Modelling spills of water-reactive chemicals

This paper describes part of a programme of work undertaken at the Health and Safety Laboratory (HSL) to investigate the behaviour of selected water-reactive chemicals. Following an accidental release, such substances react exothermically with any water present, generating acidic vapours. The STAWaRS (Source Term Assessment of Water Reactive Substances) software was developed for the Health and Safety Executive (HSE) by ESR Technology to model this complex process. The aims of the study described here were to provide experimental validation of the heats of hydrolysis used within STAWaRS, and to perform sensitivity studies on selected STAWaRS input parameters.The heat of hydrolysis of acetyl chloride was measured and showed good correlation with the value used within STAWaRS. Some of the variables that influence the severity of acetyl chloride spills are examined, with reference to predictions made by the STAWaRS model. The heats of hydrolysis of titanium tetrachloride previously measured at HSL are also discussed, and the effect of adopting these experimentally derived values for modelling spills is shown for a hypothetical land use planning case. This study demonstrates the importance of using experimentally validated values for STAWaRS input parameters.     

Modelling the response of masonry structures to gas explosions

In practice no system is infallible no matter how stringent the safety standards and procedures are concerning the release and use of gas in the process industries. Structural damage arising from an internal explosion often has serious repercussions. It is, therefore, imperative for engineers to be able to predict the extent of the damage that may occur, and to develop means to mitigate such effects.An accurate prediction of the structural behaviour requires an accurate formulation of the material's failure criteria. Experimental studies have shown that the response of masonry structures to gas explosions is non-linear. The cracking of masonry in tension and crushing of the material in compression are the major contributory sources of non-linearity.This paper presents a method of predicting the non-linear response based on the formulation of a numerical model to describe the material's failure criteria. The model has been validated using full-scale explosion test data provided by the Building Research Establishment in the UK. Although some minor discrepancies have been observed, overall the simulated values correlated very favourably with the actual test data. The probable causes of discrepancies are also discussed at the end of this paper.     

含磷单体/碳纳米管阻燃改性不饱和聚酯复合材料的制备及其性能研究

以三氯氧磷、苯酚和丙烯酸羟乙酯为原料合成了含磷阻燃单体(DPHE),并作为反应型阻燃剂通过自由基共聚,将其引入不饱和聚酯树脂中,同时添加多壁碳纳米管(MWCNTs),制备不同组分的不饱和聚酯复合材料。采用极限氧指数、UL-94垂直燃烧法表征材料的燃烧性能并评定燃烧等级;通过锥形量热测试数据对材料燃烧过程中的热释放进行研究,结果显示,阻燃不饱和聚酯具有更低的热释放速率峰值(PHRR)和总热释放量(THR)。此外,采用热重分析(TGA)和扫描电子显微镜(SEM)分别对材料的热降解性能和炭渣形貌进行研究,阐明了含磷阻燃单体和多壁碳纳米管的阻燃机理。     

Underwater LNG release: Does a pool form on the water surface? What are the characteristics of the vapor released?

One of the scenarios of concern in assessing the safety issues related to transportation of LNG in a marine environment (ship or underwater pipeline) is the release of LNG underwater. This scenario has not been given the same level of scientific attention in the literature compared to surface releases and assessment of consequences therefrom. This paper addresses questions like, (1) does an LNG spill underwater form a pool on the water surface and subsequently evaporate like an LNG spill “on the surface” producing cold, heavier than air vapors?, and (2) what is the range of expected temperatures of the vapor, generated by LNG release due to heat transfer within the water column, when it emanates from the water surface?Very limited data from two field tests of LNG underwater release are reviewed. Also presented are the results from tests conducted in other related industries (metal casting, nuclear fission and fusion, chemical processing, and alternative fuel vehicles) where a hot (or cold) liquid is injected into a bulk cold (or hot) liquid at different depths.A mathematical model is described which calculates the temperature of vapor emanating at the water surface, and the liquid fraction of released LNG that surfaces, if any, to form a pool on the water surface. The model includes such variables as the LNG release rate, diameter of the jet at release, depth of release and water body temperature. Results obtained from the model for postulated release conditions are presented. Comparison of predicted results with available LNG underwater release test data is also provided.     

A study on the influence of liquid water and water vapour on the self-ignition of lignite coal-experiments and numerical simulations

The current paper presents experimental investigations as well as numerical simulations on the influence of water and humidity on the self-ignition of combustible bulk materials.It is well known, that bulk materials may undergo self-ignition if stored under specific conditions. In some cases, large amounts of these materials are exposed to a humid surrounding, e.g. dried coal in a moist atmosphere. Due to the effects of condensation and adsorption of water, additional heat is generated and transported into the bulk material. If the pile is stored slightly below its self-ignition temperature, the bulk material can become supercritical and an ignition occurs.Experiments were carried out for German lignite coal sampled in two different particle size fractions. They showed, that subcritical deposits turned to supercritical behaviour if the relative humidity in the surrounding was suddenly increased or water was poured on the surface of the sample. Besides the experiments, a numerical model was established to describe the effects of self-heating until ignition of the deposit, including the transportation of moisture. Simulations with this model led to satisfying results when compared to the experiments.     

