A sneak peek into the phenomenology of fuel mist explosions: The key role of vapor fractions

The modern world depends greatly on hydrocarbons, which are ubiquitous, indispensable fuels used in nearly every existing industry. Although important, their use may trigger dangerous incidents, whether in their production, handling, storage, or transporting phase, especially when aerosolized. In light of proposing a standard procedure to assess the flammability and explosivity of fuel mists, a new test method was established based on the EN 14034 standards series. For the previous purposes, a gravity-fed mist generation system was designed and employed in a modified 20 L explosion vessel. This test method allowed the determination of the ignition sensitivity of several fuels. In addition, their explosion severity was represented by the explosion overpressure P_ex, and the rate of pressure rise dP/dt_ex, two thermo-kinetic parameters determined with a specifically developed control system and custom software. Nonetheless, a noticeable difference in the ignition sensitivity and the explosion severity was perceived when changing suppliers or petroleum cuts of some fuels. Moreover, sensitivity studies showed that both the droplet size distribution and the temperature of the droplets play a significant role in fuel mist explosion. These parameters can be directly related to the vapor fraction surrounding a droplet during its ignition. Consequently, this study focuses on the influence of varying the composition of three well-known and abundantly used fuels. Different petroleum cuts were introduced in different fractions into isooctane, Jet A1 aviation fuel, and diesel fuel mixtures, which were then aerosolized into a uniformly distributed turbulent mist cloud and ignited using spark ignitors of 100 J. Subsequently, complementary tests were executed in a vertical flame propagation tube coupled with a high-speed video camera allowing the visualization of the flame and the determination of the spatial flame velocity, and a tentative estimation of the laminar burning velocity. The latter was also estimated from the pressure-time evolution in the 20 L sphere using existing correlations. Indeed, the determination of the laminar burning velocity can be useful in modeling such accidents. Finally, highlighting the essential role of the mist and vapor fraction during their ignition has led to a better understanding of their explosion mechanisms.     

市政污水检查井可燃气体组分及分布影响因素研究

为研究市政污水管网内主要可燃气体成分与分布,以实现其燃爆灾害的精准防控,本文采用现场检测的方法采集污水检查井内甲烷、氢气等5种可燃气体以及总的可燃气体浓度,统计分析污水管网各可燃气体的浓度范围,研究检查井深度和季节对甲烷浓度分布的影响。研究结果表明:污水检查井内甲烷浓度占比较大,一氧化碳、硫化氢、氢气和氨气所占比例较小;沿检查井深度方向,甲烷分布规律不尽相同,大部分检查井内甲烷随着与井口距离的增大呈逐渐增大变化趋势;季节对甲烷浓度变化影响较大,夏秋两季甲烷浓度较高,春季次之,冬季未检出甲烷。     

乙醇及自由基引导对甲烷预混火焰结构影响的数值模拟

本文使用了详细化学反应动力学机理计算模拟了混合有乙醇及典型自由基引导的甲烷预混火焰结构.该反应机理由Marinov研究组研究发表,包含有56个组分以及372个反应.本文的计算使用了CHEMKIN-3以及预混火焰代码,热力学及输运部分的计算基于Sandia国家实验室和Marinov研究室发布的数据库.火焰结构中主要产物的变化,关键中间产物和次要组分的计算结果显示加入乙醇和自由基都可以减少着火延迟.本文计算了三种不同条件下的火焰结构,分别为预混CH4/O2/N2火焰;预混甲烷/乙醇火焰;和加入引导自由基在甲烷/乙醇混合燃料中.此外还有含有自由基的甲烷火焰和加入乙醇的甲烷火焰比较.     

