Modeling of the venting of an untempered system under runaway conditions

The prediction of the consequences of a runaway reaction in terms of temperature and pressure evolution in a reactor requires the knowledge of the reaction kinetics, thermodynamics and fluid dynamics inside the vessel during venting. Such phenomena and their interaction are complex and yet to be fully understood, especially reactions where the pressure generation is totally or partially due to the production of permanent gases (gassy or hybrid systems). Moreover, these phenomena cannot be easily determined by laboratory scale experiments. In this paper, a dynamic model developed to simulate the behavior of an untempered reacting mixture during venting is presented. The model provides the temperature, pressure and mass inventory profiles before and during venting. A sensitivity study of the model was performed. This modeling work provides some insight regarding the interpretation of the data obtained from untempered system venting experiments. The outcome of this work contribute to improving the design of emergency relief systems for hybrid and gassy systems, where significant progress is still to be made in the experimental and modeling areas.     

A general criterion to define runaway limits in chemical reactors

A general runaway criterion valid for single as well as for multiple reaction types, i.e. consecutive, parallel, equilibrium, and mixed kinetics reactions, and for several types of reactors, i.e. batch reactor (BR), semibatch reactor (SBR) and continuous stirred tank reactor (CSTR) has been developed. Furthermore, different types of operating conditions, i.e. isoperibolic and isothermal (control system), have been analysed. The criterion says that we are in a runaway situation when the divergence of the system becomes positive (div>0) on a segment of the reaction path. The results show that this is a general runaway criterion than can be used to calculate the runaway limits for chemical reactors. The runaway limits have been compared with previous criteria. A considerable advantage, over existing criteria, is that it can be calculated on-line using only temperature measurements and, hence, it constitutes the core of an early warning runaway detection system we are developing.     

Model-based zero emission safety concept for reactors with exothermal reactions for chemical plants

To avoid major accidents caused by runaway reactions, a new safety concept called SmartHIP¹ is introduced, with the objective to prevent runaway reactions and avoid emissions. The basic principle is based on an online model-based approach by using safety instrumented systems. Different criteria exist for calculating the hazard potential of a runaway reaction and its early detection. The approaches of the literature from the last years are analysed and divided into three different groups: Divergence, Accumulation and Adiabatic Criterion. Each approach is compared to the other by applying it to an esterification reaction of acetic anhydride with methanol. The approaches are evaluated according to different requirements, like accuracy, wide range of application or reliability.     

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。     

Calorimetric study of the inhibition of runaway reactions during methylmethacrylate polymerization processes

Reaction inhibition was adopted as a method to halt runaway phenomena during polymerization experiments. Use of reaction calorimetry coupled with a particular system for early detection of the onset of runaway (early warning detection system) has allowed to investigate the behaviour of two substances that can influence the reaction rate: hydroquinone and 1,4-benzoquinone. The process studied was the free-radical polymerization of methylmethacrylate carried out under batch conditions in bulk or in emulsion. The results show that hydroquinone and 1,4-benzoquinone behave differently: the first is an inhibitor because it completely stops the process; the second behaves as a retarder and could be used industrially to control the process and keep the reactor temperature within safe limits.     

Predictive accuracy of simplified vent area sizing methods for the case of thermal runaway reactions

A systematic comparison of the predictive accuracy of simplified design methods with respect to the relief diameter and the discharged mass flow on the basis of experimental results obtained in reactors with volumina ranging between 0.01 and 10 m³ allow for the conclusion that empirical design rules are not suited for an extrapolation. The preliminary recommended method in case of vapour systems is this of J.C. Leung and for use with gassy or hybrid systems the method by H.K. Fauske and J.C. Leung is promoted. Indeed, partly non acceptable overpredictions are evident. By using SAFIRE/VENT reasonable predictions are possible though still an oversizing can not be cut off.     

