Evaluative comparison of two methods for SADT determination (UN H.1 and H.4)

We present our results on the comparison of two methods for the SADT determination. Both methods, UN test H.1 and UN test H.4 are recommended by the international transport regulations from the UN. But during the last years the applicability of the UN test H.4 has been questioned for solid substances. Therefore, three organic peroxides and one self-reactive substance have been investigated in 5 kg and 20 kg packages as well as in the UN test H.4 in a 500 mL Dewar vessel. The SADT values determined with the different methods match. The UN test H.4 seems to be well suited for solid organic peroxides and self-reactive substances of at least 20 kg or 60 L.     

Determination of the maximum effective burning velocity of dust–air mixtures in constant volume combustion

The reactivity of a combustible dust cloud is traditionally characterized by the so-called K_St value, defined as the maximum rate of pressure rise measured in constant volume explosion vessels, multiplied with the cube root of the vessel volume. The present paper explores the use of an alternative parameter, called the maximum effective burning velocity (u_eff,max), which also is derived from pressure–time histories obtained in constant volume explosion experiments. The proposed parameter describes the reactivity of fuel–air mixtures as a function of the dispersion-induced turbulence intensity. Procedures for estimating u_eff,max from tests in both spherical and cylindrical explosion vessels are outlined, and examples of calculated values for various fuel–air mixtures in closed vessels of different sizes and shapes are presented. Tested fuels include a mixture of 7.5% methane in air, and suspensions of 500 g/m³ cornstarch in air and 500 g/m³ coal dust in air. Three different test vessels have been used: a 20-l spherical vessel and two cylindrical vessels, 7 and 22 l. The results show that the estimated maximum effective burning velocities are less apparatus dependent than the corresponding K_St values.     

The thermal hazard evaluation of 1,1-di (tert-butylperoxy) cyclohexane by DSC using non-isothermal and isothermal-kinetic simulations

1,1-Di (tert-butylperoxy) cyclohexane (DTBPH) has been widely employed in the chemical industry. Unfortunately, organic peroxides have been involved in many serious fires and explosions in manufacturing processes, storage, and transportation. This study investigated the thermokinetic parameters by isothermal kinetic and non-isothermal-kinetic simulation, using differential scanning calorimetry (DSC) tests. DSC was applied to assess the kinetic parameters, such as kinetic model, frequency factor (ln k₀), activation energy (E_a), reaction order, and heat of reaction (ΔH_d). Comparisons of non-isothermal and isothermal-kinetic model simulation led to a beneficial kinetic model of thermal decomposition to predict the thermal hazard of DTBPH. Simulations of a 0.5 L Dewar vessel and 25 kg barrel commercial package in liquid thermal explosion models were performed and compared to the results in the literature. From the results, the optimal conditions for use of DTBPH to avoid violent runaway reactions during the storage and transportation were determined. This study established the features of thermal decomposition that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.     

球接管容器气体爆炸尺寸效应的试验研究与数值分析

为了解尺寸对球形容器连接管道甲烷-空气混合物爆炸的影响规律,利用Fluent软件,采用κ-ε湍流模型、涡耗散模型(简称EDC模型)、壁面热耗散、热辐射模型及SIMPLE算法,建立了球形容器连接管道内甲烷-空气混合物爆炸的数值模型,对容器与管道内甲烷-空气预混气体爆炸的尺寸效应进行了数值模拟。结果表明:随管道内径增大,球形容器内最大爆炸压力逐渐增大,管道末端最大爆炸压力变化无明显规律;而随管道长度增加,球形容器内最大爆炸压力逐渐减小;改变管道内径,较大体积球形容器内最大爆炸压力均大于较小体积球形容器内最大爆炸压力,最大爆炸压力上升速率的规律则相反,容器体积对管道末端最大爆炸压力的影响无明显规律。     

Thermal decomposition kinetic of liquid organic peroxides

This study demonstrates the application of isothermal calorimeter for investigating the thermal decomposition of several liquid organic peroxides, such as t-Butyl peroxy acetate (TBPA), Di-tert butyl peroxide (DTBP), and Cumene hydroperoxide (CHP). The decomposition mechanism and kinetic can be identified from case to case. TBPA and DTBP undergo first order reaction, whereas CHP occurs autocatalysis. Accurate kinetic can be assessed on the basis of discerning these various schemes of given samples. Consequently, the thermal runaway or reactive hazards potential of organic peroxides can be determined, for instance as a self accelerating decomposition temperature (SADT).     

