Applications of thermal hazard analyses on process safety assessments

In 2011, a large petrochemical complex in Taiwan incurred several fire and explosion accidents, which had considerable negative impact for the industry on both environmental and safety issues. Reactive substances are widely used in many chemical industrial fields as an initiator, hardeners, or cross-linking agents of radical polymerization process with unsaturated monomer. However, the unpredictable factors during the process having risk to runaway reaction, thermal explosion, fire, and exposure to harmful toxic chemicals release due to the huge heat and gas products by thermal decomposition could not be removed from the process. This study used differential technology of thermal analysis to characterize the inherent hazard behaviors of azo compounds and organic peroxides in the process, to seek the elimination of the source of the harmful effects and achieve the best process safety practices with zero disaster and sound business continuity plan.     

化学品活性反应危险性表征方法研究

通过对国内外典型活性化学反应事故的研究,在传统和通用的化学反应危险性评价表征方法的基础上,提出使用化学反应的最大功密度表征化学反应热危险性的新方法。该方法将化学反应的热力学参数和动力学参数相结合,全面表征了反应过程的热危险性。采用加速量热仪模拟硝酸铵、过氧化氢,以及多种有机过氧化物的绝热反应放热情况,并运用测得的参数,计算得到其最大功密度,并与传统动力学计算方法得到的结果进行比较。根据对实验和计算结果的分析证明:利用最大功密度的方法评价化学反应的危险性更符合化学反应的实际情况,该方法为化学品安全生产提供可靠的技术支持。     

Improved management practice and process hazard analysis techniques for minimizing likelihood of process safety incidents in Taiwan

In Taiwan, process safety accidents often occur despite the prior implementation of process hazard analysis (PHA). One of the main reasons for this is the poor quality of the PHA process; with the main hazards not being properly identified, or properly controlled. Accordingly, based on the findings of 86 process safety management (PSM) audits, dozens of post-accident site resumption review meetings, and hundreds of PSM review sessions, this study examines the main deficiencies of management practice and PHA implementation in Taiwan, and presents several recommendations for improved PHA assessment techniques and procedures. The study additionally examines the feasibility for using PSM-related information, such as process safety information and process incident information, as a tool for further enhancing the PHA quality. Overall, the study suggests that, in addition to following the basic rules of PHA and requirements of OSHA (1992),management in Taiwan should also provide training in the enhanced assessment techniques proposed herein and take active steps to incorporate PSM information into the PHA framework in order to improve the general quality of PHA and reduce the likelihood of process safety accidents accordingly.     

基于高分遥感的危险化学品重大危险源安全布局动态管控研究*

为遏制危险化学品重特大安全事故,解决传统安全监测手段的空间局限性问题,结合高分遥感与数值模拟技术,开展危险化学品重大危险源区域安全布局动态管控研究。利用数值模拟技术模拟并确定危险化学品重大危险源重点管控范围;基于高分遥感影像提出适用于危险化学品重大危险源安全布局动态管控的变化检测方法,动态监测安全防护范围内的建筑、道路等人工构筑物的变化情况,严控事故影响范围内的人工构筑物密度;以内江市隆桥化工为实例开展示范应用。结果表明:高分遥感技术能够高效监测危险化学品重大危险源安全防护范围内的工程建设情况,有助于危险化学品企业保持足够的外部安全防护距离,降低危险化学品重特大安全事故风险。     

化学品混合物的安全监管技术研究

从分析我国化学品混合物安全监管技术出发,研究对比我国和国外在化学品混合物的危险性鉴别与分类、命名以及名录收入形式等安全监管技术方面的不同做法;指出我国在混合物危险性鉴别与分类、命名以及名录收入形式方面的缺陷和不足;提出完善化学品混合物安全监管技术是提高我国化学品混合物安全监管水平的重要手段;认为借鉴欧盟RAECH、联合国《关于危险货物运输的建议书-规章范本》及GHS的先进做法制定化学品混合物技术名称命名规则、修订现行危险化学品名录中混合物条目、引进混合物健康及环境危害估算方法,对提高我国化学品混合物的安全监管技术水平,促进化学品混合物的安全监管具有重要现实意义。     

Loss prevention in the petrochemical and chemical-process high-tech industries in Taiwan

