Water-in-triglyceride oil emulsions. Effect of fat crystals on stability

The influence of low concentrations (0.1-5%) of fat crystals on the stability of water-in-soybean oil emulsions was examined by light scattering and sedimentation experiments. Both the initial flocculation/coalescence rate and long-term stability against water separation were determined. The initial flocculation/coalescence rate increased upon addition of small amounts of fat crystals. When the crystal concentration was increased above a critical concentration (specific to a system), a decrease in the flocculation/coalescence rate occurred. The increased flocculation/coalescence rate is likely the effect of bridging of water droplets by fat crystals. Fat crystal wetting by water is an important criterion for this phenomenon to occur. Emulsion stabilization for crystal concentrations above critical is caused by a mechanical screening of water droplets. The presence of considerable amounts of crystals in oil also lowered the density difference between droplet and medium, and enhanced viscosity. The degree of increase in viscosity depended upon the emulsifier. Both a decrease in density difference and an increase in viscosity play a role in hindering flocculation/coalescence of droplets. In long-term studies of water separation, all concentrations of fat crystals stabilized the water-in-oil emulsions. The droplet size of these emulsions increased until the critical droplet size was approached where the screening effect of crystals on the droplets no longer stabilized the emulsions. The stabilizing effect for emulsions with monoolein was continuously improved by increasing the amount of crystals up to 5%. For lecithin-stabilized emulsions, an optimal effect was achieved for fact crystal concentrations of 1–2%.     

Vergleich des Koaleszenzverhaltens ruhender und umströmter Wasser‐in‐Öl‐in‐Wasser‐Einzeltropfen

Phase inversion of a water‐in‐oil emulsion to a water‐in‐oil‐in‐water double emulsion is practically used for liquid/liquid separation. For successful separation in the water leg the coalescence of the internal droplets with the surrounding continuous water phase is decisive. The determination of this coalescence phenomenon is applied for the process design. Therefore, single water‐in‐oil‐in‐water drops are investigated under static and dynamic conditions by means of high speed imaging. The influence of physical and geometrical parameters on the coalescence time and partial coalescence is determined.     

Influence of the plate-type continuous micro-separator dimensions on the efficiency of demulsification of oil-in-water emulsion

The objective of this article is to find the optimal dimensions of rectangular plate-type micro-separators in order to enhance the continuous separation of immiscible liquids. The main structure of the separators contains two plates: a hydrophobic (PTFE) upper plate and a hydrophilic (stainless steel) bottom plate which formed the contact surfaces for the fluids in the channel. The devices have two outlets, one for the aqueous phase and the other for the organic phase enabling the continuous separation and withdrawal of the separated phases. Demulsification has been carried out using Shellsol/water emulsion in the presence of a non-ionic surfactant (Tween 80). The separation efficiency is investigated as a function of micro-separator sizes, channel depths, flow rates and plate configurations. The major parameter that controls the destabilization mechanism is the ratio between the droplet size and the channel depth. When the size of the dispersed droplets remains smaller than the height of the separator (channel depths: 25–100 μm), creaming is the main demulsification mechanism. Creaming refers to the migration of the dispersed phase of an emulsion, under the influence of buoyancy. The particles float upwards and rise to the top due to the difference in the densities of the particles and the medium. The separation efficiency depends mainly on the residence time of the liquid/liquid mixture in the device regardless of the separator dimensions and channel heights. The separation rate is limited by the removal of the cream layer, formed at the top of the upper plate, from the separator. When the size of the dispersed droplets is larger than the depth of the separator (channel height of 9 μm), the separation performance and mechanism become different. The coalescence of the dispersed droplets occurs by passing through the device. The comparison of the data corresponding to creaming and coalescence phenomena emphasizes that the coalescence greatly enhance and accelerate the separation action. The phase separation in the micro-coalescer takes place considerably faster than in the micro-separators.     

