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.     

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。     

涂料生产行业RTO设备典型爆炸及泄爆过程模拟

采用Fluent软件建立典型的物理模型及数值模型来模拟RTO燃烧室发生苯气体爆炸事故及其泄爆过程。结果表明:点火源设置在RTO底部且泄爆口设置在顶部时,更有利于保证RTO设备的系统安全。泄爆口开启后,燃烧室内的压力会在20 ms内达到常压,泄爆过程普遍存在二次峰值现象。燃烧室爆炸过程中燃烧室内达到压力峰值的时间随初始温度的升高而缩短,最大爆炸压力随温度升高而减小;燃烧室内达到的爆炸压力峰值随苯蒸气-空气初始化学计量比的增大呈现先增大后减小趋势,在化学计量比为1.4时,爆炸压力峰值最大。     

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。     

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。     

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.     

高密度聚乙烯粉尘燃爆特性及泄爆实验研究

为研究高密度聚乙烯(HDPE)粉尘燃爆及其泄爆特性,通过结合热重(TG)和差示扫描量热(DSC)分析高密度聚乙烯燃爆机理,利用20 L球形爆炸测试系统、最小点火能测定仪、最低着火温度测定仪等探究粉尘质量浓度对最小点火能(MIE)、最低着火温度(MIT)、最大爆炸压力(P_max)和爆炸指数(K_st)的影响;在300 g/m³爆炸浓度及以上时,分析高密度聚乙烯泄放特性并探究在不同质量浓度下的泄放火焰特征。研究结果表明：随着HDPE粉尘质量浓度增加,最大爆炸压力先增加后减小、最低着火温度和最小点火能先减小后增加;泄爆压力峰值随着HDPE粉尘泄爆膜层数增加而升高,随着泄爆口径的增大而下降;在质量浓度为300 g/m³时,出现2次火焰长度较大值,且第2次泄放火焰更亮,燃烧面积更大;在质量浓度为400 g/m³时,产生2次火焰。研究结果可为预防聚乙烯粉尘爆炸事故以及减小相应事故损失提供参考。     

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.     

水平管道泄爆面开启压力对甲烷爆燃压力的影响*

为了研究泄爆面不同开启压力对甲烷爆燃压力的影响,针对受限空间内甲烷/空气混合物爆燃传播过程,建立由水平管道构成的数值模型。研究结果表明:水平管道内存在爆燃压力积聚和泄放的双重效应,随着泄爆面开启压力的增加,测点爆燃压力峰值增大而且测点间爆燃压力峰值差异逐渐减小;在泄爆面不同开启压力条件下,泄压效应造成泄爆面及外部空气域爆燃压力衰减,随着泄爆面开启压力的增加,泄爆面开启时间近似呈线性增大;与水平管道内和泄爆面附近测点相比,水平管道外侧测点的爆燃压力峰值和振荡幅值均显著衰减,而且随着泄爆面开启压力的增加,测点爆燃压力峰值及测点间爆燃压力峰值差异均逐渐增大。     

低压环境下不同三元圆柱锂电池热失控危险特性对比研究

为研究21700和18650新旧2型多用途锂离子电池在航空运输低压环境下的热失控特性差异,采用动压变温实验舱搭建实验平台开展实验。将实验环境压力设定为飞机巡航时的环境压力30 kPa,对比常压101 kPa,使用外部热源加热的方式触发锂电池热失控,利用热传播引发相邻电池热失控,分别从热失控温度变化特性、热释放速率和热解气体组分浓度变化进行分析。研究结果表明:能量密度更高的21700电池热失控峰值温度更高,高温危险性要高于18650电池,但触发热失控所需的热量更多,电池间热传播时间会延长;低压环境有利于降低锂电池热失控燃爆峰值温度,减小燃爆热释放速率,但会产生更多CxHy和CO等具有燃爆性的热解气体,可能会在有限空间内与氧气混合引起二次燃爆。     

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.     

Alternative method to prevent thermal runaway in case of error on operating conditions continuous reactor

Thermal runaway was studied in a continuous tubular pilot reactor under steady-state regime. Different accident scenarii were conducted by making some errors on reactant concentrations and/or temperature feed. To prevent thermal runaway, control by direct contact by solvent injection was used at different reactor locations. This injection allowed controlling the maximum reaction temperature. A simplified analytical method to estimate the maximum reaction temperature along the reactor was used.Benefit of this control method was the diminution of computational time. Furthermore, by injecting solvent to control maximum reaction temperature, there is no need to shut down the unit. The control method was validated experimentally.     

