酞酸酯类化合物在不同温度下蒸气压的定量预测模型研究

依照经济合作与发展组织(OECD)关于定量结构-活性关系(QSAR)模型的构建和使用导则,采用偏最小二乘(PLS)法进行变量筛选和回归分析,建立了不同温度下酞酸酯类化合物(PAEs)蒸气压的定量预测模型.模型仅包含温度、相对分子质量、氢原子最高净正电荷3个参数.模型的应用域(AD)可由williams图较好地表征.结果表明,温度和相对分子质量是影响PAEs蒸气压的主要因素,且温度越高、相对分子质量越小时,蒸气压越大.内部验证与外部验证结果表明该模型具有良好的稳健性和预测能力.     

改进的蒸气云爆炸模型在LNG储罐爆炸模拟中的应用

针对TNT当量法在LNG储罐蒸气云爆炸模拟中的应用进行了改进,考虑并分析了使用传统TNT模型时所忽略的LNG液池蒸发过程,通过建立LNG与地面的传热模型得出了LNG液池蒸发速率随时间变化的关系,液池的蒸发速率在最初随时间的增长较快,在增至最大值后与时间的平方根成反比逐渐减小。以3万m~3 LNG储罐连续泄漏20 min为例,根据蒸发速率与时间的关系算出了蒸气云团中的燃料量,再结合蒸气云爆炸模型利用Matlab软件进行了事故后果模拟计算,得出发生蒸气云爆炸时的死亡半径为36.629 5 m,重伤半径为83.557 6 m,轻伤半径124.725 m,财产损失半径为109.017 9 m。相较于无蒸发过程的传统模型,此计算结果更加具有参考意义。     

石油储罐油气蒸发损耗的成因、危害及对策

油气蒸发威胁安全,蒸发的油蒸气易引发爆炸,从而导致油罐爆炸着火。油蒸气是气相烃类,属有毒物品,漂浮地面易致人窒息。油蒸气还易形成光化学烟雾的二次污染物。由于油蒸气的蒸发损耗,全世界每年散失于大气中的油气约为１×１０８吨,折合人民币２４００亿元。因其所蒸发的都是油料中的最轻组分且油气蒸发还严重影响成品油质量。笔者分析了油气蒸发损耗的危害、产生原因及各种影响因素,并提出了降低油气蒸发损耗的对策     

油料蒸发损耗的危害预防

油料，尤其是轻质油料，因具有易挥发的性质，在收发及储运过程中，一部分油料蒸发的油蒸气消耗于大气中，称为蒸发损耗。据资料介绍，美、日石油的蒸发损失占年产量的3％-5％；前苏联每年由于油罐大小，损失近7％的轻质油品。目前，我国尚无权威性的统计数据，但据测定，     

油料蒸发损耗的危害及预防措施

油料，尤其是轻质油料，因具有易挥发的性质，在收发及储运过程中。一部分油料蒸发的油蒸气消耗于大气中，称为蒸发损耗。据资料介绍，美、日石油的蒸发损失占年产量的3％～5％；前苏联每年由于油罐大小呼吸，损失近7％的轻质油品。目前，我国尚无权威性的统计数据，但据测定，     

含硫油品储罐腐蚀自燃理论及实验研究

含硫油品储罐腐蚀自燃事故是炼油企业安全生产的重大威胁.本文对含硫油品储罐腐蚀进行了实验模拟研究,并对实验结果进行了分析,利用扫描电子显微镜对试样腐蚀表面进行了特征分析,并利用X射线仪对腐蚀产物的组成和结构进行了分析.在实验结果分析的基础上,从理论上分析了含硫油品储罐腐蚀自燃机理,探讨了含硫油品储罐腐蚀的自燃影响因素.研究结果可作含硫油品储罐安全设计和含硫油品炼制工艺改进的重要参考.     

二元混合液体闪点的计算

以混合溶液纯组分易燃液体闪点的饱和蒸气压为基础,应用乌拉尔定律、双液系的气-液相平衡理论,运用Le Chatelier方程和安托因方程导出二元混合液的闪点计算方法。并例举易燃液体与易燃液体组成的理想混合液、易燃液体与易燃液体组成的非理想混合液、易燃液体与不燃液体组成的非理想混合液的计算过程。乙醇溶液闪点的计算结果与现有的文献资料比较,误差在允许范围内。计算数据用Excel处理,快捷准确,用于确定二元混合液体的火灾危险性。     

基于GIS的油品储罐区风险评价及应急资源优化调运系统

为对油品储罐区事故进行迅速的风险评价和应急救援,在详细分析油品储罐区危险特性的基础上,建立了区域风险评价模型、应急资源优化调运模型和实时在线应急培训模型,将其作为功能模块与GIS技术加以整合,构建了基于GIS的油品储罐区风险评价及应急资源优化调运系统.当油品储罐区发生突发事件后,针对不同的事故类型和事故级别,该系统可对其区域风险进行评估,划分不同伤害等级范围,并在最短的时间内,通过带有"单程最大运输能力"约束的两目标连续消耗应急资源优化调运模型计算,给出合理有效的应急资源优化调运方案.无事故发生时,也可进行相应的事故模拟演练及实时在线应急培训.在西部管道油品储罐区的实例应用表明,该系统可为油品储罐区制定应急救援活动方案,提高危害防护水平提供技术支撑.     

