A methodology for assessing risk from released hydrocarbon in an enclosed area

This study presents a method for calculating the concentration of hydrocarbon releases in enclosed areas using empirical equations for the evaporation rate. The approach of the method is to estimate the hydrocarbon exposure concentration in the air under conditions assumed. A methodology for assessing risk to individual exposed workers or others using probit expressions is suggested. The toxicity criteria and available human exposure data were examined and guidelines for risk assessment suggested for benzene–air and toluene–air systems. The values of probit constants with mole fractions of lethal concentrations in a mixture of hydrocarbons and a non-toxic substance were predicted. The probit values calculated with mole fractions can be used to estimate guidelines to prevent toxicity within enclosed working areas.     

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。     

Quantitative risk analysis of toxic gas release caused poisoning—A CFD and dose–response model combined approach

Some major toxic gas release accidents demonstrate the urgent need of a systematic risk analysis method for individuals exposed to toxic gases. A CFD numerical simulation and dose–response model combined approach has been proposed for quantitative analysis of acute toxic gas exposure threats. This method contains four steps: firstly, set up a CFD model and monitor points; secondly, solve CFD equations and predict the real-time concentration field of toxic gas releases and dispersions; thirdly, calculate the toxic dose according to gas concentration and exposure time; lastly, estimate expected fatalities using dose–response model. A case study of hydrogen sulfide releases from a gas gathering station has been carried out using a three dimension FLUENT model. Acute exposure fatalities have been evaluated firstly with a simplified ideal model which assumes workers stay at original exposure location without moving. Then a comparison has been made with a more realistic model which assumes workers start evacuating according to a prearranged course as soon as hydrogen sulfide detection system alarms. These two models represent the worst and best emergency response effects, respectively, and the analysis results demonstrate significant differences. Results indicate that the CFD and dose–response combined approach is a good way for estimating fatalities of individuals exposed to accidental toxic gas releases.     

Key parametric analysis on designing an effective forced mitigation system for LNG spill emergency

Concerns over public safety and security of a potential liquefied natural gas (LNG) spill have promoted the need for continued improvement of safety measures for LNG facilities. The mitigation techniques have been recognized as one of the areas that require further investigation to determine the public safety impact of an LNG spill. Forced mitigation of LNG vapors using a water curtain system has been proven to be effective in reducing the vapor concentration by enhancing the dispersion. Currently, no engineering criteria for designing an effective water curtain system are available, mainly due to a lack of understanding of the complex droplet–vapor interaction. This work applies computational fluid dynamics (CFD) modeling to evaluate various key design parameters involved in the LNG forced mitigation using an upwards-oriented full-cone water spray. An LNG forced dispersion model based on a Eulerian–Lagrangian approach was applied to solve the physical interactions of the droplet–vapor system by taking into account the various effects of the droplets (discrete phase) on the air–vapor mixture (continuous phase). The effects of different droplet sizes, droplet temperatures, air entrainment rates, and installation configurations of water spray applications on LNG vapor behavior are investigated. Finally, the potential of applying CFD modeling in providing guidance for setting up the design criteria for an effective forced mitigation system as an integrated safety element for LNG facilities is discussed.     

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.     

普光天然气净化厂投料试车H2S泄漏安全管理

普光气田天然气净化厂是中国石化集团公司"川气东送工程"的关键组成部分,在投料试车期间,富含高浓度H2S的原料气决定了净化过程中的泄漏中毒高风险,尤其在投料试车过程中,实时监测现场H2S气体浓度是试车安全管理的关键。介绍了天然气净化厂净化工艺,分析了试车安全风险;利用安全监测系统、GasFindIR红外成像仪、有毒挥发气体分析仪等先进仪器设备建立了实时安全管理监测方法,实时监测现场H2S气体浓度。结果表明,该方法在天然气净化厂投料试车阶段发现H2S气体泄漏及时,泄漏点定位准确,泄漏量检测精确,保证了普光气田天然气净化厂投料试车作业安全的顺利进行,为高含H2S气田投料试车作业的安全管理提供了参考。     

