细水雾对油池火热释放速率影响规律的实验研究

热释放速率是描述火灾现象的重要参数,可以表征火灾发展的强烈程度。利用大尺寸的热释放速率实验测量平台开展细水雾对不同种类油池火灭火效率的实验研究,同时分析细水雾对燃烧产物一氧化碳含量的影响。结果表明,热释放速率曲线能直接反映出细水雾对火源的作用,细水雾作用下三种燃料的热释放速率均被有效抑制,且细水雾的流量越大,对油池火的灭火效果越好。燃烧产物一氧化碳在施加细水雾时出现陡增,表明细水雾隔绝氧气,造成不完全燃烧或者燃烧熄灭。     

Development of machine learning based prediction models for hazardous properties of chemical mixtures

Lower flammability limit (LFL), upper flammability limit (UFL), auto-ignition temperature (AIT) and flash point (FP) are crucial hazardous properties for fire and explosion hazards assessment and consequence analysis. In this study, a comprehensive prediction model set was constructed by using expanded chemical mixture databases of chemical mixture hazardous properties. Machine learning based gradient boosting quantitative structure-property relationship (GB-QSPR) method is implemented for the first time to improve the model performance and prediction accuracy. The result shows that all developed models have significantly higher accuracy than other regular QSPR models, with the 5-fold cross-validation RMSE of LFL, UFL, AIT, and FP models being 1.06, 1.14, 1.08, and 1.17, respectively. All developed QSPR models can be used to estimate reliable chemical mixture hazardous properties and provide useful guidance in chemical mixture hazard assessment and consequence analysis.     

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.     

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.     

Characterization of Ti powders mixed with TiO2 powders: Thermal and kinetic studies

The fire and explosion risks of metal powders admixed with solid inertants have been extensively investigated for many years. However, it remains unclear why such solid mixtures have high potential fire and explosion risk even when mixed with high percentages of non-combustible solids. This paper investigates how to interpret these risks, from a microscopic perspective, with thermal and kinetic parameters including initial ignition temperature, mass unit exothermic energy, activation energy and risk index of spontaneous combustion. The results show that the initial ignition temperature based on TG (Thermogravimetry) analysis is related to ignition sensitivity, and increased with percentage of admixed solid inertant. The unit mass exothermic energy based on DSC (Differential scanning calorimetry) analysis is related to flame spread velocity. Activation energy and the risk index of spontaneous combustion can be used to explain the reactivity and spontaneous combustion hazard, respectively, of metal powders. We conclude that thermal and kinetic parameters may provide another way to describe the fire and explosion risk of combustible powders, especially for nano metal powders due to the laboratory safety in the normative tests for explosion parameter determination.     

Lower flammability limits of flammable ternary organic mixtures: Synergistic behavior

Organic flammable liquids and their mixtures, which possess high risk of combustion and explosion, are widely used as raw materials and solvents in chemical and pharmaceutical industries. Lower flammability limits (LFL) is one of the most important parameters to characterize the combustion and explosion hazards of combustible gases and liquid vapors. The LFL of various ternary organic mixtures consist of ketone (acetone and butanone), ester (ethyl acetate) and alcohol (ethanol and isopropanol) were tested at 25 °C and atmospheric pressure. The results showed that resulted LFL values of the experiment were always lower than those calculated by volume fraction weighting method when the volume fraction of alcohol was less than 20 vol% but more than 10 vol%. The co-existence of alcohol and ethyl acetate had synergistic effect on reducing the LFL values of ternary organic mixtures and thus increased their explosive risk. The mechanism of synergistic effect was analyzed, and the results showed that the OH· and H· radicals produced by the oxidation decomposition of alcohols and esters accelerated the oxidation process of ternary organic mixtures, which led to the decrease of experimental LFL values and thus corresponding increased of their explosive risk. This study would be expected to provide some guidance for designing or choosing safer and more suitable ternary organic mixtures prior to their applications for engineering.     

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.     

