多元可燃气体爆炸极限理论预测模型研究*

为准确掌握和预测多元可燃气体的爆炸极限,开展2种多元可燃气体爆炸极限的理论预测模型研究。第1种模型针对“多种可燃气体+多种惰性气体”在空气中或氧气中混合,基于求解可燃气体绝热火焰温度的总比热特性方法以及化学平衡反应中的贫燃料(富氧)反应,提出该多元可燃气体的爆炸下限预测模型;第2种模型针对“可燃气体+惰性气体+氧气”混合,基于热平衡方程及混合气体的各组分浓度、淬灭电势及燃烧潜热,提出该多元可燃气体的爆炸极限预测模型。结果表明:在预测多元可燃气体的爆炸极限时,第1种模型具有较广泛的应用性,且表现出较高的准确度;第2种模型具有使用简单的特点,且扩展了LCR（勒夏特列原理）的应用范围。     

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.     

Evaporating liquid flow in a channel (An integral model based on shallow water flow approximation)

Liquefied Natural Gas (LNG) storage facilities generally include channels to convey potential spills of the liquid to an impoundment. There is increasing concern that dispersion of vapors generated by flow of LNG in a channel may lead to higher than limit vapor concentrations for safety at site boundary from channels that may be close to the dike walls. This issue is of recent concern to regulatory agencies, because the calculation of vapor hazard distance(s) from LNG flow in a channel is not required under existing LNG facility siting standards or regulations.An important parameter that directly affects the calculated LNG vapor dispersion distance is the source strength (i.e., the rate of vaporization of LNG flow from the wetted channel surfaces, as a function of spatial position and time). In this paper a model is presented which considers the variation of the depth of the flowing LNG with spatial location and time, and calculates the spatial and temporal dependence of the mass rate of vapor generation. Self similar profiles for the spatial variation of the thermal boundary layer in the liquid wetted wall and liquid depth variation are assumed. The variation with time of the location of the liquid spread front and the evaporation rate are calculated for the case of a constant LNG spill rate into a rectangular channel. The effects of two different channel slopes are evaluated. Details of the results and their impact on dispersion distances are discussed.     

Development of heat transfer and evaporation model of LNG covered by Hi-Ex foam

Natural gas is a kind of clean, efficient green energy source, which is used widely. Liquefied natural gas (LNG) is produced by cooling natural gas to −161 °C, at which it becomes the liquid. Once LNG was released, fire or explosion would happen when ignition source existed nearby. The high expansion foam (Hi-Ex foam) is believed to quickly blanket on the top of LNG spillage pool and warm the LNG vapor to lower the vapor cloud density at the ground level and raising vapor buoyancy. To identify the physical structure after it contacted with LN₂ and to develop heat transfer model, the small-scale field test with liquid nitrogen (LN₂) was designed. In experiment, three layers including frozen ice layer, frozen Hi-Ex layer and soft layer of Hi-Ex foam were observed at the steady state. By characterizing physical structure of the foam, formulas for calculating the surface of single foam bubble and counting foam film thickness were deduced. The micro heat transfer and evaporation model between cryogenic liquid and Hi-Ex foam was established. Indicating the physical structure of the frozen ice layer, there were a certain number of icicles below it. The heat transfer and evaporation mathematical model between the frozen ice layer and LNG was derived. Combining models above with the heat transfer between LNG, ground and cofferdam, the heat transfer and evaporation mathematical model of LNG covered by Hi-Ex foam was developed eventually. Finally, LN₂ evaporation rate calculated by this model was compared with the measured evaporation rate. The calculated results are 1.2–2.1 times of experimental results, which were acceptable in engineering and proved the model was reliable.     

基于空位溶液与DA理论的多组分气体吸附方法及验证*

为准确预测煤层气中多组分气体的吸附性能,将空位溶液与Dubinbin-Astakhov（DA）理论相结合,提出1种适用于煤层气吸附系统的多组分混合吸附模型。在模型中,吸附体系被视为气体与假设的“空位溶质”的多元混合物,吸附体系视为气相和吸附相空位溶质之间的平衡。结果表明:根据单组分气体吸附等温线,采用D-A方程计算分析了生成二元（吸附质+空位）混合物中纯组分气体的活度系数,并优化吸附参数;模型能够根据在单一温度下收集的纯组分吸附数据预测不同温度下的多组分气体吸附;模型计算结果与实测结果吻合良好,误差在10%以内,充分说明模型是切实可靠的。     

