化学放热系统热爆炸潜在危险性评价

讨论化学放热系统的热稳定性和临界条件,用化学反应物无消耗的假设推导化学放热系统热失控(热爆炸)时的动力学参数临界值,得到热失控的判据、临界点火温度和熄火温度。提出用系统安全指数概念来评价放热反应系统发生热爆炸的潜在危险性,分析化学放热系统的平衡域。用硝酸甲酯分解爆炸实例,说明如何利用安全指数对具有热爆炸可能性的系统的潜在危险性进行定量评价,其预测结果与实验结果一致。     

Thermal runaway criterion for chemical reaction systems: A modified divergence method

The chemical reaction in certain range of operating conditions may exhibit parametric sensitivity where small changes in one or more of the input parameters lead to changes in the output variables (eg. reaction temperature). The sharp rise of the reaction temperature is a critical behavior that may lead to runaway conditions. Thus, it is of vital importance to determine the critical operating parameters consisting of the parametric sensitivity region under the consideration of intrinsic safety. In this paper, a modified divergence criterion is proposed based on the trace of Jacobian matrix at the maximum temperature. The nonlinear differential equations describing the dynamic behavior of the chemical reaction is linearized locally in the vicinity of the equilibrium point by the small perturbation analysis. The relationship between the perturbation equation and parametric sensitivity of the reaction system is investigated. The critical values computed by the modified divergence criterion are compared with Morbidelli and Varma criterion (MV criterion), Adler and Enig criterion (AE criterion) and divergence criterion (Div criterion). The comparison demonstrates the validity of the new criterion. In addition, the critical explosion pressures of two kinds of hazardous chemicals are computed by the various critical criteria and compared with published experimental data. The results show that the modified divergence criterion could give smaller computational error compared with the previous criteria.     

低压环境对锂电池热失控释放温度影响

为研究锂电池在民航飞行低压特殊环境的安全性及发生热失控灾害后的高温危险性,通过可模拟飞行变动条件的动压变温实验舱开展系列实验,研究锂电池在不同低压环境下的（101,60,30 kPa）多节18650型锂离子电池热失控温度特性,采集电池池体温度及热失控喷射释放温度等参数。研究结果表明:随环境压力降低,圆柱锂电池间的热失控传播并不能被阻断,但锂电池热失控灾害所释放产生的高温区域减少,且高温持续时间变短,释放所产生温度的高温危险性随环境压力的降低而有所降低。     

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.     

Dynamic modeling and bifurcation analysis for the methyl isocyanate hydrolysis reaction

The aim of this work was to characterize the methyl isocyanate hydrolysis reaction and to identify its operational criteria. The parametric sensitivity and dynamic stability methodologies were performed at the Bhopal disaster circumstances, over the relevant operating parameter space. Stable and unstable conditions, bifurcations points, turning points and oscillatory behavior were determined. The combined methodology give useful guidance on the operative conditions selection and the appropriate strategy to overcome hazardous situations. The obtained results demonstrated high sensitivity to small perturbations (thermal runaway) and prevalent oscillatory behavior. Moreover, the following critical parameters for the studied dynamic system were defined: the inverse residence time of 1.5700103 and the heat transfer coefficient of 752.394.     

Setting optimal operating conditions for a catalytic reactor for butane oxidation using parametric sensitivity analysis and failure probability indices

Safe operation of a catalytic reactor remains a sensitive issue when highly exothermic reactions are conducted and hazardous side reactions may occur. Derivation of the optimal operating conditions must include economic but also safety criteria, technological constraints, beside controllability and stability aspects. The present work introduces a criterion based on a joint failure probability index related to uncertainty in the runaway boundaries and the random disturbances of the operating parameters. The use of such a safety criterion is even more important when setting the optimal operating policy of the reactor in the vicinity of the runaway boundaries that often correspond to a high productivity. The paper indicates how an economically efficient but more prudent operating policy can be selected, by simultaneously considering the economic and safety objectives. An example is provided for the case of an industrial fixed-bed tubular reactor, of high thermal sensitivity, used for the catalytic oxidation of butane to maleic anhydride in vapour phase. The multi-objective optimization can lead to a prudent trade-off operating solution (corresponding to a failure probability of maximum 3–4%) that limits the reactor productivity. Being based on a local and global sensitivity analysis of the reactor, the proposed rule is generally applicable by minimizing the probability with which control variables violate their safety limits.     

