Occupational chemical exposure and risk estimation in process development and design

Each year more people die from diseases caused by work than are killed in industrial accidents. Therefore, methods are needed to evaluate occupational health hazards as early as possible when the process is still under development. A method for estimating inhalative exposures and risks in petrochemical and related plants is presented. The method is simple and suffices with the limited data availability during the early design stages.The steps of the method, which utilizes preliminary process flow diagrams are as follows: first the fugitive emissions and process plot areas are estimated based on precalculated process modules representing the typical process sections (such as a distillation unit). Chemical concentration in the air is then calculated based on the wind velocity probability and the estimated process cross-sectional area. For this purpose a typical wind velocity distribution in the area is used. The worker risk of exposure to chemicals is evaluated either based on the concentration in air by using the hazard quotient method or calculating the carcinogenic chemicals intake and the resulting risk of cancer. The values are compared to the benchmarks.As a result the process route health characteristics such as fugitive emissions rate, critical wind speed, chemical concentration in air and intake amount as well as the corresponding risk of exposure are produced. By using statistical meteorological data, health risks of occupational exposure can be estimated more realistically as probabilities. The approach is capable of comparing alternative processes to select the concept which is inherently occupationally healthier. Using this method, the exposure problems of a process can be identified earlier and proper decisions can be made early in process development or predesign stage.The concentration-based method is demonstrated by a case study of six competing manufacturing routes for methyl methacrylate (MMA). The C3 is found to be the most harmful alternative to health. Both concentration-based and intake-based methods are applied. The study indicates that the intake-based risk estimation benchmark is stricter than the exposure limit-based benchmark for carcinogens.     

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.     

Modelling the mitigation of a hydrogen deflagration in a nuclear waste silo ullage with water fog

During the decommissioning of certain legacy nuclear waste storage plants it is possible that significant releases of hydrogen gas could occur. Such an event could result in the formation of a flammable mixture within the silo ullage and, hence, the potential risk of ignition and deflagration occurring, threatening the structural integrity of the silo. Very fine water mist fogs have been suggested as a possible method of mitigating the overpressure rise, should a hydrogen–air deflagration occur. In the work presented here, the FLACS CFD code has been used to predict the potential explosion overpressure reduction that might be achieved using water fog mitigation for a range of scenarios where a hydrogen–air mixture, of a pre-specified concentration (containing 800 L of hydrogen), uniformly fills a volume located in a model silo ullage space, and is ignited giving rise to a vented deflagration. The simulation results suggest that water fog could significantly reduce the peak explosion overpressure, in a silo ullage, for lower concentration hydrogen–air mixtures up to 20%, but would require very high fog densities to be achieved to mitigate 30% hydrogen–air mixtures.     

高硫油炼制企业H_2S中毒风险分析

随着企业炼油规模不断扩大及原油中含硫量不断提高,炼油企业中H2S中毒事故风险迅速增大。在对高硫油炼制企业H2S的分布及危险源状况分析的基础上,指出炼油企业存在两类H2S危险源,即含有H2S的气体和含有H2S的酸性水,炼油装置产出含H2S的气体中H2S含量一般在1%～92%,酸性水中H2S含量一般在0.01%～4.0%;介绍了不同H2S浓度等级的空气可对人产生的毒性危害后果,H2S在空气中数分钟内致人死亡的浓度为1500mg/m3;对炼油企业重大酸性气泄漏事故、酸性水泄漏事故进行定量毒性危害计算和分析,给出H2S毒性危害低危区、高危区及迅速致死区达到的下风距离及覆盖的区域面积,重大酸性气、酸性水泄漏事故迅速致死浓度可达到下风距离分别为300m和89m;指出H2S中毒已成为高硫油炼制企业的重大风险,应该加强安全措施,重点防控。     

