化学放热系统热爆炸临界值的随机性

提出了化学放热系统热爆炸临界值的随机性问题,并定义了化学放热系统的热安全度和可靠度.将LambertW函数计算出的化学放热系统临界环境温度和系统实际所处环境温度均看作随机变量,假定化学放热系统临界环境温度服从正态分布,应用应力-强度干涉理论计算化学放热系统的热爆炸概率值.化学放热系统热爆炸概率值的计算使热爆炸理论的研究从确定性理论向随机性理论发展.     

过氧化氢热爆炸研究进展

过氧化氢作为绿色环保的氧化剂,广泛应用于工业的各个领域,同时也因其热分解爆炸危险性导致了一系列严重的火灾爆炸事故。过氧化氢在高温或与一些不兼容化学物质作用下,将会激发其热危险性,进而引发热失控反应,最终导致爆炸事故的发生。结合近年来国内发生的过氧化氢热爆炸事故,简要概述了其热爆炸事故历程,并从理论研究和实验研究两个方面综述了过氧化氢热爆炸的研究进展。理论研究方面,主要介绍了化学反应失控模型和基于热动力学的研究方法,尤其对基于热失控模型的热风险评估进行了详细的阐述。实验研究方面,分析了高温条件下与杂质催化作用下过氧化氢的热危险性,包括无机杂质和有机杂质。最后就过氧化氢热爆炸的研究提出了进一步的研究方向。     

传热系数随温度线性变化的亚临界化学放热系统热安全性分析

引入化学放热系统平衡域和热安全裕度的概念与定义来评价具有潜在危险性的亚临界化学放热系统的安全性问题.分析了均温系统下传热系数随温度呈线性变化的系统的平衡域,进而提出了热安全裕度值L的定量计算并阐明了利用曲线拟合的方法计算L值.使用了Matlab软件绘出系统在3个约束参数约束的条件下ψ-ε-a的三维图形与给定系统(a为常数)时ψ-ε的二维图形,并在结合图形的基础上引入实例来评价该系统的热安全性.     

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.     

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。     

过氧化苯甲酰合成工艺热危险性分析

采用RC1e反应量热仪对过氧化苯甲酰(BPO)合成工艺危险性进行研究,测试不同Na OH溶液初始浓度(1.96 mol/L、3.93 mol/L、7.14 mol/L)下反应的放热历程,获得BPO合成反应过程中的热危险性参数,并采用PHI-TECⅡ绝热加速量热仪对产物进行热稳定性分析,最后评估该反应热风险。结果表明,Na OH浓度为7.14 mol/L时,反应初期放热速率慢,热累积度大,后期反应剧烈,绝热温升(ΔTad)及热失控时工艺反应达到的最高温度(MTSR)最大。热稳定性试验表明,合成的粗产物BPO初始分解温度、活化能、指前因子、最大放热速率到达时间为24 h时的对应温度(TD24)均低于纯BPO。利用合成粗产物BPO的TD24对反应进行危险度评估,该工艺热危险性等级均为5级,工艺危险性大。     

2-氨基-2,3-二甲基丁酰胺氧化合成热危险性研究

为研究2-氨基-23,-二甲基丁酰胺氧化合成的热危险性,采用差示扫描量热仪(DSC)测试2-氨基-2,3-二甲基丁腈和2-氨基-2,3-二甲基丁酰胺的热分解情况,采用反应量热仪(RC1)研究反应温度、双氧水滴加速度和氢氧化钠用量对反应的影响。研究结果显示,2-氨基-2,3-二甲基丁腈吸热热分解温度为149.5℃2,-氨基-2,3-二甲基丁酰胺表现为吸热和放热2段分解过程,吸热和放热分解温度分别为234.4℃和456℃。反应放热速率主要为加料控制,但是,存在一定的热累积。热失控体系最高温度(MTSR)低于2-氨基-23,-二甲基丁腈和2-氨基-23,-二甲基丁酰胺的分解温度,高于体系沸腾温度,在热失控的条件下,反应体系容易导致冲料危险;在优惠的工艺条件范围内,提高反应温度,延长滴加时间,可降低反应的MTSR,提高热转化率和反应安全性。     

