Comparisons of TGA and DSC approaches to evaluate nitrocellulose thermal degradation energy and stabilizer efficiencies

This study investigated the thermal degradation energy (activation energy, E_a) for nitrocellulose (NC) with low nitrogen content of 11.71 mass%, so-called NC3, by using two different kinds of thermal analysis instruments: thermogravimetric analyzer (TGA) and differential scanning calorimetry (DSC). A comparison of E_a for various nitrogen content NC samples at two scanning rates (5 and 10 °C min^?1) tested by TGA and DSC is also discussed in this paper. Meanwhile, our aim was to analyze the anti-degradation of E_a for NC with high nitrogen content, as so-called NC1. Thermal stability for NC1 with diphenylamine (DPA) was tested via DSC with 10 DPA concentrations in weights of 0, 0.25, 0.50, 0.75, 1.0, 1.25, 1.50, 1.75, 2.0, and 3.0 mass%. Experimental results indicated that E_a of NC3s was 319.91 kJ mol^?1. Moreover, that while dosing DPA into NC1 the best recipe could be employed to avoid any violent NC1 runaway and also can be used to distinguish the differences of thermal decomposition E_a between NC with different nitrogen contents. This study established a fast and efficient procedure for thermal decomposition properties of NC, and could be applied as an intrinsically safer design during relevant operations.     

Computational fluid dynamics (CFD) study of heat radiation from large liquefied petroleum gas (LPG) pool fires

Liquefied petroleum gas (LPG) is flammable and has risks of pool fires during its transportation, storage, and applications. The heat radiation by LPG pool fires poses hazards to individuals nearby and can lead to potential failures of ambient facilities. Due to the high costs and invasive nature of experiments for investigating large-scale pool fires, computational fluid dynamics (CFD) is employed in this study as the cost-effective and noninvasive method to simulate the process and analyze the characteristics of large hydrocarbon pool fires. Specifically, an experimentally validated 3-D CFD model has been built to simulate surface emissive power (SEP) and incident radiation of large-scale LPG pool fires with three different diameters and wind speeds. Steady-state simulations with P1 radiation and probability density function (PDF) combustion models were employed to obtain reliable data after the optimizations based on the comparisons with experimental data and empirical models. The comparison with benchmark experimental data demonstrates that the CFD model employed in this study can accurately predict the incident radiation of large LPG pool fires. A new SEP correlation is also proposed, which is specifically for LPG pool fires with a diameter between 10 m and 20 m. Additionally, the safe separation distances between LPG facilities and surrounded objects have been estimated based on the CFD simulation results. The high-resolution CFD model for large LPG pool fires in this work provides noninvasive and direct quantitative evidence to enhance the fundamental understanding on the safety of large LPG pool fires and can assist regulatory agencies in refining the safety limits in the cost-effective and time-saving manners.     

Configuration predictions of large liquefied petroleum gas (LPG) pool fires using CFD method

Liquefied petroleum gas (LPG) has potential pool fire risks due to its flammability. The configuration of pool fires plays a significant role when applying the solid flame model or point source model to assess the risks from heat radiation. However, no existing correlations can precisely predict the configuration of large LPG (100% propane) pool fires. To enhance the fundamental understanding on how pool diameter and wind velocity can influence the configuration of large LPG pool fires, an experimentally validated Computational Fluid Dynamics (CFD) model is employed to simulate fires using different burning rate models. Fire temperature profiles, flame heights, and flame tilts predicted by the CFD model were compared with empirical models and experimental data. Accordingly, new correlations for flame height and flame tilt as functions of pool diameter D and wind velocity u_w have been developed. The comparisons demonstrate that the new correlations have the best overall accuracy in the prediction of flame height and tilt for large LPG pool fires under different conditions (10 m ≤ D ≤ 20 m, 0 ≤ u_w ≤ 3 m·s⁻¹).     