Applications of dust explosion hazard and disaster prevention technology

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

云南松林燃烧过程中飞火的研究

飞火是高能量火中最复杂、最危险的现象,是在燃烧过程中由火焰热对流带出的未燃尽的木屑、炭块等可燃物,散布在火区外形成新的火点现象。飞火被看成除了传导、对流和辐射之外的第四种热量传递的方式。飞火的出现增加了新的火源,使火场的扩散由连续变成跳跃,大大加快了火灾的蔓延,有时还改变蔓延的方向。以＂3.29＂昆明安宁市森林火灾为研究对象,调查火烧迹地并取样,分析可燃物特征,并对飞火发生的距离进行模拟计算。结果表明,由于云南松林立地干燥,林内可燃物多,连续性好,地形复杂,小气候明显,易发生飞火;引发飞火的可燃物主要是云南松的球果;经验公式和模型计算的飞火距离与实际距离比较接近。     

Inerting effect of CaCO3 powder on flame spread of wood dust layer

The effect of CaCO₃ powder, a typical inert dust, on the flame spread characteristics of wood dust layers was studied using an experimental device to understand the ignition characteristics of and develop inert explosion-proof technology for deposited wood dust. The results showed that the flame spread velocity (FSV) of the mixed dust layer was affected by the dispersion effect of CaCO₃ powder and physical heat absorption. As the CaCO₃ powder mass fraction increased, the FSV of the dust layer first increased and then decreased, reaching a peak at a 50% mass fraction. Moreover, the front-end temperature of the flame gradually decreased, and the red spark faded. The combustion reaction of the mixed dust layer could be more completed, and the colour of the combustion residue changed from charcoal black to charcoal grey. The coupling effect of the initial temperature and wind speed can promote an increase in the FSV in the mixed dust layer. The Gauss–Amp model of the FSV of the wood dust layer and mass fraction of CaCO₃ powder showed that the peak of the FSV occurred when the mass fraction of CaCO₃ powder was between 40 and 50%. Thus, a good inerting and explosion-proof effect can be achieved by using CaCO₃ powder with a mass fraction of more than 50%; it can improve the whole inerting process. Inert explosion-proof technology should be considered when assessing fire and explosion risk of dust in real process industry situations.     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

中国煤矿安全技术进展

本文综述了我国在防治矿井瓦斯,矿井火灾和煤矿粉尘三个方面的技术概况。反映了为适应煤炭生产技术的发展,我国在这三方面的技术进展及所取得的效果。矿井瓦斯防治技术方面,主要介绍了矿井瓦斯涌出量的确定,瓦斯抽放工艺及装备,煤与瓦斯突出预测预报和综合防止煤与瓦斯突出技术的情况及成果。矿井火灾防治技术方面,着重介绍了矿井火灾预测预报技术,尤其是煤炭自燃发火早期预测预报技术以及煤矿自然发火防治技术中在灌浆代用材料,惰气防灭火等方面的发展及现状。煤矿粉尘防治技术方面,扼要介绍控制粉尘危险的基本途径,以防尘为中心包括降尘、除尘和防止煤尘爆炸及爆炸传播技术的一整套治理煤矿粉尘的工艺及装备,简要介绍了瓦斯煤尘爆炸的实验能力。通过本文的介绍,可以对我国在防治煤矿安全生产中主要自然灾害的技术对策和取得的成果有一个较全面的了解。     

Analysis of the chosen thermal and flammability parameters of dried sewage dust

The hazardous sludge disposal process in the form of landfills requires the determination inter alia of the flammable and explosion properties of dried sewage sludge dust, which has the ability to ignite and spontaneously combust when stored in silos. At a constant furnace surface temperature, the minimum ignition temperature of the sludge dust layer with a layer thickness of 5 mm is 270 °C, and for a layer thickness of 12.5 mm it is 250 °C. Two selected fire extinguishing powders for Class A, B, C and D fires were used in the study to determine the possibility of reducing the susceptibility of dried wastewater to ignition from heated surface, self-ignition and explosion parameters. The most effective extinguishing powder was ABC Favorit, which increased the value of the minimum ignition temperature of the layer (5 mm thick) to 360 °C and the spontaneous ignition temperature of the sludge with this powder increased by 22 °C at 169.6 cm³ in comparison to the sludge without extinguishing powder, respectively. The lowest self-ignition temperature of 136 °C was recorded for the largest tested volume (169.6 cm³) for dried sewage dust without any fire extinguishing powders. The biggest values of p_max and (dp/dt)_max dried sewage dust were recorded 4.8 bar and 113 bar/s respectively. By analysing the obtained test results, it can be assumed that dried sewage dust is a combustible material with properties similar to biomass.     

近年我国家装材料变化对住宅火灾的影响研究

住宅火灾危险性和家装材料有着紧密联系。为研究近年我国家装材料变化对住宅火灾的影响,调研了近30年我国家装材料的变化趋势,分析了常见家装材料的火灾特性变化,并完成了对不同年代常见家装材料组合的火灾危险性综合评价,结果表明:随着近30年家装材料的变化,软体家具、木质家具、地板和壁纸的燃烧性能均有所改善,但软体家具产烟能力恶化;2000年~2010年合成材料的应用使得家装材料组合的综合火灾危险性有所提升,引起大型亡人火灾的可能性更大;2010年后阻燃材料的普及使得家装材料组合的综合火灾危险性有所降低,对消防安全的作用已经凸显,但同时我国住宅火灾中“小火亡人”事故可能更为频发,未来研究应该更加关注于降低阻燃材料的烟气危害性。     

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.     