油品真实蒸汽压多元非线性回归

油品蒸气压是从事油品蒸发损耗研究、计算油品蒸发损耗量的重要参数,但是仅有美国石油学会给出的诺模图,给利用计算机来计算储罐蒸发损耗带来了很大困难.为了利用计算机来计算储罐的蒸发损耗,运用Excel中的回归功能,对原始数据进行必要的转换,进行了真实蒸气压的多元非线性回归,回归出了油品真实蒸气压计算公式.结果显示,回归的方程具有很高的精度,利用回归方程编制了计算软件,为储罐蒸发损耗计算提供帮助.     

Influence of built-in obstacles on unconfined vapor cloud explosion

The obstacle structure in the vapor cloud has a significant influence on the gas explosion. Obstacles could not only lead to the acceleration of flame, but also they may occupy some space, thus affecting the amount of combustible gas. In this paper, a new two-step method was proposed to respectively study the effects of the obstacles amount and volume blockage ratio (VBR) on the gas explosion by using Computation Fluid Dynamic software AutoReaGas, and the obstacles in the vapor cloud were set to “Solid” instead of “Subgrid”. Based on the results and analysis, it is found that the peak overpressure and the maximum combustion rate rise with the increase of the number of obstacles for a single VBR, which indicated that the vapor cloud explosion of more obstacles was more dangerous for a single VBR. However, under a single number of obstacles, the peak overpressure and the maximum combustion rate increase firstly and then decrease as VBR increases and reach the highest at the VBR of 0.74, which indicated that the intensity of vapor cloud explosion reach a peak at a certain VBR in the middle instead of the largest. In addition, the existence and structure of obstacles have little effect on the size of explosion fireball when the size and concentration of combustible gas cloud are the same.     

高温热表面油液蒸发的时变性热质传递模型与实验研究

针对高温热表面油液蒸发热质传递过程的时变性,考虑这一过程中的对流传质传热,建立了热环境作用下油液蒸发的热质传递模型方程,通过无量纲变换,求得空间浓度分布和温度场随时间的变化规律。以庚烷为试验对象,对高温热表面油液蒸发过程进行了实验研究。理论分析与实验表明:庚烷蒸发过程中,刘易斯数大于1,传热速率大于传质速率;蒸发导致的质量损失与时间平方根的成正比,与液面的面积成正比,且与质量扩散系数的平方根成正比,饱和蒸气浓度越大,蒸发速率也越大。油液蒸发计算结果与试验结果基本一致,表明了模型的有效性。     

高倍泡沫加速泄漏LNG扩散的有效性模拟试验

泡沫灭火剂在扑灭液体火灾中起到重要作用,关于低温液体蒸气云扩散控制的研究也逐渐得到应用。通过小尺寸模拟试验验证高倍泡沫加速泄漏LNG扩散的有效性,设计并进行了低温液体自然蒸发和高倍泡沫覆盖低温液体两个对照试验,测量了竖直方向上10个高度处的温度及装置整体质量,从而获取了低温液体蒸气到达泡沫层顶端时温度及蒸发速率的变化情况。结果表明,与未添加泡沫的情况对比,高倍泡沫的覆盖使泄漏低温液体在1 800 s内的蒸发量减少了6.4%,如果时间更长则减少的比例更多,且蒸发出的低温液体穿过泡沫层后蒸气温度可达0℃左右,而未添加泡沫时同等高度处蒸气温度为-75℃左右。0℃时,LNG蒸气密度已明显小于空气密度,此温度下LNG蒸气会迅速向上扩散,而不至在地表积聚,由此证明高倍泡沫能够加速泄漏低温液体蒸气向上扩散,减小了低温液体蒸气在地面积聚并引发火灾爆炸事故的可能性,从而证实了高倍泡沫加速泄漏LNG扩散的有效性。     

多元可燃性混合气体爆炸中间产物发射光谱特性实验研究

从矿井火区实际出发,选用类似于煤矿开采现场产生的多元可燃性气体:CH4,C2H6 ,C2H4,CO,H2 ,利用瞬态光谱测量系统探究了爆炸引发阶段中间产物的光谱特征,分析了组分配比、组分浓度和甲烷浓度对压力特性和中间产物光谱的影响。研究结果表明:在多组分气体加入量较小（未形成体系贫氧状态）时,3种自由基发射光谱峰值出现时间随着甲烷浓度的增大先缩短后延长;在多组分气体加入量较大（形成体系贫氧状态）时,自由基发射光谱峰值出现时间随着甲烷浓度的增大不断延长;当其以任意比例混合后,微观反应过程中关键自由基的出现顺序为:OH自由基先于O自由基, O自由基先于H自由基出现。     

Underwater LNG release: Does a pool form on the water surface? What are the characteristics of the vapor released?

