higher minimum ignition energy as well as a higher minimum ignition temperatures in cloud and in layer. In some cases, the flammability is influenced above a threshold concentration value, which can be quite high (up to 85 wt.%). Indeed, the proposed model shows a zone below the minimum ignition concentration (MIC), which does not enable an efficient or safe inerting: either the admixed inert solid does not provide a sufficient effect, or it can even facilitate the ignition of the dust by notably improving its dispersability.The influence of key parameters such as the thermal conductivity or optical properties on the efficiency of the inerting by admixed solid need to be further assessed in a future work in view to better understand the mechanisms involved and to extend the scope to other types of oxidizable materials.     

基于活化能指标的煤自燃倾向性及发火期研究

在煤的自燃及热分析动力学的基础上,结合对神东矿区3种煤样进行了热重实验,运用热重分析手段对煤从常温到燃点之间的氧化热解过程进行了研究。运用不同动力学机制模型函数分别对热重分析数据进行了处理和相关性分析,结果表明煤炭氧化热解过程符合一级化学反应动力学机制,据此求出活化能等动力学参数。对基于活化能指标的煤的自燃倾向性及自然发火期进行了初步研究。经过研究发现,该方法是科学的、客观的。     

Study on safe air transporting velocity of nanograde aluminum,iron, and titanium

The process of delivering nanograde metal powders by a high-speed carrier gas is often subject to high explosion risks. This study adopted initial flow rates of 13.1, 8.5, 6.5, and 3.5 m/s for air transporting 30-nm titanium powder, 35-nm iron powder, and 35-nm aluminum powder to gauge the impact on a pipe bend in a 20-l-apparatus. The test results revealed that the 30-nm titanium powder caused an explosion at all initial flow rates; the 35-nm iron powder also caused an explosion, but dust explosion and sintering were eliminated when the flow rate was adjusted to less than 3.5 m/s; and the 35-nm aluminum powder exhibited no explosion or sintering at all flow rates. When pure nitrogen was used for transporting nanograde metal powders, no explosions occurred for all the three types of metal powders. The minimum ignition energy for these three types of nanograde metal powders was less than 1 mJ.     

硫化亚铁引发储油罐火灾危险性的研究

笔者通过模拟储油罐中硫化亚铁的生成方式 ,分析和研究了硫化氢气体与氢氧化铁、三氧化二铁和四氧化三铁反应 ,生成的硫化亚铁的氧化倾向性 ,并采用自然氧化绝热装置 ,测定了硫化亚铁的温度变化曲线。实验研究结果表明 ,不同方式生成的硫化亚铁 ,其氧化性不同 ,自燃性也不同 ,均有较显著差异。硫化亚铁的温度变化曲线表明 ,氧化反应随着时间增加 ,其他应进行得越来越快 ,将会造成热量的聚集 ,使油品温度快速上升 ,导致油品自燃和储罐发生着火爆炸。实验研究证明 ,硫化亚铁氧化反应放出热量是构成油罐着火危险性的最大因素。     

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.     

煤质粉末活性炭自燃和热稳定性分析

针对煤质粉末活性炭最显著的热危险特性——自燃危险性进行试验。采用粉尘层最低着火温度测定系统对煤质粉末活性炭进行自燃试验,测定煤质粉末活性炭的最低着火温度;采用SDT Q600热重分析仪测定煤质粉末活性炭在氮气和空气气氛中以20℃/min的速率升温至700℃时的热解和燃烧特性,通过TG/DTG曲线计算其着火温度,并进行热稳定性评价。粉尘层自燃试验结果表明,煤质粉末活性炭最低着火温度为400℃,具有自燃危险性,易形成阴燃;氮气气氛中热解试验表明,热解过程经历了室温~120.0℃和280.0~700.0℃两次轻缓失重阶段,646.44℃时挥发分热失重速率最大,对应热失重速率峰值为0.082 6%/℃,自燃危险性较低;空气气氛中燃烧试验表明,燃烧过程经历了室温~95.5℃和300.0~600.0℃两次剧烈失重阶段,分别为吸附水分受热蒸发和氧化生成的有机官能团分解脱附导致,565.35℃时挥发分热失重速率最大,对应热失重速率峰值为13.20%/min,粉末较强的氧气吸附效应和较低的导热系数导致其自燃倾向较高,火灾危险性较大。     

