水库

什么是界面张力?它如何影响原油生产?

界面张力阻止油水分子在表面混合,从而使油水分离。了解行业专家如何测量这种力来诊断流体行为。

反映夹带气体的气泡
资料来源:Getty Images。

所有液体的分子间都具有很强的分子间内聚力。因此,液体本体中的分子在各个方向上都会受到均等的相互作用。然而,两种不混溶液体界面处的分子对液体本体具有净吸引力,从而在界面上产生一种张力,称为界面张力 (IFT)。

由于界面张力 (IFT) 作用于两种不同的液体,导致两种液体分离。界面张力是指两种液体分子之间的内聚力大于与另一种液体分子之间的粘附力。由此产生的界面区域,从能量上来说,两种液体的分子都不太适合停留在此区域。

因此,相倾向于最小化其界面面积。因此,增加界面面积需要通过施加任何外力(例如剪切力)来做功或输入能量。界面张力越低,界面面积就越容易增加。对于油水体系,降低油水之间的界面张力可以使水滴更容易在油中乳化,反之亦然。

如何测量界面张力?

界面张力 (IFT) 的测量方法包括力测量法(例如 Wilhelmy 板、Du Noµy 环),即测量作用于垂直浸没的板或环上的力,使其脱离两种不混溶流体之间的界面;液滴形状分析法(例如悬垂液滴、固着液滴、生长液滴、脉动液滴);压力测量法(例如最大气泡压力和振荡射流)。近年来,微流体装置已被引入用于测量不同流动条件下的界面张力 (IFT)。

原油与水界面张力的典型值

原油与水之间的典型界面张力值范围为20至30 mN/m,取决于温度、压力、原油中界面活性物质的含量、盐度和pH值等物理化学因素。引入外部表面活性剂可以显著降低油水之间的界面张力值,有时甚至可以达到10 -3 mN/m范围内的超低值,就像在表面活性剂强化采油方案中所做的那样。

jpt_25_IFT_graphic3.png
图 1——在其他参数保持不变的情况下,原油中悬浮的水滴在流体动力应力的影响下变形/拉伸,并根据界面张力破碎成几个子液滴。
来源:根据TM Ho 等人(2002 年)修改。

低界面张力有助于原油中水滴的乳化。

控制液滴破碎的无量纲数是毛细管数或韦伯数,取决于粘性效应或惯性效应是否主导流动,或者流动是层流还是湍流。

  • Ca = μGR/γ;当粘性效应在流动中占主导地位时,粘性应力与界面应力的比率。
  • We=πU2R / γ;流动中的特征惯性应力与界面应力之比。

当韦伯数或毛细管数达到临界值时,乳化液中的液滴会破碎,因为作用于液滴上的流体动力应力(图1)克服了将液滴维系在一起的界面张力,从而导致液滴破碎。毛细管数或韦伯数与界面张力呈1/γ的关系,这表明降低水和油之间的界面张力有助于较大液滴更容易破碎,或增强一种液体与另一种液体的乳化作用。

在从油藏生产石油的过程中,生产的流体(水和原油)​​会受到足够的剪切,由于油和水之间的界面张力较低,因此很容易达到临界液滴破碎无量纲数,如果在运输过程中存在任何界面活性生产化学品,则会进一步有助于实现这一目标。

一旦水滴乳化,界面处原油聚集体中存在的界面活性物质会赋予其粘弹性,从而稳定原油乳剂中的水。这种稳定性(图2)会随着界面活性物质浓度的增加而增强(例如,沥青质含量较高的原油乳剂更稳定)。

总体而言,低界面张力有助于原油中水的乳化。

低界面张力有助于原油乳剂中水的破乳。

当液滴在各种力(流体力学、重力、布朗运动等)的作用下聚集在一起时,液膜会流失,导致液膜内压力增加。这种压力的增加与曲率半径的减小有关(对于球形液滴,曲率半径与液膜厚度的平方根成正比)。随着液膜变薄,当液膜压力接近拉普拉斯压力时,液膜会变形为凹坑状。拉普拉斯压力 (Ξ�P = 2γ/r),即弯曲界面上的压力差,会阻止液滴流失,试图维持液滴的曲率并阻止其聚结。

