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.     

二溴海因危险性试验研究

为评价二溴海因(简称DBDMH)在使用、储运过程中的危险性,采用75℃热稳定性试验对二溴海因在高热条件下的稳定性进行了研究,采用C600微量热法测试了二溴海因的放热起始温度、分解热,并依据《联合国关于危险货物运输的建议书-试验和标准手册》对其爆炸性进行了筛选,通过固体氧化性试验和家兔皮肤刺激性/腐蚀性试验分别对二溴海因的氧化性和皮肤刺激性进行了测试。结果表明:二溴海因在75℃热稳定性试验过程中没有出现着火或爆炸,未出现自加热迹象,不属于太不稳定不能运输的物质;其分解反应只有一步,起始反应温度大约为157℃,分解热为384.8J/g,不属于爆炸品;二溴海因具有氧化性,根据《联合国关于危险货物运输的建议书-规章范本》其包装级别为Ⅱ级;在家兔皮肤刺激性/腐蚀性试验中未见不可逆损伤,对皮肤具有强刺激性。     

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。     

亚硝酸乙酯分解危险性研究

为了了解亚硝酸乙酯的分解危险性,通过微量热仪研究并确定了亚硝酸乙酯的分解热、起始分解温度、峰值温度等基础数据;通过爆轰管研究并确定了不同温度下亚硝酸乙酯的分解临界压力,对比了氮气和一氧化碳的稀释效果。研究表明:亚硝酸乙酯分解临界压力较低易发生分解,亚硝酸乙酯的分解会降低偶联反应的选择性,甚至造成装置的非计划停车。因此,为避免亚硝酸乙酯发生分解爆炸,建议严格按照亚硝酸乙酯分解物性操作。     

Thermal risk analysis of cumene hydroperoxide in the presence of alkaline catalysts

Many studies have been performed to clarify the basic thermal runaway hazards and kinetics of cumene hydroperoxide (CHP) decomposition. However, materials that are incompatible with CHP have not been clearly identified. Alkaline solutions have been used as a catalyst to form dimethylphenyl carbinol (DMPC) and dicumyl peroxide (DCPO); however, these solutions also affect the reaction and storage temperature of CHP. In this study, thermal calorimeters, differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2), were used to compare the effects of various bases on the decomposition of CHP in cumene. Specifically, the exothermic onset temperature, change in pressure over time, self-heating rate and heat of decomposition were evaluated. Moreover, to appraise the degree of hazard associated with the use of CHP, the compatibility of CHP with various substances was analyzed, and a risk matrix for thermal runaway reactions was obtained. The results of the present study could be used to design safety procedures for the production of CHP and its derivatives.     

Numerical analysis on the hot spot in reactive chemical storage

In an exothermic reactive chemical storage tank, a thermal explosion can occur when the heat generation within the storage tank is greater than the heat removal from the storage tank. In a solid system, the existence of an inflection point in the temperature versus time curve is often used as a criterion for thermal explosion. In this study the applicability of this criterion to fluid storage is examined by investigating the hot spot in the system. Transient natural convection of an exothermically reactive fluid in a vertical, cylindrical storage tank with isothermal walls is investigated numerically. The axisymmetric 2-D Navier–Stokes equations governing the flow fields are reduced by introducing the stream function–vorticity formulation and solved by the alternating-direction-implicit (ADI) technique. The reactive heat sources are represented by a zeroth-order rate expression with an Arrhenius-type rate constant. It is found that the hot spot is no longer located in the center of the tank due to the buoyancy effect. In a particular range of Rayleigh number and Frank-Kamenetskii number, the hot spot is found to move periodically. A stable steady regime, stable oscillatory regime and thermal explosion regime can be specified based on the dependence of the critical Frank-Kamenetskii number on the Rayleigh number. In the stable oscillatory regime multiple inflections in temperature versus time are found. Therefore, the existing criterion, which defines thermal explosion by the appearance of an inflection in the temperature versus time curve, is no longer applicable in reactive fluid systems. The results of nonconvective systems do, however, provide a preliminary and conservative estimate for thermal explosion of a reactive storage tank.     

Research on thermal decomposition characteristics of H foaming agent with different moisture contents

N, N-Dinitroso pentamethylene tetramine, also known as H foaming agent, is a self-reactive chemical substance commonly used in the rubber industry. Decomposition, explosion and combustion may be caused by the presence of fire or high temperature. As a high-risk chemical that is strictly regulated in China, H foaming agent has ever triggered multiple accidents. During the study of the decomposition thermal process of H foaming agent, it was found that the presence of moisture content at different levels had a significant effect on its thermal stability. The thermal characteristics of H foaming agent under different moisture contents was studied through the test means such as adiabatic calorimetry and high-pressure differential scanning calorimetry. Through isothermal calorimetry experiment, it was found that the decomposition of H foaming agent had obvious auto-catalytic characteristics. In the moisture content within the range of 0–40%, with the increase of moisture content, the initial exothermic temperature T_onset of the mixture system of H foaming agent and water decreased, while the time from initial heat release to rapid temperature rise of the reaction system (induction period) was gradually prolonged, and the temperature increment of the reaction system was increased gradually. As the proportion of moisture content in the system increased, the adiabatic temperature rise ΔT_ad of the mixture system of H foaming agent and water gradually decreased, meanwhile the time to maximum rate under adiabatic condition (TMR_ad) gradually decreased. The research results have guiding significance for finding the reasonable moisture content of H foaming agent in the drying process and determining the upper temperature limit during storage and transportation.     

