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.     

The role of recirculation loop on the risk of ethoxylation processes

Alkoxylation is performed in industry for producing non-ionic surfactants and polyethylene/polypropylene glycols. To this end, the most common type of reactor consists of a simple liquid-stirred reactor equipped sometimes with an external circulation loop to increase the reactor heat exchange capacity. More advanced chemical processes are now performed in Semi-Batch Venturi Loop reactors or in Spray Tower Loop Reactors, where the liquid phase is dispersed into the gaseous phase by means of recirculation loop. The three different reactor types used in the manufacture of ethoxylated products have been compared in terms of efficiency. However, few indications have been given in terms of accidental consequences, whose evaluation is mandatory when sound risk assessment of chemical processes is carried out. In this paper, the added risks due to the presence of the recirculation loop have been assessed by varying the operating conditions, either in terms of temperature or partial pressure of ethylene oxide (EO). The aim is, therefore, to rank the different technologies.     

环氧乙烷生产安全——热力学效应中的温度控制

从化工热力学角度出发,讨论当前工业生产常用的氧气氧化法制环氧乙烷工艺中,乙烯氧化反应单元氧化反应器易发生"飞温",而导致火灾爆炸等重大事故的原因:主副反应均为放热反应;副反应为完全氧化反应,反应热为主反应的十几倍;温度升高将导致反应选择性下降,速率加快,系统进入"自热"状况,进而导致热失控,甚至引发火灾爆炸事故。进而提出温度控制是保证氧气氧化法制环氧乙烷生产安全的关键,并建议工业生产中采用改善反应器结构、改良催化剂、改进换热方式、加入抑制剂以及采用比热容更大的甲烷气致稳等控温措施。     

Safety analysis approach based on thermodynamic and chemical reactions modelling

Safety analysis of nuclear and chemical/petrochemical facilities is the systematic process that is carried out throughout the design process to ensure that all the relevant safety requirements are met by the proposed design of the plant. Safety analysis should incorporate both deterministic and probabilistic approaches. These approaches have been shown to complement each other and both should be used in the decision making process on the safety and ability of the plant to be licensed.This paper deals with the deterministic safety approach in order to distill the experience of nuclear and chemical/petrochemical protection engineering through a safety analysis approach aiming at analysis of chemically reacting processes including thermodynamic and chemical reactions modelling that are present in both industries. For instance, there are some similarities between the Bhopal disaster and Three Mile Island-Fukushima-like H₂ deflagration-detonation scenarios in nuclear containments. The phenomenology is similar in that the temperature and the pressure caused by exothermic reactions had increased dramatically leading to a loss of containment.The study aims to translate and adapt to general chemically reacting modelling, major features of the equivalent analysis inside the nuclear containments. Compartment containment for H₂ deflagrations has been translated and adapted, with fixed tools, to the methyl-isocyanate storage tank 610 of the Bhopal plant.     

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.     

Process hazard assessment of energetic ionic liquid with kinetic evaluation and thermal equilibrium

With the continuous development of battery technology, there are new research investments in materials of various parts. In the field of electrolytes, ionic liquids (IL) are considered to be excellent electrolytes and have been widely studied in distinct energy fields. However, it is necessary to pay attention to the safety characteristics of ionic liquids at high temperature due to the application of energy, but there is little research on the reaction and kinetics of ionic liquids. To ensure the safety of ionic liquids, such as high temperature, the common ionic liquid 1-Ethyl-3-methylimidazolium nitrate ([Emim] NO₃) was selected for analysis. The exothermic mode is obtained from the data of differential scanning calorimetry. The basic reaction parameters of [Emim] NO₃ were determined with thermodynamic equation simulation. For ionic liquids in the actual situation, consider adding a heat balance model to estimate its temperature change pattern and find out the hazard temperature and related safety parameters. Temperature changes were estimated by constructing 25.0 g and 50.0 g packages to simulate material reactions and heat transfer in the external environment. The results showed that [Emim] NO₃ had shorter TMR_ad and TCL (<1 day) when the temperature was above 180 °C.     