煤中掺比伴生硫化物的自燃特性分析

为了深入探究矿井下伴生硫化物对煤自燃及着火燃烧特性的影响，向原煤中添加不同量的含硫物配制4种不同含硫量的煤样，通过TG实验、DSC测试和XRD分析，研究伴生硫化物对煤自燃及着火燃烧特性的影响规律；基于Coats-Redfern法计算煤中掺加不同伴生硫化物时煤燃烧阶段的活化能。研究结果表明:随着煤中掺比伴生硫化物的增多，煤的特征温度相应减小，而吸氧量、可燃和稳燃指数相应增大，原煤中混入伴生硫化物后更易自燃；随着煤中掺比伴生硫化物的增多，煤燃烧阶段的活化能降低，煤更易着火燃烧；伴生硫化物的主要成分为水绿矾、叶绿矾，这些物质在常温下遇水和氧气能够发生化学循环反应，反应放热促使了煤更易自燃；伴生硫化物在温度高于200℃以后整体表现为放热，在温度为565℃时达到放热峰值，这使得煤燃烧阶段的活化能降低，煤更易燃烧。     

化学放热系统热爆炸潜在危险性评价

讨论化学放热系统的热稳定性和临界条件,用化学反应物无消耗的假设推导化学放热系统热失控(热爆炸)时的动力学参数临界值,得到热失控的判据、临界点火温度和熄火温度。提出用系统安全指数概念来评价放热反应系统发生热爆炸的潜在危险性,分析化学放热系统的平衡域。用硝酸甲酯分解爆炸实例,说明如何利用安全指数对具有热爆炸可能性的系统的潜在危险性进行定量评价,其预测结果与实验结果一致。     

Coloured powder potential dust explosions

The use of Coloured powder (Holi powder orcolour dust) has been largely used in India for their festivities. Due to their popularity is extensive around the world since the popularity of the parties and events with this kind of show is increasing considerably. Despite the fact of its extensive use, its highly flammable nature is poorly known. Currently, some serious accidents related to the Coloured powder have been registered. Coloured powder organic nature implies a significant increase in the probability to form an explosive atmosphere as their use includes dust dispersion, leading to explosion hazards as has been previously reported. Moreover, it is important to take into account the effects on the flammability of the additives and the colorings existing in the Coloured powder as they might increase the hazard. To properly understand Coloured powder potential for producing an explosive atmosphere, and the attached risk of dust explosions, several samples were tested. Coloured powder from 6 different manufacturers were gathered. Each manufacturer provided several colours (between 5 and 8) which were characterized through moisture content and particle size determination. Once each sample was characterized, screening tests were performed on each sample determining whether ignition was produced or not. Those screening tests were carried out under certain conditions using the equipment for minimum ignition temperature on cloud determination (0.5 g set at 500 °C and 0.5 bar), and minimum ignition energy determination (using 100 and 300 mJ energies and 900 and 1200 mg). From those test results, important differences were seen between manufacturers, but most important, differences between colours of the same manufacturer were observed. The screening tests allowed the selection of 11 samples that were fully characterized through thermogravimetric analysis, maximum pressure of explosion, K_st, minimum ignition temperature on cloud, and minimum ignition energy. When carrying out thermogravimetric analysis, some samples increased mass at temperatures close to 300 °C and unexpectedly absorbed energy, followed by the expected combustion reaction at higher temperatures. From the obtained results it was noticed that the colour powders that included talcum in its composition did not produce explosion. Flammability and explosion tests, again, showed important differences between manufacturers and colours, and so it was possible to determine the relative flash fire and explosion risks of the various tested powders.     

硫铁化物氧化自燃的动力学分析

为研究含硫油品储油罐中硫铁化物的自燃倾向性，采用STA8000同步热分析仪对10，15，20℃/min等不同升温速率和15，20，25 mL/min等不同空气流量下的硫铁化物进行试验，并通过获得的TG-DSC曲线研究试样的自燃特性；在此基础上，根据Coat模型，利用不同反应机理函数对热重数据进行分析。结果表明:该试验条件下，硫铁化物的氧化进程符合三级反应动力学机制；得出了硫铁化物在不同升温速率和空气流量下的表观活化能；在560～746℃温度区间内，随着升温速率的增加，空气流量的加大，活化能数值明显减小，自燃倾向性增大。研究结果可为预防和控制因硫铁化物自燃引发的火灾、爆炸事故提供理论参考。     

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.     

基于热爆炸理论的煤燃点确定及动力学分析

为准确判断煤燃点,提高煤自燃灾害防治能力,依据热爆炸理论,结合煤自燃过程放热曲线,将煤自燃升温过程中微分热流曲线上第1处极小值点作为煤的燃点,计算煤着火前后放热过程动力学参数变化.结果表明:随升温速率增加,煤自燃反应放热过程逐渐向高温区域移动,煤燃点逐渐增大,反应的活化能逐渐减小;同一升温速率下燃点之后煤的活化能增大;...     

