Modeling thermal analysis for predicting thermal hazards relevant to transportation safety and runaway reaction for 2,2′-azobis(isobutyronitrile)

The pure decomposition behavior of 2,2′-azobis (isobutyronitrile) (AIBN) and its physical phase transformation were examined and discussed. The thermal decomposition of this self-reactive azo compound was explored using differential scanning calorimetry (DSC) to elucidate the stages in the progress of this chemical reaction. DSC was used to predict the kinetic and process safety parameters, such as self-accelerating decomposition temperature (SADT), time to maximum reaction rate under adiabatic conditions (TMR_ad), and apparent activation energy (E_a), under isothermal and adiabatic conditions with thermal analysis models. Moreover, vent sizing package 2 (VSP2) was applied to examine the runaway reaction combined with simulation and experiments for thermal hazard assessment of AIBN. A thorough understanding of this reaction process can identify AIBN as a hazardous and vulnerable chemical during upset situations. The sublimation and melting of AIBN near its apparent onset decomposition temperature contributed to the initial steps of the reaction and explained the exothermic attributes of the peaks observed in the calorimetric investigation.     

液体推进剂职业中毒风险评价及防护对策研究

本文以某发射场为例,通过主要危险源辨识、作业单元划分、现场调查和监测统计,利用风险指数评估法对液体推进剂职业中毒风险进行量化评价,结果表明:液体推进剂作业存在极度和高度职业中毒风险,发射场液体推进剂作业职业中度风险主要来源于液体推进剂及氮气;液体推进剂设备维修、应急救援及进罐作业存在极度职业中毒风险,转注/加注、取样为高度风险,化验及"三废"处理属于中度风险。根据评价结果并借鉴以往事故经验教训,指出职业中毒伤害与工程控制、个体防护措施和安全意识密切相关,不使用或不能正确使用呼吸防护装备是引发职业中毒的主要原因,并提出针对性的防护措施建议。     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

膨胀聚苯乙烯热分解动力学分析和寿命预测

针对既有聚苯乙烯泡沫类外墙外保温系统的防火问题,在空气和氮气气氛下对非阻燃和阻燃型膨胀聚苯乙烯泡沫进行了热重分析。样品由10℃/min、20℃/min、40℃/min和50℃/min四个升温速率从室温加热至800℃。热分解动力学参数由Flynn-Wall-Ozawa(FWO)等转化率方法和多参数非线性回归方法(multivariate non-linear re-gression method)计算,结果表明六溴环十二烷(HBCD)阻燃剂可一定程度上提高EPS的热稳定性。EPS在空气和氮气气氛下热解可认为是单步反应。非阻燃聚苯乙烯泡沫在空气和氮气气氛下的热解过程可由自催化n阶反应机理描述。阻燃EPS在空气气氛下的热解机理为自催化n阶反应,在氮气气氛下则为n阶反应机理。基于动力学参数和反应机理,对聚苯乙烯泡沫在不同温度下的寿命进行了预测。     

特警战训服面料开发技术研究

本文介绍了以芳纶纤维为主要材料的我国新一代特警战训服面料的技术研发及达到的主要性能指标。通过试验研究,开发了具有高强防撕裂、永久阻燃、耐高温、防静电、防油拒水、防酸碱等具有集成防护功能的特警战训服系列面料。     

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.     

基于层次分析法的热塑性聚氨酯及其纳米复合材料火灾危险性综合评价

聚合物的火灾危险性与热、烟、毒的释放密切相关,但采用不同指标对材料的评价结果不一致。以纳米级蒙脱土(MMT)、氢氧化铝(ATH)和聚磷酸铵(APP)为添加剂的热塑性聚氨酯(TPU)纳米复合材料为研究对象,选取其在静态管式炉、稳态管式炉和锥形量热仪中的相关实验数据,以HCN总浓度作为特殊毒性危害指标,CO和CO_2浓度为一般毒性危害指标,以热释放速率峰值、平均热释放速率、总热释放量为热危害指标,以产烟速率峰值、生烟总量为烟危害指标。进一步细分了火灾烟气中不同毒性气体对于火灾风险的影响,并运用层次分析法计算指标权重,综合评价了热塑性聚氨酯及其复合材料的火灾危险性。结果表明,当添加量为6 wt%聚磷酸铵、3 wt%氢氧化铝与3 wt%蒙脱土时,此时复合材料的火灾危险最低,证明了综合热、烟、毒三个层次来降低聚合物材料火灾危险性是可行的。     