Industrial safety has noticeably improved in recent years in Taiwan. Despite these improvements, however, serious accidents including explosions, chemical releases, and fires have still occurred in companies such as the Fu Guo Chemical Company (2001), Sin Hun Chemical Company (2005), Motech Industries, Inc. (2005) and Nanpao Resin Co. (2010). These accidents resulted in great loss of life and property, and further caused demands for improvement. Chemical disasters usually result from the combination of several mistakes or gross carelessness and are seldom caused by a single episode. To ensure the safety of operating, handling and storing chemicals, as well as to prevent chemical disasters, one must take many critical points into account, such as techniques, manufacturing processes, operators, chemicals, and emergency response. In Taiwan, the hazards and risks of high-tech companies are higher than in other industrial sectors. Therefore, a variety of safety management methods and regulations appropriate for high-tech companies have been generated. We studied the current status of the indigenous loss prevention protocols based on the safety management of petrochemical and chemical-process high-tech industries in Taiwan.     

基于QSPR方法的活性化合物热稳定性预测研究

为形成安全、可靠、便捷的活性化合物热稳定性预测方法,快速获取活性化合物热稳定性参数,采用定量结构-性质相关性(QSPR)方法,针对38种有机过氧化物和104种硝基化合物的起始放热温度和分解热,结合遗传函数算法(GFA)和“断点原则”筛选出的分子描述符,利用遗传算法(GA)优化的BP神经网络,建立活性化合物的热稳定性GA-BP预测模型,验证分析模型的性能和应用域。研究结果表明:所建立的GA-BP模型具有良好的拟合能力、稳定性和预测能力,优于线性模型,说明活性化合物热稳定性与分子结构之间存在非线性关系;同时,得出影响活性化合物热稳定性参数的主要结构因素。     

渤海湾客滚船危险货物安全运输现状分析与对策

针对近五年来渤海湾客货滚装船车载化工产品货物常见种类及危险性分布情况进行了全面的统计,阐述了渤海湾航线客货滚装船车载化学品运输现状,分析了渤海湾航线客货滚装船车载化学品运输存在的问题以及载有危险货物运输车辆客货滚装船在发生事故时可能带来的危害.提出了加强管理部门间协作、疏导与查堵相结合、制定适应渤海湾短途航运的货物危险性测试标准以及引导和促进货物生产商、经营者、运输单位提前进行货物危险性测试分类,并采用合适的包装方式及警示标志等加强载有危险货物运输车辆客滚船安全管理的重要措施.     

我国危险化学品重大危险源安全监管存在问题及建议

近些年发生的一些危险化学品重大事故和石化项目的群体性事件暴露出我国重大危险源监管体系还存在很多问题。对我国和欧美在重大危险源安全监管进行对比分析,总结出我国重大危险源安全监管存在几方面问题。重大危险源的土地利用规划未纳入城市规划控制程序;重大危险源建设项目公众参与不足;部分法规对一般危险化学品企业安全监管要求过高,重点不突出;某些安全监管提法相互重复、混乱;政府监管和企业管理界限不清晰;缺乏安全监察程序、指南,安全监察落实不到位;对化工园区安全发展认识不足。在吸收、借鉴美国和欧洲发达国家在重大危险源管理方面的经验和良好做法基础上,提出相对应的措施建议。政府部门应加快重大危险源的立法工作,在制定重大危险源的相关法规和政策时应科学、合理。     

GIS在化工园区事故应急救援辅助决策中的应用

采用GIS平台与应急决策支持技术相结合,以园区高危工艺和重大危险源作为分析对象,开发化工园区安全管理系统中的应急救援辅助决策模块,针对园区内高危工艺或重大危险源事故后果预测与事故应急救援管理的科学性和有效性,扩展为对整个化工园区的事故风险管理与事故应急救援辅助决策支持。运用该模块可实现园区内突发事故后果预测、最优救援和疏散路径规划、应急辅助决策方案生成,有效提高化工园区事故救援的科学性和效率,减少人员伤亡和财产损失,提高化工园区安全管理水平。     

Effects of ferric oxide on decompositions of methyl ethyl ketone peroxide

Methyl ethyl ketone peroxide (MEKPO) is a widely used initiator for polymerization reaction and hardener in glass-reinforced plastic. However, MEKPO is an unstable reactive chemical and has caused several serious accidents all over the world. This work studied the thermal stability of MEKPO in the presence of ferric oxide as the contaminant through calorimetric and kinetic studies. The calorimetry was performed using Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) to identify the effects of ferric oxide (different concentration) on important reactive hazards such as onset temperature and pressure hazard. Kinetic modeling was then performed to study the kinetics of the runaway reaction and estimate important kinetic parameters. The results indicate that in the low concentration range (<0.3%), ferric oxide has no significant effect on the thermal stability of MEKPO. However, in the high and intermediate concentration range of ferric oxide (i.e., 10%), the negative effect on the thermal stability of MEKPO was observed. This result is in agreement with the kinetic study result that the activation energy and frequency factor decrease dramatically in the high ferric oxide concentration range. The results provide necessary process safety information for the handling of MEKPO and also technical basis for the further study in this area.     