Influence of Oil Properties on Bed Coalescence Efficiency

Abstract

Bed coalescence efficiency of oil separation from formation water was studied on model systems involving 10 real samples of crude oil and its fractions of different characteristics. Oil components were varied and all other parameters were kept constant, and high mineralization water served as the continuous phase. All experiments were realized on a commercial WO/O4 two-stage bed coalescer. Temperature, oil content, and fluid velocity were kept constant for all samples. Model emulsion was dispersed by constant stirring during the experiment to obtain primarily droplets of 20 μm diameter. Correlations for predicting the coalescence efficiency as a function of some physical and chemical oil properties are presented. The investigated oil components ensured a wide span of viscosity, density, and interfacial tension. The influences of mean molecular weight, neutralization number, as well as the contents of n-alkenes, NSO, and aromatics on coalescence efficiency were analyzed. On the basis of the empirical dependences of coalescence efficiency on individual parameters obtained by regression analysis of the data, a general mathematical model was established.     

Neue proteinstabilisierte O/W-Emulsionen

New Protein Stabilized O/W-Emulsions The formation and stabilization of o/w-emulsions were investigated with faba bean globulin isolate and the corresponding acetylated derivative as model substances in dependence on concentration at constant pH-value and on pH-value at constant concentration as well. A centrifugal equilibrium method was developed and the protein distribution in the phases after centrifugation was determined. Optimal conditions (concentration, pH-value and preparation of emulsion) lead to a coating of the oil droplets with protein being stable against coalescence. It is possible to separate those coating droplets in a form of stabile concentrate of emulsion. The acetylated derivative is a more efficient emulsifier and stabilizer than the unmodified faba bean globulin is. For oil droplet size distribution and comparable stability less protein is needed in the case of acetylated derivative. At the same time a stronger interaction between the aqueous phase of the emulsion and the coated oil droplets was found. This is reflected by the existence of a mechanical barrier against the separation of this aqueous phase. The results fo the coalescence stable concentrates of emulsion are the reason to search for a new principle producing o/w-emulsions.     

利用受限空间装置从低浓度水包油乳状液中分离油相的研究(英文)

A miniature process for separating the oil phase from dilute oil/water emulsion is developed.This process applies a confined space apparatus,which is a thin flow channel made of two parallel plastic plates.The space between the two plates is rather narrow to improve the collisions between oil droplets and the plate surface.Oil droplets have an affinity for the plate surface and thus are captured,and then coalesce onto the surface.The droplet size distribution of the residual emulsion resulted from the separation process is remarkably changed.The oil layer on the plate weakens the further separation of oil droplets from the emulsion.Three types of plate materials,polypropylene(PP),polytetrafluoroethylene(PTFE) and nylon 66,were used.It is found that PP is the best in terms of the oil separation efficiency and nylon 66 is the poorest.The interaction between droplets in the emulsion and plate surface is indicated by the spreading coefficient of oil droplet on the plate in aqueous environment,and the influences of formed oil layer and plate material on the separation efficiency are discussed.     

Modeling fluid behavior and droplet interactions during liquid-liquid separation in hydrocyclones

A mechanical separation process in a hydrocyclone is described in which disperse water droplets are separated from a continuous diesel fuel phase. This separation process is influenced by droplet-droplet interaction effects like droplet breakup and coalescence resulting in a change of droplet size distribution. A simulation model is developed coupling the numerical solution of the flow field in the hydrocyclone based on computational fluid dynamics with population balances. The droplet size distribution is discretized and each discrete droplet size fraction is assumed to be an individual phase within a multiphase-mixture model. The droplet breakup and coalescence rates are defined as mass transfer rates between the discrete phases by the aid of user-defined functions. All model equations are solved with the CFD software package FLUENT™. The investigations show the impact of the cyclone geometry on the coupled population and separation dynamics. Cyclone separators with an optimized geometry show less steep velocity gradients increasing the coalescence rates and improving the separation efficiency. The calculated droplet size distributions at the cyclone overflow and at the underflow show good accordance with experimental data. The basic modeling approach can be extended and adapted to other disperse multiphase flow systems.     

