Thermal runaway reaction for highly exothermic material in safe storage temperature

Highly exothermic materials have caused many serious accidents involving storage and transportation, due to being thermally reactive. The safe storage and management of these materials is still a critical problem in many countries. Our aim was to study the thermal hazard of thermal reactive materials, such as a propellant, by employing differential scanning calorimetry (DSC) non-isothermal tests and isothermal tests, and then comparing the kinetic parameters by isothermal and non-isothermal of kinetics. The chosen approach was to obtain reliable thermal decomposition by a safe and effective method, which acquired the kinetic and safety parameters of storage conditions that could be applied as highly exothermic materials' reduction of loss prevention and energy potential for safer design during storage transport and processing operations.     

两种老化温度对某型双基推进剂的热分解性能的影响

目的探索某型双基推进剂在85℃和95℃条件下的热分解性能随老化时间的变化趋势。方法采用恒温加速老化试验,并对老化不同时间的样品进行热重分析(TG)和差示扫描(DSC)试验。结果计算了其两种老化温度条件下的动力学参数。结论某型双基推进剂性能良好,与老化时间相比,老化温度对其性能影响较大。     

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.     

有机溶剂对过氧化环己酮热危险性的减敏效果评价

在纯过氧化环己酮(CYHPO)储运中常添加减敏剂,以降低其热危险性。为了对比评价减敏性能,采用绝热加速量热仪测试了纯CYHPO及加入等质量邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二辛酯(DOP)、正己酸(HAA)和环己醇(CCH)后的热危险参数,并计算了上述5种样品的反应动力学常数和绝热校正数据,建立了包括初始放热温度T0和绝热反应加速度SARC的减敏效果判据,对4种减敏剂的热危险性减敏效果进行了评价。结果表明,DOP对CYHPO热危险性的减敏效果最好。     

绝热加速量热仪在化工生产热危险性评价中的应用

本文介绍了一种新型热危险性分析仪器--绝热加速量热仪的设计原理和内部结构,运行模式以及所能获得的温度、压力和最大温升速率时间等数据类型.并通过阐述其在化学动力学研究、自加速分解温度的计算、化学工艺安全性分析和化学工艺过程开发以及热爆炸事故原因调查等方面的应用,指出了绝热加速量热仪在化工生产危险评价方面的特点和优势.     

Incident investigation of mono-nitro toluene still explosion

At one of the nitro-toluene facilities, an o-nitro toluene still was in standby mode. During the standby mode feed to the still had been stopped, the column was not de-inventoried, steam flow to the reboiler was not shut off and the condenser was on total reflux. After 22 days of standby mode, steam was shut off for 5 days for annual plant maintenance. Eight days after the re-start of steam, the still exploded, hurling debris as far as one mile. The internal packing was expelled from the column and landed on the ground burning. The incident was investigated to establish the contributing factors leading to explosion. Accelerating Rate Calorimetery was extensively used to determine the onset temperature for exothermic activity in the presence/absence of a number of materials to establish the underlying cause of the accident. It was found that foulant collected in the column over a period of years accelerated the ’runaway reaction’.     

ZR-KVV电缆排布数量对燃烧特性影响的实验研究

电缆在实际布置情况下通常是多根成束装配,而电缆的排布数量对运行安全性有很大影响,研究电缆的排布数量对燃烧特性的影响具有重要意义。使用锥形量热仪,对ZR-KVV电缆以不同数量排布,研究分析其质量损失速率、热释放速率等主要燃烧性能参数。实验结果表明,当电缆受到固定火源的辐射热流影响时,质量损失速率峰值和热释放速率峰值随着水平布置电缆数量的增加呈指数递增;随着外部辐射热流强度的增强,质量损失速率峰值和热释放速率峰值增加,总热释放速率则减小。     

加速量热仪在物质热稳定性研究中的应用

加速量热仪（ARC）是一种基于绝热原理设计的热分析仪器,与其它热分析仪器相比,加速量热仪可以测量克量级的固体或高闪点液体样品,具有测试样品最大,敏感度高等特点,并能够实时记录样品放热反应过程中的温度和压力变化,以过氧化氢叔丁基为例说明加速量热仪测试结果在研究物质质变热稳定性方面的应用,得到了过氧化氢叔丁基放热分解反应的温度－时间和压力－时间关系曲线以及升温速度和压力随温度变化的曲线,通过计算和分析得到了反应系统升压速率随压力的变化曲线,计算出了过氧化氢叔丁基分解反应的动力学参数表观活化能Ea和指前因子A。     

Women and children last: An essay on sex discrimination in disasters

In general, little attention has been given to differential survival between the sexes in disasters. Consideration of physiological differences between males and females would suggest that, all things being equal, morbidity and mortality after disaster, particularly where food shortage is involved, should indicate an excess male mortality. Such statistics as exist in disasters, as in chronic underdevelopment, show that it is females and especially girl children who are at highest risk. The basis of this lies in sex discrimination which is implicit in most social systems.     

Electrochemical analysis of endosulfan using a C18-modified carbon-paste electrode

Successful applications of different analytical procedures to determine quantitatively endosulfan and its metabolites in aqueous media can be found in recent literature. Fundamentally, they have made use of solid-phase extraction (SPE) and gas (GC) or liquid chromatography (LC), sometimes coupled to mass spectrometry (MS). In this paper, a new and alternative methodology to determine quantitatively endosulfan in aqueous media is reported. A C18-modified carbon-paste electrode has been used to determine voltammetrically endosulfan, despite its unfavourable electrochemical properties and behaviour. The methodology proposed is based on the decrease experienced by the peak intensity corresponding to voltammetric signals of Cu(II) when successive and constant additions of endosulfan are carried out. This decrease is directly proportional to the concentration of endosulfan what allows to perform an indirect quantification of the pesticide. The detection limit obtained is 40 ng l⁻¹, this value being under the limits specified by European norms and EPA reports.