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.     

Influence of wind speed profile and roughness parameters on the downwind extension of vulnerable zones during dispersion of toxic dense gases

The accidental release of toxic chemicals, which are heavier than air and stored under pressure, may create an emergency scenario in an industrial plant. The extension of vulnerable distance in the downwind direction is an important criterion in framing an emergency management plan of that industrial area. There are several studies showing the role of surface level meteorological and topographical features on its propagation and dispersion just after its release from a container. In the present study, vertical variation of wind speed in the atmospheric boundary layer and surface roughness parameter have been considered to study their roles on the impact of downwind extension of vulnerable distances. A catastrophic release from a tonner having 900 kg of liquid chlorine has been considered, and SAFETI Micro developed by DNV Technica, UK has been utilized in the consequence analysis of this release. The analysis results have been explained for various atmospheric stability classes and surface wind speeds.     

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.     

CFD analysis of the dispersion of toxic materials in road tunnels

The present work is aimed at analyzing the evolution of accidental scenarios deriving from the release of toxic materials inside a tunnel. This scenario, compared to the more frequently investigated cases of fire, followed by smoke dispersion, may involve a large variety of common products characterized by widely differing physical properties; nonetheless it has been analysed in the literature less than expected. The present study compares the dispersion of two common toxic chemicals (chlorine and ammonia), in order to derive some preliminary information about the influence of the physical properties and the release rate. A reference road tunnel geometry is assumed, while the release occurs from ground level, at the centre of one lane and in the middle of the tunnel. Two study cases involving a road tanker, transporting the product as liquefied gas under pressure, were considered: a catastrophic release, from a 220 mm hole, emptying the tanker in a few tens seconds (case A), and a continuous release, from a much smaller hole (15 mm), lasting 5 min (case B). For the sake of simplicity, the release is assumed to be in gaseous phase; the dispersion of the toxic is simulated for the 5 min period following the start of the release using a CFD (Computational Fluid Dynamics) analysis, according to an RANS (Reynolds-Averaged Navier–Stokes) approach with the standard k–ε turbulence model, assuming no ventilation conditions. Structured curvilinear grids with hexaedric cells, refined according to the local concentration gradient, are used. For case A scenarios, especially for the whole release duration, dispersion is mainly governed by the “plug-flow” effect caused by the large volume of toxic entering the tunnel in a rather short time; then, the role of diffusivity and gravity becomes more important. Chlorine, heavier than air and with lower diffusivity than ammonia, progressively accumulates towards the floor; the dispersion of ammonia, which is lighter than air, appears more influenced by diffusivity than by gravity, since a limited stratification is observed. These trends are more evident for case B scenarios, where the toxic flow rates are much lower. It is expected the results will give some useful insight into the dispersion phenomenon within highly confined spaces and maybe also provide some suggestion about ventilation systems design and emergency procedures.     

Modelling and control of the dispersion of hazardous heavy gases

Dispersion of several common `heavy' gases (ethylene, propylene, ammonia, and chlorine) has been modelled on the basis of modifications in plume path theory. The model takes into account, among other things, the variations in temperature, density, and specific heat during the movement of the heavy gas plume. The effects of wind speed, density of the gas, and venting speed on the plume dispersion have been simulated. Based on the simulations a set of empirical equations has been developed. The equations have been validated by theoretical as well as experimental studies.Studies have also been carried out to simulate the effect of venting speed (manipulated by injecting hot air with the released gas) on the plume dispersion. The study reveals that the effect of venting speed on dispersion is very pronounced and can be used to reduce the risk posed by the accidental luxurious release of toxic/flammable gases. For example an increase of 20% in venting speed of chlorine (54.1 m/s) can reduce the distance up to which toxic concentration would occur by about 1100 meters.     

HAZDIG: a new software package for assessing the risks of accidental release of toxic chemicals

HAZDIG (HAZardous DIspersion of Gases) is a user-friendly PC- based software for generating scenarios for the emissions and gaseous dispersion of hazardous chemicals. It can simulate accidental as well as normal release but has been specifically developed as a tool for studying accidental release of hazardous chemicals and the consequences. HAZDIG is made-up of five main modules—data, release scenario generation, dispersion, characteristics estimation, and graphics. HAZDIG incorporates the latest models for estimating atmospheric stability and dispersion. The data needed to run the models is easy to obtain and feed—properties of chemicals, operating conditions, ambient temperature, and a few commonly available meteorological parameters. A database containing various proportionality constants and complex empirical data has been built into the system. The graphics module enhances the user friendliness of the software, and enables presentation of the results in an easy-to-understand and visually appealing manner. The output of the software is formatted so that it can be directly used for reporting the results without the need of editing.     