Prediction of methanol loss in liquid hydrocarbon phase during natural gas hydrate inhibition using rigorous models

Methanol is the most widely used natural gas hydrate inhibitor and it is only effective as a hydrate inhibitor in the aqueous phase. Methanol is not regenerated in natural gas inhibition process due to its intermittent application in most cases. However, a significant cost is associated with the process because of methanol loss while utilizing this inhibitor. In this work, several intelligent models along with a new mathematical correlation are presented in terms of methanol concentration in aqueous phase and temperature to precisely forecast the methanol loss in the saturated hydrocarbons phase. An excellent match was noticed between the calculated results and literature data.     

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.     

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.     

Numerical simulation of LNG dispersion under two-phase release conditions

The use of LNG (liquefied natural gas) as fuel brings up issues regarding safety and acceptable risk. The potential hazards associated with an accidental LNG spill should be evaluated, and a useful tool in LNG safety assessment is computational fluid dynamics (CFD) simulation. In this paper, the ADREA-HF code has been applied to simulate LNG dispersion in open-obstructed environment based on Falcon Series Experiments. During these experiments LNG was released and dispersed over water surface. The spill area is confined with a billboard upwind of the water pond. FA1 trial was chosen to be simulated, because its release and weather conditions (high total spill volume and release rate, low wind speed) allow the gravitational force to influence the cold, dense vapor cloud and can be considered as a benchmark for LNG dispersion in fenced area. The source was modeled with two different approaches: as vapor pool and as two phase jet and the predicted methane concentration at sensors' location was compared with the experimental one. It is verified that the source model affect to a great extent the LNG dispersion and the best case was the one modeling the source as two phase jet. However, the numerical results in the case of two phase jet source underestimate the methane concentration for most of the sensors. Finally, the paper discusses the effect of neglecting the ?9.3° experimental wind direction, which leads to the symmetry assumption with respect to wind and therefore less computational costs. It was found that this effect is small in case of a jet source but large in the case of a pool source.     

Predicting the flammable region reach of propane vapor clouds

Liquified gas fuels are widely used around the world, and the growth of LNG and LPG consumption continues to increase. However, using these fuels can lead to accidents if they are released to the environment. Consequently, the challenge to control and predict such hazards has become an objective in emergency planning and risk analysis. In a previous article the “Dispersion Safety Factor” (DSF) was proposed, defined as the ratio between the distance at which the lower flammability limit concentration occurs and that corresponding to the visible contour of a vapor cloud. Its interest was demonstrated by applying it to the specific case of an LNG spill. With the appropriate modifications, this factor may be applied to the dispersion of other substances; in this communication it is applied to the atmospheric dispersion of propane, and two expressions are proposed to estimate it. Due to the similarity between the properties of both gases, these expressions could probably be applied as well to the dispersion of propylene.     

Methodology for consequence analysis of LNG releases at deepwater port facilities

A methodology to perform consequence analysis associated with liquefied natural gas (LNG) for a deepwater port (DWP) facility has been presented. Analytical models used to describe the unconfined spill dynamics of LNG are discussed. How to determine the thermal hazard associated with a potential pool fire involving spilled LNG is also presented. Another hazard associated with potential releases of LNG is the dispersion of the LNG vapor. An approach using computational fluid dynamics tools (CFD) is presented. The CFD dispersion methodology is benchmarked against available test data. Using the proposed analysis approach provides estimates of hazard zones associated with newly proposed LNG deepwater ports and their potential impact to the public.     

Developing a CFD heat transfer model for applying high expansion foam in an LNG spill

Liquefied natural gas (LNG) is widely used to cost-effectively store and transport natural gas. However, a spill of LNG can create a vapor cloud, which can potentially cause fire and explosion. High expansion (HEX) foam is recommended by the NFPA 11 to mitigate the vapor hazard and control LNG pool fire. In this study, the parameters that affect HEX foam performance were examined using lab-scale testing of foam temperature profile and computational fluid dynamics (CFD) modeling of heat transfer in vapor channels. A heat transfer model using ANSYS Fluent® was developed to estimate the minimum HEX foam height that allows the vapors from LNG spillage to disperse rapidly. We also performed a sensitivity analysis on the effect of the vaporization rate, the diameter of the vapor channel, and the heat transfer coefficient on the required minimum height of the HEX foam. It can be observed that at least 1.2 m of HEX foam in height are needed to achieve risk mitigation in a typical situation. The simulation results can be used not only for understanding the heat transfer mechanisms when applying HEX foam but also for suggesting to the LNG facility operator how much HEX foam they need for effective risk mitigation under different conditions.     