Thermal hazards analysis of styrene in contact with impurities

Styrene is a reactive monomer commonly used to produce polystyrene and other copolymers. Unintended thermal runaway polymerization reactions of styrene keep reoccurring and have led to catastrophic consequences. One of the possible causes of these runaway incidents involves the contamination of the styrene monomer by incompatible species, which was not adequately investigated and documented. This study focuses on the quantification of thermal runaway hazards of styrene in contact with a series of contamination substances by adopting calorimetric analysis. Both Differential Scanning Calorimeter (DSC) and Advanced Reactive System Screening Tool (ARSST) were employed to examine the exothermic characteristics of styrene mixed with contaminating substances at different concentration levels and mixing conditions. Key safety parameters of the exothermic reaction, such as the onset temperature, the overall heat release, the maximum self-heating rate, as well as the activation energy, were obtained. The results indicated that the thermal runaway polymerization of purified styrene was significantly altered by the presence of contaminant species. Water effectively retarded and quenched the runaway polymerization at a higher temperature range. Alkaline had no substantial effect on the thermal runaway characteristics. The presence of acid solution under both static contact and vigorous mixing condition significantly promoted the thermal polymerization of styrene. A trace amount of concentrated acid initiated violent exothermic activity even at room temperature; and the severity of the reaction was profoundly impacted by the mass-transfer. Our study demonstrates significant implications in the prevention of runaway incidents during transportation and storage of styrene.     

Variability of operating safety limits with catalyst within a fixed-bed catalytic reactor for vapour-phase nitrobenzene hydrogenation

The safety in operation of a fixed-bed catalytic reactor remains a sensitive issue when a highly exothermic reaction is conducted and various process development elements such as controllability, stability, risk, and economic aspects are considered. Several model-based methods are used to estimate the safe operating region limits. Nominal conditions are set to limit the hot spot in the tubular reactor and avoid excessive thermal sensitivity to variations in the process parameters. When the catalyst or its characteristics are changed, the operating conditions have to be adjusted accordingly. The safety problem becomes more important when the production optimization requires setting the nominal operating point in the vicinity of the safety limits. This paper investigates the advantages as well as the precautions that need to be taken when using a more sophisticated model-based global sensitivity criterion (MV of Morbidelli & Varma) to routinely update the runaway critical conditions when changes in the investigated system frequently occur. A concrete example is provided for the case of an industrial fixed-bed catalytic reactor for nitrobenzene hydrogenation in vapour-phase. The analysis points out the discrepancies in predicting the runaway boundaries for complex processes between precise sensitivity-based MV-method and shortcut methods, and the importance of accounting for parameter uncertainty for both evaluation of the confidence region around the runaway boundaries and for the optimal set-point location. The close connection between the operating risk limits and the process kinetics is also highlighted even if the reactor geometry and the main flow conditions are kept unchanged.     

低压环境下不同三元圆柱锂电池热失控危险特性对比研究

为研究21700和18650新旧2型多用途锂离子电池在航空运输低压环境下的热失控特性差异，采用动压变温实验舱搭建实验平台开展实验。将实验环境压力设定为飞机巡航时的环境压力30 kPa，对比常压101 kPa，使用外部热源加热的方式触发锂电池热失控，利用热传播引发相邻电池热失控，分别从热失控温度变化特性、热释放速率和热解气体组分浓度变化进行分析。研究结果表明:能量密度更高的21700电池热失控峰值温度更高，高温危险性要高于18650电池，但触发热失控所需的热量更多，电池间热传播时间会延长；低压环境有利于降低锂电池热失控燃爆峰值温度，减小燃爆热释放速率，但会产生更多CxHy和CO等具有燃爆性的热解气体，可能会在有限空间内与氧气混合引起二次燃爆。     

基于火探管式的锂离子电池灭火技术研究

为研究锂离子电池灭火方案,基于火探管灭火技术同时利用新型清洁灭火剂Novec 1230,组装成火探管灭火系统。在灭火测试平台上以功率为200 W的电热管作为外热源引发单电池或电池模组热失控,通过改变火探管的布置位置,记录相应的灭火行为以及灭火效率,并对实验结果进行了分析。研究结果表明,当火探管灭火系统直接布置在电池正上方时,在起火后的5.6s内控制火情;随着灭火剂用量增加可以显著降低体系温度,防止电池复燃以及连锁热失控现象发生;火探管有效覆盖区域外的失控电池作为热源将继续加热临近电池,引发连锁热失控,造成灭火系统失效;根据电池热失控后的燃烧行为以及传热行为,提出相应的火探管灭火系统复合方案。     

不同外热功率下18650锂离子电池热失控特性*

为探究不同外热功率（220,170,120,70 W）下锂离子电池的热失控特性,采用动压变温实验舱作为燃爆实验舱,并利用量热仪和ISO-9705烟气分析仪监测特征参数,对荷电状态（SOC）为100%的18650型锂离子电池进行高温热失控实验。结果表明:在不同的外热功率条件下,锂离子电池进入热失控的过程呈现出相似的趋势,但是各阶段的特性却存在差异。池体表面中心温度、HRR,THR和耗氧量均随外热功率的降低而降低。高外热功率下燃爆响应时间点明显提前,池体温度更高,220 W外热功率下,燃爆响时间点为176 s,池体温度为720.6 ℃,比70 W时提前366 s,高210.03 ℃,可见高外热功率时,电池热危害性更高。热解烟气CO的峰值体积百分比浓度随着外热功率的降低而升高,而CxHy的峰值质量百分比浓度降低,,CO2的峰值体积百分比浓度降低。在70 W外热功率时,CO峰值体积百分比浓度高达0.322%,220 W时CO峰值体积百分比浓度仅为0.165%,说明低外热功率时,电池毒危害性更高。     