急倾斜上保护层开采保护效果的参数敏感度研究

为对急倾斜上保护层开采过程中,保护层开采多参数同时变化时的保护效果变化规律进行量化研究,将被保护层膨胀变形曲线的形态参数作为保护效果考察指标,基于可旋转CCD试验方案进行有限元计算,建立了保护层开采保护效果的响应面模型,得到了不同保护效果指标受多个保护层开采参数变异影响的敏感度。通过对急倾斜上保护层开采实例进行敏感度分析得到:范围相关保护效果指标受保护层开采参数变异影响的敏感度最高,位置相关保护效果指标敏感度次之,卸压程度相关保护效果指标敏感度最小。范围相关保护效果指标中,上部卸压角受侧压系数变异影响最敏感,敏感度为1.70;下部卸压角受层间距变异影响最敏感,敏感度为1.02;倾向保护范围长度受层间距变异影响最敏感,敏感度为-1.89。     

我国特种劳动防护用品产业分布特点分析

为了解我国特种劳动防护用品产业分布特点和产业市场集中程度,基于生产企业统计数据,估算我国特种劳动防护用品产业市场集中度;对比2017年和2010年数据,统计分析我国特种劳动防护用品产业的区域、产品种类、企业注册资金规模和企业从业人员数量的分布和变化,分析总结了产业发展呈现的特点,提出了加快我国特种劳动防护用品产业发展的相应建议。结果表明:当前我国特种劳动防护用品产业市场结构尚属于低集中竞争型;各区域生产企业数量按照东部、中部、西部和东北的顺序依次递减,东部生产企业占据全国企业总数的65%以上;一半以上企业的注册资金均大于1 000万元;以从业人员数量看,80%以上企业属于小型企业规模;与2010年相比,2017年我国特种劳动防护用品生产企业从业人员数量增加了6.67%,企业从业人员规模分布变化不明显,企业注册资金规模已由约7成企业在500万元以下转变为近7成超过500万元,产品种类增加了40%。研究结果可为我国劳动防护用品产业和安全产业的发展提供科学参考。     

Ignition temperatures of dust layers and bulk storages in hot environments

In many industrial installations, particulate solids (cereals, agri-food products, coal, plants, etc.) are stored or processed. Self-heating of these products, which can lead to fires and explosions, can occur in a variety of situations. Examples include large storage at room temperature, formation of a layer on a hot surface, layer deposited on a surface – insulating or conductive – in a hot environment or even storage of product exposed to heating on one side.The main parameters that determine the occurrence of self-heating are the size of the container, the temperature, the residence time and the characteristics of the product. Depending on the type of situation encountered and these implementation conditions, the analysis of self-heating risks must be based on specific models and/or parameters.This paper presents the different variants and combinations of the theoretical model from the theory of thermal runaway to represent self-heating, taking into account in particular the symmetry or asymmetry of heating, reagent consumption and boundary conditions. It also discusses their adaptation to the previous identified industrial situations.Nine products were chosen to be representative of those used in the different considered industrial situations. They were subjected to self-heating basket tests in isothermal ovens in order to determine the parameters for applying the described theoretical models. These results were compared with the results of self-heating tests in layers of different thicknesses in a hot environment, on an insulating or conductive plate, using a specially developed test protocol, as well as with the results of standardized tests of minimum ignition temperature in 5 mm layers.This led to the proposal of the most appropriate theoretical model to represent the self-heating phenomenon for each of the four identified industrial situations.This analysis can promote better design of industrial equipment and production conditions (temperatures, volumes or product flows …) in order to prevent fires and explosions.