混合流体汽液及液液界面张力分子模型

应用定标粒子理论表面张力方程以及 vd W- 1型混合规则 ,计算了混合流体的表面张力 ,对 64个二元体系 ,7个三元体系的表面张力计算平均相对偏差为 0 .80 %和 2 .43% ;应用 Boudh- Hir和 Mansoori提出的部分互溶体系的界面张力模型 ,给出了硬球直径的确定方法 ,对 37个部分互溶二元含水体系的界面张力进行了计算 ,绝对平均偏差为 1 .5m N/m,相对平均偏差为 8.9% ,计算精度满意。     

Interfacial tension of edible oils in supercritical carbon dioxide

Interfacial properties essentially influence fluid‐liquid separation processes. Thereby, interfacial tension is an important parameter that is associated with mass transfer and mutual solubility of participating compounds. For this reason, interfacial tension of a virgin olive oil with a known amount of free fatty acids was measured in supercritical carbon dioxide atmosphere at 313 K and 353 K and pressures up to 40 MPa. The obtained values were compared to different oils some of which contain appreciable amounts of volatile components. In general, interfacial tension behaviour is dominated by the effect of pressure, whereas differences between oil compositions are secondary. Besides mutual solubility interfacial tension is supposed to be associated with the compressibility of the dense fluid phase. For predicting mass transfer area some general comments on the colloidal behaviour of systems containing supercritical CO₂ are made     

旋转液滴法测界面张力的模型分析与应用

在进行旋转液滴法测界面张力的实验过程中,在液滴体积小或者界面张力值大的情况下,提高转速不能达到仪器测试的条件要求。对旋转液滴法测界面张力的模型进行分析,首先给出了旋转液滴椭圆形态计算界面张力的求解模型,对参数的敏感性进行了分析的同时刻画了椭圆边界的形态特征;其次根据建立的模型求解过程形成的数据库,建立了求解旋转液滴椭圆形态计算界面张力值的图版方法和迭代算法;再次列举出了一个新的求解方法,最后对以上各种计算方法进行了实例应用。研究认为各种方法下,推荐对液滴长度和直径都进行测量。     

Influence of phase orientation on dynamic interfacial tension measured by drop volume tensiometry

In processes involving two liquid phases, such as enhanced oil recovery, one phase is often present in a drop form (drop phase) while the other is in continuous form (bulk phase). In the present paper, the effect of such phase orientation on dynamic interfacial tension between the two phases formed by the partially miscible system composed of butanol-1 and water has been investigated by using the method of drop volume tensiometry. With butanol-rich (butanol-1 saturated by water) as the drop phase and water-rich (water saturated by butanol-1) as the bulk phase, the interfacial tension is 1.70 ± 0.02 mN/m. The interfacial tension for water-rich as the drop phase is almost identical at 1.72 ± 0.03 mN/m. Addition of a surfactant, sodium dodecyl sulfate, to the system has been studied. When the surfactant is added to the drop phase (either butanol-rich or water-rich), the magnitude of the decrease in interfacial tension is smaller than when surfactant is added to the bulk phase (water-rich or butanol-rich) or to both phases. Under otherwise identical conditions, when the water-rich acts as the drop phase, the apparent interfacial tension is higher than that when the butanol-rich acts as the drop phase.     

Interfacial tension of polycaprolactone/polystyrene blends by the imbedded fiber retraction method

Polycaprolactone (PCL) is a biodegradable polyester that is widely used in blends with synthetic and natural polymers for various applications. PCL is blended with biopolymers such as starch to improve its wet mechanical properties without impairing the biodegradability and other useful properties of starch. In spite of its importance, little is known about the interfacial tension of PCL blends. Indirect estimates of the room‐temperature interfacial tension of PCL blends using wettability methods have been reported. However, direct measurements of the interfacial tension of PCL blends have not been achieved until now, mainly because of the unsuitability of existing equilibrium methods for measuring the interfacial tension of high viscosity blends. We have measured the interfacial tension of PCL/PS blends using the imbedded fiber retraction (IFR) method. The IFR is a dynamic method that allows for the measurement of interfacial tension of high viscosity polymer blends in a relatively short period of time. The interfacial tension of PCL/PS blends was measured from 160 to 200°C. In this temperature range, the interfacial tension of PCL/PS blends is independent of temperature and has a value of 7.6 ± 1.8 dyn/cm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3145–3151, 2002; DOI 10.1002/app.10178     