Testing of dust clouds for the electrostatic-spark ignition hazard in industry. Need for a modified approach?

Current standard test methods for electric-spark minimum ignition energies (MIEs) of dust clouds in air require that a series inductance of at least 1–2 mH be included in the electric-spark discharge circuit. The reason is to prolong the spark discharge duration and thus minimize the spark energy required for ignition. However, when assessing the minimum electrostatic energy ½CU² for dust cloud ignition by accidental electrostatic-spark discharges, current testing standards require that the series inductance of at least 1–2 mH be removed from the spark discharge circuit. No other changes of apparatus and test procedure are required. The present paper questions whether this simple approach is always adequate. The reason is that in practice in industry accidental electrostatic-spark discharge circuits may contain large ohmic resistances due to corrosion, poor electrical grounding connections, poorly electrically conducting construction materials etc. The result is increased spark discharge durations and reduced mechanical disturbance of the dust cloud by the blast wave emitted by the spark. Therefore, testing for minimum ½CU² for ignition by accidental electrostatic spark discharges may not only require removal of the series inductance of 1–2 mH from the standard MIE spark discharge circuit. Additional tests may be needed with one or more quite large series resistances R_s inserted into the spark discharge circuit. The present paper proposes a modified standard test procedure for measurement of the minimum electrostatic-spark ignition energy of dust clouds that accounts for these effects.     

Simulation study on near-field structure and flow characteristics of high-pressure CO2 released from the pipeline

The accidental release of high-pressure carbon dioxide (CO₂) can cause serious damages to both humans and pipeline equipment. Therefore, it is of great significance to have a deeper understanding about the release characteristics of high-pressure CO₂ for improving the safety level of Carbon Capture and Storage (CCS) technologies. Both industrial-scale and laboratory-scale studies have been carried out to predict the release behaviors. In recent years, computational fluid dynamics (CFD) simulation has become a crucial method to study the instantaneous changes and microscopic details of the fluid behaviors. In this paper, the simulation method was employed to study the near-field structure and flow characteristics of high-pressure CO₂ released from pipelines. The Peng-Robinson Equation of State (EOS) was used to compute the thermodynamic properties of high-pressure CO₂, and SST k-ω model was applied to simulate the structure and physical parameters of the under-expanded jet. In addition, the multi-phase mixture model was introduced to study the phase transition. The non-equilibrium liquid/vapor transition is modeled by introducing ‘source terms’ for mass transfer and latent heat. Compared to the experimental results, the simulation results showed good agreement. Furthermore, the influences of operating conditions, including different stagnation pressure, stagnation temperature, and nozzle size, were analyzed.     

Thermodynamic method for the prediction of solid CO2 formation from multicomponent mixtures

The increase in GHG concentration has a direct effect on global climate conditions. Among the possible technologies to mitigate GHG emissions, CCS is being accepted to gain emission reduction. Such technology also involves cryogenic CO₂ capture processes based on CO₂ freeze-out or where the formation of solid CO₂ must be avoided. Captured CO₂ is usually transported in pipelines for the reinjection.The risk associated to the release of CO₂ is due to the changing temperatures and pressures the system may experience, which can lead to the deposition of solid CO₂ where it must be avoided. Prolonged exposure to dry ice can cause severe skin damage and its resublimation could pose a danger of hypercapnia. It is, thus, necessary to build up a tool able to predict the conditions in which CO₂ can freeze-out.A thermodynamic methodology based on cubic EoSs has been developed which is able to predict solid–liquid–vapor equilibrium of CO₂ mixtures with n-alkanes or H₂S which are usually found in equipment for acidic gas, mainly natural gas, treatment.The focus is a detailed analysis of the method performances when more than two components are present since, for such a case, literature does not provide significant modeling results.     

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.     

Release and dispersion behaviour of carbon dioxide released from a small-scale underground pipeline

The development of carbon capture and storage (CCS) brings challenges for safety issues regarding carbon dioxide (CO₂) transmission pipelines. Once a pipeline is punctured or full-bore ruptured, the leaked CO₂ is hazardous to personnel and the environment. Small-scale devices were established with the aim of studying the release and dispersion behaviour of gas and liquid CO₂ from a punctured underground pipeline. A sandbox was built to simulate the underground conditions. The parameters of the sand used in the experiments were tested. CO₂ concentrations on the ground and temperatures around the release orifice in the sand were analysed. The results indicate that in the CO₂ gas release experiments, the CO₂ concentration on the sand surface decreases with increasing horizontal distance in the form of a power function. CO₂ concentrations in upward release are slightly larger than those in horizontal release at the same location but are obviously bigger than values in downward release. The temperature-drop region is much smaller than that in air. A frozen ice ball can be generated near the release orifice during the gas phase of the CO₂-release process. In the liquid phase of CO₂-release experiments, a large amount of dry ice is generated near the release orifice. Dry ice can only be generated in the area close to the release orifice, especially in the near-field area.     

