重结晶LLM-105的热危险性分析

为了研究重结晶前后LLM-105在敞开体系、绝热体系中的热分解特性,采用溶剂-非溶剂法制备了形状规则、缺陷更少的重结晶LLM-105。以差示扫描量热仪研究了LLM-105的非等温热分解行为,利用Friedman法得到了非等温热分解动力学参数及TD24。采用加速量热仪研究了LLM-105的绝热分解行为,计算了绝热分解动力学参数及SADT。结果表明,重结晶LLM-105的非等温热分解起始温度(升温速率为10℃/min)、绝热起始分解温度、绝热最大升温速率分别为353.12℃、277.19℃、77.39℃/min,未重结晶LLM-105的相应参数值分别为341.62℃、273.77℃、136.62℃/min。重结晶LLM-105的非等温热分解起始温度、绝热起始分解温度更高,绝热最大升温速率更小。结晶品质是LLM-105的热分解特性、热危险性的重要影响因素。重结晶LLM-105具有更好的热稳定性,绝热分解反应更温和。     

Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT_ad) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR_ad). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.     

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.     

Mixing hazard evaluation of organic peroxides with other chemicals

Organic peroxides (POs) have been widely used in chemical industries as initiators of polymerization, hardening or bridge formation agents, and they are known for its self-reactive and also mixing hazard characteristics when mixed with other chemicals such as acids and alkalis. It is the purpose of this investigation to propose a simple but useful evaluation flow of mixing hazards of POs with other chemicals using conventional experimental techniques such as a glass test tube test, Dewar vessel test and DSC is proposed. 7 kinds of POs (DEPD, THP, TBEH, TBTC, MEKPO, DTBP, THHP) were mixed with sulfuric acids with various concentration, sodium hydroxide solutions, -iron(III) oxide and acrylonitrile (AN).

Based on the proposed evaluation flow the testing results were classified into 4 ranks due to the hazard criteria. Futhermore DEPD/acrylonitrile mixtures were investigated in more detail and the influences of the mixing ratio and the stirring speed were discussed.     

自反应性化学物质热危险性综合评估

自反应性化学物质热危险性评估的关键在于表征参数的选择和量化,单一的评估参数往往仅表征其热危险性的某一方面。综合考虑自反应性物质发生热分解反应的难易程度及其造成后果的严重程度两个方面,分别选取放热反应初始温度(To)和反应热(-ΔH)作为相应的表征参数,通过半正态分布函数对这两个指标进行标准化处理。在此基础上根据风险的定义提出了一种新的自反应性化学物质的热危险性综合评估指数(THI指数),并建立相应的热危险性分级标准,对自反应性化学物质的热危险性进行综合评估与分级。结果表明,建立的THI指数所确定的热危险性分级结果与基于活化能和最大绝热温度的RHI指数的反应危险性等级基本一致,该指数能够对自反应性化学物质的热危险性进行定量评估。     

A retro-synthesis approach for hazard evaluation and risk screening

Risk screening instruments can be very useful for evaluating hazards and establishing priorities for risk reduction. Further, these instruments can provide educational value to field staff when they are distributed to individuals outside of traditional process safety roles. This paper describes a retro-synthesis technique whereby risk screening instruments can be readily generated for these types of hazard evaluation and priority setting activities. Further, by utilizing a retro-synthesis approach, data gathered at the field level can often be drawn upon at a later point if a more detailed risk assessment is required. The retro-synthesis approach involves working backwards from traditional risk functions (relationships) so as to define the predominant elements for incorporation within the risk screening instrument. Compared to conventional techniques, the retro-synthesis approach utilizes deductive reasoning techniques in a manner similar to Fault Tree Analysis (FTA). However, the directional relationships that are established between causes and consequences become inverted.For example, risk can be defined as a function of “likelihood” and “severity”, where “severity” may be a function of the “energy released” and the “exposure group”. Similarly, the “energy released” is often a function of the “properties of the material involved” and the “amount of material released”. Through identifying these relationships, “risk” in this example can be characterized as a function of “likelihood”, “exposure group”, “properties of the material involved”, and “amount of material released”. Further, by highlighting the various influential parameters, the relationships between each of these parameters, as related to risk, can also be understood. Once the various terms and functions are defined, screening categories can then be developed to quantify each of the terms so as to allow for an approximation of the relative risk involved for the given scenarios.This approach benefits from being simple to develop, maintaining alignment with the mathematics required for more detailed quantitative risk assessments, and generating screening categories which can be given to field staff. Through careful construction of the screening categories field staff can then rapidly, and in a reproducible manner, screen a large number of scenarios so as to identify those situations which represent priority hazards.     

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.     