Explosion behavior of hydrogen–methane/air mixtures

The effects of enriching natural gas with hydrogen on local flame extinction, combustion instabilities and power output have been widely studied for both stationary and mobile systems. On the contrary, the issues of explosion safety for hydrogen–methane mixtures are still under investigation.In this work, experimental tests were performed in a 5 L closed cylindrical vessel for explosions of hydrogen–methane mixtures in stoichiometric air. Different compositions of hydrogen–methane were tested (from pure methane to pure hydrogen) at varying initial pressures (1, 3 and 6 bar).Results have allowed the quantification of the combined effects of both mixture composition (i.e., hydrogen content in the fuel) and initial pressure on maximum pressure, maximum rate of pressure rise and burning velocity. The measured burning velocities were also correlated by means of a Le Chatelier’s Rule-like formula. Good predictions have been obtained (at any initial pressure), except for mixtures with hydrogen molar content in the fuel higher than 50%.     

A simple model for predicting the release of a liquid-vapor mixture from a large break in a pressurized container

This paper presents a simple, accurate model for determining the amount and composition of a liquid-vapor release from a pressurized tank that develops a large break above the level of the liquid. Most models commonly used by the chemical industry assume that there is thermal- and mechanical-equilibrium between the liquid- and the vapor-phase (homogeneous equilibrium models, HEM). While this assumption is valid for releases though long pipes and nozzles, we found that it overestimates the total amount released during rapid discharges through large breaks in a vessel when there is insufficient time for the mixture to become homogeneous. We derived an analytical non-homogeneous, thermal equilibrium model that accurately determines the void fraction of the mixture at the time of the release, and the quantity of a release from a pressurized container. Our model is based on equations describing the transfer of interfacial momentum between the liquid- and the vapor- phases that develop during the quick depressurization of a vessel. The model’s predictions are verified by comparing them with actual measurements of the void fraction, and with the results of the RELAP5 model. Also, our model is used to determine emissions of nitrogen oxides and nitric acid in an actual rupture of a railcar tank. The results agreed with actual observations, whereas a homogeneous equilibrium model gave erroneous predictions.     

Evaporation characteristics of multi-component liquid

Evaporation rate of multi-component liquid such as motor gasoline is expected to change greatly with progress of evaporation because its composition changes. Therefore it is difficult to predict accurately amount of generated combustible vapor in the case that a multi-component liquid is spilt on a floor. Then, we assumed an evaporation model that composition of the vapor obeys the Raoult's law which considers the activity coefficient. Using the model, we calculated the vapor composition, the vapor pressure and the evaporation rate of the liquid. Then, comparison was done between the calculated values and the measured values obtained in this study. “Weight loss fraction” was used as a parameter signifying the progress of evaporation. The variations of the evaporation property were accurately predicted by the model. We derived a prediction model of the amount of generated combustible vapor from the relation between weight loss fraction and evaporation rate. It was found that the amount of generated vapor was expressed as a logarithmic function of time in case of a five-component liquid. Furthermore, we showed that the predicted flash point of a liquid using the composition obtained from the model was in good agreement with an experimental result.     

液化石油气爆炸范围及爆炸力的测定

液化石油气、瓦斯等可燃气体的爆炸防治是一个非常迫切需要解决的问题.利用自制可燃气体爆炸箱来模拟可燃气体爆炸,并通过光干涉甲烷测定仪来测定混合气体爆炸时的甲烷百分含量,再推算出液化石油气的爆炸范围和计算爆炸力.     

可燃气体燃爆特性综合试验装置构建与甲烷试验

为研究半开敞空间内可燃气体爆炸过程,设计带有泄压面的气体爆炸室,并在此基础上构建一套可燃气体燃爆特性综合试验装置。运用该试验装置,研究预混塔内甲烷气体分层现象以及甲烷爆炸浓度与最小点火能之间的变化规律。甲烷分层试验结果表明:静置一段时间后,预混塔中甲烷浓度随高度的增加而增大。最小点火能试验结果显示,当甲烷的试验爆炸体积分数在10%～13%时,其浓度与点火能之间呈现比较平缓的变化关系,而当其体积分数小于10%或大于13%时,浓度稍微变化,其点火能将发生明显变化。     

