Modeling of a cryogenic liquid pool boiling by CFD simulation

A boiling model is developed by Computational Fluid Dynamics (CFD) code to calculate the source term of a cryogenic liquid spill. The model includes the effect of the changing ground temperature on the vaporization rate of the cryogenic liquid. Simulations are performed for liquid nitrogen. The model can describe different boiling regimes (film, transition and nucleate). The heat flux calculated for each boiling regimes are compared to the experimental data from literature. The developed numerical model seems to have a good ability to predict the heat flux for the film boiling stage. Model development is still necessary to improve the prediction of the nucleate boiling regime. Overall, the approach shows very promising results to model the complex physical phenomena involved in in the vaporization of cryogenic liquid pool spilled on ground.     

Small-scale experimental study of vaporization flux of liquid nitrogen released on ice

One of the LNG accident scenarios is the collision of an LNG carrier on an iceberg during marine transportation. A collision can result in damages to the vessel and lead to the leakage of the contents on ice or an ice-water mixture. When cryogenic liquid comes in contact with ice, it undergoes rapid vaporization due to the difference in temperature between the ice and cryogenic liquid. This process is different from the heat transfer between water and cryogenic liquid as ice is a solid and thus heat transfer to the pool occurs primarily through conduction. In this paper, the heat transfer phenomenon between ice and cryogenic liquid was studied through a small-scale experiment and the resulting vaporization mass fluxes were reported. The experiment involved six spills with varying amount of liquid nitrogen on different ice temperature to determine its effect on vaporization mass flux. The vaporization mass fluxes were determined by direct measurement of the mass loss during the experiment. The results indicated that the vaporization mass flux was a function of release rate and ice temperature. When the release rate and ice temperature was high, the vaporization mass flux follows a decreasing trend. With further reduction in release rate and ice temperature, the vaporization mass flux was found to be independent with time. The one dimensional conduction model was validated against experimental results. The predicted temperatures and heat flux were found to be in good agreement with the experimental data.     

Experimental study and prediction of liquid nitrogen pool evaporation process on concrete surface

The vaporization rate of pool boiling process of a liquid nitrogen spilled on concrete surface was investigated by a visual experiment platform. The boiling curve for liquid nitrogen on concrete cooling process was obtained. The shapes of bubbles in three typical boiling regimes were observed. Based on the experimental results, the coefficients of the empirical formulas for nuclear boiling and film boiling are modified, and the empirical formulas for boiling of liquid nitrogen-concrete surfaces are obtained. Combined with the calculation formula of the non-steady-state semi-infinite one-dimensional heat conduction temperature, a coupled calculation model for the heat transfer and vaporization process of liquid pool on the liquid nitrogen-concrete surface is proposed. Application of this model can better predict the quality of liquid nitrogen vaporization.     

Prediction of the self-ignition temperature in lagging fires by means of isothermal calorimetry

Under certain circumstances, contamination of a porous insulation material by a combustible liquid may result in a lagging/insulation fire. In the current study, a method based on isothermal calorimetry and modelling to estimate the risk of a lagging fire, or a maximum insulation thickness for a certain system temperature, is presented. The studied system was a combination of mineral wool and rapeseed oil. Full-scale tests were performed to determine suitable ignition criteria and to validate the results from the isothermal calorimetry tests and modelling. We contaminated the lagging using two methods – a direct method and a solvent method. These methods were evaluated in the full-scale tests. The solvent method resulted in more repeatable results than the direct method, where the contaminant was poured on the insulation. Using the calorimetric measurements, we estimated the parameters for the kinetic equation. This result was used to estimate the self-ignition temperature of contaminated lagging installed on a pipe. We found that a temperature increase of 40 °C was a reasonable ignition criterion when modelling.     

Study of high-tech process furnace using inherently safer design strategies (II). Deposited film thickness model

