Modeling thermal analysis for predicting thermal hazards relevant to transportation safety and runaway reaction for 2,2′-azobis(isobutyronitrile)

The pure decomposition behavior of 2,2′-azobis (isobutyronitrile) (AIBN) and its physical phase transformation were examined and discussed. The thermal decomposition of this self-reactive azo compound was explored using differential scanning calorimetry (DSC) to elucidate the stages in the progress of this chemical reaction. DSC was used to predict the kinetic and process safety parameters, such as self-accelerating decomposition temperature (SADT), time to maximum reaction rate under adiabatic conditions (TMR_ad), and apparent activation energy (E_a), under isothermal and adiabatic conditions with thermal analysis models. Moreover, vent sizing package 2 (VSP2) was applied to examine the runaway reaction combined with simulation and experiments for thermal hazard assessment of AIBN. A thorough understanding of this reaction process can identify AIBN as a hazardous and vulnerable chemical during upset situations. The sublimation and melting of AIBN near its apparent onset decomposition temperature contributed to the initial steps of the reaction and explained the exothermic attributes of the peaks observed in the calorimetric investigation.     

综合管廊燃气舱结构形式对燃气爆炸超压的影响*

为研究地下综合管廊燃气舱结构形式对燃气爆炸超压的影响,采用数值模拟的方法,改变燃气舱高度,通风分区长度和局部开口大小,分析不同情况下的燃气爆炸超压变化规律。结果表明:冲击波传播速度随燃气舱高度的增加而减小,随着高度的增加,超压峰值曲线由“驼峰状”逐渐变为两端高中间低的“盆形”,爆炸过程产生的最大超压与高度成反比关系。超压峰值在340 m处接近0 kPa,延长通风分区并不会增加超压峰值,可以在考虑防火的要求下根据实际情况适当延长通风分区的长度。局部开口的存在使得爆炸气流能够自由泄压,超压峰值与开口的大小成反比关系。     

CH_4/N_2/O_2预混气激波火焰结构数值预测

研究激波着火现象，推导激波加热点燃可燃气控制方程组。针对甲烷预混气激波火焰结构进行数值模拟，计算了激波燃烧时的压力、温度、及不同组分随时间的变化历程。其中甲烷燃烧采用美国BERKELEY大学GRI-MECH机理，该反应机理包含177个基元反应，涉及32种组分。程序采用美国SANDIA国家实验室发展的大型化学反应动力学软件包CHEMKIN III中相关的模型、子程序和热力学数据库。计算结果表明激波火焰有其自身的结构特征。     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

煤与瓦斯突出冲击波及瓦斯气流所致伤害研究

为揭示煤与瓦斯突出过程中冲击波及瓦斯气流传播特性,针对这种突出做功随瓦斯压力、煤的普氏系数和煤的放散初速度变化的特征,运用气体动力学理论,建立冲击波超压、冲击瓦斯流速度与传播距离以及煤层瓦斯压力等参数的关系,计算不同超压下瓦斯气流传播伤害的范围。理论计算与现场测试结果表明,突出冲击波属惰性弱冲击波;波阵面上的超压传播伤害距离与突出时瓦斯膨胀的强度、巷道断面及巷道壁面的摩擦力和局部阻力等因素有关;冲击产生的高压瓦斯气流是造成巷道内大量人员窒息伤亡的主要诱因;突出能量瞬间释放没有补给,冲击波及瓦斯气流会在巷道阻力等因素作用下迅速衰减。     

膨胀聚苯乙烯热分解动力学分析和寿命预测

针对既有聚苯乙烯泡沫类外墙外保温系统的防火问题,在空气和氮气气氛下对非阻燃和阻燃型膨胀聚苯乙烯泡沫进行了热重分析。样品由10℃/min、20℃/min、40℃/min和50℃/min四个升温速率从室温加热至800℃。热分解动力学参数由Flynn-Wall-Ozawa(FWO)等转化率方法和多参数非线性回归方法(multivariate non-linear re-gression method)计算,结果表明六溴环十二烷(HBCD)阻燃剂可一定程度上提高EPS的热稳定性。EPS在空气和氮气气氛下热解可认为是单步反应。非阻燃聚苯乙烯泡沫在空气和氮气气氛下的热解过程可由自催化n阶反应机理描述。阻燃EPS在空气气氛下的热解机理为自催化n阶反应,在氮气气氛下则为n阶反应机理。基于动力学参数和反应机理,对聚苯乙烯泡沫在不同温度下的寿命进行了预测。     