最终,薄膜变薄至临界点,此时非流体动力学(分离)力占主导地位。一旦形成稳定的薄膜,空穴成核理论就可以估算其破裂时间。

液滴间孔洞形成和扩展所需的活化能 (Ea) 取决于膜厚度、界面张力 (IFT)、界面刚度和分离压力 FT 和刚度可以使用 HLD-NAC 框架估算,具体取决于表面活性剂类型、介质化学和温度。

在相转变点附近,界面张力 (IFT) 可能较低,从而导致活化能较低。与理论一致,排水和聚结的活化能随界面张力 (IFT) 的增加而线性增加。

这是工业上用于缓解原油乳化的破乳剂的作用机理之一,即通过降低油相和水相之间的界面张力来发挥作用,从而使连续介质中的水滴更容易聚结(破乳剂也会改变界面机械性质)。 

从配方的角度来看,最小界面张力对应于亲水亲油差异(HLD)为0的平衡配方条件点。

HLD 量化了油相和水相界面物质化学势的差异,并考虑了油相和水相的化学特性、体系的盐度和温度。除界面张力 (IFT) 外,其他界面扩张流变性质在 HLD 为 0 时也会经历一个最小值。

jpt_25_IFT_graphic1.png
图2”当体系界面张力最小时,乳液的稳定性最小。
资料来源:JL Salager 等人 (2012)。

对原油生产的实际影响

原油以乳状液形式产出,地层水或注入水早在多孔介质中就已乳化于原油中。然而,当乳状液进一步受到剪切时,液滴粒径分布会进一步减小。因此,现场应避免在上游注入可能降低界面张力从而促进进一步乳化的界面活性物质,尤其是在体系HLD可能向乳状液最大稳定性转变的浓度下。

一旦原油乳状液中的采出水准备通过管道输送,就必须对现有界面张力下流场对水滴进一步乳化的敏感性研究。

最后,了解添加破乳剂如何影响油水分离器中油水界面张力至关重要。破乳剂会抵消原油中天然乳化剂的作用,而天然乳化剂可以稳定油中的水滴。

虽然整体机制涉及改变界面性质和液滴絮凝,但通过注入破乳剂实现的界面张力降低应接近破乳剂-油-水体系可实现的最小界面张力,即 ​​HLD 约为 0。考虑低界面张力时的另一个重要因素是在 HLD = 0 附近存在过度剪切,因为由于超低的界面张力值,油水混合物可以用最小的能量进行乳化。

因此,针对给定的油相和水相组合选择的破乳剂必须选择HLD接近于0的破乳剂,以确保允许液滴聚结的最低界面张力。

总之,界面张力是决定原油-水体系行为的重要参数,低界面张力有助于原油中水的乳化和破乳。

降低界面张力可降低水滴破碎所需的剪切力,这可能会增加乳状液的致密性,因此在原油从井口输送到分离装置的过程中应避免这种情况。然而,一旦产生的乳状液到达油水分离装置,降低界面张力就应成为有效油水分离的首要任务。

最后,注入破乳剂后乳液不应经历强烈的剪切,因为如果油-水-破乳剂配方偏离最佳配方条件,较低的界面张力值会严重稳定乳液。

进一步阅读

J. Drelich、C. Fang 和 C. White 合著的《流体-流体体系界面张力测量》 。 《表面与胶体科学百科全书》(2002 年)。

通过微流体装置表征乳液:界面张力和聚结稳定性综述, 作者:TM Ho、A Razzaghi、A Ramachandran 和 KS Mikkonen。《胶体与界面科学进展》(2021)。

原油包水乳化液的破乳。第9部分。使用旋转滴流变仪在最佳配方下测量的新型界面流变特性,作者:M. Forgiarini、D. Langevin、JS Salager 和 R. MarquezAna,《能源燃料》(2019 年)。

乳液稳定、破乳和转化取决于配方:流动保障方面的优势还是劣势, Jl Salager和AM Forgiarini著,《能源燃料》(2012年)。

原文链接/JPT
Reservoir

What Is Interfacial Tension, and How Does It Impact Crude Production?

Interfacial tension keeps oil and water separate by resisting the mixing of their molecules at the surface. Learn how industry experts measure this force to diagnose fluid behavior.

Bubbles reflecting entrained gas
Source: Getty Images.