Comparison of blast curves from vapor cloud explosions

Several sets of blast curves are frequently used in the prediction of blast effects from vapor cloud explosions. However, they have not been validated by experiments since systematic experimental data have only become available in recent years. The aim of this paper is to present a comparison between the calculated blast curves and available experimental data. Also presented is a comparison between several blast curves. The comparison showed that for detonations and subsonic flames, the blast curves produced by one-dimensional numerical calculations are generally in agreement with experimental data. However, there is great difference between the measured and calculated overpressures for supersonic deflagrations. The experimental overpressures fall well below the calculated values and decay much faster. The discrepancy is more pronounced for less reactive mixtures. It can be concluded from the comparison that the prediction using one-dimensional numerical calculations is conservative and may be overly conservative for supersonic deflagrations.     

基于锥形量热仪实验的卷烟及其包装材料燃烧特性研究

用ISO5660锥形量热仪研究了成品卷烟及其包装材料的燃烧特性,获得了这些材料在不同热辐射强度下的点燃时间和热释放速率等火灾特性参数.结果表明:烟支及其包装材料受热辐射时均可被点燃,热辐射强度越大,引燃时间越短;随辐射强度的升高样品的热释放速率呈递增趋势;在较强热辐射强度(≥25 kW/m2)下,组合样品的火灾危险性相对较大.     

A CFD based explosion risk analysis methodology using time varying release rates in dispersion simulations

A full probabilistic Explosion Risk Analysis (ERA) is commonly used to establish overpressure exceedance curves for offshore facilities. This involves modelling a large number of gas dispersion and explosion scenarios. Capturing the time dependant build up and decay of a flammable gas cloud size along with its shape and location are important parameters that can govern the results of an ERA. Dispersion simulations using Computational Fluid Dynamics (CFD) are generally carried out in detailed ERA studies to obtain these pieces of information. However, these dispersion simulations are typically modelled with constant release rates leading to steady state results. The basic assumption used here is that the flammable gas cloud build up rate from these constant release rate dispersion simulations would mimic the actual transient cloud build up rate from a time varying release rate. This assumption does not correctly capture the physical phenomena of transient gas releases and their subsequent dispersion and may lead to very conservative results. This in turn results in potential over design of facilities with implications on time, materials and cost of a project.In the current work, an ERA methodology is proposed that uses time varying release rates as an input in the CFD dispersion simulations to obtain the fully transient flammable gas cloud build-up and decay, while ensuring the total time required to perform the ERA study is also reduced. It was found that the proposed ERA methodology leads to improved accuracy in dispersion results, steeper overpressure exceedance curves and a significant reduction in the Design Accidental Load (DAL) values whilst still maintaining some conservatism and also reducing the total time required to perform an ERA study.     

Influence of the elastic behaviour of liquids on transient flow from pressurised containments

Release of liquids from vessels and pipelines is a very important scenario in consequence assessment. When the operating pressure is significant, its evolution and the corresponding discharge rate are affected by the elastic behaviour of the liquid. Bulk modulus is the key-driver of the related fluid-dynamics and is expected to govern the elastic-to-atmospheric pressure transition. Despite the well known physical background, the availability of release models relevant to the elastic phase is rather poor, compared to those relevant to vapours, gases and atmospheric liquids. On the other hand, if the operating pressure is high, release times and dynamics are expected to be strongly affected by the elastic behaviour and prediction of release time and flow rate is fundamental. This article carries outs a general analysis of the elastic behaviour of liquids, including water and hydrocarbons. Lumped (vessel-type) and distributed (pipeline) parameters systems have been modelled with the aim to characterize the pressure evolution during the elastic phase and to evaluate the significance of the associated duration. The findings have shown that, depending on pressure and geometric features, the importance of the elastic phase is high and that the availability of reliable and relatively simple models could be beneficial in consequence assessment. The approach is strictly valid for non-boiling liquid, but accounting for vaporisation of flashing or boiling liquids such as LPG and LNG would not imply significant complications.     