Vessel outflow sensitivity to composition

The vessel composition is important when considering vessel outflow because changes in composition change the density and potentially more importantly change the shape and location of the boundary of the two-phase envelope. The influence on the phase boundary can be significant on vessel outflow as the liquid phase density is typically two orders of magnitude larger than the gas phase density for pressures and temperatures remote from the thermodynamic critical point. In this article two issues are addressed, outflow sensitivity to composition of hydrocarbon systems with a large component of methane, and outflow from systems where a petroleum fraction representation of composition is used. It is shown that approximating multi-component systems with a large methane content by methane can result in significant discrepancies in the predicted mass flow rate and vessel pressure. When a vessels composition is characterised by petroleum fractions, and the Kesler–Lee equations are used to predict thermodynamic properties, the predicted outflow is almost comparable to the predicted outflow calculated using a mole fraction representation of composition.     

A measure of human sensitivity in acute inhalation toxicity

The prediction of the probability of death or injury following the inhalation of a toxic gas or vapour is used in risk analysis. The proportion of a population responding for a given endpoint (e.g. lethality) can be related to the received dose using a probit model. Some of the coefficients in the probit equations are based on data from animal testing. Generally, experimental test animals are bred to exhibit low variability. Animal variability in response to toxic exposures may not adequately represent human variability in response to toxic exposures to the tested chemical. It is suggested that some independently established measure of human variability be used in the formulation of the probit equation constants rather than those that arise solely from the fitting of the animal data.     

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.     

基于累积接尘量的尘肺病风险评估方法

为了降低不同接尘经历劳动者的尘肺病风险,提出一种尘肺病风险评估方法.先进行粉尘种类识别、工作场所粉尘接触评估、劳动者累积接尘量评估,并确定粉尘与尘肺病风险的剂量-反应关系,进而将劳动者累积患病率的现值和增量值作为尘肺病风险评估指标,评估劳动者当前尘肺病风险、继续接尘后尘肺病风险、尘肺病风险增量、尘肺病风险增长率;最后以...     

凯达煤矿采空区煤自燃极限参数分析

为更加精准地判定采空区自燃危险区域,对煤自燃极限参数的计算方法进行改进,采用能量守恒微分方程的分析解计算煤自燃所需必要条件的极限值;以内蒙古凯达煤矿为例对该方法进行验证,根据浮煤的物性参数以及采空区环境条件,计算分析46205工作面回风侧采空区煤的自燃危险性;根据采空区漏风条件以及煤自燃所需要的氧浓度值,分析在遗煤较厚...     

Venting of deflagrations: hydrocarbon–air and hydrogen–air systems

A set of 34 experiments on vented hydrocarbon–air and hydrogen–air deflagrations in unobstructed enclosures of volume up to 4000 m³ was processed with use of the advanced lumped parameter approach. Reasonable compliance between calculated pressure–time curves and experimental pressure traces is demonstrated for different explosion conditions, including high, moderate, low and extremely low reduced overpressures in enclosures of different shape (L_max:L_min up to 6:1) with different type and position of the ignition source relative to the vent, for near-stoichiometric air mixtures of acetone, methane, natural gas and propane, as well as for lean and stoichiometric hydrogen–air mixtures. New data were obtained on flame stretch for vented deflagrations.The fundamental Le Chatelier–Brown principle analog for vented deflagrations has been considered in detail and its universality has been confirmed. The importance of this principle for explosion safety engineering has been emphasized and proved by examples.A correlation for prediction of the deflagration–outflow interaction number, χ/μ, on enclosure scale, Bradley number and vent release pressure is suggested for unobstructed enclosures and a wide range of explosion conditions. Fractal theory has been employed to verify the universality of the dependence revealed of the deflagration–outflow interaction number on enclosure scale.In spite of differences between the thermodynamic and kinetic parameters of hydrocarbon–air and hydrogen–air systems, they both obey the same general regularities for vented deflagrations, including the Le Chatelier–Brown principle analog and the correlation for deflagration–outflow interaction number.     