In the low-pressure chemical vapor deposition (LPCVD) process, there are many factors that could affect the thin film thickness and homogeneity in the thin film deposition process. Besides temperature, the volume flow rate of the reactant gas, the Mole fraction, and pressure are all affecting factors. On the basis of the forecast mode result of the thermal model of wafer temperature distribution in the previously published article, this study used the optimal method to calculate the conversion rate of the surface of each wafer under simulated conditions of various furnace temperatures and Mole fractions, as well as silane flow rates and pressures, and finally calculated the thin film growth rate and homogeneity of the surface of each wafer.This study validated four types of process conditions, and found that the results were very close to the experimental values in the previous studies, when conditions such as temperature, Mole fraction of silane, flow rate and pressure in the process were changed. This study thus concluded that the proposed process film thickness mode could meet the requirement of the process capacity. This study found that adjusting the heating zone temperature to regulate the film thickness growth rate was able to control uniformity of the film thickness. These feasible adjustment measures could be very effective on the industry commercial processes.Furthermore, the film thickness mode established in this study was used to discuss the application level of the inherently safer design strategies. This study mode could be used to adjust the temperature, mole fraction (mf), flow rate (F) and pressure (P) in the process for a single machine. Under the condition of meeting the film thickness process recipes required by the process, the silane flow rate was lowered through the adjustment of the control system. The study took the silane supply system as the basis of the case study. Based on a daily required silane consumption of 64.4 L, the daily required amount was 1.5 cylinders in the case of using 40 L high-pressure cylinders. The total daily required amount would be three 40 L high-pressure cylinders, including one more reserve amount on top of the daily required amount, which could match the inherently safer design philosophy and the principles of intensification, attenuation and limitation of effects.In terms of the factory evaluation, among all of the 12-inch furnace machines in Taiwanese wafer factories, nine out of 47 sets use silane, and the total daily consumption reaches 579.6 L. The total required amount, including the reserve, is 27 cylinders for 40 L high-pressure cylinders. As for the setting of the gas cabinet, the required amount could be reduced, since the gas supply pipeline could be designed in a multiple circuit. The minimum reactant gas input amount could be obtained in combination with the proposed film thickness mode, and the safety could be improved greatly, in accordance with the inherently safer design philosophy and the principles of intensification, attenuation and limitation of effects. In addition to the process capacity, this study also took the elevation of the inherently safer level into consideration, which could be provided to the industry for more comprehensive design consideration.     

液体石蜡乳化液的制备及对甲苯废气的吸收性能研究

以液体石蜡和水制备乳化液,以制备的乳化液吸收甲苯废气。考察了制备乳化液时油水质量比、乳化剂的质量分数、HLB值(亲水亲油平衡值)、乳化时间、乳化温度的选择及Tween 80、正辛醇、NaCl、Na2SO4对甲苯吸收效果的影响。结果表明,室温下油水质量比为7∶3,乳化剂质量分数为7%,HLB值为10,乳化时间为0.5 h时制备的乳化液稳定性最好。试验条件下乳化液对甲苯的初始吸收率可达96.53%,增加Tween 80的量和添加正辛醇能提高乳化液的吸收效果,添加NaCl和Na2SO4则降低乳化液对甲苯的吸收能力。     

Flicker Test as a Load Measurement During the Combined Effect of Heat and Noise

This study was a joint physiological and psychological experiment undertaken to determine changes in physiological and psychological human functions under the combined influence of heat, noise, and physical activity. Seven experimental situations were simulated in a climatic chamber with different configurations of three independent variables: heat (40 °C), noise (98 dB), and physical effort (30% of maximum volume of oxygen uptake—V0₂ max). Five psychological variables (critical flicker fusion—CFF, hand tremor, reaction time, subjective climate evaluation, and subjective evaluation of the given condition load) and two physiological variables (heart rate and rectal temperature) were monitored. Results indicate that CFF changed (increased) significantly when more than one experimental variable was applied. These changes coincided with significant changes in both subjective climate evaluation and subjective evaluation of a given condition load. There were no significant changes in psychomotor functions (hand tremor and reaction time). None of the observed physiological parameters were above the critical value. The results suggest that CFF can be treated as a psychophysical load indicator.     

磷矿浆催化氧化湿法脱硝研究

采用液相催化氧化NO_x的方法,通过磷矿浆中过渡金属离子的催化作用,达到净化电厂烟气中NO的目的。考察了烟气含氧量、吸收温度、磷矿浆固液比及气体流量对磷矿浆湿法脱硝的影响。结果表明,试验最佳条件为NO进口质量浓度670 mg/m~3、磷矿浆吸收温度25℃、固液比500 g/L、流量0.3 L/min、含氧量20%;优化条件下的磷矿浆脱除效率最高可达88.9%。随着磷矿浆湿法催化氧化脱硝反应的进行,p H值不断下降,导致磷矿浆逐渐失效,需补入新鲜矿浆,维持吸收液的p H值以保证良好脱硝率。     

喷雾碰壁液膜蒸发三维数值模拟

针对喷雾过程喷注碰壁形成的液膜蒸发现象进行研究,通过理论分析和实验为数据建立了相应的数值计算模型。在典型浴盆型燃烧室内,采用一个四孔喷嘴进行高压喷雾,给定初始涡流比和燃烧室壁四温度,对包含液膜蒸发的喷雾过程进行详细的三维数值模拟,获得了液滴轨迹图以及空气运动速度的空间分布和时间进程,为研究空气运动和壁温等参数对喷雾过程和液膜蒸发过程的影响以及它们之间的相互耦合作用打下了坚实的基础。     