Thermal risk in batch reactors: Case of peracetic acid synthesis

The present paper deals with accidents risk in batch reactors. It identifies the conditions for the occurrence of a thermal runaway and develops a probabilistic approach to assess the relevant risk. It investigates also the conditions for optimal synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA). The kinetic model of reversible reaction and side reaction of PAA synthesis is used to predict reactor temperature and molar ratio of PAA by ASPEN PLUS software. A sensitivity analysis is performed under different conditions such as constant temperature or adiabatic process with different concentrations of sulfuric acid. Assuming a prior cooling system failure, the conditions for reaction runaway triggering a thermal accident are identified in the case of PAA synthesis. Monte Carlo simulations are used in order to calculate the conditional probability of accident and optimize the synthesis of PAA.     

Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

Inherent thermal runaway hazard evaluation method of chemical process based on fire and explosion index

Thermal runaway hazard assessment provides the basis for comparing the hazard levels of different chemical processes. To make an overall evaluation, hazard of materials and reactions should be considered. However, most existing methods didn't take the both into account simultaneously, which may lead the assessment to a deviation from the actual hazard. Therefore, an integrated approach called Inherent Thermal-runaway Hazard Index (ITHI) was developed in this paper. Similar to Dow Fire and Explosion Index(F&EI) function, thermal runaway hazard of chemical process in ITHI was the product of material factor (MF) and risk index (RI) of reaction. MF was an indicator of material thermal hazards, which can be determined by initial reaction temperature and maximum power density. RI, which was the product of probability and severity, indicated the risk of thermal runaway during the reaction stage. Time to maximum rate under adiabatic conditions and criticality classes of scenario were used to indicate the runaway probability of the chemical process. Adiabatic temperature rise and heat of the desired reaction and secondary reaction were used to determine the severity of runaway reaction. Finally, predefined hazard classification criteria was used to classify and interpret the results obtained by this method. Moreover, the method was validated by case studies.     

Catalytic decomposition of hydrogen peroxide in the presence of alkylpyridines: Runaway scenarios studies

A number of runaway scenarios of the excess of hydrogen peroxide used during the N-oxidation of alkylpyridines, under closed and open conditions, were examined. It was found that, in most cases, if the volume of the liquid hydrogen peroxide solution occupies more than 10% of the total volume of a closed system (e.g. reactor and vent line between reactor and blockage), the production of gases raises the pressure so quickly that evaporation is completely suppressed. Higher than 70% filling levels result in complete expansion of the liquid. The MTSR(t) of the system falls rapidly if the normal process temperature is high, but if a runaway occurs exactly at the end of dosing, MTST will be very high and secondary decompositions will rapidly develop. The results of this study are currently being used to critically assess the current approaches and further the study of inherently safer designs.     

常压及低压下锂电池热失控随数量变化特性

为明确在地面常压环境和商用飞机巡航高度低气压环境下锂电池热失控火灾危险特性随电池数量的变化关系,分别于95 kPa地面常压环境和20 kPa低压环境下,开展不同电池数量梯度的热失控试验,测量热释放速率,总热释放量,烟气温度,CO、CO2和碳氢等气体的实时体积分数.结果表明:最高热释放速率和总热释放量与电池数量均呈幂函数...     

好氧堆肥反应器设计及实验研究

设计了具有气液固三相收集功能的强制通风自动搅拌好氧堆肥反应器,并对其进行了好氧堆肥性能试验,通过监测温度、p H、含水率、COD、BOD_5、重金属(Cu)、种子发芽率、热值等指标来判定堆肥效果。实验结果表明,反应器使堆肥周期大大缩短,COD、BOD_5及生物毒性降低明显,45 d后堆体基本腐熟且稳定,堆体减量30%,堆肥效果良好。独有的"耙形"搅拌有利于减少物料温度、湿度和氧气浓度的差异,加快了反应进程。底部二级过滤系统有利于改善渗滤液质量,方便渗滤液的收集及回灌。该反应器可为小型禽畜粪便堆肥反应器的研发和推广提供参考。