Are dispersion models suitable for simulating small gaseous chlorine releases?

Dispersion models are mostly validated on the basis of historical dispersion experiments. The latter imply large quantities of hazardous products (flammable or toxic gases), and are dedicated to study the dispersion of the resulting clouds on great distances from the source to reach a better knowledge of the different phases of gas dispersion (slumping, creeping, passive dispersion…).However, dispersion models have hardly been validated on small releases and therefore require more validation on small plumes of dangerous gases. Indeed, what is their reliability in case of accidents involving small amounts (e.g., chlorine leakages at swimming pools’ installations), and for small distances downwind the gas source? This information is of prime interest in so far as small releases are more likely to occur than larger ones.This paper reports on chlorine small-scale dispersion experiments and deals with the comparison between experimental data of ground level concentrations in the plume and predicted concentrations obtained from several dispersion models.     

Modelling accidental releases of dangerous gases into the lower troposphere from mobile sources

The article reports the results of different methods of modelling releases and dispersion of dangerous gases or vapours in cases of major accidents from road and rail transportation in urban zones. Transport accidents of dangerous substances are increasingly frequent and can cause serious injuries in densely inhabited areas or pollution of the environment. For quantitative risk assessment and mitigation planning, consequence modelling is necessary.

The modelling of dangerous substance dispersion by standard methods does not fully represent the behaviour of toxic or flammable clouds in obstructed areas such as street canyons. Therefore the predictions from common software packages as ALOHA, EFFECTS, TerEx should be augmented with computational fluid dynamics (CFD) models or physical modelling in aerodynamic tunnels, and further studies are planned to do this.

The goal of this article is to present the results of the first approach of modelling using these standard methods and to demonstrate the importance of the next development stage in the area of transport accident modelling of releases and dispersions of dangerous substances in urban zones in cases of major accident or terrorist attacks.     

Heavy gas dispersion by water spray curtains: A research methodology

The mitigation of the consequences of accidental releases of dangerous toxic and/or flammable cloud is a serious concern in the petro-chemical and gas industries. Nowadays, the water-curtain is recognized as a useful technique to mitigate a heavy gas cloud. The paper presents a research methodology, which has been established and undertaken to quantify the forced dispersion factor provided by a water-curtain with respect to its configuration.

The method involves medium-scale field tests, Wind-Gallery tests and numerical simulations. These different approaches are discussed and exemplified by typical results emphasizing the observed concentration reduction due to the water-curtain.     

Use of water spray curtain to disperse LNG vapor clouds

Effective safety measures to prevent and mitigate the consequences of an accidental release of flammable LNG are critical. Water spray curtain is currently recognized as an effective technique to control and mitigate various hazards in the industries. It has been used to absorb, dilute and disperse both toxic and flammable vapor cloud. It is also used as protection against heat radiation, in case of fighting vapor cloud fire. Water curtain has also been considered as one of the most economic and promising LNG vapor cloud control techniques. Water curtains are expected to enhance LNG vapor cloud dispersion mainly through mechanical effects, dilution, and thermal effects. The actual phenomena involved in LNG vapor and water curtain interaction were not clearly established from previous research. LNG spill experiments have been performed at the Brayton Fire Training Field at Texas A&M University (TAMU) to understand the effect of water curtain in controlling and dispersing LNG vapor cloud. This paper summarizes experimental methodology and presents data from two water curtain tests. The analysis of the test results are also presented to identify the effectiveness of these two types of water spray curtains in enhancing the LNG vapor cloud dispersion.     

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.     

Venting of Low Pressure Hydrogen Gas: A Critique of the Literature

The use of hydrogen is increasing in industrial processes, and its use is likely to increase further with its potential use as an energy carrier. The venting of hydrogen is inevitable at some time for almost all uses, and its propensity to ignite makes it essential that safe venting regimes are understood. The options for disposal by dilution to below the lower flammable limit, inerting, dispersion of flammable concentrations and flaring are discussed, along with the potential for ignition of releases within the flammable range and the subsequent need for flame extinguishing. The available literature on the protection of vents from external ignition is critically examined, to determine the appropriate parameters to allow selection of a disposal method. A decision-tree is presented to allow a rational appraisal of the most appropriate disposal method to be selected and precautions to be applied for adequate protection of the vent.     