二叔丁基过氧化物的热失控动力学研究

为研究二叔丁基过氧化物(DTBP)热失控危险性,利用C600微量量热仪对DTBP热分解动力学进行试验研究,测定DTBP在不同升温速率下的起始放热温度和分解热,分别用非等转化率法和等转化率法得到DTBP热分解反应的动力学参数。用非等转化率法确定反应的最佳反应级数为1,相应的活化能分别为137.75、132.60、128.61和122.93 kJ/mol,指前因子分别为8.82×1012、6.69×1012、2.06×1012和3.89×10111/s。用等转化率法确定的活化能范围为102～138 kJ/mol,并拟合出活化能与转化率的关系曲线。结合计算出的动力学参数,通过对DTBP分解机理的分析,可以推断其具有热失控危险性。     

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.     

环己酮半间歇过氧化反应过程热失控研究

采用反应量热仪(RC1e)、差示扫描量热仪(DSC)和绝热加速量热仪(ARC)对环己酮过氧化反应过程的热失控危险性进行了研究,利用冷却失效情形法对该工艺进行危险性分级。结果表明:温度的升高使环己酮过氧化反应速率加快,体系比热容增加,温度升高也使产物各种中间体及副反应活跃程度增加,提高搅拌速度也能促进环己酮氧化,而延长加料时间可以将反应热量较好地移出,但同时降低反应速率,使过氧化环己酮得率降低。依据风险评价指数矩阵法和失控情景分析法,得到环己酮半间歇过氧化反应的热失控危险程度级别为5级,而降低环己酮的加入量,危险程度等级为2级。     

Thermal risk in batch reactors: Theoretical framework for runaway and accident

Thermal safety and risk of accidents are still challenging topics in the case of batch reactors carrying exothermic reactions. In the present paper, the authors develop an integrated framework focusing on defining the governing parameters for the thermal runaway and evaluating the subsequent risk of accident. A relevant set of criteria are identified in order to find the prior conditions for a thermal runaway: failure of the cooling system, critical temperature threshold, successive derivatives of the temperature (first and second namely) vs. time and no detection in due time (reaction time) of the runaway initiation. For illustrative purposes, the synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA) is considered as case study. The critical and threshold values for the runaway accident are identified for selected sets of input data. Under the conditional probability of prior cooling system failure, Monte Carlo simulations are performed in order to estimate the risk of thermal runaway accident in batch reactors. It becomes then possible to predict the ratio of reactors, within an industrial plant, potentially subject to thermal runaway accident.     

The critical runaway condition and stability criterion in the phenol–formaldehyde reaction

The procedure of phenol–formaldehyde polymerization is a rather important and complicated reaction in the chemical industry. This exothermic polymeric reaction releases a huge amount of heat. The high amount of energy accumulated and increasing temperature in this reaction process always lead to runaway reaction and a hazard situation owing to the high released heat and improper operation. In this investigation, we used sodium hydroxide as alkali–catalyst in the phenol–formaldehyde polymerization and estimated the reaction kinetics parameters to evaluate the thermal hazard conditions. The critical temperatures and stable criteria of the runaway reaction in this exothermic polymerization were evaluated. This technique is important and useful for safe operation in the phenol–formaldehyde polymerization process.     

锂离子电池热解气体爆炸极限测定及其危险性分析

为定量研究锂离子电池热失控的危险性,利用锂离子电池在滥用条件下释放气体的种类及体积分数,计算锂离子电池热解气体爆炸极限并研究锂电池荷电状态对热解气体爆炸极限的影响。结果表明:在一定热失控条件下锂离子电池荷电状态为100%时其热解气爆炸下限为6.22%,上限为38.4%,在相同热失控条件下,锂离子电池热解气体的爆炸极限范围随着荷电状态的升高而增大,锂电池的荷电状态对热解气体的爆炸上限影响较大而对爆炸下限影响较小。在相似条件下,锂离子电池热解气体的爆炸极限范围比普通烃类气体大,一旦锂电池发生热失控会对锂离子电池运输造成潜在威胁。     