相变材料填充率影响锂电池组热失控传播特性的实验研究

复合相变材料(PCM)应用于锂电池组的热管理是当前研究的热点。然而,PCM对锂电池组热失控传播特性的影响规律仍不甚明晰。实验研究了不同PCM填充率对锂电池组的影响,分析其热失控触发时间、最高温度、质量损失和热释放速率等参数变化规律。结果发现,添加PCM后,电池表面温度、CO和SO2浓度均出现了不同程度的降低,但对热释放速率没有明显的影响。PCM填充率为0%和10%的电池组均发生了热失控传播,而30%、50%、100%的PCM填充率能有效阻隔热失控传播的发生。     

苯和甲苯硝化及磺化反应热危险性分级研究

首先介绍了化工工艺热安全性的内涵,并从反应过程热危险性分析的方法学出发,介绍间隙、半间歇化学反应工艺热危险性分级研究的总体思路及方法。然后,围绕甲苯和苯的硝化、磺化反应,用全自动反应量热仪(RC1e)和加速度量热仪(ARC)测定其反应过程的绝热温升(△Tad)、目标反应所能达到的最高温度(TM)、分解反应最大速率到达时间(θD)等参数。运用风险评价指数矩阵法(方法1)和基于失控过程温度参数的热危险评估法(方法2)分别对其硝化和磺化反应过程的热危险性进行了分级评估。结果表明,这两种方法具有良好的一致性;给定工艺条件下甲苯和苯的一段硝化反应过程的热危险度等级较低;而磺化反应的热危险较高。尽管这两种方法还有一定的局限性,但对于间歇、半间歇合成工艺的本质安全化设计、工艺热危险性的评估具有重要的参考价值和实用意义。     

Using thermal analysis with kinetic calculation method to assess the thermal stability of azo compound on construction materials

The application of construction polymers in engineering and alternative materials has always occupied a place in the market. In the production process of polymer resins, initiators can be used to lower the polymerization reaction energy threshold, which can improve reaction efficiency and reduce energy loss. However, as a commonly used energetic substance in the polymerization process, azos have caused related process hazards due to their exothermic characteristics. Because of this, it is essential to examine and analyze the thermal hazard characteristics of emerging azo substances, such as 2-cyanopropan-2-imemicarbazide (CABN). Although previous literature performs the calculation on related thermal hazard parameters of CABN, there is still exists a void for discussion in estimating the reaction model to avoid analogous hazards and enhance the existing thermal analysis. Based on the past literature, the reaction model is improved with thermogravimetric analysis as evidence. The revised thermal hazard parameters are calculated as the basis of control and mitigation measures, the kinetic model is used to estimate the modified safety parameters, and in the judgment of the runaway reaction, the critical temperature of the runaway is found by analyzing the influence of slight changes in ambient temperature on the reaction temperature. The results show that the critical temperature that causes CABN to enter the runaway reaction is delayed, and the hazard is lower than in the storage situation. Therefore, the thermal hazard to CABN mainly focuses on the safety environment and measures during storage.     

基于详细化学动力学的甲烷热着火影响因素分析

利用化学动力学软件CHEMKIN4.1,在不同初始温度、浓度、湿度和压强下,对甲烷热着火进行了详细化学动力学 模拟。通过对主要组分摩尔浓度分析和温度敏感性分析,得到了甲烷热着火过程的主要基元反应和引发热着火发生的主 要原因。通过对甲烷热着火的延迟时间、热着火发生后主要生成物摩尔浓度和反应后的温度的对比分析,揭示了初始浓 度、湿度和压强对甲烷热着火的影响规律。本研究可以为甲烷为主的气体如瓦斯、天然气等可燃气体的燃烧和爆炸提供 理论支撑,从而有效利用这些可燃气体,降低灾害的发生。     