Un-ignited and ignited high pressure hydrogen releases: Concentration – turbulence mapping and overpressure effects

Safety studies for production and use of hydrogen reveal the importance of accurate prediction of the overpressure effects generated by delayed explosions of accidental high pressure hydrogen releases. Analysis of previous experimental work demonstrates the lack of measurements of turbulent intensities and lengthscales in the flammable envelope as well as the scarceness of accurate experimental data for explosion overpressures and flame speeds. AIR LIQUIDE, AREVA STOCKAGE ENERGIE and INERIS join in a collaborative project to study un-ignited and ignited high pressure releases of hydrogen.The purpose of this work is to map hydrogen flammable envelopes in terms of concentration, velocity and turbulence, and to characterize the flame behaviour and the associated overpressure. These experimental results (dispersion and explosion) are also compared with blind FLACS modelling.     

Thermal shielding by water spray curtain

The mitigation of the consequences of storage-tank fire is a great safety concern in petro-chemical and gas industries. A technique to protect the integrity of neighbouring structures is the water spray curtain. It can be operating downward in front of or oriented to the surface to be shielded. Simple modelling, laboratory experiments and field tests for these two types of thermal shielding are presented.

Attenuation factor of 50–75% can be expected with the vertical curtain while 90% can be reached with the impinging curtain if spray overlapping is achieved.     

Validation of discharge and atmospheric dispersion for unpressurised and pressurised carbon dioxide releases

This paper discusses the validation of discharge and subsequent atmospheric dispersion for both unpressurised and pressurised carbon dioxide releases using the consequence modelling package Phast.The paper first summarises the validation of the Phast dispersion model (UDM) for unpressurised releases. This includes heavy gas dispersion from either a ground-level line source (McQuaid wind-tunnel experiments) or an area source (Kit-Fox field experiments). For the McQuaid experiments minor modifications of the UDM were made to support line sources. For the Kit Fox experiments steady-state and 20-s finite-duration releases were simulated for both neutral and stable conditions. Most accurate predictions of the concentrations for finite duration releases were obtained using the UDM Finite Duration Correction method.Using experiments funded by BP and Shell and made available via DNV's CO2PIPETRANS JIP, the paper secondly summarises the validation of the Phast discharge and dispersion models for pressurised CO₂ releases. This modelling accounted for the possible presence of the solid CO₂ phase following expansion to atmospheric pressure. These experiments included both high-pressure steady-state and time-varying cold releases (liquid storage) and high-pressure time-varying supercritical hot releases. Both the flow rate and the concentrations were found to be predicted accurately.The above validation was carried out with no fitting whatsoever of the Phast extended discharge and dispersion models.     

Modelling of discharge and atmospheric dispersion for carbon dioxide releases

This paper discusses the modelling of the discharge and subsequent atmospheric dispersion for carbon dioxide releases using extensions of models in the consequence modelling package Phast. Phast examines the progress of a potential incident from the initial release to the far-field dispersion including the modelling of rainout and subsequent vaporisation. The original Phast discharge and dispersion models allow the released chemical to occur only in the vapour and liquid phases. As part of the current work these models have been extended to also allow for the occurrence of liquid to solid transition or vapour to solid transition. This applies both for the post-expansion state in the discharge model, as well as for the thermodynamic calculations by the dispersion model. Solid property calculations have been added where necessary. The above extensions are generally valid for fluid releases including CO₂. Using the extended dispersion formulation, a sensitivity study has been carried out for mixing of solid CO₂ with air, and it is demonstrated that solid effects may significantly affect the predicted concentrations.     

Assessment of the Consequences of Accident Scenarios Involving Dangerous Substances

This paper highlights major steps in the procedure for evaluating the consequences of accidents involving dangerous substances, especially during the storage, and loading/unloading activities. The procedure relies on identifying accident scenarios that could be encountered at particular plants, followed by a modelling of these scenarios by means of available modelling systems. Finally, the resultant outcomes are identified, together with their effects on both people and property. The resources needed to perform this procedure are discussed, in order to clarify the roles of plant operators, external experts and other institutions when evaluating any accident consequences. Four examples, all relevant in industrial practice, are given in order to illustrate the procedure: the releasing of liquified petroleum gas, flammable organic solvents, toxic chlorine, and oil fuels. The results of these studies may be used for a quick order-of-magnitude estimation of accidents consequences.     