乳化炸药高压热分解试验研究

为分析压力在乳化炸药泵送事故中的影响,运用高压加速量热仪对乳化炸药、硝酸铵和含有10%水分的硝酸铵样品热分解特性进行研究。结果表明:压力对于乳化炸药,硝酸铵和含有10%水分硝酸铵样品的热分解有着显著的影响,压力条件下虽然起始分解温度基本没有变化,但是样品反应速率有了显著的升高,导致放热量增大。水分的存在阻碍硝酸铵的热分解,在乳化炸药配方中适当增加水份含量可以提高乳化炸药生产安全性。分析认为相比于温度,压力对于泵送事故的影响更为关键。     

硝酸异辛酯热安定性的实验研究

使用加速量热仪(ARC)研究硝酸异辛酯(EHN)的热分解,得到热分解温度随时间的变化曲线,自放热速率、分解压力随温度的变化曲线以及分解压力随升温速率的变化曲线。分析在绝热条件下硝酸异辛酯的热分解反应动力学和热分解过程,计算表观活化能、指前因子和反应热等参数。根据绝热热分解的起始温度和反应热数据,给出硝酸异辛酯在反应危险度等级中的分类,并计算在75℃时的反应风险指数。     

Ammonium nitrate thermal decomposition with additives

Runaway reactions present a potentially serious threat to the chemical process industry and the community; such reactions occur time and time again often with devastating consequences. The main objective of this research is to study the root causes associated with ammonium nitrate (AN) explosions during storage. The research focuses on AN fertilizers and studies the effects of different types of fertilizer compatible additives on AN thermal decomposition. Reactive Systems Screening Tool (RSST) has been used for reactivity evaluation and to better understand the mechanisms that result in explosion hazards. The results obtained from this tool have been reported in terms of parameters such as “onset” temperature, rate of temperature and pressure rise and maximum temperature. The runaway behavior of AN has been studied as a solid and solution in water. The effect of additives such as sodium sulfate (Na₂SO₄) and potassium chloride (KCl) has also been studied. Multiple tests have been conducted to determine the characteristics of AN decomposition accurately. The results show that the presence of sodium sulfate can increase the “onset” temperature of AN decomposition thus acting as AN thermal decomposition inhibitor, while potassium chloride tends to decrease the “onset” temperature thus acting as AN thermal decomposition promoter.     

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.     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

壳体厚度对传爆药慢速烤燃响应的研究

针对传爆药在制造、存贮、运输及实战环境中可能会遭受意外的热刺激,本文通过壳体厚度对传爆药慢速烤燃响应特性的影响的实验研究,来检测弹药对意外刺激的敏感程度和发生反应时的剧烈程度,并对实验结果进行了分析。实验以钝化RDX为主装药,以45#钢为壳体,利用自行设计的慢速烤燃试验系统对其进行试验。结果表明：在相同装药条件下,随着壳体厚度的增加,单位时间内传热量减少,体系升温速率减慢,炸药的烤燃时间随之增加,热爆炸延滞期增长;同时,随着壳体厚度的增加传爆药发生慢速烤燃反应的温度升高,热敏感程度降低,热安定性也随之提高。另外,在相同装药条件下,壳体厚度对慢速烤燃响应的剧烈性也有很大得影响。烤燃反应的剧烈程度随着壳体厚度的增大而减小。     

Effect of flame propagation regime on pressure evolution of nano and micron PMMA dust explosions

Experiments using an open space dust explosion apparatus and a standard 20 L explosion apparatus on nano and micron polymethyl methacrylate dust explosions were conducted to reveal the differences in flame and pressure evolutions. Then the effect of combustion and flame propagation regimes on the explosion overpressure characteristics was discussed. The results showed that the flame propagation behavior, flame temperature distribution and ion current distribution all demonstrated the different flame structures for nano and micron dust explosions. The combustion and flame propagation of 100 nm and 30 μm PMMA dust clouds were mainly controlled by the heat transfer efficiency between the particles and external heat sources. Compared with the cluster diffusion dominant combustion of 30 μm dust flame, the premixed-gas dominant combustion of 100 nm dust flame determined a quicker pyrolysis and combustion reaction rate, a faster flame propagation velocity, a stronger combustion reaction intensity, a quicker heat release rate and a higher amount of released reaction heat, which resulted in an earlier pressure rise, a larger maximum overpressure and a higher explosion hazard class. The complex combustion and propagation regime of agglomerated particles strongly influenced the nano flame propagation and explosion pressure evolution characteristics, and limited the maximum overpressure.     