Experimental investigation of gas explosion in single vessel and connected vessels

Gas explosion in connected vessels usually leads to high pressure and high rate of pressure increase which the vessels and pipes can not tolerate. Severe human casualties and property losses may occur due to the variation characteristics of gas explosion pressure in connected vessels. To determine gas explosion strength, an experimental testing system for methane and air mixture explosion in a single vessel, in a single vessel connected a pipe and in connected vessels has been set up. The experiment apparatus consisted of two spherical vessels of 350 mm and 600 mm in diameter, three connecting pipes of 89 mm in diameter and 6 m in length. First, the results of gas explosion pressure in a single vessel and connected vessels were compared and analyzed. And then the development of gas explosion, its changing characteristics and relevant influencing factors were analyzed. When gas explosion occurs in a single vessel, the maximum explosion pressure and pressure growth rate with ignition at the center of a spherical vessel are higher than those with ignition on the inner-wall of the vessel. In conclusion, besides ignition source on the inner wall, the ignition source at the center of the vessels must be avoided to reduce the damage level. When the gas mixture is ignited in the large vessel, the maximum explosion pressure and explosion pressure rising rate in the small vessel raise. And the maximum explosion pressure and pressure rising rate in connected vessels are higher than those in the single containment vessel. So whenever possible, some isolation techniques, such as fast-acting valves, rotary valves, etc., might be applied to reduce explosion strength in the integrated system. However, when the gas mixture is ignited in the small vessel, the maximum explosion pressures in the large vessel and in the small vessel both decrease. Moreover, the explosion pressure is lower than that in the single vessel. When gas explosion happens in a single vessel connected to a pipe, the maximum explosion pressure occurs at the end of the pipe if the gas mixture is ignited in the spherical vessel. Therefore, installing a pipe into the system can reduce the maximum explosion pressure, but it also causes the explosion pressure growth rate to increase.     

Green thermal analysis for predicting thermal hazard of storage and transportation safety for tert-butyl peroxybenzoate

Liquid organic peroxides, such as tert-butyl peroxybenzoate (TBPB), have been widely employed in the petrifaction industry as a polymerization formation agent. This study investigated the thermokinetic parameters of TBPB by isothermal kinetic algorithms and non-isothermal kinetic equations, using thermal activity monitor III (TAM III) and differential scanning calorimetry (DSC), respectively. Simulations of 0.5 L, 25 kg, 55 gallon, and 400 kg reactors in liquid thermal explosion models were performed and compared to the results in the literature. A green thermal analysis was developed for a reactor containing TBPB to prevent pollution and reduce the energy consumption by thermal decomposition. It is based on the thermal hazard properties, such as the heat of decomposition (ΔH_d), activation energy (E_a), self-accelerating decomposition temperature (SADT), control temperature (CT), emergency temperature (ET), and critical temperature (TCR). From the experimental results, the optimal conditions to avoid violent runaway reactions during the storage and transportation of TBPB were determined.     