Influence of inert materials on the self-ignition of flammable dusts

Flammable solid bulk materials, including dusts, often undergo spontaneous combustion and the spread of reaction fronts. By addition of inert substances, the ignition and combustion behavior can be influenced. In a series of experiments different types of coal were mixed with inert powders to study the effect of the composition on the self-ignition temperature and on the formal kinetic parameters.Hot storage tests as well as simultaneous-thermal analysis were used as experimental techniques with the latter being coupled to FTIR measurements to analyze the composition of gaseous reaction products.All conducted hot storage experiments led to the conclusion that the self-ignition temperature was increased by admixing inert material if the decomposition temperature of the inert matter was higher than the self-ignition temperature of the combustible component at the sample characteristic length. If (exothermic) decomposition of the inert material occurred before a noticeable growth of reaction rate of the combustible material, even a reduction in the self-ignition temperature could be observed. In addition, significantly higher maximum reaction temperatures were observed for the mixtures than for the combustible material alone.     

热改性活性炭吸附甲萘威的性能

在N2保护下采用不同高温对活性炭进行热改性,得到了4种改性活性炭(AC-1至AC-4)。采用气体吸附仪、Boehm滴定、傅里叶变换红外光谱仪(FTIR)对活性炭表面的物化性质进行了表征。通过等温吸附试验考察了改性前后活性炭对甲萘威的吸附性能,确定了最佳改性温度为600℃,探讨了活性炭的吸附能力与其表面物化性质之间的关系。结果表明:热改性使活性炭表面的物化性质发生了改变,活性炭对甲萘威的吸附量与其比表面积、孔容、表面酸性官能团和O元素含量具有显著相关性;活性炭对甲萘威的吸附行为符合准二级吸附动力学方程和Langmuir等温吸附方程,颗粒内扩散模型表明内扩散不是控制活性炭吸附速率的唯一阶段。     

报废梯黑铝装药提取制备硫酸铝工艺研究

为回收梯黑铝混合装药中的铝,通过单因素试验及五因素四水平正交试验对提取工艺进行优化。结果表明,五因素影响顺序为:酸液浓度>颗粒尺寸>反应温度>液固比>反应时间;提取最佳工艺条件为:酸液浓度0.8 mol/L,炸药颗粒尺寸40~50目,反应温度45℃,液固比13 mL/g,反应时间90 min;所得硫酸铝产品品质较优。     

Effect of CO2 corrosion behavior of mild steel in oilfield produced water

The corrosion rates of API X65 mild steel alloy in CO₂ – containing produced water have been studied by weight loss technique, potentiodynamic polarization technique and characterization of the corroded surface techniques. The effect of temperature, speed of rotation, pH and acetic acid concentration were studied. The optimum condition in presence and absence of protective film were also addressed. The kinetic parameters and reaction behavior were discussed in details. Corrosion rates increases with increasing temperature, acetic acid concentration, and speed of rotation, and decreased with increasing solution pH. The primary corrosion product of API X65 mild steel is ferrous carbonate (FeCO₃) at high temperatures, high pH's (alkaline media) and absence of acetic acid, which could act as a protective film so that CO₂ corrosion rate can be reduced.     

不同粒径易自燃煤常温氧化实验研究*

为探究易自燃煤在常温条件下的氧化特性,自行设计煤常温封闭氧化实验装置,采用实验研究与回归分析2种方法,分析易自燃煤发生氧化反应的气体变化过程,探究3种粒径煤样在20 ℃有限空间内的耗氧与产气特征。结果表明:易自燃煤样在16 d常温封闭氧化过程中,容器内O2体积浓度呈指数衰减、CO和CO2体积浓度呈指数增长的变化规律;在0.06~0.83 mm范围内,粒径越大,易自燃煤耗氧速率越大,CO和CO2产生速率则先增大后减小;介于中间的粒径为0.13~0.25 mm易自燃煤氧化反应最强烈,更容易发生氧化。研究结果对揭示生产环境温度下煤粒粒径对煤自燃的影响有一定的意义。     

三种液体稳定剂对过氧乙酸稳定效果的实验研究

利用绝热加速量热仪对三种过氧乙酸液体稳定剂的稳定效果进行了实验分析,并与常规实验方法获得的结论进行了比较。绝热条件下加入三种液体稳定剂后,初始分解温度分别提高了1.85℃、17.52℃和14.73℃,绝热温升分别升高了3.77℃、降低了12.56℃和17.88℃,到达最大温升速率的时间分别延长了508.93min、319.92min和247.92min,稳定效果为磷酸乙酸丁酯磷酸三丁酯,对过氧乙酸的安全生产、储存和使用具有一定指导意义。     