基于ANP的建筑安全管理绩效评价框架研究

基于政府A部门提供的502起建设工程事故调查报告,综合应用比较分析、数据挖掘、网络层次分析法(ANP)和超级决策(SD)决策软件,建立建筑安全管理绩效评价框架,包括6个一级指标和24个二级指标;通过分析各因素之间的关系,修正各个因素的权重,得出事故致因的传递路径。根据和其他偏定性研究的比较还可以发现,基于数据挖掘的ANP和SD的综合运用,更利于对真实情况进行研究模拟,在应对较大建设工程事故风险时更具有针对性和前瞻性。     

基于MATLAB分析的城市道路照明环境比

基于驾驶员在行驶过程中的注意力大部分集中在车辆的正前方,忽略了道路两侧的情况的视觉特性,更容易引发交通事故的问题。环境比为评价路边物体可视度的指标,为了保证评价的准确性,尤其是保障夜间行驶的良好视觉环境,可以根据路灯设置的基本原则及照明强度与可见度的关联特性,使用MATLAB(矩阵实验室)对环境比进行模拟分析,从理论的角度研究其相关的影响因素,提出了采取减小灯具倾斜角、缩短灯具悬臂悬挑长度以及增加路灯灯杆安装位置与路缘石的距离等措施可以提高道路照明环境比的观点,可以作为路灯改造工程、路灯灯具外形的设计以及夜间行驶事故分析的理论基础。     

贝叶斯网络在CFIT风险评价中的应用

针对事故树分析法(FTA)在风险评价中的局限性,在可控飞行撞地(CFIT)事故树的基础上,建立贝叶斯网络(BN).运用推理运算对贝叶斯网络进行定量分析,通过分析计算数据,寻找主要事故致因,并提出对应的改进措施.再将改进措施引入到贝叶斯网络中,评价相关措施的有效性.结果表明,改进措施后,高度设置错误的后验概率最大,将成为预防CFIT的工作重点.最后指出贝叶斯网络方法是对传统的基于故障树分析的风险评价方法的有益改进.     

Peculiar effect of acylamino and cyan groups on thermal behavior of 2-(1-cyano-1-methylethyl)azocarboxamide

2-(1-Cyano-1-methylethyl)azocarboxamide (CABN) is a representative of new-type azo initiator in the radical polymerization industry. The peculiar water and oil soluble characters make it a versatile rising star for the industry to initiate the polymerization of monomers in either polar or nonpolar solvents based continuous phases. This paper decodes the effect of acylamino and cyan groups on thermal stability and hazards of CABN via advanced thermokinetic analysis and numerical simulation. Initially, simultaneous thermogravimetric analyzer was employed to evaluate the thermal stability of CABN and its two structurally similar azo compounds (azos), azobisisobutyronitrile (AIBN) and azodicarbonamide (AC). Followed with calorimetric experiments by differential scanning calorimetry, the effect of two functional groups on thermal behavior parameters, such as decomposition temperature, melting point, and heat of decomposition was estimated. The results indicated that the acylamino group can improve the thermal stability of CABN but with bulkier heat release. Ultimately, through the medium of thermokinetic analysis, the thermal hazard of AIBN, CABN, and AC was simulated based on auto-ignition and thermal explosion theory. The research results would provide references for the synthesis of new-type azo initiators and process safety parameters to the polymerization industry.     

基于遗传算法的支持向量机预测有机物自燃点的研究

根据定量构效关系(QSPR)原理,研究自燃点(AIT)与其分子结构间的内在定量关系。以265种有机化合物作为样本集,随机选择238种作为训练集,27种作为测试集,用遗传算法(GA)进行变量选择,分别建立多元线性回归(MLR)模型和支持向量机(SVM)模型研究有机物的自燃点与其分子结构间的关系。通过分析,发现造成模型预测效果不佳的原因是试验数据本身存在问题。通过对2个模型的比较,结果为GA-SVM模型明显优于GA-MLR模型,说明自燃点与其分子结构间具有很强的非线性关系。     

基于SMART原则的企业安全文化评价体系研究

为持续改进企业安全管理绩效,对安全文化的关键指标进行研究并量化处理,以期对建立我国企业安全文化评价体系有建设性作用。笔者运用SMART原则确定了从3个测量维度、5个方向、18个评价指标构建了企业安全文化评价体系,运用层次分析法,并采用问卷调查及专家系统确定各评价指标的评价权重,对企业的安全文化进行研究。其结果表明提高组织安全文化水平主要从提高安全行为在组织内的受重视程度和加强组织管理两个途径入手。安全文化评价指标体系是对被评价对象进行全面考察的工作蓝本,在明确评价目标的指导下,尽可能从多方位评价企业安全文化的各个方面,最终落实到安全文化的操作层面。     