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。     

航空压力环境对锂离子电池热解气体爆炸极限影响*

针对航空锂离子电池热失控释放气体安全性研究不足的问题,采用气体拉曼光谱技术、气相色谱仪(Gas Chromatography,GC)和质谱(Mass Spectroscopy,MS)耦合来探究压力和荷电状态(State of Charge,SOC)对锂离子电池早期故障气体类型、气体动态演变及气体潜在危险性等特征的影响规律,同时综合考虑压力、电压和电池温度等多种因素分析锂离子电池热失控危害。研究结果表明:电池SOC越高且环境压力越低,电池越早触发热失控,爆炸极限越宽,其中30 kPa下100%SOC电池热解气体爆炸极限为8.01%~53.35%;SOC和环境压力越高,电池热失控越危险,释放的气体体积越多;CO,CO2,PF3,C2H4及电解液（C3H6O2、C3H6O3、C4H8O2）等气体可作为航空锂离子电池早期故障诊断特征。研究结果对保障锂离子电池在航空领域的安全运输及应用具有重要意义。     

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.     

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。     

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。     

反应性液体紧急泄放面积设计进展

为防止反应失控造成爆炸事故,减少事故损失,在介绍模拟反应失控的实验装置ARC、VSP以及RSST等的基础上,针对不同的紧急泄放类型,如气相系统、蒸气系统和混合系统的紧急泄放研究进展,进行了分析论述,旨在发现解决反应失控紧急泄放问题的更好方法,从而为进一步研究反应失控的紧急泄放问题打下基础.     

Influence of calorimetric approximations on the design of emergency relief systems

The design of an emergency relief system (that is, a pressure safety valve or a rupture disk) for vessels, which may involve runaway reactions, requires knowledge of the chemical kinetics of the reactions involved. When safety-related problems are considered this is usually achieved using calorimetric tests, coupled with some suitable approximations on the kinetics of the reacting system. In this work we have analysed the extent to which the precise knowledge of the chemical kinetics influences the size of the relief system device for different reaction conditions. Decision criteria are proposed to identify situations where approximations in the kinetic mechanism lead to underestimation in the venting area.     

细水雾对锂离子电池热失控抑制作用的实验研究

为研究细水雾对锂离子电池热失控的抑制作用,利用自设计细水雾实验装置对18650型锂离子电池热失控进行抑制实验,对比两节电池依次燃爆和不同阶段使用细水雾的温度曲线。研究表明,细水雾对于抑制锂离子电池热失控有效,但不同热失控阶段细水雾抑温效果差异较大,结合锂离子电池多米诺效应和机载灭火设备适航性要求,应尽可能将细水雾喷雾时间节点靠近初次爆炸的时间节点。提出通过准确探测初次爆炸发生和进一步增强细水雾抑制作用来控制锂离子电池热失控及多米诺效应的发生和传播。     

Modelling Complex Pipeline Network Leak Detection Systems

A novel model for detecting leaks in complex pipeline network systems has been developed. The model derives from the theory of Liapunov stability criteria. A leak is detected if the resulting eigenvalues from the deviation flow matrix have values less than a predetermined value. An advanced mesh network algorithm was used to decompose the complex pipeline network system into sub-networks. The flow model (equations of motion and continuity) which incorporates a leaking factor, k_L, is solved by a numerical technique that uses the method of characteristics and an implicit finite function. The unsteady state flow matrix of the complex pipeline network system was analysed using a modified Hardy Cross algorithm, where the velocity and pressure were computed for each node and pipeline loop in the complex network. The plots for the characteristic pressure and velocity eigenvalues show that pressure measurements are faster parameters for leak detection than volume measurements. Volume measurements appear to be suitable for larger leak systems and longer response time.     

