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.     

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.     

Safer management of process changes in chemical reactors

Nowadays many chemical industries are SMEs where multi-purpose batch or semi-batch reactors are commonly used. Vent sizing for realistic runaway scenario is not an easy task for such enterprises since they have usually few resources and use multi-purpose reactors with fast process turnovers. As a consequence these batch and semi-batch reactors are usually equipped with emergency relief systems sized once forever when the reactor is designed. This can lead to a large underestimation of the vent area in case of runaway reactions occurring when processes different from the ones considered for originally sizing the vent are carried out.The approach proposed in this work aims to identify the maximum reactor load leading to safe conditions even in case of runaway phenomena to be handled with the emergency relief system already installed (or even with a smaller vent area). This approach allows avoiding the change of the emergency relief system with a larger vent area (as required every time a new more hazardous process has to be carried out on existing reactors) at the price of lower plant productivity.     

C6H12N4+Mg+KClO4+SrSO4系统的振荡控制和安全分析

从实验和数值分析两方面研究了C6Hl2N 4+Mg+KClO4+SrSO4反应系统的振荡燃烧现象,并对反应机理进行了深层次的分析.结果表明,振荡燃烧是由化学动力学的非线性反馈引起的,即:反应系统中镁的三相与氧气的相互竞争反应造成系统的非线性化学振荡燃烧.氧化剂和可燃剂的比值,以及频率调节剂等吸热物质可调节气相镁的生成速率,能有效地控制药剂的振荡频率.选取适当的控制参数,可以使反应按照预定的、安全的过程进行,避免爆燃的产生.本文的研究结果对化工、军事等领域的安全控制具有重要意义.     

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。     

敏感性分析在燃烧毒物和自由基生成机理研究中的作用

针对燃料氧化的详细/半详细化学反应动力学机理，采用定量研究模型与出现在模型中各种参量之间关系的系统化方法--敏感性分析法，研究各基元反应对燃料过程中毒物和自由基生成的影响系数随时间的变化关系，为反应设计提供理论指导。     

Determination and assessment of the characteristic values for the evaluation of the thermal safety of chemical processes

Experience gained in the chemical industry in testing and assessing the thermal safety of chemical processes is published in this paper. Isothermal and adiabatic tests, which are the most important methods for both small and large quantities, are described and discussed. Methods for testing the thermal hazards of primary or desired reactions are also included, e.g. reaction calorimetry, adiabatic methods, investigations using a sampling method. More important are the criteria for assessing the test results. On the basis of energies produced by primary and secondary reactions and the temperature ranges within which they take place, thermal hazards can be predicted. If the rules for the safe design of batch and semi-batch reactions are observed, it is possible to control the thermal behaviour of reactions.     

N_2/CO_2/H_2O抑制甲烷爆炸化学动力学机理分析

应用敏感性分析方法对N2,CO2和H2O抑制甲烷爆炸的化学动力学机理进行了理论分析,结果表明:在N2,CO2和H2O的抑制作用下,在甲烷氧化链式反应进程中起关键"桥梁"作用的自由基——CH3和HCO的生成受到强烈抑制,从而使得甲烷氧化链式反应进程受到影响和破坏;CO2和H2O除了具有N2所具有的抑燃、抑爆特性外,还会参与甲烷氧化链式反应,并对CH4氧化放热产生阻碍作用。     

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.     

飞机防火试验中的燃烧反应动力学模型研究

使用反应路径分析法对Jet-A型航空煤油燃烧的气相燃烧机理进行简化。选用POSF-4658机理作为Jet-A燃烧的详细反应机理,该机理包含1607种燃烧组分、6633个基元反应机理。将飞机防火试验条件作为简化过程的初始条件,得到78种组分,196个反应机理的Jet-A燃烧机理。通过对Jet-A的简化反应机理、详细反应机理和JetA实验数据的比较可以发现,简化反应机理可以较准确地反映Jet-A型航空煤油在防火试验条件下的燃烧特性。利用常用的Jet-A型航空煤油简化机理计算的绝热火焰温度、点火延迟时间及层流火焰速度与本文提出的简化的计算值进行比较。结果表明,提出的简化机理在防火试验条件下具有较高的精确度。得到的Jet-A简化反应机理可为飞机防火试验的仿真研究提供燃烧场的化学反应动力学模型。     

Database-supported documentation and verification of pressure relief device design in chemical plants