Process safety management lessons learned from a fire and explosion accident caused by a liquefied petroleum gas leak in an aromatics reforming unit in Taiwan

A severe fire and explosion accident was caused by a liquefied petroleum gas leak in Taiwan in 2019. This accident resulted in the loss of approximately US$3.5 billion in output value due to a one-and-a-half-year shutdown after the accident; however, no casualties were recorded at the accident scene. An analysis of the accident pipelines demonstrated that the pipeline leak had been caused by hydrochloric acid corrosion. Cause analysis based on the accident timeline, fault tree analysis, and causal factor charting indicated inadequacies in five elements of process safety management (PSM) namely mechanical integrity (MI), management of change, emergency planning and response, process hazard analysis (PHA), and process safety information (PSI) as the root causes of the accident. Furthermore, insufficient PSI (i.e., a lack of comprehensive understanding regarding corrosion mechanisms) was deemed to have been the core problem leading to the accident. This accident revealed common shortcomings that are often overlooked in PSM implementation in Taiwan; thus, the present research can serve as a vital reference for improving PSM programs in Taiwan.     

煤矿本质安全化管理体系建立及其应用的探讨

运用安全系统工程中的事故树理论,以瓦斯爆炸事故为例分析了煤矿中的7类主要事故,并得出相应的事故树。通过对事故树的定性分析,得出事故树的最小径集和基本事件重要度排序。进而可预测基本事件的发生所能够导致的结果,可根据各基本事件的重要度排序,确定避免发生事故应采取的基本措施,并建立了煤矿本质安全化管理体系。设计出煤矿本质安全化管理体系的软件,并以瓦斯爆炸事故为例,分析了该管理体系在实际中的应用效果。     

Continuous performance assessment and improvement of integrated HSE and maintenance systems by multivariate analysis in gas transmission units

In this study, an integrated “Health, Safety, and Environment (HSE)” and maintenance systems are presented. Multivariate analysis is used for continuous performance assessment and improvement of these systems. The two subjects of “Maintenance System” and “HSE” have been individually investigated several times in different studies. However, few studies have been done to integrate these two systems and provide an integrated system for their implementation. This study evaluates current maintenance and HSE systems of a Gas Transmission Unit by Data Envelopment Analysis (DEA) and Principal Component Analysis (PCA). Moreover, decision making units (DMUs) are examined and ranked. Employees are considered as DMUs. This is done through investigating and measuring their efficiencies and identifying the inefficient and less-efficient units. Since an increase in the number of inputs does not lead to an increase in the number of outputs with the same scale, an output-oriented DEA with a Variable Returns to Scale (VRS) is used. The Fuzzy DEA (FDEA) is also used in this research to decrease uncertainty existing in qualitative indicators and human error. Finally, suggestions are given to improve those DMUs. The managers and employees of the gas transmission unit constitute the statistical population of the study. To achieve the objectives of this study, standard questionnaires with respect to HSE and Maintenance system are completed by operators. The proposed approach would help policy makers and top managers of Gas Transmission Company to have a more comprehensive and thorough understanding the working conditions with respect to the maintenance and HSE features.     

事故定性分析与事故定量预测

分析了影响事故预测准确的原因,综述了国内外许多学者在事故预测方面所做的努力。指出今后事故预测工作的主要途径是由安全系统工程专家建立计算机支持的决策支持系统(DSS),由安全专家灵活运用这个系统中的计算机辅助研究方法(CAR)。     