One of the scenarios of concern in assessing the safety issues related to transportation of LNG in a marine environment (ship or underwater pipeline) is the release of LNG underwater. This scenario has not been given the same level of scientific attention in the literature compared to surface releases and assessment of consequences therefrom. This paper addresses questions like, (1) does an LNG spill underwater form a pool on the water surface and subsequently evaporate like an LNG spill “on the surface” producing cold, heavier than air vapors?, and (2) what is the range of expected temperatures of the vapor, generated by LNG release due to heat transfer within the water column, when it emanates from the water surface?Very limited data from two field tests of LNG underwater release are reviewed. Also presented are the results from tests conducted in other related industries (metal casting, nuclear fission and fusion, chemical processing, and alternative fuel vehicles) where a hot (or cold) liquid is injected into a bulk cold (or hot) liquid at different depths.A mathematical model is described which calculates the temperature of vapor emanating at the water surface, and the liquid fraction of released LNG that surfaces, if any, to form a pool on the water surface. The model includes such variables as the LNG release rate, diameter of the jet at release, depth of release and water body temperature. Results obtained from the model for postulated release conditions are presented. Comparison of predicted results with available LNG underwater release test data is also provided.     

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.     

Minimum ignition energy of mixtures of combustible dusts

Most industrial powder processes handle mixtures of various flammable powders. Consequently, hazard evaluation leads to a reduction of the disaster damage that arises from dust explosions. Determining the minimum ignition energy (MIE) of flammable mixtures is critical for identifying possibility of accidental hazard in industry. The aim of this work is to measure the critical ignition energy of different kinds of pure dusts with various particle sizes as well as mixtures thereof.The results show that even the addition of a modest amount of a highly flammable powder to a less combustible powder has a significant impact on the MIE. The MIE varies considerably when the fraction of the highly flammable powder exceeds 20%. For dust mixtures consisting of combustible dusts, the relationship between the ignition energy of the mixture and the minimum ignition energy of the components follows the so-called harmonic model based upon the volume fraction of the pure dusts in the mixture. This correlation provides results which show satisfactory agreement with the experimental values.     

太阳辐射对纯液体蒸发行为影响的实验研究

通过蒸发实验,考察了太阳辐射对液体苯、甲苯和乙醇蒸发行为的影响.实验结果表明,苯和甲苯表面温度随时间呈现出先降低后升高的趋势,而乙醇则呈现出先降低后恒定的趋势,且环境风速越大,这种变化趋势就越明显.液体表面温度的变化不但与太阳辐射强度以及环境风速的大小有关,还与液体本身的物理性质(如热容、蒸发潜热和饱和蒸气压)有关.因此,在预测液体的蒸发速率时,必须考虑太阳辐射或周围热辐射源对液体表面温度的影响.     

Extinguishment of hydrogen laminar diffusion flames by water vapor in a cup burner apparatus

Transient computations with full hydrogen chemistry were performed to reveal the flame structure and extinguishment process of co-flow, hydrogen diffusion flame suppressed by water vapor. As the concentration of water vapor was increased, the flame detached away from the burner brim and formed an edge flame at the flame base. Water vapor showed larger chemical inhibition effect than nitrogen when extinguishing hydrogen flame, which was attributed to its enhanced third body effect in the reaction H + O₂ + M = HO₂ + M. The minimum extinguishing concentration (MEC) of water vapor and nitrogen was predicted by Senecal formula and perfectly stirred reactor (PSR) model respectively. The MECs predicted by PSR model agree with the MECs calculated by Fluent, which shows that 1) the flame extinction is controlled by the flame base, and 2) radiation absorption is negligible. The measured MECs are in a reasonable agreement with the values calculated by Fluent, which demonstrates the accuracy of the CFD model. A simple model was used to investigate the relative importance of extinguishing mechanisms of water vapor. The results show that in a co-flow configuration the thermal cooling and chemical inhibition effect are the main extinguishing mechanisms in suppressing hydrogen diffusion cup burner flame.     