Experimental characterization of emulsion formation and coalescence by nuclear magnetic resonance restricted diffusion techniques

Nuclear magnetic resonance (NMR) is explored as a technique for noninvasively monitoring emulsion droplet formation and destabilization. The method makes use of the fact that the diffusion of oil molecules within oil-in-water emulsion droplets results in attenuation of a coherent magnetic signal that emanates from those molecules. If oil diffusion is limited by the size of the droplet, the shape of a plot of attenuation over time is directly affected by the droplet radius. We use this approach to determine noninvasively the effect of surfactant type, surfactant concentration, pH, and ionic strength on droplet sizes within a 40 wt% octane and water emulsion, stabilized by Tween 20 or β-lactoglobulin (β-Lg). We find that addition of the low-molecular-weight Tween 20 forms finer emulsion droplets than does addition of the protein, and that the Tween 20 emulsion is sensitive to surfactant concentration below a threshold “saturation” concentration. The droplet sizes in β-Lg-containing emulsions increase as pH increases above the isoelectric point and as ionic strength increases. The fact that the NMR technique does not mistake clusters of droplets for single large droplets makes the analysis of these effects unambiguous. We further extend the use of NMR diffusion techniques to monitor the effect of surfactant type, surfactant concentration, and convection on the rate of droplet coalescence. The ability of NMR methods to distinguish between large single droplets and droplet clusters makes it well-suited to monitor coalescence processes independently from flocculation.     

Effect of lipid type on water‐in‐oil‐emulsions stabilized by phosphatidylcholine‐depleted lecithin and polyglycerol polyricinoleate

Water‐in‐oil (W/O, 30:70) emulsions were prepared with phosphatidylcholine‐depleted lecithin [PC/(PI,PE) = 0.16] or polyglycerol polyricinoleate (PGPR) as emulsifying agents by means of pressure homogenization. The effect of lipid type (medium‐chain triacylglycerols, sunflower, olive, butter oil, or MCT‐oil/vegetable fat blends) was investigated in relation to particle size distribution, coalescence stability and the sedimentation of the water droplets. A significant correlation (p <0.05) was observed between the interfacial pressure caused by the addition of lecithin to the pure lipids and the specific surface area of the emulsion droplets (r_s = 0.700), and between the viscosity of the lipids used as the continuous phase (reflecting the fatty acid composition) and the specific surface area of the emulsion droplets (r_s = 0.8459) on the other hand. Blends of vegetable fat and MCT‐oil led to reduced coalescence stability due to the attachment of fat crystals to the emulsion droplets. Lecithin‐stabilized W/O emulsions showed significantly higher viscosities compared to those stabilized with PGPR. It was possible to adjust the rheological properties of lecithin‐stabilized emulsions by varying the lipid phase.     

疏水性油水分离膜及其过程研究进展

油水分离是治理含油废水和含水油液的重要工业过程。本文概括了疏水性油水分离膜的类型与制备方法,包括常规分离膜和高度疏水/超亲油分离膜。前者为常规微滤、超滤及纳滤过程用膜;后者由构筑高度疏水（水滴接触角≥120°）表面方法得到,形式有金属网膜、纤维膜、滤纸、复合膜及不对称膜,其为制备耐污染的疏水性油水分离膜提供了新思路。指出了疏水性膜用于油水分离的过程原理及应用现状：含油废水除油中,疏水性膜可实现O/W乳液的破乳、粗粒化油滴、滤除油滴及吸附油分子几方面的功能;含水油液除水中,膜被用来截留水滴,可直接得到净化的油品。最后,指出了其过程规模化应用前尚需解决的重要问题,特别是高度疏水/超亲油分离膜的制备、相关过程研究的深入及其规模化试验等方面需着力加强。     

Edible oil-in-water emulsions stabilized by hydrophile–lipophile balanced sucrose ester

Conventional emulsions are mostly stabilized by surfactants and for stabilization of oil-in-water emulsions the surfactants should be hydrophilic or with HLB numbers larger than seven. In this work, we report that edible oil-in-water emulsions can also be stabilized by surfactants with an HLB value close to seven. With edible sucrose ester C-1807 (HLB no. = 7) as emulsifier and three edible oils (canola oil, olive oil, soybean oil), edible oil-in-water emulsions can be stabilized by C-1807 at concentrations beyond its critical aggregation concentration (CAC). Although monomeric C-1807 behaves as an inferior emulsifier, they assemble to form multilamellar vesicles in water at concentrations higher than the CAC giving a viscoelastic/gel-like aqueous phase which is partly responsible for emulsion stabilization. Specifically, at 2 wt%, high internal phase emulsions (HIPEs) with ϕ_o = 0.75 can be obtained, which are stable against cooling–heating cycles between 5 and 30°C during storage. The vesicles disperse in the aqueous lamellae surrounding the oil droplets, which together with the viscoelastic/gel-like continuous phase prevents them from flocculation and coalescence.     