The use of water sprays for mitigating chlorine gaseous releases escaping from a storage shed

Accidental releases of toxic gases in partially confined spaces, like a storage shed, can sometimes be controlled by water sprays. This paper presents the results of experimental field tests during which various water sprays were used to mitigate chlorine gaseous releases. The releases (source strength: 1–4 kg/min) simulated a loss of containment occurring at an industrial chlorine storage installation (5 m³). The mitigation performances of different water sprays were investigated for diverse configurations, and under various atmospheric conditions. The best chlorine concentration reduction was achieved close to the source by a mobile upward water spray, with a maximum concentration reduction of a factor 10 at a distance of 5 m downstream from the source, and for a release flow rate of about 2 kg/min. The good performances of a fixed downward flat fan water spray were also pointed out (mean concentration reduction of a factor 2–5 for the whole series of experiments carried out), with an optimum of effectiveness at a distance of 10 m downstream from the source. In low wind speed conditions (U₁₀<1 m/s), the downward flat fan water spray was more effective for weak release flow rates. The mitigation effectiveness by absorption remained slight (<3%).     

A dynamic approach for evaluating the consequences of toxic gas dispersion in the chemical plants using CFD and evacuation modelling

Accidental releases of toxic gas in the chemical plants have caused significant harm to the exposed occupants. To evaluate the consequences of these accidents, a dynamic approach considering the gas dispersion and behavior evacuation modelling has been proposed in this paper. This approach is applied to a hypothetical scenario including an accidental chlorine release in a chemical plant. CFD technique is utilized to calculate the time-varying concentration filed and evacuation modelling is used to obtain the evacuation routes. The exposure concentrations in the evacuation routes are calculated by using the code of data query. The integrated concentration toxic load model and probit model are used to calculate the probability of mortality of each occupant by using the exposure concentrations. Based on this dynamic approach, a new concept of average probability of mortality (APM) has been proposed to quantify the consequences of different accidental scenarios. The results show that APM decreases when the required detection time decreases or emergency evacuation mode is implemented. The impact of the detection time on APM becomes small as the wind speed increases. The effect of emergency evacuation mode is more obvious when the release occurs in an outdoor space.     

Modelling of time-varying dispersion for elevated pressurised releases without rainout

Many commonly used atmospheric dispersion models are limited to continuous or instantaneous releases only, and cannot accurately simulate time-varying releases. The current paper discusses a new enhanced dispersion formulation accounting for time-varying effects resulting from a pressure drop in a vessel or pipe, and presuming no rainout. This new formulation is implemented in the Unified Dispersion Model (UDM), and is planned to be included in a future version of Phast.First existing methods are summarised for modelling finite-duration and time-varying releases, and limitations of these methods are identified.Secondly the new mathematical model is summarised. The new formulation presumes a number of ‘observers’ to be released at successive times from the point of discharge. The UDM carries out pseudo steady-state calculations for each observer, where the release data correspond to the time at which the observer is released. Subsequently the model applies a correction to the observer concentrations to ensure mass conservation when observers move with different velocities. Finally effects of along-wind diffusion (due to ambient turbulence) are included by means of Gaussian integration over the downwind distance. This results in reduced concentrations while the cloud travels in the downwind direction.The benefits of the new UDM methodology are illustrated for the case of a H₂S toxic release from a long pipeline representative of some extremely sour fields in the Middle East that are now being developed. Using corrected observer concentrations and along-wind diffusion significantly reduces toxic effect distances when compared to the current Phast 7.1 approach.     

Numerical study on the initial expansion of two-phase cloud from an instantaneous release

In industries some dangerous liquefied gases may accidentally release and it may form a flammable or toxic mixture after mixing with air. One tool that is being developed in industry for two-phase cloud dispersion modeling is computational fluid dynamics (CFD). In this paper, the dispersion processes of different dangerous materials including liquefied chlorine, liquefied ammonia and liquefied petroleum gas were simulated in the same condition to analyze the characteristics of the initial expansion processes by CFD tool. The heat and mass transfer between droplets and the vapor after an instantaneous release event was calculated by using the Eulerian–Lagrangian method. The results from a number of 3-D CFD based studies were compared with the available small-scale experimental results. The results show that the present model and numerical simulation are reliable.     