基于本质安全的微反应器中苯乙烯聚合的数值模拟

重大化工事故往往是由多米诺效应引发的一连串故障而导致的。为实现苯乙烯聚合反应的本质安全,采用本质安全设计原则,设计了T型微反应器以替换传统釜式反应器。先通过计算流体力学(CFD)方法建立了三维稳态模型,再通过UDF(User Defined Functions)添加组分输运方程源项和能量方程源项,对苯乙烯自由基聚合反应进行了数值模拟,研究在微尺度条件下,反应温度、混合反应管道长度及形状对反应结果的影响。结果表明:由于微反应器可提高传热传质效率,在一定范围内反应温度可以控制在3 K以内;反应管道由0.15 m增长至1.5 m后,转化率可提高2倍左右;0.15 m直管形状改进为螺旋状后,转化率可至少提升4%。     

数值分析方法在一起高危工艺分析中的应用

以二级放热反应为研究对象,在反应体系温度、浓度均匀分布的假设基础上,根据反应速率方程和热平衡方程,建立高危工艺反应的温度和转化率随时间变化的数学模型。采用数值计算技术,以一阶差分代替微分,并结合工艺中的恒温过程、绝热过程和飞温过程,编写计算程序求得其转化率、温度在不同时间点的数值解,揭示爆炸事故的发展过程,定量分析操作参数的影响和转化率、温度随时间分布的规律。同时通过对绝热反应时间、冷凝器的冷却能力的分析,结合冷凝器的移热能力和反应放热对反应体系热积累的影响,讨论防止反应失控发生的可能性。最后探讨冷凝器热负荷余量、反应物投料浓度比等因素对控制反应失控的影响。     

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。     

Simulation study on near-field structure and flow characteristics of high-pressure CO2 released from the pipeline

The accidental release of high-pressure carbon dioxide (CO₂) can cause serious damages to both humans and pipeline equipment. Therefore, it is of great significance to have a deeper understanding about the release characteristics of high-pressure CO₂ for improving the safety level of Carbon Capture and Storage (CCS) technologies. Both industrial-scale and laboratory-scale studies have been carried out to predict the release behaviors. In recent years, computational fluid dynamics (CFD) simulation has become a crucial method to study the instantaneous changes and microscopic details of the fluid behaviors. In this paper, the simulation method was employed to study the near-field structure and flow characteristics of high-pressure CO₂ released from pipelines. The Peng-Robinson Equation of State (EOS) was used to compute the thermodynamic properties of high-pressure CO₂, and SST k-ω model was applied to simulate the structure and physical parameters of the under-expanded jet. In addition, the multi-phase mixture model was introduced to study the phase transition. The non-equilibrium liquid/vapor transition is modeled by introducing ‘source terms’ for mass transfer and latent heat. Compared to the experimental results, the simulation results showed good agreement. Furthermore, the influences of operating conditions, including different stagnation pressure, stagnation temperature, and nozzle size, were analyzed.     

球形压力容器中甲烷-氢气-空气爆炸过程数值模拟及实验研究

为研究受限空间内甲烷-氢气-空气混合气体爆炸特性参数分布规律,在20 L球形压力容器装置内开展甲烷-氢气-空气混合气体爆炸实验,探究掺氢比变化对当量比为1的甲烷-氢气-空气混合气体爆炸过程的影响;运用Fluent数值模拟软件,采用标准k-ε湍流模型,结合层流有限速率燃烧模型,探究混合气体爆炸过程中燃烧特性(爆炸温度、压力、密度等)与反应时间的变化规律。研究结果表明：爆炸过程中,添加一定氢气时爆炸压力峰值、爆炸压力上升速率峰值增大,而到达峰值时间缩短;反应初期,中心点火处密度下降,反应釜各处密度持续上升;距离点火点越远,密度变化越大,反应釜中压力分布基本相同。研究结果可为甲烷-氢气-空气混合燃料的安全使用提供相关参考。     

Prediction of thermal hazards of chemical reactions

A large number of products of the chemical industry are produced using potentially hazardous reactions. The experimental investigation of the hazards of all reactions involved in production processes would be very expensive. The primary reactions—desired reactions which are part of the process—and the secondary reactions—undesired successive or side reactions—should both be considered. In this paper the methods of prediction of thermodynamic and kinetic properties of reactions are discussed.Thermodynamic data are of eminent practical importance because low heats of reaction may indicate that no further experimental investigations are necessary. For primary reactions, e.g. polymerization, diazotization and hydrogenation reactions, reaction enthalpies have been obtained by experimental methods. Typical data can be found in the public literature for the different reaction classes. When compared with theoretical thermodynamic data estimated by the chetah computer program, the agreement is satisfactory. chetah implements Benson's second-order group contribution technique (Benson, 1976).For secondary reactions, especially exothermic decomposition reactions, typical heats of reaction—mostly measured by DSC—have been associated with functional groups. Decompositions and other undesired exothermic reactions that proceed from the same functional group, e.g. a nitro group, have about the same heat of reaction.For the estimation using the chetah program, decomposition reactions have to be assumed which are typical for the functional group. The reaction yielding the maximum exothermic reaction energy was selected. The comparison of experimental heats of reaction with estimated data shows satisfactory agreement.In principle it is also possible to predict kinetic data of secondary reactions, but sufficient experimental data are missing.     