基于层次分析-模糊综合评判的电解车间安全现状评价研究

根据电解车间安全评价存在的模糊性和随机性的特点,建立涵盖职工素质、工艺过程、生产设备、职业卫生、安全管理一级指标的安全现状综合评价指标体系;运用层次分析(AHP)理论,用标度取值方法、分根法分别构造模糊判断矩阵和计算各单因素的权重值;运用模糊综合评判(fuzzy comprehensive evaluation)理论,提出安全现状二级模糊综合评价方法;在组织专家对评价指标打分和确定模糊等级的基础上,结合前面得出的权重值,对某电解车间的安全现状进行了综合评价,得出其安全状况为"一般";在评价过程中,分析了指标体系中一级指标的状况,为制定安全措施提供了指导。笔者认为,该方法对于提高电解车间安全现状综合评价的客观性和准确性具有理论意义和实用价值。     

过程工业计算机辅助安全防护层分析技术进展

介绍当前过程工业安全防护层分析(LOPA)的基本内容,研讨LOPA方法与深层次的危险和可操作性分析方法(HAZOP)之间的关系以及计算机辅助HAZOP的研究进展。针对人工LOPA方法的缺点,开发了SDG-HAZOP软件平台,为计算机辅助LOPA平台研发创造了先决条件。应用计算机辅助LOPA方法,使防护层的设置具有更好的针对性、合理性和有效性,发挥对事故的预防和预警作用,并具有良好的发展前景。     

基于人工神经网络理论的建筑物火灾安全评价研究

依据建筑物火灾危险性的影响因素,应用人工神经网络理论及系统安全方法,建立了建筑物火灾危险性的评价指标体系,该方法摆脱了评价过程中的随机性和参评人员主观上的不确定性及其认识上的模糊性等缺点,大大提高了准确性。为了验证评价模型的准确性,将该理论应用到某高校图书馆火灾危险性评价中,快速、准确地得到了安全评价结果,取得了满意效果,为建筑物防火设计以及安全管理提供了可行的依据。     

Learning from the application of nuclear probabilistic safety assessment to the chemical industry

This paper introduces the new approach of risk analysis established by the French Ministry of the Environment and develops the benefits of applying nuclear probabilistic safety assessment approaches to the chemical industry.In the aftermath of the AZF disaster in Toulouse on 21 September 2001, a new law was proposed by the French government asking for the investigation of all representative scenarios and the assessment of the probability of the resulting dangerous phenomena to demonstrate an acceptable level of safety. Therefore, any accident is investigated from a global point of view, according to its gravity and its probability.In 2000, the French Ministry of the Environment asked the Institute for Radiological Protection and Nuclear Safety (IRSN), and in particular its Systems and Risk Protection Assessment (SESPRI) and its Industrial Risks, Fire and Containment Assessment and Study (SERIC) departments, to conduct a Probabilistic Safety Assessment (PSA) study of an LPG distribution facility, specially for the BLEVE scenario. This study has showed the power of PSA for defining and prioritizing actions to be carried out to improve safety of facilities; however, it requires credible data for reliability and failure of the equipment, not available in generic failure databases.Since 2007, IRSN has taken several initiatives in collaboration with operators in order to provide more precise and representative failure rates for main safety equipment, ready to use in future PSA relative to LPG plants.     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.     

Risk-based inspection (RBI) of a gas pressure reduction station

One of the principles of corrosion management is proper inspection methodology, and in particular the risk-based inspection (RBI). Occasionally a large percentage of the total risk of a unit is concentrated in a small part of the equipment, which can be reduced by using risk management techniques. In this study, a semi-quantitative risk-based inspection method has been performed in a gas station with for its components (pipelines, filters, etc.), to identify the existing damage mechanisms and also to rank its equipment in terms of inspection intervals. In this regard, RBI was performed for the gas station which consisted of phases (Phase A & Phase B) with Class 300 and Class 600 equipment. According to documented conditions and reviewed records the main damage mechanism for the investigated components in the gas station was identified as wall thinning due to erosion corrosion and external corrosion. In terms of inspection, results showed that most of the equipment studied had medium risk level and a few had medium to high level of risk. In this regard, the corrosion rates of Class 300 and Class 600 equipment were also studied and compared, and it was indicated that the corrosion rates were higher at locations for Class 300 equipment where more pressure drop had occurred. Overall, based on the obtained corrosion rates and obtained risk matrixes, it was concluded that wall thinning (erosion-corrosion) was the determining risk factor for equipment inspected in the gas pressure reduction station.