Reconsidering autoignition in the context of modern process safety: Literature review and experimental analysis

Autoignition is regarded as the spontaneous combustion of a fuel without an apparent ignition source. With respect to fires and explosions in the process industries, the autoignition hazard is one that requires management and consideration. Despite the importance of understanding the autoignition hazard, the literature on the topic is often disappointingly sparse and inconsistent. Experimental methods don't adequately represent real-world conditions and are complicated by experimental error, invoking the need for a reconsideration of autoignition as it pertains to process safety. This work utilized the ASTM E659 method to study potential experimental error for the purpose of improving the process safety community's understanding of autoignition phenomena. Of interest to this study were effects of humidity and suspected occurrences of cool flames, two sources of error which have not been fully explained in the literature. For the fuels tested, results show that humidity has only a slight effect on overall autoignition behavior. However, this study's examination of cool flames suggests that they could be a common occurrence in this testing method. Analysis of these experiments show that cool flames can feature significant exothermic effects and are thus of concern from a perspective of risk management. In addition, this work proposes a novel criterion for a more conservative assessment of autoignition experiments, which results in less subjectivity of analysis.     

Numerical study on the spontaneous ignition of pressurized hydrogen release through a tube into air

Spontaneous ignition of pressurized hydrogen release through a tube into air is investigated using a modified version of the KIVA-3V CFD code. A mixture-averaged multi-component approach is used for accurate calculation of molecular transport. Autoignition and combustion chemistry is accounted for using a 21 step kinetic scheme. Ultra fine meshes are employed along with the Arbitrary Lagrangia–Eulerian (ALE) method to reduce false numerical diffusion. The study has demonstrated a possible mechanism for spontaneous ignition through molecular diffusion.

In the simulated scenario, the tube provided additional time to achieve a combustible mixture at the hydrogen–air contact surface. When the tube was sufficiently long under certain release pressure, autoignition would initiate inside the tube at the contact surface due to mass and energy exchange between low temperature hydrogen and shock-heated air through molecular diffusion. Following further development of the hydrogen jet downstream, the contact surface became distorted. Turbulence plays an important role for hydrogen/air mixing in the immediate vicinity of this distorted contact surface and led the initial laminar flame to transit into a stable turbulent flame.     

Numerical simulation of flame propagation and localized preflame autoignition in enclosures

A novel computational approach based on the coupled 3D Flame-Tracking–Particle (FTP) method is used for numerical simulation of confined explosions caused by preflame autoignition. The Flame-Tracking (FT) technique implies continuous tracing of the mean flame surface and application of the laminar/turbulent flame velocity concepts. The Particle method is based on the joint velocity–scalar probability density function approach for simulating reactive mixture autoignition in the preflame zone. The coupled algorithm is supplemented with the database of tabulated laminar flame velocities as well as with reaction rates of hydrocarbon fuel oxidation in wide ranges of initial temperature, pressure, and equivalence ratio. The main advantage of the FTP method is that it covers both possible modes of premixed combustion, namely, frontal and volumetric. As examples, combustion of premixed hydrogen–air, propane–air, and n-heptane–air mixtures in enclosures of different geometry is considered. At certain conditions, volumetric hot spots ahead of the propagating flame are identified. These hot spots transform to localized exothermic centers giving birth to spontaneous ignition waves traversing the preflame zone at very high apparent velocities, i.e., nearly homogeneous preflame explosion occurs. The abrupt pressure rise results in the formation of shock waves producing high overpressure peaks after reflections from enclosure walls.     

