硫酸羟胺的自加速分解温度和稳定性研究

通过快速筛选热分析试验对硫酸羟胺热危险性进行定性分析,对其热分解过程进行初步研究,获得温度、压力变化规律;再运用C80微量热仪对硫酸羟胺进行深入分析,得到硫酸羟胺的化学反应动力学参数,根据Semenov模型计算其自加速分解温度（SADT）。试验结果表明：由RSD初步筛选试验得到硫酸羟胺在164．2℃时即发生分解放热;用C80法得到硫酸羟胺的起始热分解温度为137．1℃,并计算了该物质在3种典型包装下的自加速分解温度。由SADT得到储存、运输过程中硫酸羟胺的控制温度,从而为减少硫酸羟胺事故的发生提供必要的参考数据。     

4种硝酸酯热安定性的绝热试验研究

利用绝热加速量热仪(ARC)对硝酸正丙酯(NPN)、硝酸异丙酯(IPN)、太根(TEGDN)、敌根(DEGDN)4种硝酸酯的热稳定性进行了绝热试验研究,得到绝热放热曲线和热分解特征参数。分析了4种物质分解过程的特点,对测试结果进行了修正。计算得到动力学参数和自加速分解温度SADT,以此作为评估热安定性的判据。结果表明,4种硝酸酯在外界热作用下容易发生分解,反应速度较快,伴随明显的热效应和压力效应。4种硝酸酯的热安定性由好到差排序为:IPN、NPN、TEGDN、DEGDN。     

Study on the early stage of runaway reaction using Dewar vessels

In this paper, compared with a UN cylindrical 500 mL Dewar (H.4 in the UN tests), a spherical 1 L Dewar vessel was used to study the early stages of runaway reactions of several liquid and solid samples, including three organic peroxides and a reactive material. The samples were filled in the vessels and the temperature profiles versus times at different positions of the samples were measured. As a result, the minimum temperatures, defined as the SADT, were averagely 10 K lower than those measured in the cylindrical Dewar vessels. At the same time, the temperature profiles of solids in the spherical Dewars tended to be homogeneous. The heat transfer coefficient of a spherical Dewar is only 0.18 W/K/m, one-eighth of a conventional cylindrical Dewar vessel. Meanwhile it has a low phi factor. These factors are essential to simulate low heat loss bulk conditions in the equilibrium process and at the early stage of a runaway reaction. To characterize the ability of the adiabaticity of a storage vessel, it can be seen that a spherical Dewar could simulate the plant process having critical storage size of a reactive-material, r₀, approximately 0.6 m. It is recommended that such a technique is used to investigate the SADT of an unstable material in larger scale packaging or a material with very weak heat release in industry.     

Micro calorimeter study on the thermal stability of lithium-ion battery electrolytes

With the extensive applications of lithium-ion batteries, many batteries explosion accidents were reported. The thermal stability of lithium-ion battery electrolyte could substantially affect the safety of lithium-ion battery. The C80 micro calorimeter was used to study the thermal stability of several commonly used organic solvents and electrolytes. The samples were heated in argon atmosphere and air atmosphere, respectively. The chemical reaction kinetics was supposed to fit by an Arrhenius law, then the self-accelerating decomposition temperature was calculated. It is found that most of the samples are stable in argon atmosphere while decomposing in air atmosphere, and the single organic solvent is more stable than the electrolyte generally.     

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.     

醇对过氧化氢热危险性的影响研究

为了防止过氧化氢在生产、储存、运输和使用过程中因为混入杂质导致火灾爆炸事故,利用绝热加速量热仪对过氧化氢及其掺杂醇类物质后的放热分解过程进行了试验研究.结果表明,醇使过氧化氢的初始放热分解温度、活化能和SADT均降低,热危险性增加;正丙醇对过氧化氢热分解的促进作用大于无水甲醇和无水乙醇.     

自反应性化学物质的热危险性评价方法

笔者进行的研究工作 ,给出了利用C80微量量热仪所测得的自反应性化学物质的热流速曲线 ,从而求解该物质的化学反应动力学参数 ,以及在Semenov模型下求解其自加速分解温度SADT(Self AcceleratingDecompositionTemperature)的方法 ,并将一些有机过氧化物、氧化剂和可燃剂的混合物的自加速分解温度的推算结果与实测值进行了比较。实验证明 ,该推算方法结论准确 ,是一种安全、简便、实用的反应性化学物质热危险性的评价方法     

Investigation of an accidental explosion in a nitromethane rectification process

An explosion that occurred during a nitromethane rectification process is investigated. Experiments were performed in an effort to elucidate the cause of the explosion. All test samples analyzed, including reaction product, crude product, 99% pure product and raffinate, were collected from the accident site. Gas chromatography was used to analyze the components of the samples, thermal analysis determined the exothermic character of the samples and the sample evaporating experiment recorded the reaction phenomena occurring at low liquid level. Based on the experimental results, the excess heat released by the decomposition of overheated raffinate is pinpointed as the root cause of the explosion.     

Decomposition effects on the mass burning rate of organic peroxide pool fires

The mass burning rate of pool fires of organic peroxides do not vary appreciably with the pool size as have been observed for the hydrocarbons. Instead the decomposition temperature largely controls the same. The dependence of mass burning rate on the decomposition temperatures namely self-accelerating decomposition temperature (SADT) and extrapolated onset temperature measured by differential scanning calorimetry (DSC) for organic peroxide pool fires are identified and correlations are developed.