Thermal hazard in a batch process involving hydrogen peroxide

Hydrogen peroxide is a versatile and interesting reagent for many industrial processes; nevertheless, it is very sensitive to impurities that can catalyze its decomposition, so that the desired reaction could be accompanied by undesired parallel and consecutive reactions. As an example, the butadiene free radical polymerization with hydrogen peroxide in the presence of an organic solvent was studied. Batch polymerization occurs in the liquid phase at about 120 °C. Because of the involved reactive compounds and the relatively high temperature, this is an intrinsically dangerous reaction. Therefore calorimetric data can give important information about safety and process optimization during the scale-up. The aim of this research project was to study the influence of impurities on the overall heat of reaction. The experiments were made in a high-pressure reaction calorimeter. The study has revealed that impurities do indeed affect the reaction course. Most importantly, the presence of carboxylic acids and/or ionic iron must be avoided and the recycle of unreacted reagents must be carefully controlled to minimize the build-up of these impurities.     

支线机场安全动态预警技术研究

提升支线机场安全管理能力是中国支线机场未来发展面临的一个重大问题,为提高我国支线机场安全管理水平,本文基于系统动态的风险管理思想,针对支线机场安全风险发生随机、动态和系统的特点,结合支线机场安全管理实践,构建了支线机场三维风险识别图,以时间维为主线,空间维为基础,逻辑维为依据,多层次地识别支线机场面临的风险,以提高支线机场风险识别结果的客观性和全面性;将风险概率、风险损失、风险可预测性、风险可控制性纳入了支线机场安全风险分析过程,构建了支线机场安全多维风险评价函数,从而能更系统、全面地对支线机场面临的各种风险因素进行评价;通过上述支线机场风险管理技术的应用,可提高对支线机场安全风险的辨别、分析和控制能力,达到对支线机场安全风险进行实时、动态监控的预警目标,进而减少支线机场安全风险的潜在损失。     

职业危害因素混合接触综合评价方法概述

作业场所同时接触多种职业危害因素的综合危害性日益引起广泛关注,如何对其进行科学的评价成为职业危害研究者面临的重要课题。本文对不同危害因素的混合危害作用的评价方法进行了系统的总结与归纳,探讨了混合作用的描述方法,分析了毒理学、流行病学、风险评价三大类方法应用于混合危害作用评价时的基本原理、核心思路和实施流程,此外对三种方法的特点进行了对比分析。     

Process hazard assessment of energetic ionic liquid with kinetic evaluation and thermal equilibrium

With the continuous development of battery technology, there are new research investments in materials of various parts. In the field of electrolytes, ionic liquids (IL) are considered to be excellent electrolytes and have been widely studied in distinct energy fields. However, it is necessary to pay attention to the safety characteristics of ionic liquids at high temperature due to the application of energy, but there is little research on the reaction and kinetics of ionic liquids. To ensure the safety of ionic liquids, such as high temperature, the common ionic liquid 1-Ethyl-3-methylimidazolium nitrate ([Emim] NO₃) was selected for analysis. The exothermic mode is obtained from the data of differential scanning calorimetry. The basic reaction parameters of [Emim] NO₃ were determined with thermodynamic equation simulation. For ionic liquids in the actual situation, consider adding a heat balance model to estimate its temperature change pattern and find out the hazard temperature and related safety parameters. Temperature changes were estimated by constructing 25.0 g and 50.0 g packages to simulate material reactions and heat transfer in the external environment. The results showed that [Emim] NO₃ had shorter TMR_ad and TCL (<1 day) when the temperature was above 180 °C.     

企业职业危害综合评价和风险分级系统及其应用

我国企业职业危害形势依然十分严峻,2007年共诊断各类职业病14296例,较2006年增加了24．11％。由于国家在一段时期内不太可能大幅度增加监管人员数量,因此,实施企业职业危害分级监管成为职业危害监管工作的一个紧迫需求。本文从提高企业监管信息化水平角度出发,开发企业职业危害综合评价和风险分级系统。系统即可为政府实施职业危害分级监管提供强有力的技术支撑,也可应用在企业的作业场所职业危害管理工作中,从而提高政府和企业职业危害管理工作技术水平和效率。     

硫化油生产过程的活性反应危害识别与评估

利用差示扫描量热仪（DSC）、反应量热仪（RC1和快速筛选仪（RSD）等仪器设备,对硫化油合成过程的热特征和压力特征进行系统研究,发现该反应为微吸热的过程,但仍应严格控制工艺参数,如压力、温度等。防止反应器中混入水等低沸点物质,导致容器超压。反应器内避免混入空气、硝酸等禁忌物料,防止因活性反应而引发灾害性燃爆事故。     

Dust collector explosions: A quantitative hazard evaluation method

A methodology is presented to evaluate the explosion hazard of typical bag and cartridge dust collectors. The evaluation accounts for the expected development of suspended dust concentrations greater than the dust MEC during the normal pulsing of the bags or cartridges to remove part of the attached dust. Equations are presented to calculate these concentrations and also the associated partial volume explosion pressures resulting from the ignition of these dust clouds. Five quantitative examples are presented. The methodology also includes considerations of potential upset condition full volume explosions associated with the detachment of about half the dust on the bags or cartridges. A flow chart is offered to implement this hazard evaluation method for special situations in which the need for dust explosion protection may not be obvious.     