Functions of Demulsifiers in the Petroleum Industry

There are an increasing number of crude oil fields that are now producing both crude oil and water emulsions; such fields are both onshore and offshore. These emulsions are formed during oil exploitation due to the presence of natural surfactants, such as asphaltenes and resins. These molecules strongly stabilize the water/oil interface and prevent coalescence of water droplets. As water/oil phase separation is necessary before oil transportation and refining, demulsifiers are used to break water-in-oil emulsions. This review presents the crude oil emulsion formation, factors affecting demulsification of crude oil emulsion such as demulsifier chemical structure, water content, partition coefficient (K_P), and demulsifier concentration. This review also covers the kinetics and mechanism of the demulsification process.     

聚结技术及其乳化油水分离性能

聚结分离是一种利用油、水两相对材料浸润性的不同而实现乳化液滴聚结长大并最终通过重力沉降实现油水分离的物理方法,这种方法结构可控性好、分离效率高、运行成本低,是乳化油水分离领域的研究热点。本文首先对聚结分离方法进行详细阐述,介绍了聚结分离原理和影响因素;总结了近年来国内外学者对聚结材料表面改性和修饰等方面的研究。通过调控聚结材料的表面具有特殊浸润性,可显著提高油水分离效率;系统介绍聚结分离器的分类及其应用。最后阐述了聚结分离技术在石油化工领域的应用。本文对聚结分离技术进行展望,指出可以进一步研究实际液滴聚结过程和分离效果影响因素,应深入研究分离器在乳化油水分离过程中液滴聚结行为、机理、控制机制将是研究的重点。     

Influence of soybean protein isolates-phosphatidycholine interaction on the stability on oil-in-water emulsions

Soybean protein isolates and phospholipids present specific surface properties with synergistic or antagonistic effects on emulsion stability. Oil-in-water emulsions (25∶75 w/w) were prepared using native and denatured soybean isolates (NSI and DSI, respectively) with the addition of phosphatidylcholine (PC) (protein/PC ratio 100∶1 to 10∶1). The effect of ionic strength was also studied by adding sodium chloride (0–100 mM) to the aqueous phase. Analysis of NSI/PC and DSI/PC emulsions showed that the creaming rate diminished upon addition of PC, with the creamed phase showing more stability than those of the control systems. In DSI/PC systems, the coalescence process was partially controlled, as evidenced by a decrease in the size of oil droplets. Both systems were altered by the presence of sodium chloride, with an increase in the creaming rate attributable to flocculation and the coalescence of droplets. Under these conditions, DSI/PC emulsions exhibited a stronger protein-phospholipid interaction than those of NSI/PC.     

脱气除油旋流系统流场分布及分离特性

目前我国大部分油田已进入高含水阶段,且采出液中常带有大量伴生气,采用旋流分离法实现采出液高效分离对于简化陆上油田地面处理工艺及提升海上平台经济环保的采出液处理技术具有重要意义。脱气除油旋流系统由GLCC型气液分离器和油滴重构旋流器串联组成,设计的目的是在保证高效脱气的同时进一步改善对小油滴的去除效果,实现油气水三相高效分离。本文基于计算流体动力学（computational fluid dynamics,CFD）方法,利用种群平衡模型（population balance model,PBM）模拟油滴破碎与聚结,对脱气除油旋流系统内部流场特性及粒度分布进行模拟分析,并采用数值模拟与试验相结合的研究方法,对比分析不同含气体积分数和气相出口分流比对脱气除油旋流系统分离性能的影响规律。结果表明：含气体积分数与气相出口分流比对脱气除油旋流系统分离效率的交互作用较显著,在研究范围内综合脱气效率和除油效率可以得到,含气10%、20%、30%的最佳分流比分别为25%、30%、35%,数值模拟结果与试验结果吻合良好,验证了数值模拟方法的可靠性。另外,含气体积分数越大,油滴重构旋流器的油滴分层重构现象越明显,油滴重构旋流器可以在一定程度上改善含气情况下油水分离效果差的现象,脱气除油旋流系统对油气水三相分离的适用性较好。     