Mechanisms of high-pressure hydrogen gas self-ignition in tubes

This paper describes a numerical and experimental investigation of hydrogen self-ignition occurring as a result of the formation of a shock wave. The shock wave is formed in front of high-pressure hydrogen gas propagating in a tube. The ignition of the hydrogen–air mixture occurs at the contact surface of the hydrogen and oxidant mixture and is due to the temperature increase produced as a result of the shock wave. The required condition for self-ignition is to maintain the high temperature in the mixture for a time long enough for inflammation to take place. The experimental technique employed was based on a high-pressure chamber pressurized with hydrogen, to the point of a burst disk operating to discharge pressurized hydrogen into a tube of cylindrical or rectangular cross section containing air. A physicochemical model involving gas-dynamic transport of a viscous gas, detailed kinetics of hydrogen oxidation and heat exchange in the laminar approach was used for calculations of high-pressure hydrogen self-ignition. The reservoir pressure range, when a shock wave is formed in the air that has sufficient intensity to produce self-ignition of the hydrogen–air mixture, is found. An analysis of governing physical phenomena based on the experimental and numerical results of the initial conditions (the hydrogen pressure inside the vessel, and the shape of the tube in which the hydrogen was discharged) and physical mechanisms that lead to combustion is presented.     

Use of detailed kinetic mechanisms for the prediction of autoignitions

This paper describes how automatically generated detailed kinetic mechanisms are obtained for the oxidation of alkanes and how these models could lead to a better understanding of autoignition and cool flame risks at elevated conditions. Examples of prediction of the occurrence of different autoignition phenomena, such as cool flames or two-stage ignitions are presented depending on the condition of pressure, temperature and mixture composition. Three compounds are treated, a light alkane, propane, and two heavier ones, n-heptane and n-decane.     

Risk and mitigation of self-heating and spontaneous combustion in underground coal storage

While the self-heating and spontaneous combustion of coal is a known challenge at coal mines and storage sites, there are known methods for mitigating this challenge for typical open stockpile storage. However, closing the storage will reduce access for corrective action, and it is then important to manage the storage and its transport system with added attention without unduly adding cost or hindering availability. This paper aims to discuss the risk, prevention and extinguishing of fires in closed coal storage facilities, particularly in light of the experience with the Salmisaari underground rock storage facility in Finland. The observed autoignition events have indicated an array of contributing factors, some of which are unique to underground silo storage facilities. On the other hand, many features of the storage facilities can be compared with other extant closed storage systems. The factors affecting fire risk are described and the associated fault and event trees are outlined for autoignition at underground storage. Drawing upon the experiences with past events of self-heating and spontaneous combustion, recommendations are given on cost-effective preventive, corrective and other mitigating action for minimising fire risk and promoting storage availability.     

有障碍物半开口管道内氢气燃烧数值模拟研究

基于有障碍物氢气燃烧实验装置进行数值模拟研究,采用Fluent软件分析了半开口管道内障碍物对氢气/空气燃烧特性的影响。结果表明:障碍物会促进实验管段内氢气火焰加速,随着障碍物阻塞率和数量的增加,火焰加速更快且燃烧压力峰值更大;在相同阻塞率下,障碍物形状对氢气火焰速度和燃烧压力峰值的影响很小;燃烧压力随障碍物间距的增大先增大后减小,障碍物间距为3倍管道内径时产生的燃烧压力峰值最大。     

飞机防火试验中的燃烧反应动力学模型研究

使用反应路径分析法对Jet-A型航空煤油燃烧的气相燃烧机理进行简化。选用POSF-4658机理作为Jet-A燃烧的详细反应机理,该机理包含1607种燃烧组分、6633个基元反应机理。将飞机防火试验条件作为简化过程的初始条件,得到78种组分,196个反应机理的Jet-A燃烧机理。通过对Jet-A的简化反应机理、详细反应机理和JetA实验数据的比较可以发现,简化反应机理可以较准确地反映Jet-A型航空煤油在防火试验条件下的燃烧特性。利用常用的Jet-A型航空煤油简化机理计算的绝热火焰温度、点火延迟时间及层流火焰速度与本文提出的简化的计算值进行比较。结果表明,提出的简化机理在防火试验条件下具有较高的精确度。得到的Jet-A简化反应机理可为飞机防火试验的仿真研究提供燃烧场的化学反应动力学模型。     

