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。     

环氧乙烷水溶液失控反应特性研究

为了系统研究环氧乙烷水溶液失控反应热动力学参数的变化规律,采用等温扫描量热仪C600和绝热量热仪VSP-2分别对环氧乙烷水溶液进行了量热试验研究,得到了纯环氧乙烷的热稳定性数据,以及不同质量分数环氧乙烷水溶液的起始放热温度、最高放热温度和压力、放热量、绝热温升及失控反应过程的温度、压力变化等。结果表明,纯环氧乙烷发生失控反应的起始温度接近360℃,其放热量高达2 600 k J/kg。水加入环氧乙烷能够显著降低体系的起始放热温度至200℃以下。随环氧乙烷水溶液质量分数升高,失控反应致灾后果的严重程度明显提高。最高温度和压力、温升和压升速率、放热量及绝热温升随环氧乙烷质量分数升高而增大,而达到最大反应速率的时间减小。     

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。     

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。     

醋酸乙烯聚合体系热失控风险评估及失控抑制

为实现对醋酸乙烯(VAC)聚合反应热失控行为的风险评估及紧急抑制,采用VSP2绝热量热仪对醋酸乙烯聚合反应体系在不同危险场景条件下的热失控过程和失控抑制进行试验模拟。依据苏黎世危险性分析法(ZHA)中的失控反应严重度评估判据,评估醋酸乙烯聚合反应的热失控风险程度,提出紧急情况下抑制剂的加入时间及加入量。结果表明,醋酸乙烯聚合反应失控后绝热温升(ΔT_(ad))超过100℃,最大反应速率到达时间(TMRad)约为10 min,其热失控风险程度仅次于不可接受水平。聚合体系温度不高于73℃时,通过加入不低于参与聚合反应的醋酸乙烯质量20%的常温溶剂,可有效阻止失控反应发生。     

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.     

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。     

加氢站用45 MPa高压储氢瓶式容器火烧试验模拟*

为研究加氢站用高压储氢容器在火灾下的安全性能,采用计算流体力学（CFD）方法对45 MPa高压储氢瓶式容器火烧试验过程进行模拟研究,结合气瓶火烧试验,分析高压储氢容器火灾下的热响应过程,研究不同因素对储氢容器压力泄放装置动作时间的影响。结果表明:613 s以内试验压力与模拟数据的最大相对误差为3.9%,模型误差在可接受范围;不同充装介质对安全泄放装置动作时间影响不大;不同充装压力对容器内介质压升速率影响较大,充装水平较高时压力泄放装置更快动作,较低的充装压力下容器内介质温升较快;不同环境温度对介质温升影响较小。     

硝酸异辛酯的热安全性研究

为了研究十六烷值改进剂—硝酸异辛酯(EHN)的热稳定性与热危险性,采用C600微型量热仪测试硝酸异辛酯的热分解特性.利用热分析技术考察温升速率对EHN热分解特性的影响,并利用活化能、TMRad(在绝热条件下最大反应速率到达时间)和自加速分解速率(SADT)方法评价此改进剂的危险性.结果表明,EHN发生分解反应的起始放热温度和最大放热温度均随着温升速率的增加而增大,且四种温升速率的反应机理是一致的.计算得到EHN热分解活化能在143.6-213.6kJ/mol之间.通过绝热条件下TMRad评价得出EHN在常温常压条件下不易发生危险失控,EHN自加速分解温度为98℃＞75℃,即在常温条件下储运是安全的,为储运硝酸异辛酯提供有力的数据支持.     

Fe3+掺杂对双氧水热稳定性的影响

为了定量考察Fe3+掺杂对双氧水热稳定性的影响,利用泄放尺寸实验仪(VSP2)研究了无Fe3+及Fe3+质量分数为0.003%、0.01%、0.02%时的27.5%双氧水(质量分数)热分解特性,得到了这4种样品绝热自分解过程的温度及压力数据,计算得到初始温度为40 ℃时不同Fe3+质量分数的双氧水在绝热条件下到达最大反应速率所需时间(TMRad).结果表明,为保证双氧水在一般环境条件下安全稳定存储,需要控制双氧水中Fe3+的质量分数低于9.2×10-6.     