BLEVE: A new approach to the superheat limit temperature

Several methods proposed for calculating the value of the superheat limit temperature were analysed. The results obtained indicate that the procedures based on the thermodynamic stability approach introduce a significant uncertainty into the final values, depending on which equation of state is used. We propose a new approach based on the energy balance in the initial liquid mass just before the explosion. The temperature obtained using this method, T_sl−E, corresponds to the situation in which the energy transferred adiabatically between the cooling liquid and the vaporising liquid fractions is at its maximum. This leads to a minimum content of energy in the remaining liquid. Although these two approaches are equivalent—the procedures based on the thermodynamic stability approach use also the minimum energy state as a criterion—the new proposed method only uses the properties of the substance to obtain T_sl−E. Thus, T_sl−E represents the behaviour of each substance as a function of its molecular structure, while this influence is lost if a simple equation of state is used. Finally, some considerations are made on the limitations of the superheat limit temperature as a criterion for establishing whether an explosion is or is not a BLEVE.     

Comparing tools of varying complexity for calculating the gas dispersion

When handling flammable and/or toxic liquids or gases, the gas dispersion following a release of substance is a scenario to be considered in the risk assessment to determine the lower flammability distance (LFD) and toxicity thresholds. In this work a comparison of different gas dispersion tools of varying complexity ranging from a simple Gaussian model over a boundary layer model (BLM) and a Lagrangian model to CFD (in this case ANSYS CFX v14) is presented. The BLM covers the special case of liquid releases with formation of a pool. It does not only solve the gas dispersion but also calculates the evaporating mass flow out of the pool. The simulation values are compared to each other and to experimental data resulting mainly from our own open air experiments covering the near field and carried out on the Test Site Technical Safety of BAM (BAM-TTS) for different release types (pool evaporation, gas release) and topologies. Other validation data were taken from literature and cover large scale experiments in the range of several 100 m.     

Experimental research of the dynamic behavior of the natural gas suspension pipeline aerial crossing during pigging process

Suspension pipeline aerial crossings (SPAC) are mainly used to carry pipeline segments over large obstacles that are not suitable for trenchless technologies. It may suffer great vibrations and displacements during the pigging process due to the dynamic pigging loads and insufficient constraints from cables. Based on similarity criteria, an experimental scale model based on the Nujiang natural gas SPAC was designed and established. The vibration and displacement of the scale model were measured under different pigging velocities and liquid deposit volumes. The experimental results reveal that the natural gas SPAC vibrates during the pigging process, but the displacement versus time forms a U curve instead of a sinusoidal like curve. The extremum of the displacement is positively related to the pigging velocity and liquid deposit volume. In particular, the extremum increases by 0.37% with a 1% increase in the pigging velocity, while the displacement increases by 0.62% with a 1% increase in the liquid deposit volume. Under certain pigging conditions, or with damaged constraint components, the displacement extremum could be unacceptable. A low pigging velocity and a short time interval between two pigging operations are suggested to guarantee the safety of the natural gas SPACs. Besides, based on the experimental data, an empirical formula is developed to obtain the SPAC displacement-time curve with consideration of the span length, the pipeline diameter, the pigging velocity, the length and holdup of the liquid column. This formula can help to determine a suspicious displacement overrun, and to develop a data basis for choosing a safe pigging scheme of SPACs. This research provides insightful information to understand the mechanism of the SPAC's dynamic response as well as a practical tool to calculate the SPAC's displacement during the pigging process.     

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.     

Flammability envelopes for methanol,ethanol, acetonitrile and toluene

The flammability envelope was experimentally determined up to the point of vapor saturation for four flammable liquids: methanol, ethanol, acetonitrile, and toluene. The experimental apparatus consisted of a 20-L spherical chamber with a centrally located 10 J fuse wire igniter. The liquid was injected and vaporized into the chamber via a septum and a precision syringe. Nitrogen and oxygen were mixed from pure components using a precision pressure gauge. Pressure versus time data were measured for each ignition test. Flammability was defined as any ignition resulting in an increase in pressure of 7% over the initial pressure, as per ASTM E 918–83. All data were obtained at an initial temperature of 298 K and 1 atm. The experimental values of the LFL agreed well with published values. Limiting oxygen concentrations (LOC) were also determined—although these were somewhat lower than published values.The calculated adiabatic flame temperature (CAFT) method was used to model the data using a threshold temperature of 1200 K. A reasonable fit of the flammability envelope was obtained, although this could be improved with a higher threshold temperature.