Fire and Explosion Characteristics of 3-Methyl Pyridine at 270°C with High Oxygen Concentrations

The mixture of 3-methyl pyridine (3-picoline) and steam is used in the production of vitamin B3 in the gas phase. The aim of this study was to investigate the influence of inert steam (H₂O) on the flammability characteristics of 3-picoline in the manufacturing process. Four practical vapour mixing ratios of 3-picoline/steam mixtures, 5, 10, 30 and 100 vol% 3-picoline, were selected in this study. A series of flammability tests were employed for determining their fire and explosion characteristics. Fire tests H₂O: 3-picoline 5,10, 30 and 100 vol% were carried out in a 20-L-Apparatus under simulated conditions of 760 mmHg, 270°C, together with high oxygen concentrations (42 and 21 vol%) used in the real process.The experimental results showed that the safety-related parameters and flammability hazard degrees were all able to be significantly reduced while substantial amount of steam was infused into the 3-picoline/steam system. While the steam proportion was up to 97 vol%, 3-picoline/steam would be non-flammable. As a result, dosing steam to the process is one of the effective methods to prevent the relevant processes from incurring fire and explosion hazards, not to mention its economical benefit.     

Explosion prevention and weighting analysis on the inerting effect of methane via grey entropy model

Explosion prevention is vital for process safety and daily life. In practice, inerting is viewed as an ideal method to reach basic explosion prevention as well as to diminish flammability risk in normal operation, storage, and transportation of materials. This study deals with the inerting effect on the explosion range for methane via grey entropy model, comparatively detected under the different inert gases of nitrogen (N₂), argon (Ar), and carbon dioxide (CO₂), which have various loading inerting concentrations: 10 (90 vol% air), 20 (80 vol% air) and 25 vol% (75 vol% air). The inert influences were determined via the experimental 20-L-apparatus investigations under 1 atm, 30 ^OC, combined with the grey entropy model, which is one of the most prevailingly used grey system theories for weighting analysis and decision-making of the fire and explosion assessment for practical operations. The results indicated that CO₂ had better inerting capacity than the others, as derived from our grey entropy theoretical soft computing calculations. Through the combination of the grey entropy weighting analysis model and the flammability investigations in this study, the concluded decision-making was feasible and useful for the practical applications of inert gases for preventing fire and explosion hazards in relevant processes.     

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.     

火灾中硅酸盐水泥制品的膨胀爆炸与开裂

本文介绍了四川消防科研所自1972年以来开展的钢筋混凝土建筑构件和建筑材料耐火性能研究工作中关于硅酸盐水泥制品在火灾温度条件下膨胀、爆炸与开裂方面的实验研究情况。通过对有关各类以硅酸盐为重要成分的建筑构件和制品的反复试验研究与理论分析，初步掌握了一定程度的膨胀、爆炸以及开裂的物理、化学变化特征。着重指出了应用于建筑中的硅酸盐水泥制品－诸如混凝土构建或装修板材之类，它们的这些特性对建筑物的防火、灭火都有很大的威胁，应该对其产生的根本原因和预防对策进行更加深入的研究，以避免因制品的破坏而导致火灾蔓延和减少消防人员在扑救火灾过程中所造成的不必要的伤亡。     

Thermal hazard analysis of 1-((cyano-1-methylethyl) azo) formamide and effect of incompatible substances on its thermal decomposition

1-((cyano-1-methylethyl) azo) formamide (CABN) is an azo compound that exhibits high thermal sensitivity and self-reactivity. Because of incorrect operation, incompatible substances and other dangerous conditions, thermal explosion accidents may occur during the manufacturing, storage, and transportation of CABN. The pyrolysis characteristics of CABN and its mixture for various heating rates were assessed using differential scanning calorimetry. The results showed that incompatible substances increased the risk of CABN. Moreover, the thermal runaway of CABN under an adiabatic condition was studied using an adiabatic rate calorimeter to obtain the parameters under adiabatic condition. Based on the experimental data, the kinetic parameters of CABN and its mixtures were obtained. In addition, a thermal decomposition kinetic model of CABN was created using Thermal Safety Series. All experiments have shown that the conditions and parameters of CABN must be strictly controlled.     

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.     