COALESCENCE BETWEEN SMALL BUBBLES: EFFECTS OF SURFACE TENSION GRADIENT

1 INTRODUCTIONThe rate of coalescence between bubbles is important to the stability of foams,the mo-bility control in tertiary oil recovery,and a broad class of operations in which gas orvapor is the dispersed phase.Therefore,it is very important that the mechanism of thecoalescence process be understood,so that the effects of the physical properties oncoalescence can be assessed.     

CO2-环烷烃/芳香烃界面张力的测定与估算

CO₂驱油技术是利用CO₂采出被束缚在地层中的剩余油，提高采收率，同时实现CO₂掩埋。由于CO₂可降低原油的界面张力，CO₂-原油系统的界面张力数据是CO₂采油技术的重要基础数据。本研究采用悬滴法，选取原油系统中环烷烃和芳香烃典型代表，测定了40~120℃，0.27~14.70 MPa下，CO₂-环戊烷/环己烷/环辛烷/ 甲苯/乙苯/乙基环己烷六个二元体系的界面张力。分析了压力、温度、碳原子数及烷烃分子结构对界面张力的影响。结果表明，界面张力与压力呈线性关系；较低压力下，界面张力随温度的升高而降低，在较高压力下则呈现相反趋势；CO₂-形态结构相同组分的界面张力随着碳数的增加而增大；分子间作用力对界面张力存在一定的影响。通过分析多种因素的影响，总结现有的CO₂-原油(正构烷烃、环烷烃、芳香烃)实验数据，提出关联方程，将表面张力关联为温度、压力、碳原子数和偏心因子的函数，相关系数(R² )为0.958，均方根误差(RMSE)及平均相对偏差(AARD)分别为1.12和11.01%。     

离子液体表面活性剂的合成与应用(Ⅵ)——离子液体表面活性剂的界面张力

离子液体表面活性剂在油/水界面吸附,降低界面张力。随着疏水烷基链长的增加,降低表面张力的能力增大。吡啶基表面活性剂比咪唑基表面活性剂具有更高的疏水性和降低界面张力能力。在高浓度无机盐存在下,离子液体表面活性剂降低界面张力的能力提高,界面张力可达10~(-2)mN/m,优于传统表面活性剂。     

Performance Comparison Between Internal Olefin Sulfonates and Alpha Olefin Sulfonates

Comparison of surface and interfacial properties of internal olefin sulfonates (IOS) and alpha olefin sulfonates (AOS) shows that hydrocarbon chain branching has a significant influence on interfacial properties at the air–water, pentadecane–water and parafilm–water interfaces. The isomeric branched IOS shows a higher critical micelle concentration and are more effective in reducing the surface tension at the air–water interface by occupying a larger area per molecule. IOS exhibits better dynamic air–water interfacial properties due to a lower meso-equilibrium surface tension. The equilibrium interfacial tensions for AOS and IOS have no remarkable difference at the pentadecane–water interface. The water wettability and electrolyte tolerance are enhanced with branched hydrocarbon chain olefin sulfonates.     

结合吸附模型预测油水液滴的界面流变性质

界面活性分子在油水界面的吸附将改变其界面性质,如界面张力、界面流变性质,从而影响乳状液体系的稳定。通过吸附模型较为准确地描述活性分子在界面上的吸附行为,是定量描述油水界面性质的有效方法之一。以Span80为界面活性物质,模拟油、去离子水为实验介质,研究了低于及超过临界胶束浓度(实验中确定为0.45 mmol·L^-1)下界面张力及界面扩张模量的影响特性,表现为界面扩张模量随Span浓度的增加而先增大后减小的趋势。将描述纯扩散弛豫的Lucassen-van den Tempel模型,同Langmuir、Frumkin、reorientation和rigorous reorientation(严格重排)吸附模型相结合,用于预测含活性分子油水界面张力及扩张流变的性质;结果表明,结合严格重排吸附模型能够准确地预测油水界面张力,界面扩张模量、相角、弹性和黏性模量随浓度、频率的变化趋势。     

天然混合羧酸盐ASP复合驱油体系的研究

Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding systems on interfacial tension is discussed, in which a low-price natural mixed carboxylate (SDC) is used as the major surfactant. The results indicate that the optimal composition is SDC (0.5%), alkaline NaHCO3/Na2CO3 with mass ratio of 1 (1.0%), and hydrolyzed polyacrylamide(0.1%). In the coreflood experiment, their oil recovery is increased by about 25.2% and 26.8% original oil in place, respectively.     