Outflow from fractured pipelines transporting supercritical ethylene

This paper describes a methodology for predicting outflow from a rupture in a pipeline transporting supercritical ethylene. Ethylene outflow is of particular interest and is a challenging scenario to model as typical operating temperatures are a few degrees above the critical temperature, 283 K. Thus when the pipe fractures the initial rapid depressurisation induces a number of propagation waves to travel up the pipeline initiating phase changes and fundamentally changing the nature of the outflow problem.The methodology presented is primarily based on an outflow model for compressed volatile liquid outflow as this is demonstrated to be the flow regime upstream of the pipe fracture after a small time interval following pipe fracture. The model is validated using a more complex commercially available pipeline model, PROFES for propane outflow as experimental data at relatively low pressure and short pipes exist in the open literature and has been used to validate the models considered here.Finally the ethylene outflow methodology has been applied to a number of different ethylene pipeline scenarios with a range of operating temperatures, pressures and pipeline diameters of interest to confirm that predicted outflow rates trend as expected.     

Case study: Assessment on large scale LPG BLEVEs in the 2011 Tohoku earthquakes

After the 2011 Tohoku earthquakes, several chemical and oil complexes on the Pacific Ocean shoreline of northeast Japan experienced massive losses. In Chiba, a refinery operated by Cosmo Oil lost 17 LPG storage vessels which were either heavily damaged or totally destroyed by fires and explosions in the refinery. These large vessels ranged in size from 1000 to 5000 m³. The estimated volume of LPG at the time of the incident was between 400 and 5000 m³ for each vessel. Five boiling liquid expanding vapor explosions (BLEVEs) of LPG occurred, resulting in huge fire balls measuring about 500 m in diameter.A BLEVE is defined as the explosive release of expanding vapor and boiling liquid when a container holding a pressure-liquefied gas fails catastrophically. It is thus important to estimate the physical properties of superheated liquids: the thermodynamic and transport properties, the intrinsic limits to superheating and depressurization, and the nature of thermodynamic paths. Also it is hoped to provide better understanding of the vessels designed, manufactured, installed, and operated to reduce or eliminate the probability that a sequence of events will result in BLEVE or loss of primary containment. Knowledge of these matters is still incomplete. The objective of this research is to estimate the significant BLEVE phenomenon in very large scale spherical vessels based on published information in Japan. There are some models predicting BLEVEs. However, it is essential to know if this is true for very large scales such as spheres since validation is usually rare to provide confidence in estimating the superheated liquids behaviors. To this end, comparing with the information on this event, the conditions in the five LPG vessels at the time of the BLEVE were determined in terms of: duration of vessel failure (time to BLEVE); mass fraction in the vessel with time; temperature distribution in the liquid and vapor region and pressure within the vessel (e.g. initial pressure and internal high-speed transient pressure during failure), by means of a computer program AFFTAC Analysis of Fire Effects on Tank Cars, which solves heat conduction, stress and a failure model of the tank, a thermodynamic model of its fluid contents, and a flow model for the lading flowing through the safety relief device. Subsequently, the consequences from the sphere BLEVE, such as the expected fireball diameter and duration and the expected blast overpressure produced by the BLEVE failures, are also subjects of active research. Here the blast using the methods of PHAST and SFPE Handbook of Fire Protection Engineering was calculated.Results suggest that methodologies here used gave reasonable estimations for such real and huge BLEVEs in a validated way, which may provide valuable guidance for risk mitigation strategy with regard to LPG facility in design, emergency planning, resiliency, operations, and risk management.     

Modelling three-phase releases of carbon dioxide from high-pressure pipelines

This paper describes the development and experimental validation of a three-phase flow model for predicting the transient outflow following the failure of pressurised CO₂ pipelines and vessels. The choked flow parameters at the rupture plane, spanning the dense-phase and saturated conditions to below the triple point, are modelled by maximisation of the mass flowrate with respect to pressure and solids mass fraction at the triple point. The pertinent solid/vapour/liquid phase equilibrium data are predicted using an extended Peng–Robinson equation of state.The proposed outflow model is successfully validated against experimental data obtained from high-pressure CO₂ releases performed as part of the FP7 CO2PipeHaz project (www.co2pipehaz.eu).The formation of solid phase CO₂ at the triple point is marked by a stabilisation in pressure as confirmed by both theory and experimental observation. For a fixed diameter hypothetical pipeline at 100 bar and 20 °C, the flow model is used to determine the impact of the pipeline length on the time taken to commence solid CO₂ discharge following its rupture.     