基于详细化学动力学的甲烷热着火影响因素分析

利用化学动力学软件CHEMKIN4.1,在不同初始温度、浓度、湿度和压强下,对甲烷热着火进行了详细化学动力学 模拟。通过对主要组分摩尔浓度分析和温度敏感性分析,得到了甲烷热着火过程的主要基元反应和引发热着火发生的主 要原因。通过对甲烷热着火的延迟时间、热着火发生后主要生成物摩尔浓度和反应后的温度的对比分析,揭示了初始浓 度、湿度和压强对甲烷热着火的影响规律。本研究可以为甲烷为主的气体如瓦斯、天然气等可燃气体的燃烧和爆炸提供 理论支撑,从而有效利用这些可燃气体,降低灾害的发生。     

Flame propagation behavior of aluminum nanopowder in bulk layer

The flame propagation parameters of aluminum nanopowder in the bulk layer were investigated. The aluminum nanopowder produced by the method of the electrical explosion of wires used in this study. The aluminum bulk layer was ignited by open flame, heated body, or electric spark. The flame propagation behavior is described as a two-stage process: 1) flame propagation over the surface layer and deep into the sample; 2) the thermal explosion mode. It was found that the type of ignition source influences the parameters of the first stage of the combustion. The minimum ignition energy for the aluminum nanopowder bulk layer was measured. The effect of the bulk layer inclination angle on flame propagation parameters was determined. The obtained results can be useful in assessing the fire hazard and organizing safe processes of industrial production during the use, storage, handling, and transportation of metal nanopowders.     

混合金属粉尘爆炸最小点火能量影响因素研究*

为探究混合金属粉尘爆炸危险性及与单一粉体爆炸特性差异，确保车间安全生产，采用粉尘云点火能量测试系统对车间混合金属粉尘及铝粉最小点火能量在不同影响因素下的变化规律及2种粉尘火焰变化特征进行测试。研究结果表明:混合金属粉尘和铝粉最小点火能量在一定范围内（38~96 μm）与粒径呈正相关性，当混合金属粉尘粒径大于75 μm时，所需最小点火能量大于1 000 mJ，其爆炸敏感性迅速降低，此时铝粉仍有较强爆炸敏感性；2种粉尘最小点火能量随质量浓度增加呈先降低后升高的趋势，最小点火能分别为295，15 mJ，对应的敏感质量浓度为600，1 000 g/m3，混合金属粉尘在质量浓度为500~700 g/m3时具有较大爆炸危险性；同铝粉相比，混合金属粉尘点火能量更高、火焰燃烧时间更短、火焰高度更低、爆炸剧烈程度更弱。     

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.     

Evaluation of the spontaneous combustion tendency of corrosion products in oil tanks based on TOPSIS methodologies

Spontaneous ignition of the corrosion products of an oil tank may lead to an explosion. To evaluate the spontaneous combustion tendency of corrosion products in oil tanks, the thermodynamic characteristic parameters of the corrosion products of oil tanks were obtained by thermogravimetry as evaluation indexes. Then, the objective weights of these indexes were calculated via the CRITIC method, and TOPSIS theory was used to comprehensively evaluate the spontaneous combustion tendency of corrosion product samples from oil tanks. The results show that the weight of the mass loss rate at the ignition point is the highest, and the apparent activation energy of the corrosion products is not the decisive factor affecting their spontaneous combustion tendency. As such, the spontaneous combustion tendency of the corrosion products of oil tanks cannot be based on only the apparent activation energy. The spontaneous combustion tendency of the corrosion products of a gasoline tank is lower than that of a diesel tank. The higher the heating rate is, the stronger the tendency of spontaneous combustion will be.     

Influence of inert materials on the self-ignition of flammable dusts

Flammable solid bulk materials, including dusts, often undergo spontaneous combustion and the spread of reaction fronts. By addition of inert substances, the ignition and combustion behavior can be influenced. In a series of experiments different types of coal were mixed with inert powders to study the effect of the composition on the self-ignition temperature and on the formal kinetic parameters.Hot storage tests as well as simultaneous-thermal analysis were used as experimental techniques with the latter being coupled to FTIR measurements to analyze the composition of gaseous reaction products.All conducted hot storage experiments led to the conclusion that the self-ignition temperature was increased by admixing inert material if the decomposition temperature of the inert matter was higher than the self-ignition temperature of the combustible component at the sample characteristic length. If (exothermic) decomposition of the inert material occurred before a noticeable growth of reaction rate of the combustible material, even a reduction in the self-ignition temperature could be observed. In addition, significantly higher maximum reaction temperatures were observed for the mixtures than for the combustible material alone.