Pool evaporation: Experimental tests at medium-scale with gasoline

Pool evaporation is a major source of flammable vapour clouds. Predicting the evaporation rate of a liquid hydrocarbon pool is therefore a key issue of dispersion modelling for safety concerns. This paper presents small- and medium-scale experiments of pool evaporation carried out with liquid hydrocarbons (pentane, heptane), hydrocarbon “gasoline-like” mixtures and gasoline. Liquid mass loss was measured and the evaporation rate deduced with its evolution in time. Other observations are highlighted, regarding the evolution of liquid temperatures, mixture compositions, and scale effects like the influence of pool length on surface evaporation rate. Comparisons with well-known correlations are then shown. The authors finally suggest a new semi-empirical correlation with a set of parameters fitted on the performed experiments.     

拱顶储罐气相层惰化过程数值模拟及工艺参数研究

针对油罐在检测、维修前须先将气相层可燃气体用氮气惰化到安全浓度，现场凭经验操作效率低且难以掌握氮气合理用量，容易造成氮气浪费或达不到安全浓度引发事故的问题，为确保惰化过程的安全经济，以常见拱顶储罐为例，首先利用改进后的公式法得出多组分可燃气体惰化效果评价指标；然后根据所得指标采用仿真对储罐气相层惰化过程进行数值模拟，并验证了仿真结果的正确性；最后采用仿真计算方法开展储罐气相层氮气惰化工艺参数的影响研究。研究结果表明:惰化效率与进口压力无关，只随进口流速变化，且大于1 m/s流速后，惰化效率已显著变化，此时可以增加进口管道数量，进一步提高惰化效率。理论研究结果可为现场实施提供参考和指导。     

水面LNG液池扩展模型的分析与对比研究

为了评价在开阔水面上的液化天然气（LNG）火灾和蒸气云爆炸灾害后果，分析了LNG水面扩展动态过程；对比分析了Fay模型、FERC模型和计算流体力学软件FLACS的计算结果，探讨了LNG液池面积随时间的动态变化过程，分析了泄漏量、泄漏速率等参数对LNG液池扩展半径的影响；根据液池扩展模型的计算结果，确定了LNG液池的最大面积，并以此分析了LNG流淌火灾的辐射危害。研究结果表明:对于相同的泄漏条件，3种方法模拟的泄漏LNG水面扩展动态过程相似，一般情况下，FLACS模型，FERC模型和Fay模型所计算的最大液池半径依次增大;由于FERC模型与FLACS软件的模拟结果接近且偏于保守，故此在一般的工程应用时，采用FERC模型即可方便快捷地获得较为准确的结果。     

某宾馆火灾烟气扩散及疏散模拟研究

利用计算机模拟技术,对宾馆火灾烟气扩散和人员疏散过程进行了计算模拟.首先基于客房的火灾可燃物分析,设定了火灾增长功率曲线.利用大涡火灾模型,计算了火灾发生后,起火房间、疏散通道及疏散出口内的影响人员疏散的温度、有毒气体浓度以及能见度发展趋势,给出火灾条件下可用安全疏散时间.通过精细网格人员疏散模拟,分析了人员所需安全疏散时间及安全疏散行为方式,研究表明人员可以安全疏散.该方法可作为宾馆火灾安全分析参考.     

Numerical analysis of phase behavior during rapid decompression of rich natural gases

The effect of the condensation process on the gas and liquid phase behavior during rapid decompression of rich natural gases is studied in the paper numerically. A one-dimensional mathematical model of transient thermal two-phase flow of compressible multi-component natural gas mixture and liquid phase in a shock tube is developed. The set of mass, momentum and enthalpy conservation equations are solved for the gas and liquid phases. The approach to model a liquid condensation process during rapid decompression of rich natural gas mixture is proposed. The mass transfer between the gas and the liquid is taken into account by introducing the appropriate terms into the governing equations. Thermo-physical properties of multi-component natural gas mixture are calculated by solving the Equation of State (EOS) in the form of the Soave–Redlich–Kwong (SRK-EOS) model. The proposed liquid condensation model is integrated into the GDP model. A simple case of GDP model, where the liquid was not considered, was extensively validated on base and dry natural gases. The proposed two-phase model is validated against the experiments where the decompression wave speed was measured in rich natural gases at low temperature. It shows a good agreement with the experimental data.