煤矿水害风险量化评价方法

为提高煤矿防治水管理水平,预防和消除矿井水害,在层次分析法的基础上建立中性值作为参照对象对矿井水害风险进行实时评判的方法。根据《煤矿防治水细则》建立以矿井水文地质类型、矿井涌水量标准分数、突水预兆、采掘面位置、探水结果为准则层的层次结构模型,并对各评价指标赋权。依据制定的水害风险评价指标的评分细则和监测监控数据并结合其权重得到水害评价总得分。通过总得分与中性参照分数比较得出预测结果:水害评价总得分大于中性参照分数,证明水害的威胁小,分数越高越安全;反之则水害的威胁较大,分数越低越危险,这时需要加强防治水的力度,令评价分数管控大于中性参照分数。这种方法依赖于井下监测监控数据进行量化评价,能实时、客观、全面且准确地反映煤矿水害的风险情况。     

Characterization of Ti powders mixed with TiO2 powders: Thermal and kinetic studies

The fire and explosion risks of metal powders admixed with solid inertants have been extensively investigated for many years. However, it remains unclear why such solid mixtures have high potential fire and explosion risk even when mixed with high percentages of non-combustible solids. This paper investigates how to interpret these risks, from a microscopic perspective, with thermal and kinetic parameters including initial ignition temperature, mass unit exothermic energy, activation energy and risk index of spontaneous combustion. The results show that the initial ignition temperature based on TG (Thermogravimetry) analysis is related to ignition sensitivity, and increased with percentage of admixed solid inertant. The unit mass exothermic energy based on DSC (Differential scanning calorimetry) analysis is related to flame spread velocity. Activation energy and the risk index of spontaneous combustion can be used to explain the reactivity and spontaneous combustion hazard, respectively, of metal powders. We conclude that thermal and kinetic parameters may provide another way to describe the fire and explosion risk of combustible powders, especially for nano metal powders due to the laboratory safety in the normative tests for explosion parameter determination.     

高校学生宿舍火灾风险与综合评价

高校为我国培养了多种专业人才.随着高等教育规模的不断扩大,高校安全问题已成为全社会关注的焦点,特别是学生宿舍火灾问题.通过对高校学生宿舍火灾多发的原因和特性分析得出,学生安全意识差、消防知识匮乏、人员密度大、建筑物耐火等级低等是造成高校学生宿舍火灾的主要原因.依据火灾安全特征及相关规定,应用系统理论的观点,提出学生宿舍火灾风险辨识应从学校系统内部因素、外部环境和管理层次三维角度进行分析.构建宿舍火灾风险评价的安全评价体系,运用模糊综合评价的方法,结合实例探讨该方法的可行性.     

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。     

改进LEC法在水利水电工程建设期危险源评价中的应用

在水利水电工程建设期的安全管理中,危险源的管理处于十分重要的地位。水利水电工程施工企业通常采用作业条件危险性评价法（LEC法）进行风险评价。LEC法十分依赖评估小组的实际经验。针对LEC法的局限性,提出用于水利水电工程建设期危险源评价的改进LEC方法,以提高企业的危险源管理水平。     

Safety evaluation of major hazard installations based on regional disaster system theory

Major accidents have catastrophic effects on humans and all of society. To prevent the occurrence of major accidents, it is essential to strengthen the management of major hazard installations. Generally, effective identification and reasonable evaluation of major hazard installations are the basic steps in safety management. At present, the evaluation methods for major hazard installations mainly focus on consequence analysis and probabilistic analysis without considering the vulnerability of hazard-affected bodies. Therefore, the proposed method will introduce regional disaster system theory and comprehensively analyze hazard-formative factors, the hazard-formative environment and hazard-affected bodies to achieve a more complete and effective assessment of major hazard installations. Hazard-formative factors are evaluated based on the rapid ranking method, hazard-formative environments are evaluated based on Bayesian networks, and hazard-affected bodies are evaluated based on the fuzzy comprehensive evaluation method. A tank group and a chemical industrial park are used to verify the feasibility and effectiveness of the new method.