All liquids have strong intermolecular cohesive forces between their molecules. As such, the molecules present in the bulk experience equal interaction from all directions. However, the molecules present at the interface of two immiscible liquids have a net attractive force towards the bulk of the liquid, resulting in a tension across the interface known as interfacial tension (IFT).

IFT results in the separation of two different liquids due to the cohesive forces between molecules of each liquid dominating the adhesive forces between the molecules from the other liquid. The interface thus created is a region where the molecules of either liquid are energetically less desirable to stay at.

Consequently, phases tend to minimize their interface area. As a result, increasing the interfacial area requires the work or energy input by applying any external force (e.g., shear). The lower the interfacial tension, the easier to increase the interfacial area. For oil and water systems, lowering the interfacial tension between oil and water makes it easier to emulsify the water droplet in oil and vice versa.

How is interfacial tension measured?

IFT is measured using the force measurement method (e.g., Wilhelmy plate, Du Noüy ring) where the force acting on a vertically immersed plate or ring is measured to detach it from the interface between two immiscible fluids or drop shape analysis method (e.g., pendant drop, sessile drop, growing drop, pulsating drop) or through pressure measurement (e.g., maximum bubble pressure and oscillating jet). Microfluidic devices have recently been introduced to measure IFT under different flow conditions.

Typical values of interfacial tension between crude oil and water

The typical interfacial tension values between crude oil and water range from the low 20s to high 30s mN/m and depend upon the physicochemical factors such as temperature, pressure, content of interfacially active species in the crude oil, salinity, and pH. Introducing an external surfactant can significantly lower the interfacial tension values between oil and water, sometimes to ultralow values in the 10-3 mN/m range, as done during surfactant-enhanced oil recovery programs.

jpt_25_IFT_graphic3.png
Fig 1—Water droplets suspended in crude oil deform/stretch under the influence of hydrodynamic stress and break into several daughter droplets depending upon the interfacial tension, given that other parameters remain fixed.
Source: Modified from T.M. Ho, et al. (2002).

Low interfacial tension aids the emulsification of water droplets in crude oil.

The dimensionless number that governs the droplet breakup is the Capillary number or Weber number, depending on whether viscous effects or inertial effects dominate the flow or if the flow is laminar or turbulent.

  • Ca = μGR/γ; the ratio of viscous stresses to interfacial stresses if viscous effects dominate the flow.
  • We = ρU2R/γ; the ratio of characteristic inertial stresses in the flow to the interfacial stresses.

At a critical value of the Weber or Capillary number, a droplet in an emulsion will break up as the hydrodynamic stresses (Fig. 1) acting on the droplet overcome the interfacial tension forces holding the drop together, leading to its breakup. The is Capillary or Weber number scales as 1/γ with interfacial tension, suggesting that lowering the interfacial tension between water and oil facilitates easier breakup of a larger droplet or enhanced emulsification of one liquid into another.

During the production of oil from the reservoir, the produced fluids (water and crude) experience enough shearing that the critical drop breakup dimensionless number is easily achieved given the low interfacial tension between oil and water, which is further aided if there are any interfacially active production chemicals present during the transport.

Once the water droplets are emulsified, the interfacially active species present in crude aggregate at the interface give it a viscoelastic character, stabilizing the water in crude oil emulsions. This stability (Fig. 2) increases as the interfacially species concentration increases (e.g., more stable emulsion for higher asphaltene crudes).

Overall, low interfacial tension helps emulsify water in crude oil.

Low interfacial tension aids the demulsification of water in crude oil emulsions.

When droplets are forced together by various forces (hydrodynamic, gravitational, Brownian, etc.), the intervening liquid film drains, increasing pressure within the film. This pressure increase is related to the decreasing radius of curvature (proportional to the square root of film thickness for spherical droplets). As the film thins, it can deform into a dimpled shape as the film pressure approaches the Laplace pressure. The Laplace pressure (ΔP = 2γ/r), the pressure difference across a curved interface, resists this drainage, attempting to maintain droplet curvature and hindering coalescence.

Eventually, the film thins to a critical point where non-hydrodynamic (disjoining) forces dominate. Once a stable film forms, hole nucleation theory can estimate its rupture time.