In this paper the results of a multi-year analysis of the pressure relief devices located in several plants in major chemical sites are summarized. The analysis consisted of a systematic evaluation of existing safety valves and rupture discs including the identification of the service conditions and design cases as well as the sizing calculations of the individual device and associated piping. Furthermore, from the total amount and the hazardous potential of the effluents the necessity of retention systems is evaluated to ensure a safe disposal.Because the knowledge in the field of emergency pressure relief changed very rapidly in recent years, the design of some safety devices was not according to the state of the art. An essential part of the verification program was the recommendation of measures to find the most economical yet technically correct way to correct these deficiencies. Rather than by carrying out wholesale replacement of an incorrectly sized safety device or vent line, often a reduction of the mass flow rate to be discharged, for example, by an orifice in a supply line, is sufficient.Results of the analysis were recorded on a novel database to capture the sizing information and maintain correct pressure relief device sizing into the future. The systematic databased approach has been used for the evaluation of about 4000 safety devices so far. The procedure has been proven to enable an experienced design engineer to carry out the analysis of a great number of pressure relief devices in a time-saving, reliable and reviewable way.     

卤素类阻燃剂的阻燃基础理论

本文从阻燃化学反应,化学键能,热传递和反应动力学角度分析勖类阻燃剂的阻燃机理。     

大型气相化学动力学软件包CHEMKIN及其在燃烧中的应用

燃烧化学反应动力学是计算燃烧学中的重要内容之一。本文介绍了处理气相化学动力学的大型软件包ＣＨＥＭＫＩＮ的结构和不同版本的特点,并描述了它在燃烧问题中的应用。最后通过一个算例对Ｈ２／Ｏ２／Ｎ２均相绝热等压燃烧体系进行了处理和计算,以具体说明该软件包的应用效果。     

易燃混合气体爆炸完全基元反应模型数值模拟

采用完全基元反应模型和高精度ENO格式对易燃混合气体爆炸过程进行了数值研究,对H2/O2/Ar混合气体起爆和爆轰波传播过程的数值模拟结果表明,计算的爆轰波阵面参数和实验相当符合,对轰波反应区化学反应的研究表明,参与反应的不同组分具有不同类型的变化特征,这些特征为爆炸灾害的预防设计提供了线索。     

A little knowledge is a dangerous thing – Unexpected reaction case studies make the case for technical discipline

The old saying, “what you don't know can't hurt you,” implies that ignorance is bliss. “A little knowledge is a dangerous thing,” may be closer to the truth; however, it is not the little that we know that is dangerous, but that which is not known. By design, the processes used in the chemical industry are reactive, and the intended reaction receives much scrutiny. However, other reactions occur, often unexpectedly, and possibly with severe consequences. The lessons we learn from these reactions must drive the improvement of our process development and technology management processes and the culture that shapes those processes, a culture of Technical Discipline.Technical Discipline, analogous to Operating Discipline in the manufacturing organization, is a culture committed to fully identifying and characterizing chemical and reaction hazards, and properly documenting and communicating those hazards to create a permanent knowledge and understanding within the organization operating that process.A culture of Technical Discipline will reveal reaction hazards that might otherwise remain unknown until being unveiled in a dramatic and unexpected fashion. Until you fully identify and characterize the hazards of the materials you handle in your processes…what you don't know can hurt you.     

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.     

基于重要性分析的甲烷/乙烯混合燃烧框架机理构筑

建立了基于重要性分析的详细化学机理分析平台,利用耦合组分化学存活时间和敏感性系数的重要性参数,确定详细机理中的准稳态组分,通过移除这些组分及其相关反应,得到了计算精度较高的框架机理。针对目前燃烧学界较为关注的混合燃烧问题,以甲烷、乙烯这两种典型低碳碳氢燃料为研究对象,对其详细化学反应机理进行了分析,利用重要性分析法构筑框架机理,并对甲烷/空气和甲烷/乙烯/空气预混火焰进行了数值计算。与详细机理相比,框架机理所涉及的组分数与基元反应数都得到了大幅度的降低,计算时间明显减少,但对火焰温度及反应物、生成物、中间组分浓度的预测与采用详细机理得到的结果吻合良好,证明了重要性分析法的有效性与可靠性。     

磷酸活性炭自燃过程反应动力学研究

为研究磷酸活性炭的自燃危险性,以自制的磷酸活性炭(活化温度为300,500和700℃)为考察对象,利用同步热分析仪(STA)对活性炭氧化放热动力学进行试验研究。根据在2,5,10和20℃/min等4种不同升温速率下得到的活性炭DSC/TG曲线,结合Friedman-Reich-Levi动力学方法对反应过程中可能存在的反应机理进行初步判断。研究表明,随着活化温度的升高,活性炭的起始放热温度和最大放热温度随之升高;活性炭整个氧化反应过程中,活化能随着转化率的改变呈现一定规律性变化;碳氧化学反应和气体扩散共同影响活性炭氧化过程,且在不同阶段对氧化的贡献不同。     

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.