Diphenylmethane diisocyanate self-polymerization: Thermal hazard evaluation and proof of runaway reaction in gram scale

Thermal analysis by differential scanning calorimetry and thermogravimetric/differential thermal analysis mass spectrometry, adiabatic calorimetry, a gram-scale heating test, and infrared spectroscopy were performed to evaluate the thermal hazards of diphenylmethane diisocyanate (MDI) and prove the occurrence of a runaway reaction. The self-polymerization of MDI was found to occur at about 340 °C under rapid heating conditions. Carbon dioxide was eliminated and heat was generated to allow polymerization. Under adiabatic and closed conditions, the runaway reaction of MDI can begin at least from 220 °C. Besides it is highly probable that the runaway reaction of MDI can begin from a lower temperature in an actual process scale. More heat was generated than in the previous case and the pressure rose rapidly. A closed 2-mm-thick glass vessel exploded because of the runaway reaction of MDI even if the temperature was lower than 300 °C. Therefore, MDI could cause fatal runaway reactions below 300 °C, where MDI had been assumed to self-polymerize by eliminating carbon dioxide previously.     

Validation of the UN criteria for the uncooled sea transport of liquid organic peroxides: Full-scale test and modeling

In the years 1987 and 1988 TNO and Akzo Nobel investigated the thermal safety of non-temperature-controlled sea transport of organic peroxides, by modeling and experimenting on several scales. A full-scale test was organised in the summer of 1989, in co-operation with the former Nedlloyd company, in which a sea container with palletised packages, filled with soybean oil as inert liquid and fully equipped with temperature measuring equipment, was transported from Rotterdam, The Netherlands, to Beira, Mozambique, and back. The trip took 2 months.To answer questions stated by the workgroup International Group of Experts on the Explosion Risk of Unstable Substances—subgroup on Energetic and Oxidising Substance (IGUS-EOS) during its meeting in Washington, DC, USA, April 2006, the original data of the sea-container trip were reviewed and applied in a new mathematical model of the sea-container filled with packages, and traveling through tropical sea areas.Analysis of the data from the full-scale test led to defining a worst combination of adverse temperature conditions: constant dead sailing of the wind (wind direction and speed equal to that of the ship), and sunny weather 12 h/day and a mean ambient temperature of 30 °C during 28 days.The effect of sunny weather was put into the model by assigning 24 h averaged excess temperatures to the sun-exposed surfaces. New simulations showed no runaway for the sea container, if filled with an organic peroxide having an self-accelerating decomposition temperature (SADT) of exactly 55 °C.The exaggerated worst case with an improbable mean ambient temperature of 33 °C also does not lead to a runaway.Therefore, the UN criteria for temperature control for organic peroxides are appropriate.     

初始压力对连通容器甲烷-空气混合物泄爆压力的影响

建立球形容器与管道、2个球形容器与管道组成的2种形式的连通容器试验装置,研究初始压力对连通容器甲烷-空气混合物泄爆压力的影响。结果表明:连通容器内泄爆超压随初始压力增加而增大,并与初始压力近似成线性关系;对于2个球形容器与管道组成的连通容器,起爆容器的泄爆超压始终小于传爆容器;泄爆方式和点火方式对连通容器泄爆超压有较大影响,大容器点火时,2个容器的泄爆压力差随初始压力增加而增大,但小容器点火时,2个容器的泄爆压力差随初始压力的增加变化较小;初始压力对不同结构和尺寸的连通容器的泄爆压力的影响不同,当令初始压力对大容器点火时,小容器内泄爆压力受影响最大,而当对单球形容器与管道组成的连通容器的小容器点火时,小容器内泄爆压力受影响最小。     

不同形状受限空间内油气爆燃特性的实验研究

基于实验对4个不同形状的20L容器内的油气爆燃过程进行了研究,探讨了不同形状受限空间内爆炸压力荷载的变化和火焰行为的区别。结果表明:管道（短管和长管）的压力时序曲线较容积式受限空间（球形容器和立方体容器）的压力时序曲线更复杂,并且出现压力振荡;随着初始浓度的增加,超压值和平均升压速率均先增大后减小,在浓度为1.74%时达到最大值,此时,超压从大到小依次为:长管>短管>立方体>球形容器,平均升压速率从大到小依次为:短管>立方体>长管>球形容器;在爆燃初期,立方体中火焰行为为半球状层流火焰→扁平层流火焰,火焰速度先增大后减小,最大速度为12.5 m/s,长管中火焰行为为半球状层流火焰→拉伸指状火焰,火焰速度一直增大,最大速度为40 m/s。     