Modeling the vapor source term associated with the spill of LNG into a sump or impoundment area

The recent publication of evaluation protocols for vapor source term models and vapor dispersion models have influenced the modeling approaches that can be used for approval of new and expansion projects at LNG receiving terminals. In the past few years the scientific basis of integral vapor source term models has been questioned with growing concerns regarding their validity. In this paper, the shallow water equations (SWEs) were solved to study the characteristics of the evaporating LNG pool associated with a constant flow rate spill of LNG into a concrete sump. In the early stages of pool spreading, the leading edge thickness profile of the SWE model scales with the square root of the distance from the leading edge as the pool spreads. After the edge of the pool reaches the wall, the reflected wave forms a hydraulic jump that travels back towards the center of the pool at a speed that is considerably slower than the initial spreading of the pool. Once the hydraulic jump reaches the center, the pool assumes a nearly flat free surface for the rest of the spill. The pool spreading and the rate of evaporation from the SWEs were then compared to the solution provided by the integral model, PHAST. The two approaches were found to agree well with one another. The SWE model was also used to demonstrate the influence of an elevated spill source. With an elevated source, the LNG pool spreads faster, significantly increasing the initial rate of vaporization and peak vaporization rate. This increase in the initial rate of vaporization could lead to an increase in the vapor cloud hazard distance. The SWE model was also used to demonstrate the influence of an inclined sump floor in the shape of an inverted cone where the spilling LNG accumulates in the low vertex of the cone. Inclined sump floors can be used to significantly reduce the cumulative evaporation, making them attractive as a possible mitigation approach in cases where a containment sump is located close to a property boundary.     

Critical aspects for collision induced oil spill response and recovery system in ice conditions: A model-based analysis

The recovery effectiveness for oil spills in ice conditions depends on a complex system and has not been studied in depth, especially not from a system risk control perspective. This paper aims to identify the critical aspects in the oil spill system to enable effective oil spill recovery. First, a method is developed to identify critical elements in a Bayesian Network model, based on an uncertainty-based risk perspective. The method accounts for sensitivity and the strength of evidence, which are assessed for the different Bayesian Network model features. Then, a Bayesian Network model for the mechanical oil spill recovery system is developed for the Finnish oil spill response fleet, contextualized for representative collision accident scenarios. This model combines information about representative sea ice conditions, ship-ship collisions and their associated oil outflow, the oil dispersion and spreading in the ice conditions, and the oil spill response and recovery of the fleet. Finally, the critical factors are identified by applying the proposed method to the developed oil spill response system model. The identified most critical system factors relates collision aspect: Forcing Representative Scenario, Representative Accident Location, Impact Speed, Impact Location, Impact Angle and response aspect: Response Vessel Operability.     

LPG船液货泄漏事故风险评估系统研究

通过对液化石油气(LPG)船舶液货舱泄漏事故危险度因素分析,建立液化气液体货物泄漏源强、蒸气释放源强和蒸气扩散计算模型,并制定泄漏事故风险评价流程,基于VB语言编写泄漏事故风险评估系统。利用该系统能够计算得出泄漏事故发生后蒸发气在不同时刻不同区域的蒸发气浓度、爆炸或火灾后对生命财产的伤害半径以及伤害程度等相关参数。对某航行状态下的LPG实船进行模拟分析,结果表明能够对LPG船舶泄漏事故进行有效风险评估,并能对船舶航行安全应急预案的制定和事故后海事鉴定提供一定的技术帮助。     

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.     

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.