Alternative method to prevent thermal runaway in case of error on operating conditions continuous reactor

Thermal runaway was studied in a continuous tubular pilot reactor under steady-state regime. Different accident scenarii were conducted by making some errors on reactant concentrations and/or temperature feed. To prevent thermal runaway, control by direct contact by solvent injection was used at different reactor locations. This injection allowed controlling the maximum reaction temperature. A simplified analytical method to estimate the maximum reaction temperature along the reactor was used.Benefit of this control method was the diminution of computational time. Furthermore, by injecting solvent to control maximum reaction temperature, there is no need to shut down the unit. The control method was validated experimentally.     

基于层次分析法的热塑性聚氨酯及其纳米复合材料火灾危险性综合评价

聚合物的火灾危险性与热、烟、毒的释放密切相关,但采用不同指标对材料的评价结果不一致。以纳米级蒙脱土(MMT)、氢氧化铝(ATH)和聚磷酸铵(APP)为添加剂的热塑性聚氨酯(TPU)纳米复合材料为研究对象,选取其在静态管式炉、稳态管式炉和锥形量热仪中的相关实验数据,以HCN总浓度作为特殊毒性危害指标,CO和CO_2浓度为一般毒性危害指标,以热释放速率峰值、平均热释放速率、总热释放量为热危害指标,以产烟速率峰值、生烟总量为烟危害指标。进一步细分了火灾烟气中不同毒性气体对于火灾风险的影响,并运用层次分析法计算指标权重,综合评价了热塑性聚氨酯及其复合材料的火灾危险性。结果表明,当添加量为6 wt%聚磷酸铵、3 wt%氢氧化铝与3 wt%蒙脱土时,此时复合材料的火灾危险最低,证明了综合热、烟、毒三个层次来降低聚合物材料火灾危险性是可行的。     

开敞空间可燃气云爆炸冲击波超压及灾害动力响应研究评述

为了进一步梳理和分析开敞空间可燃云爆炸冲击波超压传播规律及灾害动力响应方面的各项研究成果,推进可燃气体爆炸安全防控,减少人员伤亡和经济损失。在分析现有研究的基础上,总结开敞空间可燃气云爆炸冲击波超压传播规律及灾害动力响应研究等方面存在的不足,提出开敞空间多元混合气体爆炸冲击波超压传播规律研究、多影响参数下可燃气云爆炸冲击波超压传播规律定量分析、基于可燃气云爆炸冲击波超压作用下的承载体动力响应等未来研究的关键技术问题。     

Ignition temperatures of dust layers and bulk storages in hot environments

In many industrial installations, particulate solids (cereals, agri-food products, coal, plants, etc.) are stored or processed. Self-heating of these products, which can lead to fires and explosions, can occur in a variety of situations. Examples include large storage at room temperature, formation of a layer on a hot surface, layer deposited on a surface – insulating or conductive – in a hot environment or even storage of product exposed to heating on one side.The main parameters that determine the occurrence of self-heating are the size of the container, the temperature, the residence time and the characteristics of the product. Depending on the type of situation encountered and these implementation conditions, the analysis of self-heating risks must be based on specific models and/or parameters.This paper presents the different variants and combinations of the theoretical model from the theory of thermal runaway to represent self-heating, taking into account in particular the symmetry or asymmetry of heating, reagent consumption and boundary conditions. It also discusses their adaptation to the previous identified industrial situations.Nine products were chosen to be representative of those used in the different considered industrial situations. They were subjected to self-heating basket tests in isothermal ovens in order to determine the parameters for applying the described theoretical models. These results were compared with the results of self-heating tests in layers of different thicknesses in a hot environment, on an insulating or conductive plate, using a specially developed test protocol, as well as with the results of standardized tests of minimum ignition temperature in 5 mm layers.This led to the proposal of the most appropriate theoretical model to represent the self-heating phenomenon for each of the four identified industrial situations.This analysis can promote better design of industrial equipment and production conditions (temperatures, volumes or product flows …) in order to prevent fires and explosions.