DETERMINATION OF SOLID SURFACE TENSION FROM CONTACT ANGLES: THE ROLE OF SHAPE AND SIZE OF LIQUID MOLECULES

Accurate surface tension of Teflon® AF 1600 was determined using contact angles of liquids with bulky molecules. For one group of liquids, the contact angle data fall quite perfectly on a smooth curve corresponding to γ_sv = 13.61 mJ/m², with a mean deviation of only ±0.24 degrees from this curve. Results suggest that these liquids do not interact with the solid in a specific fashion. However, contact angles of a second group of liquids with fairly bulky molecules containing oxygen atoms, nitrogen atoms, or both deviate somewhat from this curve, up to approximately 3 degrees. Specific interactions between solid and liquid molecules and reorientation of liquid molecules in the close vicinity of the solid surface are the most likely causes of the deviations. It is speculated that such processes induce a change in the solid-liquid interfacial tension, causing the contact angle deviations mentioned above. Criteria are established for determination of accurate solid surface tensions.     

基团贡献法推算有机混合液体表面张力

本文在作者曾经提出的推算液体混合物表面张力计算方法的基础上,考查了不同纯组分摩尔表面积的计算公式对液体混合物表面张力推算精度的影响.通过对100个二元体系、10个三元体系和2个四元体系的推算,找到了合适的计算公式.二元体系、多元体系的推算偏差分别为2.45%和4.42%,对于非含一元醇-水体系,式(3)为好,其偏差为2.45%,对含一元醇-水体系式(6)有明显的改善,其推算偏差为6.98%.     

Drop rise velocities and fluid dynamic behavior in standard test systems for liquid/liquid extraction—experimental and numerical investigations

The fluid dynamic behavior of single organic droplets rising in a quiescent ambient liquid is investigated experimentally and numerically. Three standard test systems for liquid/liquid extraction recommended by the European Federation of Chemical Engineering (EFCE) but without the respective transfer component have been chosen for the investigations: toluene/water, n-butyl acetate/water, and n-butanol/water, representing systems with high, medium, and low interfacial tension. Simulations are performed using the academic code Navier, which features a sharp interface representation and a variational formulation of the curvature. The validity of both correlations and the results obtained by dynamic numerical simulation is discussed in terms of terminal rise velocity, aspect ratio, and the onset of shape oscillation. The numerical results show excellent agreement with experiments in all three test systems, and with simulations in the n-butanol/water system published recently by Bertakis et al. (2010). The presented numerical method is applicable for a wide range of interfacial tension, whereas the investigated correlations lose accuracy with decreasing interfacial tension.     

驱油阴/两性表面活性剂复配体系协同效应研究

针对某油藏A区块,利用阴离子/两性表面活性剂的协同作用,进而达到油水超低界面张力,且两性表面活性剂十二烷基甜菜碱在浓度为0.1%~0.5%的范围内,降低油水界面张力的效果达到10~(-2) mN/m数量级,在加入阴离子表面活性剂的条件下,复配体系可以使油水界面张力达到超低界面张力。通过探讨表面活性剂的总浓度以及复配比对油水界面张力的影响,最终得到阴离子/两性表面活性剂复配体系可在较高矿化度和较低的浓度(0.4%)范围内达到10~(-3) mN/m的超低界面张力,并在此基础上对两者的协同作用进行分析。     

Effects of oil phase viscosity on interfacial tension behaviour of oil/alkaline systems as measured by the spinning drop tensiometer

This note examines the effects of oil phase viscosity on the interfacial tension of reacting systems (acidic crude oils in contact with alkaline solutions) as measured by the Spinning Drop Tensiometer. Surfactants are produced by chemical reactions at the interface, thereby causing the shape of the oil droplet in the tensiometer to change continuously. The rates of droplet elongation/contraction are necessarily influenced by the oil phase viscosity, thereby affecting directly the measured interfacial tension. The principal conclusion of this work is that although oil phase viscosity exerts a significant effect on the dynamic interfacial tension after attainment of the minimum value, it makes for only a small absolute change in the magnitude of the minimum interfacial tension itself.     