二氧化钛/累托石制备及其光催化性能研究

以累托石和四氯化钛为原料制备了二氧化钛／累托石复合材料,考察了各种制备条件如灼烧温度、复合反应温度、HCI／TiCl4等对光催化性能的影响。X射线衍射及红外光谱对材料的分析表明,反应中发生了聚合钛离子与累托石中阳离子的交换反应。酸性红B水溶液的脱色效率的结果表明,不同实验条件对复合材料的光催化性能都有不同程度的影响。初步探讨了影响光催化性能的机理及材料制备的最佳条件。     

聚氯乙烯电缆料老化前后的火灾危险性研究

利用微型燃烧量热计（MCC）、热重分析（TGA）、实时红外光谱（RTFTIR）以及热重-红外联用技术（TG-FT-IR）研究了PVC电缆料老化前后火灾危险性的变化。MCC结果表明,老化后的PVC的最大热释放速率增加了56.3%,总热释放量从10.6kJ/g增加到16.8kJ/g,点燃温度也由302℃提前到282℃。TG-FTIR和RTFTIR的分析结果显示,PVC的主要降解产物有水、碳氢化合物、二氧化碳和一氧化碳。PVC达到最大降解速率的温度约为240℃,与MCC、TG的结果相符合。PVC的裂解气体中包含CO2和CO,还有剧毒气体HCl。这些实验数据说明PVC材料在使用过程中火灾危险性加大,为老城区电气线路和设备的改造提供了理论依据和实验基础。     

A transportation network assessment tool for hazardous material cargo routing: Weighing exposure health risks,proximity to vulnerable areas,delay costs and trucking expenses

The inherent risks associated with accidental releases of hazardous materials during transport have drawn attention and concerns in the recent decades. The aim of this study is to propose a tool for evaluation and comparison of the transportation networks which can be used to assess the routing options between origins and destinations of the cargos for their suitability for transporting hazardous material cargos by tanker trucks and to identify routes which provide lower accidental release risks, lower public exposure risks, and offer economical benefits. Each route segment of transportation networks were evaluated using specific criteria which included health risk and cost of delay in case of an accidental release of materials, trucking cost and proximity to vulnerable areas. Since, the health impact of hazardous materials differ depending on the characteristics of the material being transported as well as release quantities and atmospheric conditions; this paper aimed in providing a tool that can be used to estimate the impact radius (for health risks) after accidental release of hazardous materials by taking into account different atmospheric conditions based on the meteorological data and solar elevation angle. The Gaussian air dispersion model paired with ArcGIS using Python programming were employed to estimate the health risk impact zones by considering the meteorological data, and accordingly to analyze road segments for cost impacts (delay and trucking costs), and the proximity to vulnerable areas. The route assessment tool was demonstrated with a case study. The results of this study can efficiently aid decision makers for transportation of hazardous materials.     

“8·29”充装台充装现场氧气瓶爆炸事故原因分析

介绍了较为少见的充装台充装过程中氧气瓶爆炸事故,描述了事故爆炸后的现场。对爆炸气瓶碎片进行化学成分分析、机械性能、金相试验、内壁附着物化学成分分析和能谱分析。通过分析认定,由于误操作油脂混进氧气瓶,高压氧气和油脂接触发生剧烈的自燃氧化放热,使瓶内的氧气迅速升温升压,超出气瓶承压极限导致气瓶爆炸。结合工作经验,提出要严格气瓶充装前的检验,加强气瓶使用和经销单位的安全监管等防范措施和建议,对氧气瓶的安全管理具有参考价值和实际意义。     

An Overview of the Nature of Hydrocarbon Jet Fire Hazards in the Oil and Gas Industry and a Simplified Approach to Assessing the Hazards

High pressure jet fires pose a serious hazard to offshore installations operated by the oil and gas industry as demonstrated by the Piper Alpha incident. Following the Piper Alpha incident a major initiative by the offshore oil and gas industry operators led to the production of Interim Guidance Notes which provided guidance to operators on how to assess jet fire hazards. However, many areas of uncertainty were identified where no data was available. Areas of particular concern identified in the Interim Guidance Notes were two-phase jet fires, the effect of confinement on jet fires and their behaviour with water deluge. Since that time a considerable body of experimental research has been undertaken. Based on this recent data, this paper reassesses jet fire hazards in an offshore environment and provides updated guidance on the hazards they pose, including tabulated data and simple calculation techniques for predicting jet fire hazards.     

Ventilation theory and dispersion modelling applied to hazardous area classification

Critical formulae given in the current Explosive Atmospheres Hazardous Area Classification Standard IEC 60079-10-1 (2008) [BS EN 60079-10-1, 2009] to determine the expected gas cloud volume which is used to determine area classification do not have any scientific justification. The standard does allow the alternative use of Computational Fluid Dynamics (CFD) methods, which serve to compound the concern with these formulae: the predicted volume of the gas cloud from CFD models being several orders of magnitude smaller than that given by the formulae in question. To resolve such major discrepancies, replacement of the current formulae with a scientifically validated approach is proposed. Integral models of dispersion and ventilation have been used routinely for many years in the analysis of major hazards in the chemical industry. This paper presents an adaptation of these models to determine the expected volume of a gas cloud arising from a release of gas from a pressurised source. A very simple integral jet model is presented for outdoor dispersion, extended to the case of indoor dispersion, from which the volume of the gas cloud is derived. The single free parameter, an entrainment coefficient, is fixed by comparison with data on a free jet, and then predictions of the model are compared with CFD calculations (which themselves have been validated against experimental data) for dispersion within an enclosed volume. The results of this simple integral model are seen to agree very well with the CFD predictions. The methodology presented here is therefore proposed as a scientifically validated approach to Hazardous Area Classification.     

