Dynamic model based safety analysis of a three-phase catalytic slurry intensified continuous reactor

Safety analysis like the HAZOP (HAZard OPerability) study can be much more efficient if a dynamic model of the system under consideration is available to evaluate the consequences of hazard deviations and the efficiency of the proposed safety barriers. In this paper, a dynamic model of a three-phase catalytic slurry intensified continuous chemical reactor is used within the context of its HAZOP (HAZard OPerability) study. This reactor, the RAPTOR®, is an intensified continuous mini-reactor designed by the French company AETGROUP SAS that can replace batch or fed-batch processes in the case of highly exothermic reactions involving hazardous substances. The highly hazardous hydrogenation of o-cresol under high pressure and temperature is taken as an example of application. Deviations as a temperature increase of the cooling medium or no cooling medium flow can produce an overheating of the reactor. Thus, three possible safety barriers are evaluated by simulation: shut off the gaseous reactant feed, shut off the liquid reactant feed or stop the agitation. The more efficient actions are the stopping of the agitation and/or of the gas reactant feed. The simulation results can efficiently help the reactor design and optimisation. Safety analysis can also be one of the criteria to compare batch and intensified continuous processes.     

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.     

Influence of parameter uncertainty on modeling of industrial ammonia reactor for safety and operability analysis

Chemical reactors represent probably the most hazardous units of chemical industry. Safety analysis of a chemical reactor requires basic knowledge of all particular processes which can be described by mathematical models. Most of the model parameters involved in the prediction of reactor behavior are uncertain. These uncertainties can cause discrepancies mainly in the prediction by models with nonlinear behavior and they can be the source of confusion in the design of chemical reactors and consequently also in the safety and operability analysis.The main aim of this work was to analyze the influence of uncertainties in the model parameters on the prediction of operating quantities by mathematical models with nonlinear behavior. Such analysis can be used for safety and operability analysis of an industrial catalytic ammonia reactor. The industrial fixed-bed reactor was used by a mathematical model with nine parameters. Analyses of the influence of uncertainty in a single model parameter and their combination were carried out by the Monte Carlo approach. It is shown that even a small uncertainty in one of the key parameters or in a combination of these key parameters can result in several steady states results of the operating quantities and can be the source of confusion in the design and consequently also in the safety and operability analysis.     

一种新型危险化工工艺安全评估方法的设计

在安全生产过程中,建设项目风险评价在我国经过几十年的发展,无论在模型亦是方法上均有所进步,但对化工项目进行危险化工工艺风险等级评价的研究并不多见。本文按照危险化工工艺表征涉及的影响因素,在参考了日本劳动省"六阶段"的定量评价表以及危险度评价法并对15种危险化工工艺定性分析的基础上,提出了一种基于危险度评价法的更为全面的危险化工工艺辨识方法。该评价方法可用于确定危险化工工艺的风险等级。为化工企业工艺危险的实时评估和安全管理提供技术支撑和科学途径。     

Use of isoperibolic calorimetry for the study of the effect of water concentration,temperature and reactor venting on the rate of hydroxylamine thermal decomposition

Hydroxylamine, NH₂OH, thermal decomposition has been responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting the rate of its decomposition are not understood. In this work, isoperibolic calorimetric measurements were performed in a metal reactor, in the temperature range 130–150 °C, employing 30–80 ml solutions containing 1.4–20 g of pure hydroxylamine (2.8–40 g of the supplied reagent). The calorimetric measurements were performed in order to assess the effects that NH₂OH concentration, temperature and reactor venting has on NH₂OH rate of decomposition. The measurements showed that increased concentration or temperature, results in faster reactions and probably higher pressure generation per mass of reactant, with concentration having a more pronounced effect. However, when both factors work synergistically the result is dramatically worse in terms of reaction rate. The pressure generation is also different, thus indicating that different reaction pathways predominate each time. Venting the produced gases in stages resulted in the highest mass loss of the solution.     

Equipment selection for the optimal system unavailability of jacketed reactors with discrete cost data

This study introduces a method that selects equipment, so as to reach the required unavailability level, by carrying out an optimization analysis which considers the reliability data and cost of the equipment. A more practical optimization problem has been formulated using the objective function based on the discrete function and constraints.For the cooling system of a jacketed reactor, an optimization analysis was performed on equipment that have different failure rates depending on their costs in order to reach the target unavailability level required by the system. The integer programming was used for this optimization analysis. When the method developed through this study is used, cost can be reduced and the target level of the system unavailability can be reached by selecting proper equipment for chemical plants through the optimization analysis. This is more cost efficient than the former method of selection, which does not perform any economical analysis thus leading to the usage of overly expensive equipment with low failure rates.     