Investigation on the self-decomposition and explosion hazard of azo compounds

Azo compounds are self-reactive chemicals that violently produce flammable gases with heat release (i.e., an exothermic reaction). However, the explosion mechanism and ignition probability of azo compounds have not been clearly defined for storage or transportation. In this study, explosion scene analyses and various pyrolysis tests were performed to evaluate the thermal decomposition characteristics and explosion phenomena of azo compounds in a storage facility. The chemical debris collected from a fire scene was determined to be similar to the pyrolyzate of one of the tested azo compounds used by Py-GCMS. The minimum amounts of azo compounds, which could be ignited by self-decomposition heat, were calculated from the results of differential scanning calorimetrys and the heat transfer equation. The results were used to discuss a safety and response strategy for preventing the propagation of an explosion accident, namely a chemical backdraft.     

Applications of thermal hazard analyses on process safety assessments

In 2011, a large petrochemical complex in Taiwan incurred several fire and explosion accidents, which had considerable negative impact for the industry on both environmental and safety issues. Reactive substances are widely used in many chemical industrial fields as an initiator, hardeners, or cross-linking agents of radical polymerization process with unsaturated monomer. However, the unpredictable factors during the process having risk to runaway reaction, thermal explosion, fire, and exposure to harmful toxic chemicals release due to the huge heat and gas products by thermal decomposition could not be removed from the process. This study used differential technology of thermal analysis to characterize the inherent hazard behaviors of azo compounds and organic peroxides in the process, to seek the elimination of the source of the harmful effects and achieve the best process safety practices with zero disaster and sound business continuity plan.     

Flammability estimation of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Ionic liquids (ILs) are known as room temperature molten salts, which are considered green replacement to traditional organic solvents. The fire hazards of traditional organic solvents mainly depend on the combustibility of their vapors, thus ILs are generally regarded as nonflammable owing to their low volatility. However, recent studies show that ILs may combust due to the potential hazards of thermal decomposition, indicating the issue of fire and explosion of ILs are eager to be evaluated during the applications. In this study, the fire and explosion hazards of IL 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C₆mim][NTf₂]) are explored in different aspects. The traditional definition of the flammability for the common organic solvent is not thoroughly applicable to [C₆mim][NTf₂] due to the low volatility. Furthermore, the common definition of reactivity for traditional organic solvents also fails to apply, because the decomposition reaction is indeed an endothermic reaction. However, the auto-ignition of some decomposition products will result in fire and explosion hazards for [C₆mim][NTf₂]. Therefore the application of such data in safety purposes should be very careful.     

The explosion parameters of methanol under variable pressures and 423 K

The high-temperature and high-pressure methanol one-step oxidation has been the primary process for the mass production of dimethoxymethane. However, the risk of explosion for this process is still not properly defined. This paper presents new results from the experimental study on the explosion characteristics, including the explosion pressure and the explosion limits for methanol/air mixtures with a variable oxygen level, under an initial pressure between 0.3 MPa and 0.75 MPa and at the initial temperature of 423 K. The upper explosive limits were found to increase along with the initial pressure. If the limits for normal air are known, the oxygen effect on flammability is predictable from the thermal balance method. With a correlation for the pressure effect and a method for the oxygen effect, we can have the flammable range predictable.     

Coupling effects of the explosion shock wave and heat radiation on the dynamic response of a fixed-roof tank

The occurrence of leakage in large tank farms or oil deposits can lead to fire or explosion accidents. Coupling effects of fire and explosion loadings can cause considerably more damage to adjacent tanks or buildings than either loading individually does. In this study, the combined loadings of the explosion shock wave and heat radiation from a pool fire on a neighboring empty fixed-roof tank were numerically investigated. The effects of the explosion shock wave intensity and relative height of the explosion center [the ratio of the height of the explosion center to the height of the tank (h_r)] were analyzed. The results indicate that tanks damaged by explosion shock waves have decreased fire resistance and critical buckling temperature. Moreover, the thermal buckling deformation of the predamaged tank largely depends on the explosion shock wave. With an increase in the explosion shock wave intensity or a decrease in h_r, the explosion shock wave has greater influence on the fire resistance of the tank, and the critical buckling temperature decreases. This paper can provide an understanding of the dynamics of a tank under explosion shock wave loading, and of the critical failure criterion and failure modes of a target tank under the coupled loading of the explosion shock wave and an adjacent pool fire.     

