Safety relief analysis for methanol-acetic anhydride system by stationary methods and dynamic simulation

The Leung method proposed by the Design Institute of Emergency Relief Systems (DIERS) is widely used in the design of relief systems involving two-phase flow. However, this method is not always suitable for all the situations. The calculating results may be unacceptably large, especially under high overpressure. To aid selection of appropriate vent sizing methods, a typical vapor system experiment (esterification of methanol-acetic and anhydride) was conducted by the vent sizing unit (VSU) of accelerating rate calorimeter (ARC). Seven different stationary methods were used to calculate the venting size under overpressure of 10%, 20%, 50%, 100% and 200%. Through the systematic comparison of different methods, a conservatism order of stationary methods was summarized as well as the selecting principles for these methods were discussed. Process simulation was also applied to investigate the relationship between reactor temperature/pressure and its relief size, which could be used in the prediction of vent size in vapor system conveniently without complex calculating procedure.     

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.     

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.     

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.     

Investigation of a drum explosion of 30% aqueous KOCN

A 30% aqueous solution of KOCN placed in a 55 gallon HDPE drum at 50 °C began venting gas almost immediately. Although a vent was kept open the drum exploded within 1–2 h of being filled. This report reviews the steps taken after the accident to find its cause and to recommend safe operating conditions. The DIERS vent sizing package (VSP), used as a closed system adiabatic reactor, was able to simulate the incident under controlled laboratory conditions. Data were thereby collected for the first time on the runaway kinetics of the KOCN hydrolysis. Isothermal data were obtained in a highly sensitive microwatt heat flow calorimeter in an open system. It was demonstrated that even under isothermal conditions, the hydrolysis rates accelerated once underway, reaching maxima in 30 h at 25 °C and 6.7 h at 40 °C. There is satisfactory agreement of these results with other work on 0.5% KOCN solutions reported in earlier studies.     

Numerical simulation of the thermal inertia of an adiabatic reaction calorimeter in reaction thermal safety process

Obtaining accurate thermal risk assessment parameters of chemical processes and substance properties is essential for improving the safety of chemical production and substance use and storage, and the adiabatic reaction calorimeter (ARC) has been employed by many researchers for this purpose. However, with the improvement and upgrading of the instrument, an examination of the factors that affect its detection accuracy is warranted. A simplified reaction model of the adiabatic thermal decomposition of tert-butyl peroxyacetate was constructed using computational fluid dynamics in which the adiabatic thermal decomposition kinetic model and fluid-solid coupling model were combined to simulate heat transfer. To verify the reliability of the parameters of the numerical calculation model, the effects of the sample cell's material, wall thickness, and mass were investigated in relation to the thermal inertia of the ARC. The results indicated that the thermal inertia of the system was lowest when the sample cell was composed of titanium. When the sample pool's composition is determined, the thermal inertia of the system can be reduced to a certain extent through an approximate increase in the sample mass. Finally, an analysis of the heat flow cloud diagram of the wall of sample pools made from different materials revealed that the thermal conductivity of titanium was high; this information can assist in controlling the adiabatic process.     

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。     

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.     

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.     

氯化钠和二氧化硅对过硫酸铵热稳定性的影响

采用绝热加速量热仪（ARC）对分析纯过硫酸铵、含10%氯化钠杂质的过硫酸铵以及含10%二氧化硅杂质的过硫酸铵进行热分析实验,得到了实验过程中温度、温升速率和压力等数据,计算了3组样品的反应动力学参数,引入热惰性因子对实验数据进行修正,得到了3组样品在严格绝热条件下的热危险性参数,分析了3组样品的反应过程和热危险性。通过Semenov理论计算了3组样品的自加速分解温度（SADT）。结果表明,过硫酸铵加入氯化钠或二氧化硅杂质后,热危险性增大,自加速分解温度降低,更容易发生反应且反应更剧烈。     

苯和甲苯硝化及磺化反应热危险性分级研究

首先介绍了化工工艺热安全性的内涵,并从反应过程热危险性分析的方法学出发,介绍间隙、半间歇化学反应工艺热危险性分级研究的总体思路及方法。然后,围绕甲苯和苯的硝化、磺化反应,用全自动反应量热仪(RC1e)和加速度量热仪(ARC)测定其反应过程的绝热温升(△Tad)、目标反应所能达到的最高温度(TM)、分解反应最大速率到达时间(θD)等参数。运用风险评价指数矩阵法(方法1)和基于失控过程温度参数的热危险评估法(方法2)分别对其硝化和磺化反应过程的热危险性进行了分级评估。结果表明,这两种方法具有良好的一致性;给定工艺条件下甲苯和苯的一段硝化反应过程的热危险度等级较低;而磺化反应的热危险较高。尽管这两种方法还有一定的局限性,但对于间歇、半间歇合成工艺的本质安全化设计、工艺热危险性的评估具有重要的参考价值和实用意义。     

过氧乙酸溶液的热爆炸分析

为有效预防生产、储运和使用中过氧乙酸引发的火灾爆炸事故,采用绝热加速量热仪模拟了15%和10%浓度的过氧乙酸溶液的热爆炸过程,得到了两种浓度的PAA溶液的热分解温度、压力、温升速率随时间变化的关系曲线,并用速率常数法分别计算了反应级数n、表观活化能Ea和指前因子A。经过绝热修正,得到最危险状态下的温度和压力等相关热危险参数,并基于Semenov热爆炸理论推算了三种包装条件下两种样品的不可逆温度和自加速分解温度。结果表明,15%PAA和10%PAA溶液热分解反应级数均为一级,表观活化能分别为1044kJ·mol-1和1032kJ·mol-1;绝热条件下初始放热温度分别为429℃和293℃;自加速分解温度受反应系统到达最大反应速率的时间、物料存储规模及散热条件的影响,建议PAA应储存在通风背阴处且单个包装容积应控制在25L以下。     