Laboratory scale analysis of the influence of different heat transfer mechanisms on liquid nitrogen vaporization rate

The prediction of the potential hazards associated to accidental liquefied natural gas (LNG) spills has motivated a number of different studies including experimental and numerical approaches. Most of these studies focus on dispersion predictions, however there is limited information regarding source term of it: liquid spill and vaporization. There is a need of further improvements on the understanding of these phenomena and the quantification of the most important parameters that can affect them.The vaporization of cryogenic liquids is governed by the heat transfer phenomena including conduction, convection and thermal radiation mechanisms. The present work investigates the contribution of each of these heat transfer modes to the vaporization rate of cryogenic liquid nitrogen (LN₂) contained in a Dewar flask using well controlled and instrumented laboratory scale experiments. LN₂ vaporization rate was measured with individually controllable contributions from convective (generated by an electric fan) and thermal radiative (generated by light bulb) heat transfer in the presence of a baseline conductive heat transfer rate.In both cases of convection and radiation analysis the experimental study showed that they can play a significant role in the vaporization rate of LN₂. It was observed that the radiative heat absorbed by the LN₂ during the vaporization experiment represents only 50%–65% of the incident radiation that would reach the LN₂ pool surface if no vapour was present. Convective heat transfer generated by the fan was shown to have had the most significant contribution to the total heat transfer. As expected, this contribution was significantly higher than the one from bulb radiation. The experimental data also showed that the liquid level in the Dewar play a key role in the resulting amount of convective heat transfer. This could be attributed to the fact that lower liquid level the side walls of the Dewar were high enough to hold a layer of vapour and limit air motion directly above the liquid surface, thus limiting the heat transfer by convection.     

A method of analysis for gas explosions: H2Se case study

This paper presents a methodology for conducting a simplified gas-explosion analysis when there are uncertainties about the amount of fuel involved and the mode of combustion. The methodology is illustrated by a case study of an explosion of a cloud of hydrogen-selenide (H₂Se), nitrogen and air. Hydrogen-selenide (H₂Se) diluted with N₂ is used in a reactor vessel to produce solar cells. An explosive mixture could be created if the reactor vessel failed and its contents mix with ambient air. Mixtures of 20% or 6% H₂Se in N₂ were considered as feedstock into the reactor. It was determined theoretically that an explosion involving either mixture would challenge the reactor room's integrity. However, it is unlikely that a local ignition will propagate in the dilute 6% H₂Se mixture, because its adiabatic flame temperature is only 850 K; the 20% mixture is borderline flammable. Because of the proximity of personnel to the reactor room and the high toxicity of H₂Se, any damage to the room boundary is considered unacceptable. To prevent accidental mixing of H₂Se with air in the reactor, a nitrogen buffer was installed between the reactor vessel and the ambient air.     

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.     

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%).     

Risk assessment methodology for high-pressure CO2 pipelines incorporating topography

This paper presents a risk assessment methodology for high-pressure CO₂ pipelines developed at the Health and Safety Laboratory as part of the EU FP7 project CO2Pipehaz.Traditionally, consequence modelling of dense gas releases from pipelines at major hazard impact levels is performed using integral models with limited or no consideration being given to weather bias or topographical features of the surrounding terrain. Whilst dispersion modelling of CO₂ releases from pipelines using three-dimensional CFD models may provide higher levels of confidence in the predicted behaviour of the cloud, the use of such models is resource-intensive and usually impracticable. An alternative is to use more computationally efficient shallow layer or Lagrangian dispersion models that are able to account for the effects of topography whilst generating results within a reasonably short time frame.In the present work, the proposed risk assessment methodology for CO₂ pipelines is demonstrated using a shallow-layer dispersion model to generate contours from a sequence of release points along the pipeline. The simulations use realistic terrain taken from UK topographical data. Individual and societal risk levels in the vicinity of the pipeline are calculated using the Health and Safety Laboratory's risk assessment tool QuickRisk.Currently, the source term for a CO₂ release is not well understood because of its complex thermodynamic properties and its tendency to form solid particles under specific pressure and temperature conditions. This is a key knowledge gap and any subsequent dispersion modelling, particularly when including topography, may be affected by the accuracy of the source term.     