Using thermal analysis with kinetic calculation method to assess the thermal stability of azo compound on construction materials

The application of construction polymers in engineering and alternative materials has always occupied a place in the market. In the production process of polymer resins, initiators can be used to lower the polymerization reaction energy threshold, which can improve reaction efficiency and reduce energy loss. However, as a commonly used energetic substance in the polymerization process, azos have caused related process hazards due to their exothermic characteristics. Because of this, it is essential to examine and analyze the thermal hazard characteristics of emerging azo substances, such as 2-cyanopropan-2-imemicarbazide (CABN). Although previous literature performs the calculation on related thermal hazard parameters of CABN, there is still exists a void for discussion in estimating the reaction model to avoid analogous hazards and enhance the existing thermal analysis. Based on the past literature, the reaction model is improved with thermogravimetric analysis as evidence. The revised thermal hazard parameters are calculated as the basis of control and mitigation measures, the kinetic model is used to estimate the modified safety parameters, and in the judgment of the runaway reaction, the critical temperature of the runaway is found by analyzing the influence of slight changes in ambient temperature on the reaction temperature. The results show that the critical temperature that causes CABN to enter the runaway reaction is delayed, and the hazard is lower than in the storage situation. Therefore, the thermal hazard to CABN mainly focuses on the safety environment and measures during storage.     

Thermal hazards analysis of styrene in contact with impurities

Styrene is a reactive monomer commonly used to produce polystyrene and other copolymers. Unintended thermal runaway polymerization reactions of styrene keep reoccurring and have led to catastrophic consequences. One of the possible causes of these runaway incidents involves the contamination of the styrene monomer by incompatible species, which was not adequately investigated and documented. This study focuses on the quantification of thermal runaway hazards of styrene in contact with a series of contamination substances by adopting calorimetric analysis. Both Differential Scanning Calorimeter (DSC) and Advanced Reactive System Screening Tool (ARSST) were employed to examine the exothermic characteristics of styrene mixed with contaminating substances at different concentration levels and mixing conditions. Key safety parameters of the exothermic reaction, such as the onset temperature, the overall heat release, the maximum self-heating rate, as well as the activation energy, were obtained. The results indicated that the thermal runaway polymerization of purified styrene was significantly altered by the presence of contaminant species. Water effectively retarded and quenched the runaway polymerization at a higher temperature range. Alkaline had no substantial effect on the thermal runaway characteristics. The presence of acid solution under both static contact and vigorous mixing condition significantly promoted the thermal polymerization of styrene. A trace amount of concentrated acid initiated violent exothermic activity even at room temperature; and the severity of the reaction was profoundly impacted by the mass-transfer. Our study demonstrates significant implications in the prevention of runaway incidents during transportation and storage of styrene.     

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。     

不同外热功率下18650锂离子电池热失控特性*

为探究不同外热功率（220,170,120,70 W）下锂离子电池的热失控特性,采用动压变温实验舱作为燃爆实验舱,并利用量热仪和ISO-9705烟气分析仪监测特征参数,对荷电状态（SOC）为100%的18650型锂离子电池进行高温热失控实验。结果表明:在不同的外热功率条件下,锂离子电池进入热失控的过程呈现出相似的趋势,但是各阶段的特性却存在差异。池体表面中心温度、HRR,THR和耗氧量均随外热功率的降低而降低。高外热功率下燃爆响应时间点明显提前,池体温度更高,220 W外热功率下,燃爆响时间点为176 s,池体温度为720.6 ℃,比70 W时提前366 s,高210.03 ℃,可见高外热功率时,电池热危害性更高。热解烟气CO的峰值体积百分比浓度随着外热功率的降低而升高,而CxHy的峰值质量百分比浓度降低,,CO2的峰值体积百分比浓度降低。在70 W外热功率时,CO峰值体积百分比浓度高达0.322%,220 W时CO峰值体积百分比浓度仅为0.165%,说明低外热功率时,电池毒危害性更高。