Vent sizing for gas-generating runaway reactions

Exothermic runaway reactions that generate non-condensible gas as the temperature increases, as is typical of decompositions for example, can reach extremely high rates of pressure rise necessitating emergency relief of the process vessel containing the reactant. Sizing of a relief device using presently recommended methods (e.g. DIERS) frequently leads to extremely large and expensive vents. This paper presents a methodology that leads to a simple but much improved method for vent sizing, fully allowing for two-phase release of the gas—liquid mixture. A number of examples are presented which lead to interesting conclusions about the influence of plant variables.     

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.     

Planning protection measures against runaway reactions using criticality classes

A systematic approach to the assessment of thermal risks linked with the performance of exothermal reactions at industrial scale was proposed a long time ago. The approach consisted of a runaway scenario starting from a cooling failure and a classification of these scenarios into criticality classes. In the mean time these tools became quite popular and many chemical companies use them. Recently, the international standard IEC 61511 required the use of protection systems with reliability depending on the risk level. Since the criticality classes were developed as a tool for the choice of risk reducing measures as a function of the criticality, it seems obvious that the criticality classes may be used in the context of the standard IEC 61511, which provides a relation between the risk level and the reliability of protection systems.Firstly, the runaway scenario and the criticality classes will be shortly described. Secondly, the assessment criteria for severity and probability of occurrence of a runaway scenario will be described together with the required data and their interpretation in terms of risk. Thirdly, the assessment procedure is exemplified for the different criticality classes. Finally, the design of protection measures against runaway and the required IPL and SIL are based on the risk assessment obtained from the criticality classes. This approach allows minimising the required data set for the safety assessment and for the definition of the protection system designed in order to avoid the development of the runaway.     

常见三元锂电池热失控过程分析

以三元锂电池模组为研究对象,在SOC为100%的条件下加热诱发热失控,结合视频分析和热流分析,总结不同型号三元锂电池热失控的过程规律。NCM111和NCM523电池在热失控过程中产生大量烟气,NCM622和NCM811电池在热失控过程中产生猛烈火焰。整个电池组热失控过程经历时间最长的是NCM111电池,最短的是NCM622电池,NCM523和NCM811电池在失控时间上具有一定的相似性。三元锂电池的辐射热流会出现多个峰值,其中NCM111、NCM523和NCM811电池都是第一个峰值最大,NCM622电池是最后一个峰值最大。在各电池组中,NCM622电池热流值峰值最大,约为328 kW/m²。     

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.     

The runaway scenario in the assessment of thermal safety: simple experimental access by means of the catalytic decomposition of H2O2

The runaway scenario can serve as a basis for the assessment of thermal process risks. In this context, the time to maximum rate (TMR_ad), i.e., the time between cooling failure and thermal explosion, can be a measure of the time in which safety measures must be taken. This paper highlights the discussion of TMR_ad by presenting the catalytic decomposition of hydrogen peroxide with potassium iodide. The experimental procedure is easily practicable and imposing for the students. An overview of the theoretical background is given before presenting the experiment.     

Thermal instability and runaway criteria: The dangers of disregarding dynamics

Two exemplary exothermic processes, synthesis of nitroglycerine in a continuous stirred tank reactor (CSTR) and synthesis of the explosive RDX in a CSTR, are used to demonstrate the dangers of ignoring the system dynamics when defining criteria for thermal criticality or runaway. Stability analyses are necessary to prescribe such criteria, and for these systems prove the presence of dangerous oscillatory thermal instability which cannot be detected using the steady state thermal balances.     

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.     

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.     

Thermal runaway reaction for highly exothermic material in safe storage temperature

Highly exothermic materials have caused many serious accidents involving storage and transportation, due to being thermally reactive. The safe storage and management of these materials is still a critical problem in many countries. Our aim was to study the thermal hazard of thermal reactive materials, such as a propellant, by employing differential scanning calorimetry (DSC) non-isothermal tests and isothermal tests, and then comparing the kinetic parameters by isothermal and non-isothermal of kinetics. The chosen approach was to obtain reliable thermal decomposition by a safe and effective method, which acquired the kinetic and safety parameters of storage conditions that could be applied as highly exothermic materials' reduction of loss prevention and energy potential for safer design during storage transport and processing operations.     

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.     

过氧丙酸分解反应的失控泄放特性研究

为研究过氧丙酸分解反应的失控泄放特性,利用泄放模式实验装置对过氧丙酸在不同泄放口径和泄放压力下的顶部和底部的泄放过程进行了试验模拟,得到了过氧丙酸的失控特性参数和不同条件下的泄放特征。结果表明:过氧丙酸失控反应泄放易出现二次峰值现象,初次峰值为气相泄放,二次峰值为气液两相泄放;二次峰值的出现取决于泄放口径及泄放时的物料温度,与泄放压力无关;恒压泄放容易出现非平衡泄放,导致较高最大累积压力和较高的釜内物料温度;底部泄放能够使釜内物料快速排空。     

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.     

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,...     

BIPB的热分解动力学和失控反应模拟

为了评估双(叔丁过氧基)二异丙苯(BIPB)的热危害,对其热分解过程进行多速率的动态扫描C80热分析,用几种简单的热危害评估方法分析其热危害。然后应用模式法、无模式法(Friedman微分等转化率法)分别对试验结果进行处理,得到分解动力学数据,并用ASTM E 698法得到活化能数据,同时用C80、ARC和DSC的试验数据验证分解动力学数据的可靠性。最后利用无模式法的分解动力学数据进行BIPB绝热条件下和非绝热的2m3球形容器中的失控反应模拟,得到类似工艺条件下BIPB的安全控制温度。     

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.     

锂离子电池热失控危险性研究进展

锂离子电池广泛应用的同时也出现了燃烧、爆炸等安全问题.针对锂电池热失控及火灾问题,综述了电池内部热失控演变过程、热失控气体释放及其燃爆风险,以及热失控和火灾发生时有毒有害气体的危害性等方面近年来的研究进展.最后提出今后主要研究方向是电池模块/电池包内热失控气体释放和流动过程研究、气体爆炸危险性动态变化规律研究和大容量高比能富镍电池单体/模块热失控特性和规律研究等.     

Cushioning the impact of toxic release from runaway industrial accidents with greenbelts

The three aspects of accidents in chemical process industries which cause most serious damage—explosions, fires, and toxic releases—can all be controlled to some extent if greenbelts are present around the affected industry. We have recently developed and validated a system of methodologies for greenbelt design. In this paper we present the application of these models in designing greenbelts and forecasting their role in cushioning the impact of accidental release of toxic gases. With properly located and designed greenbelts as much as 33% of the accidental release of SO₂, 43% of H₂S, and 51% of NH₃ under stable atmospheric conditions (in which the dispersion is very slow and the release thus has maximum toxic impact) can be absorbed.