Methodology for global sensitivity analysis of consequence models

A methodology is presented for global sensitivity analysis of consequence models used in process safety applications. It involves running a consequence model around a hundred times and using the results to construct a statistical emulator, which is essentially a sophisticated curve fit to the data. The emulator is then used to undertake the sensitivity analysis and identify which input parameters (e.g. operating temperature and pressure, wind speed) have a significant effect on the chosen output (e.g. vapour cloud size). Performing the sensitivity analysis using the emulator rather than the consequence model itself leads to significant savings in computing time.To demonstrate the methodology, a global sensitivity analysis is performed on the Phast consequence model for discharge and dispersion. The scenarios studied consist of above-ground, horizontal, steady-state discharges of dense-phase carbon dioxide (CO₂), with orifices ranging in diameter from ½ to 2 inch and the liquid CO₂ stagnation conditions maintained at between 100 and 150 bar. These scenarios are relevant in scale to leaks from large diameter above-ground pipes or vessels.Seven model input parameters are varied: the vessel temperature and pressure, orifice size, wind speed, humidity, ground surface roughness and height of the release. The input parameters that have a dominant effect on the dispersion distance of the CO₂ cloud are identified, both in terms of their direct effect on the dispersion distance and their indirect effect, through interactions with other varying input parameters.The analysis, including the Phast simulations, runs on a standard office laptop computer in less than 30 min. Tests are performed to confirm that a hundred Phast runs are sufficient to produce an emulator with an acceptable degree of accuracy. Increasing the number of Phast runs is shown to have no effect on the conclusions of the sensitivity analysis.The study demonstrates that Bayesian analysis of model sensitivity can be conducted rapidly and easily on consequence models such as Phast. There is the potential for this to become a routine part of consequence modelling.     

Parametric study of the explosivity of graphite-metals mixtures

The explosivity of dust clouds is greatly influenced by several parameters which depend on the operating conditions, such as the initial turbulence, temperature or ignition energy, but obviously also on the materials composition. In the peculiar case of a mixture of two combustible powders, the physical and chemical properties of both dusts have an impact on the cloud flammability and on its explosivity. Nevertheless, no satisfactory ‘mixing laws’ predicting the mixture behavior are currently available and the composition variable to be considered for such models greatly depend on the safety parameters which have to be determined: from volume ratios for some thermal exchanges and ignition phenomena, to surface proportions for some heterogeneous reactions and molar contents for chemical reactions. This study is mainly focused on graphite/magnesium mixtures as they are encountered during the decommissioning activities of UNGG reactors (Natural Uranium Graphite Gas). Due to the different nature and reactivity of both powders, these mixtures offer a wide range of interests. Firstly, the rate-limiting steps for the combustion of graphite are distinct from those of metals (oxygen diffusion or metal vaporization). Secondly, the flame can be thickened by the presence of radiation during metal combustion, whereas this phenomenon is negligible for pure graphite. Finally, the turbulence of the initial dust cloud is modified by the addition of a second powder. In order to assess the explosivity of graphite/magnesium clouds, a parametric study of the effects of storage humidity, particle size distribution, ignition energy, and initial turbulence has been carried out. In particular, it was clearly demonstrated that the turbulence significantly influences the explosion severity by speeding up the rate of heat release on the one hand and the oxygen diffusion through the boundary layer surrounding particles on the other hand. Moreover, it modifies the mean particle size and the spatial dust distribution in the test vessel, impacting the uniformity of the dust cloud. Thus, the present work demonstrates that the procedures developed for standard tests are not sufficient to assess the dust explosivity in industrial conditions and that an extensive parametric study is relevant to figure out the explosive behavior of solid/solid mixtures subjected to variations of operating conditions.     

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。     

受限空间环境压力对三元锂离子电池热失控影响*

为研究三元锂离子电池在空运低压环境中的安全性,通过自主设计搭建的封闭式变压实验舱开展相关实验,对不同荷电状态（SOC）下的三元锂离子电池在不同压力环境（101,80,60,40 kPa）下的热失控特性进行研究,采集电池热失控过程中的温度以及实验舱内的压力变化,并对热失控后实验舱内的气体成分进行分析。结果表明:三元锂离子电池热稳定性随着SOC的升高而下降,常压下100%SOC的电池热失控温度可达650.8 ℃,初始环境压力越低,相同SOC的电池热失控最高温度越低。随着环境压力的降低,相同SOC的电池在热失控后会生成更多CO,且电解液占比升高。研究结果可为锂离子电池空运安全性研究提供理论依据。     

二叔丁基过氧化物的热失控动力学研究

为研究二叔丁基过氧化物(DTBP)热失控危险性,利用C600微量量热仪对DTBP热分解动力学进行试验研究,测定DTBP在不同升温速率下的起始放热温度和分解热,分别用非等转化率法和等转化率法得到DTBP热分解反应的动力学参数。用非等转化率法确定反应的最佳反应级数为1,相应的活化能分别为137.75、132.60、128.61和122.93 kJ/mol,指前因子分别为8.82×1012、6.69×1012、2.06×1012和3.89×10111/s。用等转化率法确定的活化能范围为102～138 kJ/mol,并拟合出活化能与转化率的关系曲线。结合计算出的动力学参数,通过对DTBP分解机理的分析,可以推断其具有热失控危险性。