锂离子电池组热失控蔓延热传递机制的影响研究

分析通风和电池组数量对电池组热失控发展蔓延热传递机制的影响.选择荷电状态(SOC)为100％的镍钴锰(NCM523)三元锂离子动力电池组作为研究对象,改变电池组底部外加热源的热流量和加热时间,利用多物理场仿真软件COMSOL,进行热滥用导致不同风速通风环境和不同电池数量电池组热失控过程的模拟.结果表明:随着风速不断增大...     

基于QRA角度评价LNG储罐类型的选择

为提高LNG储存的安全性,基于QRA(定量风险评价),利用应急危险定位分析软件分别进行了LNG中小型储罐及大型储槽泄漏事故分析和LNG带压储罐充注压力专项对比分析。结果表明:立式圆柱常压储罐应选择高径比接近于1的罐体而压力罐的选择受高径比的影响很小;当对常压储罐高度有要求时,球形罐是比立式圆柱罐更好的选择;在大型LNG储槽中,常压储槽自身压力很大,可以起到抑制BOG(蒸发气体)产生的作用;在饱和状态下,压力罐的充注压力并非越小越好,需进行针对性分析计算,选取最适合的充注与设计压力。掌握LNG储罐事故后果与罐体形状与类型之间的关系可加强并丰富对其储罐类型选择的认识,可较好的为提高其储存安全性提供数据支撑与理论基础。     

Decomposing deflagration properties of acetylene under low temperatures

In this study, the decomposing deflagration properties of acetylene under temperatures down to −60 °C and pressures up to 0.2 MPa in a 1-L cylindrical closed vessel were experimentally investigated. The gases were ignited by an electric spark at the center of the vessel. The lower-limit pressures of decomposing deflagration by electric spark ignition were determined. The lower-limit pressure at 10 °C was 0.15 MPa, and it gradually increased with decreasing temperature. The lower-limit pressure at −60^oC was 0.18 MPa. The flame propagation properties, such as the pressure, were measured with pressure transducers mounted along the vessel. The maximum decomposing deflagration pressures and pressure rising rates also increased with decreasing temperature.     

反应失控型火灾爆炸事故预测

介绍了一种预测反庆失控灾害的方法,通过实验测定容器的时间常数,预测能够引起反应失控的最低环境温度,发生反应失控时的危险温度,以及达到最大反应速度反需的时间,预测结果与实际情况具有良好的一致性。     

低压环境对锂电池热失控释放温度影响

为研究锂电池在民航飞行低压特殊环境的安全性及发生热失控灾害后的高温危险性,通过可模拟飞行变动条件的动压变温实验舱开展系列实验,研究锂电池在不同低压环境下的（101,60,30 kPa）多节18650型锂离子电池热失控温度特性,采集电池池体温度及热失控喷射释放温度等参数。研究结果表明:随环境压力降低,圆柱锂电池间的热失控传播并不能被阻断,但锂电池热失控灾害所释放产生的高温区域减少,且高温持续时间变短,释放所产生温度的高温危险性随环境压力的降低而有所降低。     