Thermal hazard evaluation for γ-valerolactone production by using formic acid as hydrogen donor

Aiming at the green and sustainable energy substitution and supply, biomass valorization has become a potential strategy to face the energy crisis and increasing demand all over the world from long-term perspectives. Among the bio-based chemicals, γ-valerolactone (GVL) production from hydrogenation of levulinic acid (LA) and its esters has attracted great interests due to its wide applications, such as fuel, solvent, and additives. However, the safety evaluation for this hydrogenation reaction has received few attentions. To fill this gap, thermal hazard evaluation for GVL production from LA hydrogenation by using formic acid (FA) as hydrogen donor was first performed. The process conditions were optimized by using orthogonal experimental method for further calorimetry study. Thermal stability of chemicals and thermal risk of reaction process under adiabatic conditions were investigated by applying differential scanning calorimetry and accelerating rate calorimeter Phi-Tec II, respectively. The results revealed that the chemicals were stable in temperature range from 30 to 250 °C except FA due to its evaporation and decomposition with endothermic behaviors. The reaction process under isothermal and adiabatic conditions demonstrates that the decomposition of FA was rapid and followed by the hydrogenation of LA to GVL. Based on kinetic model under adiabatic conditions and risk matrix, the thermal runaway risk was found to be medium, indicating that certain safety measures should be properly designed and taken for loss prevention. This work could benefit the safety design and thermal risk prevention for GVL production by using FA as hydrogen donor.     

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。     

基于本质安全的化工工艺物质危险指数研究

建立了基于本质安全的化工工艺物质危险性的评价体系,包括火灾危险性、爆炸危险性以及毒性等3个评价指数.基于风险的思想,各个评价指数均包括概率指标与后果指标.为了全面反映化工工艺的实际情况,在各个评价指数中均对所有物质的相应指数值加和.参数的取值以以往的指数法为基础,为了消除边界波动效应,取值采用内插法.由于各个指数的量纲...     

化工企业安全风险管控信息系统的研究与应用

为提升企业的安全风险管控水平,以R化工厂的甲醇成品罐区为例,运用系统的危险源辨识方法对其设备、工艺过程、切罐、倒罐操作程序、生产作业活动等进行系统全面的危险源辨识,形成安全风险信息数据库。基于安全风险信息数据库,开发各种风险管控工具。利用信息化技术,构建安全风险管控信息系统,对企业实行动态化的安全管理。     

一种基于层次分析法的危险化学品源安全评价综合模型

危险化学品源的安全评价是安全生产管理中的一项重要内容.目前用于危险化学品源安全评价与分级的常用方法有后果分析法、道指数法、蒙德指数法以及使用临界系数判别重大危险源的方法等.在实际应用中,单独使用某一方法时,由于存在各种片面性问题而得不到满意的评价结果; 几种方法同时使用时,其评价指标、评价结果以及结果的形式又会互相冲突.为解决上述问题,建立了基于层次分析法的综合评价模型.首先,根据安全评价要求构建3层次的评价体系,在各层次中构造判断矩阵,并计算4种常用方法相对综合评价模型的置信度; 其次,对各方法统一危险分级标准,均采用危险分数划定危险级别,并取各危险分数的加权平均值--综合危险分数作为综合评价模型下的危险源分级标准.采用综合评价模型可消除单一方法进行评价时的片面性和偏差,同时,评价结果的一致化使得判断危险化学品源的危险级别以及由此采取相应级别的管理措施成为可能,将更有利于实际安全生产管理指导.     

危险化学品企业实施安全评价工作绩效分析

2006年安全生产工作取得了较好的成绩,呈现总体稳定趋向好转的发展态势,事故死亡人数总量也较大幅度下降。但是,在危险化学品行业非但没有得到扭转,事故死亡人数反而上升了16.2%。对此,我们有必要加强对危险化学品的安全管理。在安全评价方面,危险化学品企业实施安全评价后是否对企业的发展有实际的绩效,对此,我们对全国320家实施过安全评价的危险化学品企业进行了调研分析,尤其在安全设施、安全管理水平、事故发生频率等方面,并从中得出结论,进而了解评价过程中存在的不足,以及提出合理的对策措施。     

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.     

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.