Thermal safety assessment for solid organic peroxides

The thermal hazards of dicumyl peroxide (DCP) and benzoyl peroxide (BPO), self-reactive chemicals are identified and characterized using high-pressuredifferential scanning calorimeter, and simultaneous thermogravimetric analyzer, a C80 micro-calorimeter is used. The apparent exothermic onset temperature of DCP is found to be between the range of 112–122 °C for different heating rates in DSC tests. There are two coupled peaks of BPO around 105 °C at both the heating rates of 4.0 and 8.0 °C/min while no endothermic peak showed at lower heating rates. Furthermore, another endothermic peak appears immediately after the exothermic peak at about 211 °C of DCP under high-pressure conditions. For BPO, the endothermic peak before the exothermic peak disappears as the pressure increases to 1.0 and 1.5 MPa. The average values of apparent activation energy calculated by Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods during the conversion rate between 15 and 75% of DCP are 80.69 and 74.05 kJ/mol, and that of BPO are 119.96 and 112.93 kJ/mol, respectively. According to the isothermal tests, the thermal decomposition of DCP behaviors is an n-th order reaction while BPO conforms to the laws of autocatalytic reaction.     

氢化锆对太安空中爆炸及热安全性能影响的研究*

为研究氢化锆对太安空中爆炸及热安全性的影响,分别对氢化锆/太安混合炸药（ZrH2/PETN）和太安单质炸药开展空中爆炸实验和热分析实验,得到相应的压力时程曲线和TG、DSC热分解曲线。研究结果表明:氢化锆的添加会降低混合炸药的压力峰值,但能显著提高其正相作用时间,氢化锆含量为10%、20%时,氢化锆/太安混合炸药的正相冲量与太安相当。同时与纯太安相比,氢化锆/太安混合组分的最大质量损失速率下降约51.07%~60.04%,热爆炸临界温度及自加速分解温度最大提高约8.78%和9.93%,但混合组分中氢化锆的加入并未改变太安的热分解机理,说明氢化锆作为惰性热稀释剂能够改善其热安全性。     

过氧化苯甲酸叔丁酯热危险性实验研究

为了研究TBPB的热危险性,采用液体自燃点测试仪研究TBPB自燃点随浓度的变化规律,应用快速筛选量热仪研究不同升温速率下TBPB的热分解,同时利用差示扫描量热仪研究TBPB热流-温度变化规律。研究结果表明:当TBPB浓度为0.83 g/L时,自燃温度达到最低值125.1 ℃,浓度是影响其自燃温度的重要指标;随升温速率升高,初始分解温度逐渐升高,可见升温速率越高,TBPB分解的初始温度越高,当环境温度未达到初始分解温度时,相对较安全;TBPB最低起始反应温度为95.4 ℃,平均放热量为893.28 J/g,运用Kissinger,Ozawa 这2种方法得出E1=84 063.2 J/mol,E2=86 442.3 J/mol,指前因子为1.69×109,反应级数为0.92。其放热量较大,起始反应温度较低,热量无法及时移出时,极易发生燃烧爆炸事故。     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

Explosion properties of highly concentrated ozone gas

The explosive self-decomposition characteristics of gaseous ozone with a concentration of up to almost 100 vol% were quantitatively investigated using a closed system with an electric spark device. The lower self-decomposition (explosion) limit for ozone diluted with oxygen at room temperature and atmospheric pressure was 10–11 vol%, and so ozone at more than 10–11 vol% will lead to an explosive chain decomposition reaction leading to its complete conversion to oxygen in a vessel. The lower explosion limit shifts to a higher concentration with a decrease in pressure. The limit was about 80 vol% under a reduced pressure of 10 Torr. We also confirmed that explosion trigger energy (minimum ignition energy) is strongly dependent on ozone concentration and pressure. For example, the minimum trigger energy for 15 vol% ozone at a pressure of 76 Torr (about 220 mJ) was more than 20-fold that at atmospheric pressure (about 10 mJ), and that for 13 vol% ozone (about 580 mJ) was approximately 30 times higher than that for 20 vol% (about 20 mJ) at the same pressure of 76 Torr. Moreover, the physical characteristics of the trigger energy sources (e.g. spark gap and electrode tip angle) leading to the decomposition (explosion) of ozone were investigated under various conditions.     

杂质对硝酸铵水溶液临界爆炸温度的影响

利用自制装置对含杂质的硝酸铵水溶液临界爆炸温度进行测试研究.结果表明,Cl-单独作用在一定程度上抑制硝酸铵溶液的热分解,提高了其临界爆炸温度;pH值一定时,随着Cl-浓度的增大,硝酸铵水溶液的临界爆炸温度呈指数形式降低;Cl-浓度一定时,pH值越小,硝酸铵水溶液的临界爆炸温度越低;油脂会降低硝酸铵溶液的热稳定性.该结果...