Case study: Assessment on large scale LPG BLEVEs in the 2011 Tohoku earthquakes

After the 2011 Tohoku earthquakes, several chemical and oil complexes on the Pacific Ocean shoreline of northeast Japan experienced massive losses. In Chiba, a refinery operated by Cosmo Oil lost 17 LPG storage vessels which were either heavily damaged or totally destroyed by fires and explosions in the refinery. These large vessels ranged in size from 1000 to 5000 m³. The estimated volume of LPG at the time of the incident was between 400 and 5000 m³ for each vessel. Five boiling liquid expanding vapor explosions (BLEVEs) of LPG occurred, resulting in huge fire balls measuring about 500 m in diameter.A BLEVE is defined as the explosive release of expanding vapor and boiling liquid when a container holding a pressure-liquefied gas fails catastrophically. It is thus important to estimate the physical properties of superheated liquids: the thermodynamic and transport properties, the intrinsic limits to superheating and depressurization, and the nature of thermodynamic paths. Also it is hoped to provide better understanding of the vessels designed, manufactured, installed, and operated to reduce or eliminate the probability that a sequence of events will result in BLEVE or loss of primary containment. Knowledge of these matters is still incomplete. The objective of this research is to estimate the significant BLEVE phenomenon in very large scale spherical vessels based on published information in Japan. There are some models predicting BLEVEs. However, it is essential to know if this is true for very large scales such as spheres since validation is usually rare to provide confidence in estimating the superheated liquids behaviors. To this end, comparing with the information on this event, the conditions in the five LPG vessels at the time of the BLEVE were determined in terms of: duration of vessel failure (time to BLEVE); mass fraction in the vessel with time; temperature distribution in the liquid and vapor region and pressure within the vessel (e.g. initial pressure and internal high-speed transient pressure during failure), by means of a computer program AFFTAC Analysis of Fire Effects on Tank Cars, which solves heat conduction, stress and a failure model of the tank, a thermodynamic model of its fluid contents, and a flow model for the lading flowing through the safety relief device. Subsequently, the consequences from the sphere BLEVE, such as the expected fireball diameter and duration and the expected blast overpressure produced by the BLEVE failures, are also subjects of active research. Here the blast using the methods of PHAST and SFPE Handbook of Fire Protection Engineering was calculated.Results suggest that methodologies here used gave reasonable estimations for such real and huge BLEVEs in a validated way, which may provide valuable guidance for risk mitigation strategy with regard to LPG facility in design, emergency planning, resiliency, operations, and risk management.     

甲烷-空气预混气体泄爆过程的实验研究

对甲烷-空气预混气体在球形容器和球形管道连通容器内的泄爆过程进行实验研究,根据实验结果得出在较小的泄压面积时,与密闭容器爆炸实验比较,不能降低容器内的最大压力,反而会增大容器内的最大压力。通过实验结果分析,泄爆口安装在远离点火源的位置,当发生预混气体爆炸时能较好地降低容器内的最大压力,起到保护容器的作用。     

加氢站用45 MPa高压储氢瓶式容器火烧试验模拟*

为研究加氢站用高压储氢容器在火灾下的安全性能,采用计算流体力学（CFD）方法对45 MPa高压储氢瓶式容器火烧试验过程进行模拟研究,结合气瓶火烧试验,分析高压储氢容器火灾下的热响应过程,研究不同因素对储氢容器压力泄放装置动作时间的影响。结果表明:613 s以内试验压力与模拟数据的最大相对误差为3.9%,模型误差在可接受范围;不同充装介质对安全泄放装置动作时间影响不大;不同充装压力对容器内介质压升速率影响较大,充装水平较高时压力泄放装置更快动作,较低的充装压力下容器内介质温升较快;不同环境温度对介质温升影响较小。     

过氧乙酸溶液的热爆炸分析

为有效预防生产、储运和使用中过氧乙酸引发的火灾爆炸事故,采用绝热加速量热仪模拟了15%和10%浓度的过氧乙酸溶液的热爆炸过程,得到了两种浓度的PAA溶液的热分解温度、压力、温升速率随时间变化的关系曲线,并用速率常数法分别计算了反应级数n、表观活化能Ea和指前因子A。经过绝热修正,得到最危险状态下的温度和压力等相关热危险参数,并基于Semenov热爆炸理论推算了三种包装条件下两种样品的不可逆温度和自加速分解温度。结果表明,15%PAA和10%PAA溶液热分解反应级数均为一级,表观活化能分别为1044kJ·mol-1和1032kJ·mol-1;绝热条件下初始放热温度分别为429℃和293℃;自加速分解温度受反应系统到达最大反应速率的时间、物料存储规模及散热条件的影响,建议PAA应储存在通风背阴处且单个包装容积应控制在25L以下。