矿井乏风通入燃煤锅炉混烧的最佳配伍参数研究*

为优化矿井乏风通入燃煤锅炉的配伍参数,采用Design-Expert软件的响应面分析法,以燃煤锅炉的主燃区顶端水平面平均温度和燃尽区顶端水平面的NO平均浓度为评价指标,按照3因素3水平正交组合设计试验方法,研究乏风中甲烷体积分数、燃尽风风率以及锅炉负荷的不同配伍比例对燃煤锅炉的变化影响,并建立3个因素的评价指标数学模型,分析各因素的主次关系和因素间交互作用大小,使得锅炉中煤粉放热量和氮氧化物的生成量均达到理想水平。研究结果表明:单因素中燃尽风风率对温度的影响最大,锅炉负荷对NO生成影响最大,交互作用下燃尽风风率与锅炉负荷对温度的影响和对NO浓度的影响均最显著。最优配伍参数为:乏风中甲烷浓度0.25%、燃尽风风率33.51%、锅炉负荷564.11 MW,在此参数下的温度响应值为1 691.41、NO浓度响应值为0.000 315 89。在最优参数下得到的预测值与试验值的误差在允许范围内,即吻合度较好,可为四角切圆锅炉掺烧矿井乏风提供参考。     

Anaerobic digestion modeling of the main components of organic fraction of municipal solid waste

The organic fraction of municipal solid waste (OFMSW) is composed of several heterogeneous organic and inorganic wastes. The diversity of composition, the high volatile solid content and the biodegradable material that this waste offers make it quite an interesting option for anaerobic digestion (AD). Depending on the substrate composition, the biological degradation and kinetics of the AD could vary. Biochemical methane potential (BMP) tests are used as a tool to evaluate the methane production of several fractions of OFMSW, in order to study the influence of each fraction in the final mixture. The kinetic parameters of methane curves and the prediction of final productions are studied by different approaches to model equations using linear, exponential, logistic and Gaussian models. The analyses of the fractions indicate that organic substrates such as meat/fish which are in a small proportion in the final mixture, obtain major productivities (291 ± 3 mlCH₄/gVS), however others such as paper (217 ± 5 mlCH₄/gVS) could have their productivity enhanced due to their high VS present in the final mixture. Both the Gomperzt and the first order model fit reasonably with all the fractions, although substrates with lag phase adjust only to the Gompertz model explaining 99% of the experimental results.     

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.     

Effect of inert species on the laminar burning velocity of hydrogen and ethylene

The maximum laminar burning velocity (LBV) of a fuel-air mixture is an important input parameter to vapor cloud explosion (VCE) blast load prediction methods. In particular, the LBV value has a significant impact on the predicted blast loads for high reactivity fuels with the propensity to undergo a deflagration-to-detonation transition (DDT). Published data are available for the maximum LBV of many pure fuel-air mixtures. However, little test data are available for mixtures of fuels, particularly for mixtures of fuels and inert species. Such mixtures are common in the petroleum refining and chemical processing industries. It is therefore of interest to be able to calculate the maximum LBV of a fuel/inert mixture based on the mixture composition and maximum LBV of each component.This paper presents measured test data for the maximum LBV of H₂/inert and C₂H₄/inert mixtures, with both nitrogen and carbon dioxide as the inert species. The LBV values were determined using a constant-volume vessel and the pressure rise method. This paper also provides a comparison of the measured LBV values with simplified LBV prediction methods.     