基于CONE和MCC的典型电缆燃烧性能研究

采用锥形量热仪和微燃烧量热仪对四类不同护套材料的八种电缆样品进行燃烧性能分析,研究结果表明：电缆燃烧热释放过程不仅与护套、绝缘的材料密切相关,也与电缆结构密不可分;对于护套材料相同而大小或结构不同的电缆点燃时间和到达第一个峰值的时间以及第一个峰值最大热释放速率基本一致;聚烯烃无机阻燃材料电缆能够有效降低热释放速率峰值,CO2、CO释放量也明显低于橡胶电缆、普通PVC电缆和阻燃PVC电缆;微燃烧量热仪和锥形量热仪实验数据存在一定的相关性,微燃烧量热仪实验数据可以对电缆锥形量热仪实验的第一燃烧阶段燃烧行为进行预测。     

Sub-cooled and flashing liquid jets and droplet dispersion I. Overview and model implementation/validation

Many accidents involve two-phase releases of hazardous chemicals into the atmosphere. This paper describes the results of a third phase of a Joint Industry Project (JIP) on liquid jets and two-phase droplet dispersion. The aim of the project is to increase the understanding of the behaviour of sub-cooled non-flashing and superheated flashing liquid jets, and to improve the prediction of initial droplet size, droplet dispersion and rainout.Phase III of the JIP first included scaled experiments for materials with a range of volatilities (water, cyclohexane, butane, propane and gasoline). These experiments were carried out by Cardiff University including measurements of flow rate and initial droplet size across the full relevant range of superheats. See the companion paper II for further details of these experiments and the derivation of new refined correlations for droplet size distribution and Sauter Mean Diameter. Furthermore large-scale butane experiments were carried out by INERIS (France) to ensure that for more realistic scenarios the derived droplet size correlations are accurate.Model validation and model improvements were carried out by DNV Software, including validation of release rate and initial droplet size against the above scaled and large-scale experiments. New correlations for droplet size distribution and Sauter Mean Diameter (SMD) were implemented into the Phast discharge model. These were compared against a range of other droplet size and rainout correlations published in the literature, in conjunction with validation against an extensive set of experiments. It was shown that the new droplet size correlation agrees better against experimental data than the existing Phast correlation. To further improve the rainout prediction, the Phast dispersion model (UDM) was also extended to allow simultaneous modelling of a range of droplet sizes and distributed rainout (rather than rainout at one point).     

Dilution with air to minimise consequences of toxic/flammable gas releases

Dilution has long been considered a solution to many problems of toxic/flammable material releases. It implies diluting to a concentration that is below physiologically dangerous levels for a toxic substance (generally below TLV), or to a level below LFL for a flammable material release, ensuring that the process adopted for dilution does not itself enhance the risks.

In this paper, we discuss the dilution of a gaseous release by deliberate and cautious mixing with air to reduce its concentration to a harmless level. The idea bears its origin to the Bhopal Gas Tragedy where some families saved themselves by turning the ceiling fans on when MIC reached their bedrooms at the dead of very cold night on December 2–3, 1984. The air pushed in by the fans diluted the MIC to below the harm level.

Some of the advantages of using air dilution are: no cost of air, no air storage needed, no need to treat the air after use as in case of water curtains; required equipment, its maintenance and staff training in its use are very likely to cost less than in other ways of handling a release.

Air dilution may not be feasible in all cases, such as gaseous release within a congested equipment layout, release that forms a liquid pool, etc. The method needs to be evaluated for each case.     

Mitigation of hydrogen fluoride aerosols by dry powders

Fluid bed tests were used to determine overall reaction rates for eight different dry powders of low hazard and toxicity before and after reaction with HF. In flow chamber tests, a representative oxide, hydroxide and carbonate were used to measure the efficiency of mitigation of an HF aerosol cloud. The results show that dry powders provide a valid alternative to water spray mitigation. Powder efficiencies are higher than water efficiencies at constant weight ratio.

At present, no attempt has been made to provide any technical designs or layouts for powder mitigation systems. However, the technology for smaller systems is available through manufacturers of dry powder chemical fire extinguisher equipment. When these powders are kept dry and under nitrogen atmosphere, a shelf life of several years can be expected.