加油站火灾事故致因分析与应急处置

笔者通过对我省加油站火灾事故的研究后认为,加油站发生火灾事故是人、物、环境和管理诸因素相互作用的结果,其主要致因如下：（1）油蒸气失控油品在油罐、管道或卸油、加油等处渗漏导致油品在空气中蒸发形成油蒸气;油蒸气具有扩散性,在加油站的空间不易控制,     

化工装置连锁爆炸实例研究

化工装置发生爆炸时往往是两三种类型的爆炸连锁式地相继发生,这使预防控制和评估爆炸事故更加困难,如何将单类爆炸研究成果合理应用于实际成为关键.本文对尿素合成塔连锁爆炸的实例进行了剖析,揭示了其气相爆炸到蒸气爆炸再到蒸气云火球的连锁爆炸机理,并运用相关计算模型对爆炸过程进行了计算,得到了爆炸波最大迭加位置、气相最大爆压、蒸发体积、闪蒸总功、筒体抛射功、TNT当量、以冲击波计的安全距离、火球最大直径、持续时间、辐射通量的计算值.     

浮顶油罐密封圈油气分布数值模拟

浮顶油罐一二次密封空间内的油气在雷击作用下可导致起火事故。为研究浮顶油罐一二次密封空间内的油气浓度影响因素,利用CFD方法进行了数值模拟,并建立了浮顶油罐实验模型,检测一二次密封空间内不同位置处的油气体积分数,两者表征的油气浓度情况较吻合;借助该模拟方法进一步分析温度、风速和二次密封泄漏面积对浮顶油罐一二次密封空间内的油气浓度的影响,研究结果表明:①二次密封泄漏面积增加,密封空间内的油气浓度降低。②温度上升,一二次密封空间的油气浓度升高;当风速较高时,温度对油气浓度变化趋势的影响也更大。③风速增加时,空间内的油气分布差异变大,油气浓度最大值变大。     

Mutual effects between dynamic leakage behavior and the pressure/temperature in a LNG tank with external heat fluxes

The objective of this work is to investigate and model the mutual effects between the dynamic pressure/temperature in the LNG tank and the leakage behavior with external heat fluxes. The results suggest that the pressure and temperature in tank during leakage change with the comparison results between the heat flux consumed in liquid boil-off and the external heat flux supplied. At the liquid leakage stage, when the external heat flux is not very high, the pressure in tank tends to increase significantly, even results in tank explosion. It increases more and more heavily with higher and higher external heat fluxes. At the vapor leakage stage, large amount of vapor spray out, which results in a high generation rate of vapor by the liquid boil-off. The pressure in tank normally decreases to be low, which is unfavorable for the LNG tank explosion. Therefore, at this vapor leakage stage, blocking the leakage hole as soon as possible is not always a right choice for fire fighters. Finally, it is suggested that reducing the heat flux into the tank, either at the liquid leakage stage or in vapor one, is key to the tank safety.     

Analysis and assessment of the Qingdao crude oil vapor explosion accident: Lessons learnt

A devastating crude oil vapor explosion accident, which killed 62 people and injured 136, occurred on November 22, 2013. It was one of the most disastrous vapor cloud explosion accidents that happened in Qingdao's storm drains in China. It was noted that blast overpressure and flying debris were the main causes of human deaths, personal injuries and structure damages. Two months after the accident, it was reported that there were three contentious issues in the investigation report. First issue was the discrepancy between the temperature of the crude oil vapor explosive limits which were measured by the investigation panel and the temperature reported by the local fire department. Second issue was the contradiction between the upper explosive limit and vapor pressure of the crude oil vapor. The last issue was the location of the ignition source which led to the explosion.In the present study some specific features of this accident and various causes led to the explosion, high casualties and severe damages were analyzed. Three contentious issues in the official investigation report were investigated and tested in detail. The first element tested was the explosive limits and limiting oxygen concentration of the crude oil vapor at different temperatures. Based on theoretical analysis and field investigations, the last two elements in the report were analyzed from multiple perspectives. Based on the TNO Multi-Energy model and PROBIT equations, damage probability of affected people at the leaking site was also estimated. The investigation concluded with a result that precautions need to be taken to prevent flammable gas explosions in the drainage systems. Key steps were explicitly discussed for improving the hazard identification and risk assessment of similar accidents in the future.     