热效应对焦煤甲烷解吸迟滞特征的影响研究*

为揭示煤中甲烷气体的储运机制，选取井下煤样研究不同温度条件下甲烷气体的等温吸附解吸实验。基于Langmuir模型、等量吸附热计算模型和解吸迟滞系数对实验数据进行分析，研究煤中甲烷气体解吸迟滞现象的热力学特征。结果表明:随温度升高，Langmuir模型得到的吸附常数均呈下降趋势；甲烷解吸迟滞现象明显，迟滞程度随温度升高缓慢下降；受解吸迟滞效应影响，相邻温度区间内吸附曲线的等量吸附热较为相近，不同温度区间内解吸曲线的等量吸附热高于吸附曲线，差异显著；解吸迟滞现象影响煤层甲烷含量预测的准确性，并且解吸曲线的热力学特征规律性较差。     

A CART technique to adjust production from longwall coal operations under ventilation constraints

Methane emissions in longwall coal mines can arise from a variety of geologic and production factors, where ventilation and degasification are primary control measures to prevent excessive methane levels. However, poor ventilation practices or inadequate ventilation may result in accumulation of dangerous methane-air mixtures. The need exists for a set of rules and a model to be used as guidelines to adjust coal production according to expected methane emissions and current ventilation conditions.In this paper, hierarchical classification and regression tree (CART) analyses are performed as nonparametric modeling efforts to predict methane emissions that can arise during extraction of a longwall panel. These emissions are predicted for a range of coal productivities while considering specific operational, panel design and geologic parameters such as gas content, proximate composition of coal, seam height, panel width, cut height, cut depth, and panel size. Analyses are conducted for longwall mines with and without degasification of the longwall panel. These models define a range of coal productivities that can be achieved without exceeding specified emissions rates under given operating and geological conditions.Finally, the technique was applied to longwall mines that operate with and without degasification system to demonstrate its use and predictive capability. The predicted results proved to be close to the actual measurements to estimate ventilation requirements. Thus, the CART-based model that is given in this paper can be used to predict methane emission rates and to adjust operation parameters under ventilation constrains in longwall mining.     

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.     

Effects of hydrogen addition on propagation characteristics of premixed methane/air flames

An experimental study has been conducted to investigate the effects of hydrogen addition on the fundamental propagation characteristics of methane/air premixed flames at different equivalence ratios in a venting duct. The hydrogen fraction in the methane–hydrogen mixture was varied from 0 to 1 at equivalence ratios of 0.8, 1.0 and 1.2. The results indicate that the tendency towards flame instability increased with the fraction of hydrogen, and the premixed hydrogen/methane flame underwent a complex shape change with the increasing hydrogen fraction. The tulip flame only formed when the fraction of hydrogen ranged from 0 to 50% at an equivalence ratio of 0.8. It was also found that the flame front speed and the overpressure increased significantly with the hydrogen fraction. For all equivalence ratios, the stoichiometric flame (Φ = 1.0) has the shortest time of flame propagation and the maximum overpressure.     

Dustiness in workplace safety and explosion protection – Review and outlook

Behavior of dust/air mixtures is very complex and difficult to predict since it depends on material properties as well as boundary conditions. Without other influences airborne particles deposit due to gravity but the time it takes for total deposition as well as easiness of resurrection depends very much on the specific dust sample and the boundary conditions. It still lacks a complete understanding of all interacting reasons and one approach is using experimentally determined characteristics, one is named dustiness.Dustiness is the tendency of dust to form clouds and to stay airborne. Dustiness is determined with two basic principles, which are light attenuation and ratio of filled-in and measured mass. Assessment of dustiness of industrial powders has been done for a long time regarding work place safety. Dustiness is used there to determine inhalable fraction and to evaluate health risks. Lately it became interesting in dust explosion protection as well. Dustiness could be used to optimize determination of zones, adaption of venting area and/or for positioning of suppression systems.Dustiness can be useful in many ways but is not a physical property of dusts, therefore it depends on material properties such as density, particle size distribution, shape and water content as well as boundary conditions or determination method. This makes it very difficult to compare dustiness for different techniques and apparatuses and determination method as well as results should be considered carefully. This work gives an overview of existing standards, recent research and suggests improvements to the new dustiness as proposed for dust explosion protection.