连续搅拌釜式反应器放热反应失控事故预防

运用敏感度方法研究连续搅拌釜式反应器(CSTR)放热反应的参数敏感性行为及规律,探讨CSTR反应器的安全操作区域和敏感操作区域.研究发现:无因次活化能小于4的反应系统,其整个操作参数空间都是安全的;无因次活化能大于4的反应系统,只有选择无因次活化能小于其临界值,反应系统才能安全、稳定地运行;临界无因次反应热的值与无因次丹克莱尔数和无因次反应热有关;丹克莱尔数和无因次反应热越大,则临界无因次反应热越小,安全操作区域也越小.     

Causes and consequences of thermal runaway incidents—Will they ever be avoided?

A study of runaway incidents involving thermal chemical reactions in the UK over the past 25 years (1988–2013) has been carried out. The objective of this study is to determine possible causes of thermal runaway incidents. A statistical analysis of the underlying problems that led to thermal runaway incidents has been provided. A comparison of the current study on thermal runaway incidents with those identified prior to 1988 has been carried out. This study clearly shows that lessons have not been learnt from thermal runaway incidents caused by operator errors, management failures and lack of organised operating procedures. These factors have been the possible causes of about 77% of all the thermal runaway incidents analysed in this study. The number of fatalities and injuries as a result of thermal runaway incidents has increased by ∼325% and ∼279%, respectively, in the last 25 years even though the number of incidents was significantly less. On the basis of this analysis, several recommendations have been proposed that could help to minimise the risks associated with any thermal runaway incidents in the future.     

Early detection and identification of dangerous states in chemical plants using neural networks

The suitability of pattern recognition for safety diagnosis of chemical plants will be discussed. Therefore, experiments in a miniplant and with a process simulator are carried out. The process characteristics are treated with different recognition methods and classified with the aid of expert know how. Afterwards, the trained system can be used for process diagnosis. The capability of neural networks for this problem could be shown.     

An incident investigation on an unexpected loss of containment and damage to PHI-TEC II during acrylonitrile runaway tests

This article investigates a laboratory incident that occurred during the analysis of a thermal runaway reaction of acrylonitrile monomer. This failure, which was attributed to an human error, resulted in financial losses and corresponding unexpected results. The incident not only damaged the interior of the vessel and other instrument parts, but also exposed the researchers to considerable danger, necessitating their escape from the laboratory. The failure characteristics are discussed, and countermeasures are developed to prevent such a type of incident from reoccurring.     

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.     

Thermal risk in batch reactors: Theoretical framework for runaway and accident

Thermal safety and risk of accidents are still challenging topics in the case of batch reactors carrying exothermic reactions. In the present paper, the authors develop an integrated framework focusing on defining the governing parameters for the thermal runaway and evaluating the subsequent risk of accident. A relevant set of criteria are identified in order to find the prior conditions for a thermal runaway: failure of the cooling system, critical temperature threshold, successive derivatives of the temperature (first and second namely) vs. time and no detection in due time (reaction time) of the runaway initiation. For illustrative purposes, the synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA) is considered as case study. The critical and threshold values for the runaway accident are identified for selected sets of input data. Under the conditional probability of prior cooling system failure, Monte Carlo simulations are performed in order to estimate the risk of thermal runaway accident in batch reactors. It becomes then possible to predict the ratio of reactors, within an industrial plant, potentially subject to thermal runaway accident.     

过氧化苯甲酰合成工艺热危险性分析

采用RC1e反应量热仪对过氧化苯甲酰(BPO)合成工艺危险性进行研究,测试不同Na OH溶液初始浓度(1.96 mol/L、3.93 mol/L、7.14 mol/L)下反应的放热历程,获得BPO合成反应过程中的热危险性参数,并采用PHI-TECⅡ绝热加速量热仪对产物进行热稳定性分析,最后评估该反应热风险。结果表明,Na OH浓度为7.14 mol/L时,反应初期放热速率慢,热累积度大,后期反应剧烈,绝热温升(ΔTad)及热失控时工艺反应达到的最高温度(MTSR)最大。热稳定性试验表明,合成的粗产物BPO初始分解温度、活化能、指前因子、最大放热速率到达时间为24 h时的对应温度(TD24)均低于纯BPO。利用合成粗产物BPO的TD24对反应进行危险度评估,该工艺热危险性等级均为5级,工艺危险性大。     