Study of the influence of melamine polyphosphate and aluminum hydroxide on the flame propagation and explosion overpressure of aluminum magnesium alloy dust

When aluminum magnesium alloy dust floats in the air, a certain ignition energy can easily cause an accidental explosion. To prevent and control the occurrence of accidental explosions and reduce the severity of accidents, it is necessary to carry out research on the explosion suppression of aluminum magnesium alloy dust. This paper uses a vertical glass tube experimental device and a 20 L spherical explosive experimental device to carry out experimental studies on the suppression of the flame propagation and explosion overpressure of aluminum magnesium alloy dust with melamine polyphosphate (MPP) and Al(OH)₃. With increasing MPP and Al(OH)₃ concentrations, the flame brightness darkened, the flame velocity and propagation distance gradually decreased, and P_max and (dp/dt)_max decreased significantly. When the amount of MPP added reached 60%, the flame propagation distance decreased to 188 mm, which is a decrease of 68%, and the explosion overpressure decreased to 0.014 MPa, effectively suppressing the explosion of aluminum magnesium alloy dust. The experimental results showed that MPP was more effective than Al(OH)₃ in inhibiting the flame propagation and explosion overpressure of the aluminum magnesium alloy dust. Finally, the inhibitory mechanisms of the MPP and Al(OH)₃ were further investigated. The MPP and Al(OH)₃ endothermic decomposition produced an inert gas, diluted the oxygen concentration and trapped active radicals to terminate the combustion chain reaction.     

Experimental study on thermal and toxic hazards connected to fire scenarios in road tunnels

The problem of toxic smoke in case of an accident with fire scenario is particularly severe in long tunnels and immediate effects from combustion product exposure often include fatalities. Notwithstanding extensive studies on fire simulation in tunnel, there is still a substantial lack of information on the different toxic products from combustion of light or heavy vehicles. In particular, there is a need for reliable test methods suitable to provide toxic products yields connected to defined accidental fire scenarios. In this paper, experimental runs in a laboratory scaled tunnel, simulating accidental fires of different heat release rates allowed firstly to characterize the thermal profiles in pool and car fires and to compare results by an analytical pool fire model. Results were compared as well with those obtained in a real scale tunnel, so as to quantitatively assess the scaling effect. A series of experiments was performed simulating an accidental scenario including pool fire from collision between a light vehicle and a HazMat heavy vehicle. An extensive set of experimental data allowed performing with good accuracy and reproducibility a complete characterization of toxic gases from car model fires, together with carbon monoxide and oxygen trends. The results obtained under different heat release rates allowed evidencing the dependence of the yields of toxic gases upon the considered scenario. Based on the intrinsic toxicity data of identified compounds, it is possible to draw practical conclusions, useful to assess the potential hazard associated to exposure to toxic smoke in road tunnel.     

Study on convection and dispersion characteristics of dense gases in urban environment considering trees

Although several studies on the dispersion of heavy toxic gas released from ruptured tanks on vehicles during transportation have considered complex terrain such as urban buildings, the influence of trees on the flow field in urban areas during gas dispersion tends to be ignored. In this study, a Computational Fluid Dynamics (CFD) model was proposed to investigate the characteristics of gas release and dispersion from loaded vehicle in the urban environment. In this model, the tree crown was treated as a porous medium, and the influence of drag due to the crown was incorporated into the model by a momentum source term through a user-defined function. In this study, the dynamic characteristics of chlorine (Cl₂) dispersion under the conditions of building distribution, tree species and porosities were comprehensively analysed, to cover the influence of urban complexity, leaf density, and tree planting configuration. The results show that compared with flat terrain, the presence of urban buildings will prolong the dense gas retention time and increase the dangerous distance. It is found that the horizontal dispersion distance can increase by 63% and the isosurface of 25 ppm hazardous gas can increase by 130% with the introduction of buildings. Compared with the terrain with only buildings, the introduction of arbors or shrubs can result in a 147% or 359% increase in the maximum concentration. Also, trees will prolong the dispersion duration. It is also found that the higher the porosity, the less the wind blocking effect, and the weaker the ability of capturing gas. The wind field affected by arbores and shrubs are different in height, and arbores capture more Cl₂. Planting short shrubs around buildings can effectively reduce the spread of harmful gases.     

n-Compartment mathematical model for transient evaluation of fluid curtains in mitigating chlorine releases

A simple n-compartment mathematical model is developed to study the effectiveness of fluid curtains and transient behaviour in mitigating the effects of an accidental chlorine release. The model is obtained considering chemical and physical absorption effectiveness of the toxic cloud by a reacting liquid curtain. The characteristics of the curtain and the evolution were deeply studied by means of replicated wind tunnel experimental runs, according to different operating parameters. An analytical solution of the model is presented. A fairly good agreement was verified between the model predictions and the original experimental results here presented.