燃气加热炉火焰视频监控系统设计

为了持续监测燃气工业加热炉燃烧状况,保障锅炉运行安全,根据燃气火焰的特点,利用数字图像处理技术,设计了相应的燃气加热炉火焰视频监控系统。通过图像预处理、火焰特征提取、火焰特征分析三个步骤,可实现对炉膛火焰燃烧状态进行实时判定,包括火焰燃烧或熄灭、燃烧是否充分、是否稳定。仿真实验结果表明,该系统能准确地从监控视频中检测和识别火焰燃烧状态,并能将燃烧特征量和特征分析结果存储到数据库以供事后查询。     

600 m3湿式氢气贮柜燃烧爆炸伤害效应预测

建立了某动力公司600m^3易燃易爆湿式氢气贮柜燃烧爆炸事故的6种模型,给出边界条件和计算过程,提出爆炸事故伤害效应预测指标。进行燃烧爆炸事故伤害效应预测,为氢气贮柜发生燃烧爆炸事故危害性评估提供了理论依据。     

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.     

干燥条件下高硫煤低温氧化特性研究

为进一步揭示不同环境条件下高硫煤的低温氧化特性,选取含硫量较低、自燃倾向性较高的褐煤,向其添加不同比例的FeS2,配制成含量分别为3%,5%,7%的混合高硫煤样,利用中国矿业大学自行研制的煤氧化模拟试验系统,测试分析干燥混合煤样在低温氧化过程中,交叉温度和指标气体CO产生量体积的变化。试验结果表明,在低温干燥的条件下,随着FeS2含量的增加,煤样的氧化特性受到抑制:交叉点温度升高;指标气体CO产生量在相同温度时体积降低。因此,在高硫煤层自燃火灾防治过程中,应尽量控制煤层周围环境的干燥度。     

Safety parameters for oxygen-enriched flames

The utilization of low-quality gaseous fuel from biomass gasification and the abundance of oxygen-rich streams obtained as a by-product of nitrogen-air separation by membrane technology has incentivized the development of sustainable oxygen-enriched combustion technologies in the last decades. However, a dearth of experimental and numerical analysis addressing the reactivity and safety aspects of these mixtures at initial low temperatures can be observed in the current literature.In this work, the heat flux burner was adopted for the measurement of the laminar burning velocity of methane in oxygen enriched air at different equivalence ratios. Results were compared with numerical data obtained by means of detailed kinetic mechanisms developed at the University of Bologna and the Gas Research Institute (GriMech3.0). Simplified correlations for the estimation of the laminar burning velocity with respect to the oxygen content at any equivalence ratio were developed, tested and evaluated.An elemental reaction-based function was found appropriate for the estimation of the overall reactivity of the investigated mixtures. Besides, numerical analyses were performed to characterize the flame structures in terms of temperature and product distribution under several initial conditions. These results gave further insights into the reaction mechanisms of gaseous fuels in the case of oxygen-enriched air, highlighting potential bottlenecks for kinetic model refinements. Eventually, relevant safety parameters were estimated, in particular the flammability range of the fuel/oxidant mixture, in terms of lower and upper flammability limits.     

Shock-induced ignition of hydrogen gas during accidental or technical opening of high-pressure tanks

This paper is devoted to the numerical and experimental investigation of hydrogen self-ignition as a result of the formation of a primary shock wave in front of a cold expanding hydrogen gas jet. Temperature increase, as a result of this shock wave, leads to the ignition of the hydrogen–air mixture formed on the contact surface. The required condition for hydrogen self-ignition is to maintain the high temperature in the area for a time long enough for hydrogen and air to mix and inflammation to take place.

Calculations of the self-ignition of a hydrogen jet are based on a physicochemical model involving the gas-dynamic transport of a viscous gas, the kinetics of hydrogen oxidation, the multi-component diffusion, and the heat exchange. We found that the reservoir pressure range, when a shock wave formed in the air during depressurization, has sufficient intensity to produce self-ignition of the hydrogen–air mixture formed at the front of a jet of compressed hydrogen. We present an analysis of the initial conditions (the hydrogen pressure inside the vessel, the temperature of the compressed hydrogen and the surrounding air, and the diameter of the hole through which the jet was emitted), which leads to combustion.     