地下复杂组合受限空间火灾分区现象与初期模式实验研究

主要介绍地下狭长与组合受限空间油料介质火灾分区现象、初期火灾主要模式模拟实验研究结果与讨论;地下组合受限空间火灾呈现出特殊的分区现象。一般可分为燃烧区、新鲜空气补充区、烟气流区、过渡区和火焰后面的“惰化区”五区。有上下两层的地下复杂组合受限空间可分为燃烧区、烟气流区、新鲜空气补充区和“惰化区”4区。地下受限空间(包括组合受限空间、容积式受限空间和狭长受限空间)密闭条件下火灾初期模式主要有：爆炸、爆炸减弱、爆炸增强、燃烧、爆燃向爆轰发展。地下复杂组合受限空间下部与下部狭长受限空间分别全开口条件下着火后火灾主要模式为爆炸、燃烧、爆炸后持续燃烧、爆炸后短时燃烧、爆炸后发展为出口外爆炸;爆炸又可分为爆炸强度逐步加强、爆炸由爆燃发展为爆轰、爆炸强度逐步减弱。     

甲烷/空气混合气燃爆特性的实验研究

对不同初始压力和温度条件下的甲烷/空气混合气的爆炸极限进行实验研究,利用最大-最小准则来确定爆炸极限.分析了温度和压力对甲烷/空气混合气燃爆特性的影响.采用氮气作为惰性气体,对其防爆抑爆效果进行了实验研究.     

对危化品生产与储存场所定量安全评价的比较研究

分别用道化法和蒙德法对某化工厂的氨合成塔单元进行了定量安全评价,另外还用蒙德法对该厂的液氨储存单元进行了定量安全评价.结果表明：对于火灾、爆炸及毒性危险性共存的单元,应选用蒙德法对其进行安全评价;当被评价单元主要危险物质的毒性较小,并且需要对危险所造成的影响范围、财产损失和停工日有较具体的评价时,应选用道化法对其进行安全评价;当被评价单元主要危险物质具有较大的毒性,并且要求对毒性的危害有较具体的评价时,应选用蒙德法对其进行安全评价.     

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.     

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.     

粉尘爆炸特征和预防措施探讨

随着现代工业的发展,粉末技术得到了广泛应用,使得粉末产物日益增多.许多粉体加工企业对粉体的相关危害知识没有深刻的认识,这些物质在安全生产、储存、运输和应用过程中,安全管理比较混乱,没有做到很好的防护,缺乏必要的防火防爆设施,再加上操作人员思想上的麻痹大意.粉尘爆炸的危险性大大增加,粉尘爆炸的事故也频繁发生.粉尘爆炸具有很强的破坏力,往往造成重大人员伤亡和严重损失,已经越发成为工业安全不可忽视的重要问题.本文从粉尘爆炸的基本特征出发,论述了粉尘爆炸的机理、条件、特点.根据粉尘爆炸需要的条件,从可燃物、助燃物和点火源三个方面,提出了在实际生产中,预防粉尘爆炸的一些具体措施,以期指导安全生产.     

Cause analysis of the fire and explosion during crude oil desulfurization in China

A serious fire and explosion accident that resulted in massive crude oil leakage and severe environmental pollution occurred on 16 July, 2010, in Dalian Port, China. To investigate the root cause of accident and conduct a wide-range investigation, desulfurizing agent JH02, which has a similar ingredient to the desulfurizing agent HD used in Dalian Port, and TS02 were employed in this study to determine the role of desulfurizing agents in the accident. The thermal behavior of crude oil, desulfurizing agents, and their mixtures was measured by using a C80 calorimeter. By using the calorimetric data, the kinetic parameters of the chemical reaction, such as activation energy, pre-exponential factor, and self-accelerating decomposition temperature of crude oil, as well as JH02, TS02, and their mixtures, were calculated and compared. The results indicated that the direct cause of the accident was the thermal runaway initiated by the increasing instability of the crude oil–desulfurizing agent mixture. Excess pressure in the oil pipeline triggered the physical explosion, but it alone was not enough to cause a serious damage. Furthermore, a stable desulfurizing agent such as TS02 could not ensure a safe desulfurizing process. The results of this study would benefit the safety management of desulfurizing processes during production and storage.