Modelling and control of the dispersion of hazardous heavy gases

Dispersion of several common `heavy' gases (ethylene, propylene, ammonia, and chlorine) has been modelled on the basis of modifications in plume path theory. The model takes into account, among other things, the variations in temperature, density, and specific heat during the movement of the heavy gas plume. The effects of wind speed, density of the gas, and venting speed on the plume dispersion have been simulated. Based on the simulations a set of empirical equations has been developed. The equations have been validated by theoretical as well as experimental studies.Studies have also been carried out to simulate the effect of venting speed (manipulated by injecting hot air with the released gas) on the plume dispersion. The study reveals that the effect of venting speed on dispersion is very pronounced and can be used to reduce the risk posed by the accidental luxurious release of toxic/flammable gases. For example an increase of 20% in venting speed of chlorine (54.1 m/s) can reduce the distance up to which toxic concentration would occur by about 1100 meters.     

Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT_ad) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR_ad). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.     

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.     

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.     

Use of bifurcation analysis for identification of a safe CSTR operability

Exothermic reactions are the most interesting systems for safety analysis because of their potential safety problems and the possibility of exotic behavior like multiple steady states. An operability and safety analysis of an exothermic reaction (hydrolysis of propylene oxide to tri-propylene glycol with consecutive reactions in a CSTR) with cooling is reported in this work. The information obtained from the bifurcation diagram is used to identify a set of unsafe operation points, which have been chosen on the base of requirement of maximal production of the process. An important information of safe reactor operation is the time in which the operator must handle a critical situation. For this reason, dynamics simulation of a failure in the cooling medium flow rate has been done and discussed for each of the selected operation points.     

库房火灾事故中弹药热安全性研究*

为研究不同火灾条件下弹药发生慢速烤燃的升温速率,以典型地面仓库和舰船舱室火灾为研究对象,建立仿真模型,模拟计算发生火灾时弹药贮存环境的热激源强度及其演化规律,针对发动机在此类环境下的热安全性开展仿真计算,分析其响应规律。研究结果表明:不同火灾条件下弹药慢速烤燃的升温速率有很大区别且往往高于标准慢速烤燃试验常用的升温速率3.3 K/h。随着慢速烤燃升温速率的提高,发动机烤燃点火时间提前,点火时刻发动机中间位置温度下降,两端温度升高,且点火位置向发动机喉部移动。研究结果可以指导弹药库房的设计及弹药安全性增强设计。     

A method of analysis for gas explosions: H2Se case study

This paper presents a methodology for conducting a simplified gas-explosion analysis when there are uncertainties about the amount of fuel involved and the mode of combustion. The methodology is illustrated by a case study of an explosion of a cloud of hydrogen-selenide (H₂Se), nitrogen and air. Hydrogen-selenide (H₂Se) diluted with N₂ is used in a reactor vessel to produce solar cells. An explosive mixture could be created if the reactor vessel failed and its contents mix with ambient air. Mixtures of 20% or 6% H₂Se in N₂ were considered as feedstock into the reactor. It was determined theoretically that an explosion involving either mixture would challenge the reactor room's integrity. However, it is unlikely that a local ignition will propagate in the dilute 6% H₂Se mixture, because its adiabatic flame temperature is only 850 K; the 20% mixture is borderline flammable. Because of the proximity of personnel to the reactor room and the high toxicity of H₂Se, any damage to the room boundary is considered unacceptable. To prevent accidental mixing of H₂Se with air in the reactor, a nitrogen buffer was installed between the reactor vessel and the ambient air.     

Integration of Recursive Operability Analysis,FMECA and FTA for the Quantitative Risk Assessment in biogas plants: Role of procedural errors and components failures

With more than 350 GWh per year and thousands of installations around the world, biogas is an appealing strategy in the field of energy production and industrial waste optimization. In this sense, it is of paramount importance to address the risk associated with such plants, as an increasing trend of accidents have been recorded in the last 20 years. In this work, a representative biogas production plant was considered, and a risk assessment was carried out through the combination of Recursive Operability Analysis and Failure Mode and Effects Criticality Analysis. The methodology is rigorous and allows for both the identification and the quantification of accidental scenarios due to procedural errors and equipment failures, which miss in the literature for the case of biogas. The analysis allows the automatic generation of the Fault Trees for the identified Top Events, which can be numerically solved. Results show that the most critical accidental scenario in the biogas plant here considered is the formation of an explosive air-biogas mixture, which can occur in both anaerobic digester and condensate trap. The calculated probabilities agree with the results available in literature on similar plants. Pumps and Distributed Control System were found to be the most critical components.