Gas-phase thermal explosions in catalytic direct oxidation of alkenes

The metal-based catalytic oxidation of alkenes to the corresponding epoxides is playing a significant role in the modern chemical industry. Nevertheless, these key processes are still lacking proper understanding with respect to the gas-phase runaway behaviour (thermal explosion) and to the hot spot formation on the catalytic surface, under the typical process conditions.This work aims to enlighten these aspects by considering either the catalytic or the gas-phase chemistry for the development of reactor operative diagrams, in order to define the best-operating conditions with respect to the selectivity, the productivity, and the process safety aspects.The proposed methodology has been applied to the oxidation of ethylene and propylene for the direct oxidation process by pure oxygen, considering a detailed kinetic model accounting for the homogeneous reactions, coupled with the heterogeneous catalytic mechanisms.Sensitivity and reaction path analyses were performed to individuate the ruling species and reactions determining the transition to runaway conditions.     

Trends in chemical hazards in Japan

In the past, the chemical industry in Japan has been the cause of a number of major industrial accidents. Subsequent to each accident, specific lessons have been learned. These lessons learned have been implemented in terms of safety education of the employees and/or safety measures of the equipment and facilities resulting in a rapid decrease of corresponding accident frequencies. In this paper, we summarized both recent and past major accidents caused by chemical substances in fixed installations in Japan. Case studies show that runaway reactions are among the main causes of major accident occurrences in the chemical process industry in Japan. A recent fatal poisoning accident caused by H₂S gas generated during maintenance work again highlights the necessity of adequate safety management in a chemical factory. Therefore, even if hazard evaluation of chemical substances and chemical processes is necessary to prevent runaway reactions, human error is also an important factor contributing to reaction hazards [Wakakura, M. (1997) Human factor in chemical accidents, J. Safety Eng. High Press. Gas. Safety Inst. Japan, 34, 846].     

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.     

Critical runaway conditions and stability criterion of RDX manufacture in continuous stirred tank reactor

The energetic material cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX) has been widely used as explosive and propellant ingredients in the military industry. It is usually produced by hexamine nitration reaction in continuous stirred tank reactor (CSTR). This manufacturing process is quite dangerous and always causes fire incidents or explosion owing to its thermal instability in its nitration reaction or purification processes. In this investigation, we used its reaction kinetics parameters to evaluate the thermal hazard conditions and stable reaction criteria in the reaction systems of continuous stirred tank reactor.     

Hazards from carbon dioxide capture, transport and storage

Carbon capture and storage (CCS) is a developing technology which raises a number of issues in terms of safety. CCS involves a chain of processes comprising capture of carbon dioxide, transport and injection into underground storage. In work carried out for the IEA Greenhouse Gas R&D Programme, a number of high-level hazard identification (HAZID) studies have been performed with the help of industry experts. The HAZIDs considered a carbon capture and storage chain involving capture, pipeline transport and injection. HAZID has been performed at a high-level for such a CCS chain with three types of capture technology and using pipeline transport. It is hoped that the results of the HAZID studies will be of use to those carrying out CCS projects, but should not be a substitute for them carrying out a full suite of integrated hazard management processes. A number of example hazards have been described to raise awareness of the range of hazards in a CCS process and to identify barriers which could prevent, minimise, control or mitigate CCS hazards. Bow-tie diagrams have been produced to record the information from this study and to organise it in a systematic way so that it is far less likely that contributors to and mitigators of hazards will be missed. The diagrams are available in Excel spreadsheet format so that they can be used as the starting point for development by specific CCS projects. CCS technology is still advancing and a number of knowledge gaps in terms of safety have been identified which require further development.     

Safety assessment for accident of cooling loop failure (ACLF) in lunar nuclear power reactor (LNPR)

The safety assessment of an accident in the lunar base power plant is investigated for the stability of the operation. The lunar surface reactor is modeled for this study. The accident of cooling loop failure (ACLF) is one of the important scenarios for the virtual case in the moon nuclear power plant (NPP). The newly designed lunar nuclear power reactor (LNPR) is suggested for the commercial purpose. The system dynamics (SD) is used for the simulation of the safety assessment. The cyclic variation of the lunar surface temperature can affect to the physical situation of the coolant, which is expressed by the time step. The result shows the performance possibility of the long term cooling increases slightly in the short period of the time step. The dynamical simulation of the lunar environment is performed for the conceptual design of the NPP.     