Acid/Base Components in the Molecular Theory of Adhesion

A method has been devised to determine the acid/base parameters of reference liquids as absolute numbers, and not as values relative to a conventional set of parameters for water. Contact angle measurements are employed, using three liquids on three solids. The theory calls for the solution of nine simultaneous, nonlinear equations in nine variables-and unreasonably formidable task.

A preliminary set of solutions has been computed, for one set of polar liquids on five solids. These results must be rejected on grounds of physical reasonableness. They also fail the test of predicting liquid-liquid interfacial tension, which for miscible liquids must be negative or zero.     

Effect of composition on the linear viscoelastic behavior and morphology of PMMA/PS and PMMA/PP blends

Here, the effect of concentration on the morphology and dynamic behavior of polymethylmethacrylate/polystyrene (PMMA/PS), for PS with two different molecular weight, and polymethylmethacrylate/polypropylene (PMMA/PP) blends was studied. The blends concentrations ranged from 5% to 30% of the dispersed phase (PS or PP). The dynamic data were analyzed to study the possibility of inferring the interfacial tension between the components of the blend from their rheological behavior using Palierne [Palierne JF. Rheol Acta 1990;29:204-14] [1] and Bousmina [Bousmina M. Acta 1999;38:73-83] [2] emulsion models. The relaxation spectrum of the blends was also studied. The dynamic behavior of 85/15 PS/PMMA blend were studied as a function of temperature. It was possible to fit both Palierne and Bousmina's emulsion models to the dynamic data of PMMA/PS blends, to obtain the interfacial tension of the blend. This was not the case for PMMA/PP. The relaxation spectrum of both blends was used to obtain the interfacial tension between the components of the blends. The values of interfacial tension calculated were shown to decrease when the concentration of the blends increased. It was shown using morphological analysis that this phenomenon can be attributed to the coalescence of the dispersed phase during dynamic measurements that occurs for large dispersed phase concentration. When the ‘coalesced’ morphology is taken into account in the calculations the interfacial tension inferred from rheological measurement did not depend on the concentration of the blend used. The values of interfacial tension found analyzing the dynamic behavior of one of the PMMA/PS blend were shown to decrease with temperature.     

Acid/Base Components in the Molecular Theory of Adhesion

A method has been devised to determine the acid/base parameters of reference liquids as absolute numbers, and not as values relative to a conventional set of parameters for water. Contact angle measurements are employed, using three liquids on three solids. The theory calls for the solution of nine simultaneous, nonlinear equations in nine variables–and unreasonably formidable task.

A preliminary set of solutions has been computed, for one set of polar liquids on five solids. These results must be rejected on grounds of physical reasonableness. They also fail the test of predicting liquid-liquid interfacial tension, which for miscible liquids must be negative or zero.     

PREDICTION OF PRESSURE GRADIENT AND HOLDUP IN HORIZONTAL LIQUID–LIQUID SEGREGATED FLOW WITH SMALL EÖTVÖS NUMBER

This experiment utilized two-phase oil-water flows in a 26.1 mm diameter horizontal steel pipe to investigate segregated flow pattern. Data on pressure gradient and in situ phase distribution were obtained to come up with different combinations of phase superficial velocities, which ranged from 0.05 to 0.96 m/s. For the current liquid–liquid system having a small Eötvös number, we focused on identifying the effect of the interfacial tension and wall-wetting properties. Direct observation showed that oil and water started to mix when mixture velocity was increased. Also, at higher mixture velocities wherein the flows of two phases were initially separated, the droplets of one phase appeared in the mixed layer with negligible thickness. A closure relationship, which describes the interfacial mass transfer between liquid phases, was introduced into the framework of the two-fluid model. The model predictions agree well with the measured data. Similarly, an approach performance was evaluated based on the experimental data reported in previous literature.