Explosion limits of mixtures relevant to the production of 1,2-dichloroethane (ethylene dichloride)

A simple method exists to estimate the limiting oxygen concentration (LOC) based upon the lower explosion limit (LEL) by assuming (1) that the LOC lies at the apex of the explosion area, (2) that the LEL is unaffected by nitrogen addition and (3) that the apex of the explosion area lies on the stoichiometric line. This estimation method is assessed for mixtures relevant to the production of 1,2-dichloroethane. To this end, the explosion areas of ethylene/hydrogen/nitrogen/air, ethylene/nitrogen/air and ethylene/1,2-dichloroethane/hydrogen chloride/nitrogen/air mixtures are determined at typical process conditions. The experiments are performed in a closed spherical 8 l vessel. The mixtures are ignited by fusing a coiled tungsten wire, placed at the centre of the vessel. A 5% pressure rise criterion is used to determine the explosion limits. The experimental procedure is based upon EN 14756. It is found that a safe estimate of the LOC of ethylene/hydrogen/nitrogen/air mixtures can be found based upon the LEL of these mixtures.     

Numerical simulation of flame propagation and localized preflame autoignition in enclosures

A novel computational approach based on the coupled 3D Flame-Tracking–Particle (FTP) method is used for numerical simulation of confined explosions caused by preflame autoignition. The Flame-Tracking (FT) technique implies continuous tracing of the mean flame surface and application of the laminar/turbulent flame velocity concepts. The Particle method is based on the joint velocity–scalar probability density function approach for simulating reactive mixture autoignition in the preflame zone. The coupled algorithm is supplemented with the database of tabulated laminar flame velocities as well as with reaction rates of hydrocarbon fuel oxidation in wide ranges of initial temperature, pressure, and equivalence ratio. The main advantage of the FTP method is that it covers both possible modes of premixed combustion, namely, frontal and volumetric. As examples, combustion of premixed hydrogen–air, propane–air, and n-heptane–air mixtures in enclosures of different geometry is considered. At certain conditions, volumetric hot spots ahead of the propagating flame are identified. These hot spots transform to localized exothermic centers giving birth to spontaneous ignition waves traversing the preflame zone at very high apparent velocities, i.e., nearly homogeneous preflame explosion occurs. The abrupt pressure rise results in the formation of shock waves producing high overpressure peaks after reflections from enclosure walls.     

中小企业作业场所有毒有害物质危险评价方法

针对中小企业职业卫生管理中专业人员、技术及资源缺乏的特点建立了一种作业场所有毒有害物质危险评价分级的简便方法。该方法建立在物质的毒性评估和暴露评估基础之上,能对有毒有害物质的危害性进行科学、客观的评价,而且该方法实用性很强,无需太多的专业知识和技术的要求,很好满足了中小企业在有毒有害物质危险评价方面的需求。此外,在危险评价分级基础上,对不同的危害等级提出了相应的控制策略,为中小企业制定作业场所有毒有害物质的控制措施提供有价值的参考。     

Medium-scale experiments on vented hydrogen deflagration

A series of medium-scale experiments on vented hydrogen deflagration was carried out at the KIT test side in a chamber of 1 × 1 × 1 m³ size with different vent areas. The experimental program was divided in three series: (1) uniform hydrogen–air mixtures; (2) stratified hydrogen–air mixtures within the enclosure; (3) a layer deflagration of uniform mixture. Different uniform hydrogen–air mixtures from 7 to 18% hydrogen were tested with variable vent areas 0.01–1.0 m². One test was done for rich mixture with 50% H₂. To vary a gradient of concentration, all the experiments with a stratified hydrogen–air mixtures had about 4%H₂ at the bottom and 10 to 25% H₂ at the top of the enclosure. Measurement system consisted of a set of pressure sensors and thermocouples inside and outside the enclosure. Four cameras combined with a schlieren system (BOS) for visual observation of combustion process through transparent sidewalls were used. Four experiments were selected as benchmark experiments to compare them with four times larger scale FM Global tests (Bauwens et al., 2011) and to provide experimental data for further CFD modelling. The nature of external explosion leading to the multiple pressure peak structure was investigated in details. Current work addresses knowledge gaps regarding indoor hydrogen accumulations and vented deflagrations. The experiments carried out within this work attend to contribute the data for improved criteria for hydrogen–air mixture and enclosure parameters to avoid unacceptable explosion overpressure. Based on theoretical analysis and current experimental data a further vent sizing technology for hydrogen deflagrations in confined spaces should be developed, taking into account the peculiarities of hydrogen–air mixture deflagrations in presence of obstacles, concentration gradients of hydrogen–air mixtures, dimensions of a layer of flammable cloud, vent inertia, etc.     