基于VSP2的引发剂质量分数对醋酸乙烯聚合反应失控特性及安全泄放设计影响研究

为了解决醋酸乙烯聚合反应失控所引起的超压问题,通过VSP2绝热量热仪研究了醋酸乙烯聚合反应的失控特性,并通过Leung's法对某醋酸乙烯聚合反应器的安全泄放面积进行了计算;然后,在其他条件不变的情况下,研究引发剂质量分数对失控特性和泄放面积的影响,结果表明,引发剂质量分数对反应总放热量的影响不大,体系绝热温升为105~115℃;但引发剂质量分数越大,失控反应的最大温升速率和最大压升速率越大。这是因为引发剂质量分数越大,在相同泄放压力和最大累积压力下,单位质量反应物的放热速率就越大,也就需要更大的泄放面积;最后,引入无量纲数W~*、G~*和A~*,拟合出它们与引发剂质量分数X*的关系式,结果表明,在研究范围内所需安全泄放面积随引发剂质量分数线性增大。     

高温环境下18650型锂离子电池热失控过程的数值分析

采用ANSYS对高温条件下铜棒代替锂离子电池的空白试验进行数值模拟,获得拟合的陶瓷化纤棉毯的比热容;然后对18650型锂离子电池的热响应进行模拟,通过模拟结果与试验数据的比较分析,获得锂离子电池内部的反应放热量;最后应用得出的陶瓷化纤棉毯比热容和化学反应热对高温环境下18650型锂离子电池的热失控进行模拟,研究18650型锂离子电池热失控的变化规律.结果表明:20W加热条件下,锂离子电池的放热反应热为30 kJ;锂离子电池在加热1 287 s后发生热失控,热失控持续113 s后锂离子电池温度达最高,之后开始缓慢减小;锂离子电池热失控温度为500 K,热失控前温度几乎是线性增加,之后热失控导致温度迅速增加(呈指数倍增长);锂离子电池保温材料陶瓷化纤棉毯的温度变化是非线性的.     

模组箱体空间内磷酸铁锂电池热失控及其传播行为研究

为了探究储能用锂离子电池在真实应用场景下的热失控及其传播行为特征,选用86 Ah方形磷酸铁锂(LiFePO₄)电池,对其在热滥用触发方式下的热失控行为及模组箱体空间与开放空间中的传播行为规律进行了实验研究。单体实验结果表明,电池热失控产生的高温烟气会导致模组箱体内沿高度方向出现明显温度梯度,模组底部与顶部温度测点的最大温差达118.4℃。传播实验结果表明,模组箱体空间内热失控电池通过产气及喷出高温电解液向其他电池传热,在热失控电池影响下,模组箱体空间内3块电池上表面所能达到的最高温度均高于开放空间实验12℃～150℃,模组空间内热失控电池向同侧两块电池的传热量高于开放空间实验225 kJ和44.4 kJ。但箱体环境中有限的氧气供给会减缓电池在热失控时的内部放热反应进程,模组箱体空间实验中电池热失控峰值温度较开放空间实验低33℃～145℃,并且模组箱体空间实验中热失控完全传播所用时间较开放空间实验滞后213 s。研究结果对于锂离子电池模组的安全设计和热失控传播阻隔具有一定的参考价值与指导意义。     

传热系数随温度线性变化的亚临界化学放热系统热安全性分析

引入化学放热系统平衡域和热安全裕度的概念与定义来评价具有潜在危险性的亚临界化学放热系统的安全性问题.分析了均温系统下传热系数随温度呈线性变化的系统的平衡域,进而提出了热安全裕度值L的定量计算并阐明了利用曲线拟合的方法计算L值.使用了Matlab软件绘出系统在3个约束参数约束的条件下ψ-ε-a的三维图形与给定系统(a为常数)时ψ-ε的二维图形,并在结合图形的基础上引入实例来评价该系统的热安全性.