硝酸异辛酯热安定性的实验研究

使用加速量热仪(ARC)研究硝酸异辛酯(EHN)的热分解,得到热分解温度随时间的变化曲线,自放热速率、分解压力随温度的变化曲线以及分解压力随升温速率的变化曲线。分析在绝热条件下硝酸异辛酯的热分解反应动力学和热分解过程,计算表观活化能、指前因子和反应热等参数。根据绝热热分解的起始温度和反应热数据,给出硝酸异辛酯在反应危险度等级中的分类,并计算在75℃时的反应风险指数。     

Medium-scale experiments on vented hydrogen deflagration

A series of medium-scale experiments on vented hydrogen deflagration was carried out at the KIT test side in a chamber of 1 × 1 × 1 m³ size with different vent areas. The experimental program was divided in three series: (1) uniform hydrogen–air mixtures; (2) stratified hydrogen–air mixtures within the enclosure; (3) a layer deflagration of uniform mixture. Different uniform hydrogen–air mixtures from 7 to 18% hydrogen were tested with variable vent areas 0.01–1.0 m². One test was done for rich mixture with 50% H₂. To vary a gradient of concentration, all the experiments with a stratified hydrogen–air mixtures had about 4%H₂ at the bottom and 10 to 25% H₂ at the top of the enclosure. Measurement system consisted of a set of pressure sensors and thermocouples inside and outside the enclosure. Four cameras combined with a schlieren system (BOS) for visual observation of combustion process through transparent sidewalls were used. Four experiments were selected as benchmark experiments to compare them with four times larger scale FM Global tests (Bauwens et al., 2011) and to provide experimental data for further CFD modelling. The nature of external explosion leading to the multiple pressure peak structure was investigated in details. Current work addresses knowledge gaps regarding indoor hydrogen accumulations and vented deflagrations. The experiments carried out within this work attend to contribute the data for improved criteria for hydrogen–air mixture and enclosure parameters to avoid unacceptable explosion overpressure. Based on theoretical analysis and current experimental data a further vent sizing technology for hydrogen deflagrations in confined spaces should be developed, taking into account the peculiarities of hydrogen–air mixture deflagrations in presence of obstacles, concentration gradients of hydrogen–air mixtures, dimensions of a layer of flammable cloud, vent inertia, etc.     

壳体缓释技术对带壳装药慢速烤燃反应烈度的缓解作用研究

为了研究2种典型壳体缓释技术对弹药慢速烤燃响应烈度的缓解作用,基于试验条件分别建立无缓释设计、侧壁加工应力槽和端盖加工泄压孔的带壳PBX装药慢速烤燃仿真模型,提出使用热分解反应动力学模型和燃烧反应模型模拟计算不同约束条件下带壳PBX装药从开始加热发生热分解反应到点火燃烧以及炸药与壳体耦合作用的烤燃过程的计算方法。研究结果表明：通过侧壁加工应力槽以及端盖加工泄压孔的缓释结构设计,可以有效地降低壳体破裂时炸药内部的压力及反应度,以达到缓解反应烈度的目的。     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.     

Ammonium nitrate thermal decomposition with additives

Runaway reactions present a potentially serious threat to the chemical process industry and the community; such reactions occur time and time again often with devastating consequences. The main objective of this research is to study the root causes associated with ammonium nitrate (AN) explosions during storage. The research focuses on AN fertilizers and studies the effects of different types of fertilizer compatible additives on AN thermal decomposition. Reactive Systems Screening Tool (RSST) has been used for reactivity evaluation and to better understand the mechanisms that result in explosion hazards. The results obtained from this tool have been reported in terms of parameters such as “onset” temperature, rate of temperature and pressure rise and maximum temperature. The runaway behavior of AN has been studied as a solid and solution in water. The effect of additives such as sodium sulfate (Na₂SO₄) and potassium chloride (KCl) has also been studied. Multiple tests have been conducted to determine the characteristics of AN decomposition accurately. The results show that the presence of sodium sulfate can increase the “onset” temperature of AN decomposition thus acting as AN thermal decomposition inhibitor, while potassium chloride tends to decrease the “onset” temperature thus acting as AN thermal decomposition promoter.     

二甲亚砜热稳定性的实验研究

采用先进的绝热加速量热仪为手段,对二甲亚砜的热稳定性进行了系统研究,其内容涉及纯二甲亚砜的热稳定性、加酸碱和硫化物等杂质后二甲亚砜的热稳定性,包括初始放热温度、温升速率、温度-压力等;通过修正试验数据,消除了热惰性因子的影响;得到了二甲亚砜的热稳定性特性。研究表明,在酸、碱存在时,二甲亚砜在室温下即可发生强烈的放热反应,导致二甲亚砜的分解温度提前。该实验研究结果,对二甲亚砜的安全生产工艺过程控制具有重要参考价值。     

绝热加速量热仪在化工生产热危险性评价中的应用

本文介绍了一种新型热危险性分析仪器--绝热加速量热仪的设计原理和内部结构,运行模式以及所能获得的温度、压力和最大温升速率时间等数据类型.并通过阐述其在化学动力学研究、自加速分解温度的计算、化学工艺安全性分析和化学工艺过程开发以及热爆炸事故原因调查等方面的应用,指出了绝热加速量热仪在化工生产危险评价方面的特点和优势.