Mapping human vulnerability and risk due to chemical accidents

Chemical accidents in the vicinity of densely populated areas can cause colossal damage. Close proximity of chemical facilities to the general public has been identified as a major issue for increased human exposure in 43% of the accidents investigated by the U.S. Chemical Safety Board (CSB). This emphasises the need for incorporating societal factors in risk assessment to plan actions in order to minimise exposure during accidents. The purpose of this research is to develop a model for the assessment of human vulnerability and risk due to chemical accidents. A GIS based methodology is proposed which uses computer aided hazard modelling tools and technical guidelines to model accidents and assesses population vulnerability. The population vulnerability is determined based on a set of societal indicators derived from relevant research work, expert opinions and suggestions by World Bank. Risk is defined as the probable magnitude of harm to humans and dependent on both the degrees of hazard and vulnerability. A case study is carried out by applying the methodology to Meghnaghat Industrial Area in Bangladesh. Accident scenarios are built and hazard modelling software ALOHA is used to spatially display accident footprints. Vulnerability of population is assessed using data from Bangladesh Bureau of Statistics (BBS) and field survey. The hazard footprints and vulnerability map are superimposed using mapping software ArcGIS to generate a composite risk map. The risk map is used to assess existing land use and recommendations are made for future land use planning. The composite risk map is expected to be of help for effective community response, emergency response planning and allocation of medical and support services during emergencies.     

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.     

受限空间中CO与水蒸汽阻尼瓦斯爆炸的反应动力学模拟研究

为了探求一氧化碳与水蒸汽参与瓦斯爆炸的化学反应动力学过程的阻尼效应,建立了受限空间中瓦斯爆炸反应的数学模型。数值计算结果表明,结果表明在瓦斯爆炸过程中,瓦斯-空气混合气体含有10%的一氧化碳,虽然会延迟瓦斯爆炸时间,抑制瓦斯爆炸,但是H、O自由基浓度、瓦斯爆炸温度和压力比不加入一氧化碳时升高,同时对CO2、NO的生成起促进作用;当混合气体中含有10%的水蒸汽时,H、O自由基浓度降低,瓦斯爆炸温度和压力也随之降低,致灾性气体CO2、NO的生成得到抑制。虽然一氧化碳对瓦斯爆炸有一定的阻尼效应,但是由于一氧化碳对部分致灾性气体的生成有促进作用,因此,在阻尼瓦斯爆炸方面,水蒸汽的效果要好于一氧化碳。     

Occupational Exposure to Polycyclic Aromatic Hydrocarbons During Diesel Combustion

Identification and determination of polycyclic aromatic hydrocarbons (PAHs) in Diesel exhaust in the working environment and assessment of workers’ occupational exposure to these suspected human carcinogens were the aim of this experimental investigation.

The range of exposure factors calculated on the basis of 9 individual PAH concentrations determined in personal air samples shows that time-averaged concentration of these compounds did not exceed the Polish Maximum Admissible Concentration (MAC) value for PAHs, that is, 2 μg·m^–3. The highest concentrations of PAHs were determined in the breathing zone of forklift operators. The maximum exposure factor was 0.427 μg·m^–3 (about 1/4 of MAC).