Flammability of gas mixtures containing volatile organic compounds and hydrogen

An experimental program was conducted to evaluate the accuracy of some current methods for predicting the flammability of gas mixtures containing hydrogen and flammable or nonflammable volatile organic compounds (VOCs) in air. The specific VOCs tested were toluene, 1,2-dichloroethane, 2-butanone, and carbon tetrachloride. The lower flammability limits (LFLs) of gas mixtures containing equal molar quantities of the components were determined in a 19.4-l laboratory flammability chamber using a strong spark ignition source and a pressure criterion for flammability. All but one of the LFL values for the individual components were in agreement with earlier literature values. However, the LFL of 1,2-dichloroethane was found to be significantly lower than the range of values reported for previous determinations in smaller chambers. Two methods for calculating the LFL of mixtures were considered. The Group Factor (atomic) Contribution Method was determined to be generally more accurate than the LeChatelier Method for estimating the LFL of the gas mixtures reported here, although the LeChatelier Method was usually more conservative. The Group Factor Method predicted higher values (nonconservative) for the LFLs of several mixtures than were experimentally measured. For the case of a mixture of hydrogen and carbon tetrachloride, the Group Method estimation of the LFL was seriously in error.     

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.     

隧道受限火灾合理纵向通风风速范围研究*

为探究公路隧道不同受限程度火灾的适宜纵向通风风速,基于FDS模拟分析5种纵向通风速度下不同近壁距离火源顶棚下方烟气最高温度的分布特性、烟羽流倾角及烟气分层状况,提出合理纵向通风风速范围。研究结果表明:在隧道中心线上近火源下游,顶棚下方的最高温度沿纵向均呈指数衰减。不同贴壁距离和纵向通风风速下,均出现烟气分岔流动,随着贴壁距离减小羽流撞击处温升、火羽流偏移角显著增加。当风速小于1.6 m/s时,火源上游出现大量高温烟气回流;而当风速超过2.4 m/s时,分岔流动现象越明显,各偏移角变小,火源下游逐渐后移的烟气层严重失稳。因此,不同受限程度下火灾合理纵向风速为1.6~2.4 m/s。     

碳酸盐对密闭空间粉尘爆炸压力影响的试验研究

为了预防和缓解工业粉尘爆炸并研究惰性粉尘对粉尘爆炸的惰化作用,在Siwek 20 L球形爆炸装置内,针对高爆镁粉和高灰分煤粉,选用碳酸钙(CaCO3)、碳酸氢钠(NaHCO3)、碳酸氢钾(KHCO3)等3种碳酸盐作为惰化剂,讨论惰化剂浓度、粒径及点火能量对最大爆炸压力的影响。结果表明,惰化剂粒径越小,浓度越高,对粉尘爆炸的惰化作用越强;粉尘爆炸的净升压与点火能量无关,点火头主要起引燃作用;当惰化剂浓度递增至60%时以上,粉尘爆炸压力急剧下降,直至不爆。此外,CaCO3的抑制效果明显优于NaHCO3、KHCO3,故推荐采用CaCO3来控制粉尘爆炸风险。     

An experimental study on the burning rate of a continuously released n-heptane spill fire on an open water surface

Spill fires are common during oil product storage and transportation after a loss of containment. Since the burning fuel is moving and the fuel depth is quite shallow, the burning rate in a spill fire is different from that of a pool fire with a static burning zone. Unlike pool fires, which have been studied for decades and have well-established correlations for burning rate, research on spill fires is inadequate. In this paper, continuously released n-heptane spill fire experiments were conducted on open water surfaces with varying fuel discharge rates. The pool diameters were measured, and the spill fire burning rates were estimated based on a dynamic balance between fuel supply and combustion. The burning rates in n-heptane pool fires from the literature were reviewed and compared with the estimated burning rates in spill fires of the same dimension. The spill fire burning rate was found to be close to that in a pool fire during the initial burning phase but lower than that in a bulk burning pool fire and that in a “fuel-level-controlled” pool fire. The distinction between the burning rates of spill fires and pool fires is explained by the heat balance analysis of the fuel layer. A model for the spill fire burning rate was proposed accordingly. The results calculated with the presented model are closer to the measured data than those calculated with pool fire models.