原油油气职业卫生标准研究

我国目前尚未制订原油油气卫生标准,多数引用溶剂汽油卫生标准,研究表明原油油气毒性较溶剂汽油大,为保障油运装卸作业人员的健康,科学地监测与控制油气污染,确定合理的作业环境,制订原油油气卫生标准是十分必要的。该研究通过色-质联用分析,表明原油蒸气成份大多为C9以下烷烃、环烷烃及少量的芳香烃。采用大、小鼠为对象的急性毒性实验研究,获得大庆、胜利、渤海3种原油油气的LC50分别为49.54g/m3、77.54g/m3、417.50g/m3;亚慢性毒性实验研究表明,原油油气对动物神经系统的影响较为突出。现场劳动卫生学调查统计表明油轮、油码头作业人员,除了在装船、装罐作业状态下受到较大油气浓度危害外,大部分时间处于100mg/m3以下油气浓度环境,但长期从事油运装卸作业,表现出一定的健康异常,其主要症状是神衰症候群发生率明显增高,植物神经功能障碍,血象异常,其次为心率、心电图的改变等。根据上述研究结果,该研究认为原油装卸贮运作业场所原油油气时间加权平均容许浓度确定为100mg/m3(以总烃计)较为适宜。     

埋地油罐事故伤害范围模拟评价

分析埋地油罐可能发生的火灾爆炸事故,建立事故模拟模型,模拟爆炸物质完全燃烧的质量依据化学计量浓度确定,事故伤害范围的计算用G.M莱克霍夫在砂质土壤中爆炸的冲击波计算方法。对50 m3埋地油罐模拟,油蒸气形成爆炸性混合气体爆炸伤害范围较大,安全范围与《汽车加油加气站设计与施工规范》中相关规定相符合。模拟方法用于埋地储罐的定量安全评价,为罐区选址、建设、安全距离确定及安全预案制定提供参考。     

Experimental analysis of the evaporation process for gasoline

This paper presents the findings from a study on the evaporation process of 93 RON (research octane number) unleaded gasoline. The parameters measured in the experiment included the weight, the RVP (Reid vapor pressure) and the viscosity of gasoline, the concentration of NMHC (non-methane total hydrocarbon) in the oil vapor and the concentration of the main vapor constituent. Results showed that the parameters changed significantly as evaporation processed. The weight loss reached 86.36% after 300 days and presented a logarithmic curve with time. The RVP decreased from 38 kPa to 9.6 kPa. The viscosity of gasoline increased from 8.6 × 10^?4 Pa s to 1.51 × 10^?3 Pa s. All the concentrations of NMHC and the main constituent of vapor decreased in varying amounts. Most of the changes might be attributed to the evaporation of volatile hydrocarbons.     

Evaporation characteristics of multi-component liquid

Evaporation rate of multi-component liquid such as motor gasoline is expected to change greatly with progress of evaporation because its composition changes. Therefore it is difficult to predict accurately amount of generated combustible vapor in the case that a multi-component liquid is spilt on a floor. Then, we assumed an evaporation model that composition of the vapor obeys the Raoult's law which considers the activity coefficient. Using the model, we calculated the vapor composition, the vapor pressure and the evaporation rate of the liquid. Then, comparison was done between the calculated values and the measured values obtained in this study. “Weight loss fraction” was used as a parameter signifying the progress of evaporation. The variations of the evaporation property were accurately predicted by the model. We derived a prediction model of the amount of generated combustible vapor from the relation between weight loss fraction and evaporation rate. It was found that the amount of generated vapor was expressed as a logarithmic function of time in case of a five-component liquid. Furthermore, we showed that the predicted flash point of a liquid using the composition obtained from the model was in good agreement with an experimental result.     

高压、超高压油气井装备抗内压强度设计计算分析*

为解决传统计算公式与方法已几乎无法满足目前对高压、超高压油气井装备强度设计的需求,利用理论分析方法,对不同抗内压强度计算公式进行详细分析,引入压力容器行业高压、超高压的计算公式与方法,并对某高温高压井抗内压强度进行分析,提出适用于超高压油气井的油套管抗内压强度计算公式。研究结果表明:不同抗内压强度公式的基本思想与设计准则不同,在使用时应注意限制条件,现有的抗内压强度计算公式不适用于高压、超高压油气井,材料性能不能充分利用且存在一定安全隐患;对超过100 MPa的油气井,可以采用弹塑性理念计算抗内压强度,对于油套管可以减小强度等级同时增加壁厚来满足抗内压强度要求。研究结果对高压、超高压油气井装备抗内压强度设计具有一定参考价值。     

On the mechanism of a BLEVE occurrence due to fire engulfment of tanks with overheated liquids

The BLEVE (boiling liquid expanding vapor explosion) effect that involves the formation of a fireball occurs at the engulfment by fire of a tank with a highly flammable liquid or a liquid gas. Heating of the tank causes elevation of the liquid phase temperature and pressure inside the tank. A partial rupture of the dry tank walls is possible, with the formation of a rarefaction wave propagating into the liquid phase. An evaporation wave moves after the rarefaction wave and cause a rapid increase of pressure, exceeding the initial pressure before depressurization. Rapid violent destruction of the tank occurs. The mechanism of a BLEVE initiation is considered using Van der Waals isotherms. The following criterion for the possibility of a BLEVE was formulated. If the final state is located on an unstable part of the Van der Waals isotherm, a BLEVE takes place. Limiting values of the temperatures for overheating of certain highly flammable liquids and liquid gases (propane, n-butane, n-pentane, isopentane) were calculated using the proposed method, and were found to be in good agreement with experimental data available in the literature.