Pressure relief sizing of reactive system using DIERS simplified methods and dynamic simulation method

Incidents involving uncontrolled chemical reactions continue to result in fatality, injury and economic loss. These incidents are often the result of inadequate pressure relief system designs due to a limited knowledge of the chemical reactivity hazard. A safe process design requires knowledge of the chemical reactivity of desired as well as undesired chemical reactions due to upset conditions. Simplified, cost effective methods to relief system sizing are presented by The Design Institute of Emergency Relief Systems (DIERS). They require multiple experiments, and sizing is only valid for the system composition and thermal inertia represented by the small scale experiments. Results are often conservative, especially for gassy systems. Detailed, dynamic computer simulation is highly accurate and can be used for iterative design and multiple scenario evaluation.In this study, an accelerating rate calorimeter (ARC^®) and a low thermal inertia calorimeter (automatic pressure tracking adiabatic calorimeter – APTAC™) were used to collect chemical reactivity data for the dicumyl peroxide and toluene system. Results of the pressure relief system sizing using the dynamic simulation method are presented and compared with DIERS simplified methods.     

On the divergence criterion for runaway detection: Application to complex controlled systems

It is well-known that, for certain values of the operative parameters influencing the dynamic behavior of a chemical reactor, a phenomenon known as thermal runaway (that is, a loss of the reactor temperature control) may arise. Such a situation can be really dangerous because above a certain threshold temperature value unwanted side reactions or, worse, decompositions of the reacting mixture may be triggered evolving high amounts of flammable or toxic gases that can cause reactor pressurization and, eventually, its explosion. For this reason, since the beginning of the previous century a number of studies concerning the prediction of the so called runaway boundaries has been carried out. In this work, a modified version of the divergence criterion for runaway detection, originally developed by Zaldívar and co-workers, is presented. Such a modified divergence criterion is capable of treating whatever type of complex controlled reacting system (taking into account not only temperature control but also dosing strategies) and its reliability has been demonstrated for isoperibolic semibatch reactors using literature experimental data concerning the nitration of 4-Chlorobenzotrifluoride in mixed acids and the nitric acid oxidation of 2-octanol to 2-octanone and further carboxylic acids.     

Catalytic decomposition of hydrogen peroxide in the presence of alkylpyridines: Runaway scenarios studies

A number of runaway scenarios of the excess of hydrogen peroxide used during the N-oxidation of alkylpyridines, under closed and open conditions, were examined. It was found that, in most cases, if the volume of the liquid hydrogen peroxide solution occupies more than 10% of the total volume of a closed system (e.g. reactor and vent line between reactor and blockage), the production of gases raises the pressure so quickly that evaporation is completely suppressed. Higher than 70% filling levels result in complete expansion of the liquid. The MTSR(t) of the system falls rapidly if the normal process temperature is high, but if a runaway occurs exactly at the end of dosing, MTST will be very high and secondary decompositions will rapidly develop. The results of this study are currently being used to critically assess the current approaches and further the study of inherently safer designs.     

Importance of accounting for the piping system and boundary conditions in determining the maximum surge pressure following heat-exchanger tube-rupture

Shell-tube type heat exchangers are often used to exchange heat between a high-pressure fluid and a low-pressure fluid, and the pressure difference between the two fluids could be significantly high. If the difference in the design pressure between the low-pressure (LP) and high-pressure sides is greater than that covered by American Petroleum Institute (API 520 and 521) 10/13^th rule, dynamic analysis is required to ascertain that the maximum surge pressure that could be reached does not compromise the integrity of the LP side of the exchanger. API guidelines also notes that attention should also be given not only to the shell-side of the heat exchanger under evaluation, but also to the “upstream and downstream systems” This paper offers further insight into the importance of including the surrounding piping systems around the subject heat-exchanger where a tube-rupture scenario is considered, and also directs attention to the importance of correctly specifying the appropriate boundary conditions (B.C.) at the far ends of both the upstream and downstream piping systems. It demonstrates the effects of specifying different B.C. on the maximum pressure surge via a case study of a hot separator vapour condenser in a bitumen hydrotreating unit, where the process fluid on the tube-side is a vapour–liquid mixture at 9660 kPa(g). The vapour mass fraction of the process fluid is approximately 0.5, and is mostly hydrogen. The fluid on the LP side is cooling water connected to the plant supply and return cooling systems as well as another adjacent low pressure condenser. The design pressure for the cooling water piping system and the adjacent condenser is 1380 kPa(g).     

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.