Thermal research on the uncontrolled behavior of styrene bulk polymerization

Thermal runaway can occur during the styrene bulk polymerization process because of easily formed local hotspots resulting from the high viscosity of reactants and the difficulty of heat dissipation. To obtain the thermal hazard characteristics, the polymerization behavior of styrene was investigated using differential scanning calorimetry (DSC) at a scanning rate of β = 2 °C/min. Experimental results showed that the exothermic peaks obtained for heat initiation were different from those obtained when initiator was added. The exothermic peak changed from one to two after the initiator was added. The exothermic onset temperature (T₀) was also reduced. Phi-tech II was utilized to study the bulk polymerization of styrene in an adiabatic environment. The adiabatic temperature rise (ΔT_ad), starting temperature of uncontrolled polymerization (T_star), maximum temperature (T_end), and heat of polymerization (ΔH) under different conditions were acquired. When the dose of the additive was increased, the starting temperature of uncontrolled polymerization (T_star) decreased and the adiabatic temperature rise (ΔT_ad) increased gradually. Severity grading was performed based on the severity evaluation criteria of runaway reaction. The results can help designers decide whether it is necessary to take certain measures to reduce risk.     

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.     

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.     

Probe into effect of the initiator on the thermal runaway hazards of methyl methacrylate bulk polymerization

The bulk polymerization of methyl methacrylate (MMA) is of great importance in chemical industry, but the polymerization process is highly hazardous, and few reports have focused on the effect of initiators on its thermal hazards. In this work, to thoroughly explore the thermal hazard characteristics, the runaway behavior of MMA bulk polymerization is investigated by a combination of thermodynamics experimental and kinetics theoretical methods. The results indicate that the presence of initiator exhibits an undesirable thermal hazard to the MMA bulk polymerization, and its exothermic behavior is also greatly influenced by the type and concentration of initiator. For azobisisoheptanenitrile (ABVN), azodiisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO) initiators as examples, the AIBN-initiated reaction has the shortest adiabatic induction period (39.51 min), whereas the BPO-initiated polymerization exhibits the strongest maximum temperature-rising rate and maximum pressure-rising rate. Under adiabatic runaway, the temperature and pressure change significantly with increasing AIBN concentration, revealing a great potential risk of thermal runaway. Kinetic parameters are calculated to further understand the thermal runaway mechanisms, showing a strong agreement with the adiabatic experimental data. Finally, based on the cooling failure scenario, severity grading is determined by the evaluation criteria. The current work provides extensive data as a reference and guidance for the process design and optimization of MMA bulk polymerization from the perspective of safety.     

Diphenylmethane diisocyanate self-polymerization: Thermal hazard evaluation and proof of runaway reaction in gram scale

Thermal analysis by differential scanning calorimetry and thermogravimetric/differential thermal analysis mass spectrometry, adiabatic calorimetry, a gram-scale heating test, and infrared spectroscopy were performed to evaluate the thermal hazards of diphenylmethane diisocyanate (MDI) and prove the occurrence of a runaway reaction. The self-polymerization of MDI was found to occur at about 340 °C under rapid heating conditions. Carbon dioxide was eliminated and heat was generated to allow polymerization. Under adiabatic and closed conditions, the runaway reaction of MDI can begin at least from 220 °C. Besides it is highly probable that the runaway reaction of MDI can begin from a lower temperature in an actual process scale. More heat was generated than in the previous case and the pressure rose rapidly. A closed 2-mm-thick glass vessel exploded because of the runaway reaction of MDI even if the temperature was lower than 300 °C. Therefore, MDI could cause fatal runaway reactions below 300 °C, where MDI had been assumed to self-polymerize by eliminating carbon dioxide previously.     

Calorimetric study of the inhibition of runaway reactions during methylmethacrylate polymerization processes

Reaction inhibition was adopted as a method to halt runaway phenomena during polymerization experiments. Use of reaction calorimetry coupled with a particular system for early detection of the onset of runaway (early warning detection system) has allowed to investigate the behaviour of two substances that can influence the reaction rate: hydroquinone and 1,4-benzoquinone. The process studied was the free-radical polymerization of methylmethacrylate carried out under batch conditions in bulk or in emulsion. The results show that hydroquinone and 1,4-benzoquinone behave differently: the first is an inhibitor because it completely stops the process; the second behaves as a retarder and could be used industrially to control the process and keep the reactor temperature within safe limits.     

基于本质安全的微反应器中苯乙烯聚合的数值模拟

重大化工事故往往是由多米诺效应引发的一连串故障而导致的。为实现苯乙烯聚合反应的本质安全,采用本质安全设计原则,设计了T型微反应器以替换传统釜式反应器。先通过计算流体力学(CFD)方法建立了三维稳态模型,再通过UDF(User Defined Functions)添加组分输运方程源项和能量方程源项,对苯乙烯自由基聚合反应进行了数值模拟,研究在微尺度条件下,反应温度、混合反应管道长度及形状对反应结果的影响。结果表明:由于微反应器可提高传热传质效率,在一定范围内反应温度可以控制在3 K以内;反应管道由0.15 m增长至1.5 m后,转化率可提高2倍左右;0.15 m直管形状改进为螺旋状后,转化率可至少提升4%。     

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.