The activation energy (Ea) required for hole formation and expansion between droplets depends on film thickness, interfacial tension (IFT), interfacial rigidity, and disjoining pressures FT and rigidity can be estimated using the HLD-NAC framework, depending on surfactant type, medium chemistry, and temperature.

Near the phase inversion point, IFT can be low, leading to low activation energies. Consistent with theory, the activation energy for drainage and coalescence increases linearly with increasing IFT.

This is one of the action mechanisms of demulsifiers that are used in the industry for crude oil emulsion mitigation, i.e., they work by reducing the interfacial tension between the oil and water phases, which allows easier coalescence of water droplets in the continuous medium (demulsifiers also alter the interfacial mechanical properties). 

From a formulation point of view, the minimum interfacial tension corresponds to a point of balanced formulation condition corresponding to a hydrophilic-lipophilic difference (HLD) of 0.

HLD quantifies the difference in chemical potential of interfacial species between oil and water phases and considers the chemical character of the oil and water phases, the salinity of the system, and temperature. Apart from IFT, other interfacial dilational rheological properties also pass through a minimum at HLD of 0.

jpt_25_IFT_graphic1.png
Fig 2—Stability of emulsions is minimum at the minimum interfacial tension of the system.
Source: J.L. Salager, et al, (2012).

Practical implications for crude oil production

Crude oil is produced as an emulsion where the formation water or injected water emulsifies in the crude oil as early as within the porous media. However, the droplet size distribution is reduced further when the emulsion experiences further shearing. Therefore, injection of interfacially active species upstream that could potentially reduce the interfacial tension to facilitate further emulsification should be avoided in the field, especially at the concentration where the HLD of the system may shift to maximum stability of the emulsions.

Once the produced water in crude oil emulsions is ready for transportation through pipelines, it is crucial to do a sensitivity study on further emulsification of water droplets due to the flow field at the existing interfacial tensions.

Finally, it is critical to understand how adding demulsifiers affects the interfacial tension between oil and water in oil-water separation vessels. Demulsifiers counteract the effects of natural emulsifiers present in the crude that stabilize the water droplets in the oil.

While the overall mechanism involves modifying interfacial properties and flocculation of droplets, the IFT reduction by injecting the demulsifier should be near the minimum interfacial tension achievable for the demulsifier-oil-water system, i.e., around HLD approximately 0. Another important factor when considering the low interfacial tension is the presence of excessive shearing near HLD = 0, as the oil-water mixture can be emulsified with minimal energy due to the ultralow interfacial tension values.

Therefore, the demulsifier selected for a given oil and aqueous phase combination must be chosen such that the HLD of nearly 0 to ensure the lowest interfacial tensions that allow drop coalescence.

In conclusion, the interfacial tension is an important parameter that dictates the behavior of crude oil-water system where low interfacial tensions aids both emulsification as well as demulsification of water in crude oil.

Lowering the interfacial tension reduces the extent of shearing required for water droplet breakup which potentially increases the emulsion tightness and should be avoided during the transport of crude from wellhead to the separation plant. However, once the produced emulsion reaches the oil-water separation plant, lowering the interfacial tension should be a priority for effective oil-water separation.

Finally, the emulsion should not experience intense shearing after the injection of the demulsifier, as the lower interfacial tension values can stabilize the emulsions severely if the oil-water-demulsifier formulation is away from the optimum formulation condition.

For Further Reading

Measurement of interfacial Tension in Fluid-Fluid Systems by J. Drelich, C. Fang, and C. White. Encyclopedia of Surface and Colloid Science (2002).

Emulsion Characterization via Microfluidic Devices: A Review on Interfacial Tension and Stability To Coalescence by TM Ho, A Razzaghi, A Ramachandran, KS Mikkonen. Advances in Colloid and Interface Science (2021).

Breaking of Water-In-Crude Oil Emulsions. Part 9. New Interfacial Rheology Characteristics Measured Using a Spinning Drop Rheometer at Optimum Formulation by M. Forgiarini, D. Langevin, J.S. Salager, R. MarquezAna Energy Fuels (2019).

Emulsion Stabilization, Breaking, and Inversion Depends Upon Formulation: Advantage or Inconvenience in Flow Assurance by J.l. Salager, A.M. Forgiarini. Energy Fuels (2012).