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。     

双氧水绝热分解特性的安全泄放研究

反应热失控是引起设备超压的重要因素之一,可靠的安全泄放装置是防止设备发生超压破坏的最有效方法。为了对双氧水储罐的泄放面积进行设计,利用泄放口尺寸测试装置VSP2(Vent Sizing Package 2)对封闭环境下质量分数为20%的H_2O_2进行测试,得到反应失控过程中的热力学参数,并依此推算出不同泄放压力下的安全泄放面积A。结果表明,在绝热条件下,20%H_2O_2的起始分解温度为70℃,比反应热为435.49 k J/kg,最大压力为6.26 MPa。双氧水反应体系的泄放类型为缓和混合体系,采用DIERS设计方法和OMEGA方法计算不同泄放压力下的泄放面积。安全泄放面积随泄放压力增加而增大。VSP2具有很低的热惯量,可为失控反应安全泄放设计提供基础数据,以提高设计的可靠性。     

反应失控条件下过氧化二叔丁基-甲苯体系的安全泄放研究

安全泄放是在失控条件下降低反应体系风险最为经济有效的技术措施。为了研究泄放口的设计,利用高性能绝热量热仪PhiTEC II对质量分数20%的过氧化二叔丁基(DTBP)-甲苯(C7H8)体系进行了测试,得到热惯量1.06条件下温升速率、压升速率随温度变化的数据。结果表明:该DTBP体系的起始分解温度为148℃,其反应体系属蒸汽和气体共同作用的混合体系;采用Leung方法和OMEGA方法对该体系的安全泄放量和泄放装置的泄放能力进行了计算,求得当泄放压力为0.25 MPa时的泄放面积为0.001 4 m2;低热惯量的绝热量热仪Phi-TEC II可以为失控反应的压力泄放设计提供基础数据,有利于提高安全泄放设计的可靠性。     

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。     

丁二烯聚合放热危险特性和安全泄放面积计算

为探讨丁二烯的聚合放热危险特性,并为某化工厂丁二烯储罐安全泄放设计提供依据,利用新型绝热量热仪VSP2,对丁二烯的聚合放热过程及加有阻聚剂对叔丁基邻苯二酚(TBC)的丁二烯的聚合放热过程进行试验研究,得到温度、压力随时间变化的数据。用Leung法和平衡速率模型(ERM),分别计算得到该厂丁二烯储罐的安全泄放流量和泄放能力,并最终确定其安全泄放面积。结果表明:丁二烯聚合反应的起始放热温度为70.26℃,反应失控后体系的最高温度和最高压力分别达到194.07℃和1.06 MPa,具有较大的危险性;阻聚剂TBC能有效阻止丁二烯的聚合;丁二烯聚合反应的泄放类型为蒸气型泄放,计算得到该化工厂丁二烯储罐的安全泄放面积为0.06 m2。     

双氧水热失控时的泄放面积评估

为了保证50％双氧水热失控时在储罐中的安全泄放,利用VSP2(Vent Sizing Package 2)模拟了50％双氧水在带放空测试池中绝热条件下的热失控过程,得到了过程的温度、压力、温升速率变化情况,利用DIERS通用方法计算了50％双氧水安全泄放所需的放空口面积,得到了放空口面积的计算公式.结果表明,储罐设置足够的放空口面积可保证双氧水的安全泄放,在充装系数为0.8时所需的放空面积为0.005 2 V/m.     

异丙醇与丙酸酐酯化反应的安全控制条件

针对异丙醇与丙酸酐酯化合成丙酸异丙酯工艺的反应失控危险性,利用泄放尺寸实验仪(VSP2)研究了其反应的放热特性,选择自催化模式模拟得到了反应动力学参数,并与实验数据进行了对比验证;利用得到动力学模型,模拟了该工艺在半间歇模式、反应温度为70℃时,中试规模(＞ 100L)条件下的反应特点,分析了反应失控的危险性,并针对加料程序进行了优化设计,得到最佳控制方法.     

釜式反应器反应失控的温度与压力预测

釜式反应器因反应失控导致爆炸、火灾和有毒物料泄漏事故时有发生.对其反应失控内在规律的研究有助于采取针对性防范措施.本文从事故案例中分析和总结了化工生产中反应失控火灾爆炸事故的原因和事故特征.利用反应系统热量平衡原理和物料气-液相平衡原理,分别对间歇、半连续和连续式釜式反应器建立了反应失控所达到的最大温度和压力预测方法.结合釜式反应器的操作,应用此预测方法计算表明,半连续釜式反应器失控时继续加料,反应失控的绝热温升最大,连续和间歇釜式反应器次之,而半连续釜式反应器失控时停止加料绝热温升值较小;反应器内液体物料的蒸气压以比温升速度更大的速度上升.     

制冷系统中的安全装置及安全检查

为了预防制冷系统发生事故，确保人们生产、生活的安全，制冷与空调系统的管理及操作人员必须认真学习制冷技术，特别应该熟悉和掌握制冷系统中安全装置的基本常识，以利于制冷系统的安全管理和安全检查，做到及时发现问题及时整改。一、制冷系统中的安全装置及其作用在制冷系统中常用的主要安全装置（附件）有安全问、易馆塞、紧急泄氛器、高低压力控制器、油压压差控制器和压力表等。1．安全问在制冷系统中一般采用弹簧式安全阀，其作用是当制冷系统内尚压压力超过限定值时，阀门自动开启，使制冷剂通过安全阀自动泄放至低压系统或排至大…     

无火焰泄放装置性能检测技术研究*

为有效提高无火焰泄放装置产品质量特性和应用技术,避免或减轻爆炸事故发生造成的灾害程度,选择玉米淀粉粉尘为测试粉尘,采用1 m3爆炸罐进行扇形无火焰泄放装置爆炸泄放实验。结果表明:扇形无火焰泄放装置不适合重复使用。当扇形无火焰泄放装置重复进行爆炸泄放实验时,爆炸罐内压力会呈现升高趋势,而外场压力和温度呈现下降趋势,且阻火元件孔隙内残留大量玉米淀粉粉尘燃烧后生成的炭黑以及积聚部分高温燃烧的粉尘,致使阻火元件损坏失效。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Prediction of the relief of gas explosion in a tubular vessel by venting using a mathematical model

The relief of a gas explosion in a tubular vessel by venting can be predicted by using a mathematical model. In this model, the flame acceleration is represented by an increase in the burning velocity. The movement of a vent cover can be included. The model assumes that the vent is blocked by the vent cover prior to the explosion. the venting ratio was the most influential parameter in terms of relieving the pressure. In the case of a large venting ratio, the flame acceleration made a highly significant contribution, whereas for small venting ratios, the weight of the vent cover contributed to the relief more than the flame acceleration. When the pressure is required to be reduced significantly, the venting ratio, the vent open pressure and the weight of the vent cover must all be reduced.