针对C3H8／空气扩散火焰的PCA简化机理构筑

C3H8是液化石油气（LPG）的主要成分,其火焰结构的数值预测对于消防等相关行业具有重要意义。单步或总包反应过于简单,不能描述碳氢燃料的氧化机制,而耦合燃料详细机理的燃烧模拟计算量大,且描述反应的数学系统具有极强的“刚性”,限制了反应机理的实际应用,而去除冗余反应和组分的简化机理具有描述燃烧的全面性优点,且降低了数学系统的“刚性”,因此耦合简化机理的火焰结构数值预测具有优势。本文采用基于矩阵分析的主成分（PCA）分析技术,分析研究了wang等发展的469步C3H8详细反应动力学机理,获得了组分的重要性排序,基于此分别构筑了320步和214步两个简化机理,针对典型扩散火焰的计算,表明建立的两个简化机理具有较高的模拟可靠性,同时也提供了一种框架简化机理的构筑方法。     

WalkSafe: a school-based pedestrian safety intervention program

OBJECTIVE: To evaluate the effectiveness of the WalkSafe program, an elementary school-based pedestrian safety program in a single high-risk district in Miami-Dade County. METHODS: Sixteen elementary schools were identified in a single high-risk district and enrolled in a one-year study. All schools implemented the WalkSafe program on the last week of January 2003. A pre, post, and three-month post testing of pedestrian safety knowledge was conducted. An observational component was also implemented at four schools that were randomly chosen. Engineering recommendations and law enforcement initiatives were also performed. RESULTS: A total of 6467 children from K-5th grade from 16 elementary schools participated in the program. Of these 5762 tests were collected over three different testing times. A significant difference (p-value < 0.001) was found between the pre and post testing conditions across all grade levels. There was no significant difference found between the post and three-month post testing conditions across all grade levels (p-value > 0.05). The observational data collected at four schools across the different testing times demonstrated a significant difference found between pre and post testing conditions for Group A (stop at the curb and look left, right, left) and also for Group B (midstreet crossing and darting out) (p-value < 0.05). There was no difference found between comparing the pre-test or post-test condition with the three-month post-test time. There were many environmental modifications that were recommended and actually performed. CONCLUSION: The WalkSafe program implemented in a single high-risk district was shown to improve the pedestrian safety knowledge of elementary school children. The observational data demonstrated improved crossing behaviors from pre-test to post-testing conditions. Future research will focus on sustaining the program in this district and expanding the program throughout our county.     

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.     

含硫油品储罐自燃机理及事故原因分析

通过企业现场调研并结合若干事故案例的剖析分析了含S油品储罐自燃事故的发生原因,总结了事故的主要影响因素。在建立含S油品储罐自燃的事故树（FTA）图的基础上,通过最小割集的计算与分析,探讨了事故的主要原因及发生条件,并提出了相应的预防控制措施。     

点火提前角对焦炉气天然气混燃发动机燃烧特性的影响分析

为了研究不同点火提前角对焦炉气与天然气混燃发动机燃烧特性的影响,对一台6缸焦炉气发动机,运用CATIA建立其燃烧室模型。在相同的条件下,运用CFD分析软件研究了6种点火提前角（θig）下焦炉气与天然气发动机的燃烧特性。模拟表明:随着θig的提前,缸内的压力、温度、NO生成量的峰值都会升高且提前,当θig推迟到-12 ℃A以后时,出现严重的后燃现象,使得排放温度升高;当θig提前到-25 ℃A之前时,NO的生成量和缸内流速迅速增加,快速燃烧在压缩上止点之前10 ℃A范围内,发动机做负功;当θig为-15 ℃A时,虽然NO的生成有所增加,但是增加的不是很大,并且压力、温度、快速燃烧都在做功行程接近上止点的位置。