烷基苯联合装置风险及控制研究

烷基苯联合装置含有国家安全监管总局首批重点监管的15种危险化工工艺中的加氢工艺、烷基化工艺两种,装置工艺介质为易燃、易爆、有毒及强腐蚀性物质,生产中潜在危险性较大;开展工艺风险研究,落实控制措施,对于提高装置本质安全性具有极为重要意义.首先探讨了工艺危险和要害部位,确认装置主要风险为火灾、爆炸和毒性危害;然后应用HAZOP方法,以加氢反应进料加热炉、烷基化反应器为分析对象,研究了工艺状态参数温度、压力、物料流量等方面出现偏差的原因、后果及安全措施;还对氢气泄漏发生火灾、爆炸和苯泄漏发生火灾、爆炸、人员中毒进行了事故后果定量分析,提出了相应的安全措施,以消除或降低工艺危险,保障装置安全.     

Model-based hazard identification in multiphase chemical reactors

Chemical productions operated in extreme conditions (high pressure, high temperature) require a detailed analysis of all potentially dangerous situations that can lead to a major industrial accident and thus cause a loss of life and property. Many accidents in the near or distant history underline the need of a detailed safety analysis in process industries, not only in the phase of plant design but also during the operation of the plant. It would be shown that simulation of a chemical unit using an appropriate mathematical model and the nonlinear analysis theory can be a suitable tool for safety analysis. This approach is based on mathematical modeling of a process unit where both the steady-state analysis, including the analysis of the steady states multiplicity and stability, and the dynamic simulation are used. Principal objective of this paper is to summarize problems regarding the model-based hazard identification in processes. A case study, focused on phenomena of multiple steady states in ammonia synthesis reactor will be presented. The influence of the model complexity and model parameters uncertainly on the quality of safety analysis would be underline.     

unipol气相法聚乙烯聚合过程的危险分析与控制

在聚乙烯工业生产中,聚合过程本身存在着一些固有危险因素,如反应过程中热量的移出、聚合原料以及聚合助剂的燃爆危险等,一直都是从事安全工作人员关注的重点。很多相关的技术研发公司均采取的不同的手段,加以应对。其中,美国UCC公司的un ipol气相法聚乙烯工艺,针对这些危险因素采取了一定的控制措施,较好的解决了这些问题。例如,为了解决反应聚合反应热量的问题,采用循环气大量循环,在流化床反应器外消除反应热,同时,在循环气内加诱导冷凝剂的方法吸收聚合反应放出的热量。就此,本文从化工过程安全的角度,对un ipol气相法聚乙烯工艺中,聚合过程存在的固有危险因素产生的原因及其可能导致的结果和在工艺中针对这些问题采取的控制措施及其工作原理加以分析。     

Experimental analysis of gas explosions at non-atmospheric initial conditions in cylindrical vessel

Accidental gas explosions in industrial equipment are seldom initiated at atmospheric conditions. Furthermore, fuel–air mixtures are generally turbulent due to rotating parts or flows. Despite these considerations, few studies have been devoted to the analysis of explosion properties at conditions of temperature and pressure different from ambient and in the presence of turbulence; therefore, experiments are still needed, even at lab-scale, e.g. for the design of mitigation system as venting devices.In this work, experimental explosion tests have been performed in 5 l, cylindrical tank reactor with stoichiometric methane–air mixtures at initial pressure and temperature up to 600 kPa and 400 K, centrally ignited or top ignited, and with the effect of initial turbulence level by varying the velocity of the mechanical stirrer.     

Study of Major Accidents Involving Chemical Reactive Substances: Analysis and Lessons Learned

The objective of this paper is to present the results of the analysis performed on a selection of accidents included in the MARS database. This is a database of past accidents that occurred in Europe maintained by the European Commission, in order to help the Member States to meet the requirements of the Seveso and Seveso II directives. The study is focused on those accidents that involve reactions between chemical substances, whether wanted or unwanted, that generated a hazardous situation by loss of control of such reactions. Runaway reactions are known to be especially dangerous, given that many times they are unexpected, or their possible consequences underestimated, so sometimes chemical industries are not ready to cope with the effects of loss of control of reactive processes. The aim of the analysis is to obtain lessons learned from past accidents in order to prevent similar situations in the future, or to reduce their consequences. Understanding the causes of past accidents, including equipment failures, deviations in the expected course of a reaction, or deficiencies in process operations performed, can help to a better understanding of similar processes. Industries working with potentially dangerous chemicals should consider introducing lessons learned into their safety management systems.