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.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

Control of accidental releases of hydrogen selenide and hydrogen sulphide in the manufacture of photovoltaic cells: a feasibility study

Industrial and regulatory communities are concerned about the need to control routine and accidental releases of toxic gases. This paper outlines an approach for evaluating control systems for new technologies when there is only limited experience. The approach is illustrated by identifying and evaluating specific options to control releases of hydrogen selenide (H₂Se) and hydrogen sulphide (H cells. Routine emmisions can be controlled with a system composed of a Venturi scrubber, a packed-bed scrubber, and a carbon adsorption bed. Accidental releases can be controlled by the proper design of a ventillation system combined with either a Venturi and packed-bed scrubber and carbon-a or a containment-scrubbing equipment followed by carbon adsorption. The annualized costs of these controls (≈$0.01/Watt-peak (W_p)), are small compared with current (≈$6/W_p) and projected (≈$1/W_p) production costs. Thus, systems which could control accidental releases of highly toxic H₂Se and H₂S in CuInSe₂ photovoltaic cell manufactu These systems can effectively reduce emmisions of toxic gas to levels needed to protect the health of the public.     

Accounting for the effect of concentration fluctuations on toxic load for gaseous releases of carbon dioxide

In Great Britain, advice on land-use planning decisions in the vicinity of major hazard sites and pipelines is provided to Local Planning Authorities by the Health and Safety Executive (HSE), based on quantified risk assessments of the risks to the public in the event of an accidental release. For potential exposures to toxic substances, the hazard and risk is estimated by HSE on the basis of a “toxic load”. For carbon dioxide (CO₂), this is calculated from the time-integral of the gas concentration to the power eight. As a consequence of this highly non-linear dependence of the toxic load on the concentration, turbulent concentration fluctuations that occur naturally in jets or plumes of CO₂ may have a significant effect on the calculated hazard ranges. Most dispersion models used for QRA only provide estimates of the time- or ensemble-averaged concentrations. If only mean concentrations are used to calculate the toxic load, and the effects of concentration fluctuations are ignored, there is a danger that toxic loads and hence hazard ranges will be significantly under-estimated.This paper explores a simple and pragmatic modification to the calculation procedure for CO₂ toxic load calculations. It involves the assumption that the concentration fluctuates by a factor of two with a prescribed square-wave variation over time. To assess the validity of this methodology, two simple characteristic flows are analysed: the free jet and the dense plume (or gravity current). In the former case, an empirical model is used to show that the factor-of-two approach provides conservative estimates of the hazard range. In the latter case, a survey of the literature indicates that there is at present insufficient information to come to any definite conclusions.Recommendations are provided for future work to investigate the concentration fluctuation behaviour in dense CO₂ plumes. This includes further analysis of existing dense gas dispersion data, measurements of concentration fluctuations in ongoing large-scale CO₂ release experiments, and numerical simulations.     

Phast validation of discharge and atmospheric dispersion for pressurised carbon dioxide releases

The consequence modelling package Phast examines the progress of a potential incident from the initial release to the far-field dispersion including the modelling of rainout and subsequent vaporisation. The original Phast discharge and dispersion models allow the released substance to occur only in the vapour and liquid phases. The latest versions of Phast include extended models which also allow for the occurrence of fluid to solid transition for carbon dioxide (CO₂) releases.As part of two projects funded by BP and Shell (made publicly available via CO2PIPETRANS JIP), experimental work on CO₂ releases was carried out at the Spadeadam site (UK) by GL Noble Denton. These experiments included both high-pressure steady-state and time-varying cold releases (liquid storage) and high-pressure time-varying supercritical hot releases (vapour storage). The CO₂ was stored in a vessel with attached pipework. At the end of the pipework a nozzle was attached, where the nozzle diameter was varied.This paper discusses the validation of Phast against the above experiments. The flow rate was predicted accurately by the Phast discharge models (within 10%; considered within the accuracy at which the BP experimental data were measured), and the concentrations were found to be predicted accurately (well within a factor of two) by the Phast dispersion model (UDM). This validation was carried out with no fitting whatsoever of the Phast extended discharge and dispersion models.