De-emulsification of 2-ethyl-1-hexanol/water emulsion using oil-wet narrow channel combined with low-speed rotation

Low-speed rotation of disc in an internal circulation of a novel de-emulsification with rotation-dise horizental contactor (RHC-D) realized de-emulsification for O/W emulsions due to repeated coalescence in oil-wet narrow channels at a low rotation speed. For three emulsions included ethanol/water/2-ethyl-1-hexanol, ethanol/water/2-ethyl-1-hexanol/SDS (Sodium Dodecyl Sulfonate) and 2-ethyl-1-hexanol/water/SDS emulsion, deemulsification ratios of oil phase could reach 1, 1 and 0.67 respectively at 170 r·min^-1, and de-emulsification ratios increased obviously after agitating 10 min. De-emulsification experiment in the seam indicated that oil droplet sizes in O/W emulsion became larger after de-emulsification. The main de-emulsification mechanism in RHCD was the coalescence of oil droplets in oil-wet narrow channels. With increase of the rotation speed, oil droplets dispersed better in the aqueous phase. However, de-emulsification effect enhanced due to the increase of the coalescence rate at a bit higher rotation speed. In addition, internal circulation made those O/W emulsions to be broken repeatedly, consequently de-emulsification ratio increased. Repeated de-emulsification through internal circulation might make continuous extraction of ethanol come true at a low rotation speed.     

Emulgieren mit mikrostrukturierten Systemen

Emulsification using Microstructured Systems In the last century, research on several methods for the production of emulsions has been carried out. In order to disperse one phase into another phase which is immiscible or poorly miscible in the first phase, several kinds of processes are available. An example for emulsions where small oil droplets are dispersed into a continuous water phase is mayonnaise. In margarine, water droplets are dispersed into a continuous oil phase. In this publication, three emulsification methods are presented. First of all membrane emulsification was developed by Nakashima in the early 1990ies. This process uses microporous membranes to disperse one phase into another one. The disperse phase is pressed through the pores and detached by the flow of the continuous phase. This results in the production of an emulsion with a narrow droplet size distribution at mild process conditions. Another process using membranes for the production of emulsions is premix membrane emulsification, developed by Suzuki in the late 1990ies. Droplets of a coarse emulsion are disrupted by passing the entire emulsion through the pores of a membrane. Compared to the aforementioned method, higher production rates are possible. Nakajimaapplied the so called microchannels in emulsification technology. Compared to other emulsification methods, these three processes provide several advantages.     

油水乳液分离沼气实验研究

研究了柴油-水乳液体系在水合物生成条件下对沼气（CO₂/CH₄）中CO₂的捕集能力。阻聚剂Span20被加入到乳液中以分散水滴和水合物颗粒。综合考虑了温度、原料气组成、压力和乳液含水率对柴油-水乳液体系分离能力的影响。从实验结果可以看出,吸收-水合耦合分离效果明显优于单独的吸收分离,且分离平衡后,浆液中水合物分散均匀,流动性良好。乳液体系分离能力在一定范围内随着温度降低和含水率的增加而增强。综合考虑乳液分离能力和流动特性表明,温度270.15～272.15 K,体系含水率 20%～25%（vol）和初始推动力为3.2 MPa左右时为最合适的分离条件,在对应条件下经过两级模拟分离,气相中CO₂浓度能从31%（mol）降到近10%（mol）,超过87%（mol）的CO₂被水合物浆液捕集。     

Efficient Encapsulation of a Water-Soluble Molecule into Lipid Vesicles Using W/O/W Multiple Emulsions via Solvent Evaporation

We developed a novel method for preparing lipid vesicles with high entrapment efficiency and controlled size using water‐in‐oil‐in‐water (W/O/W) multiple emulsions as vesicle templates. Preparation consists of three steps. First, a water‐in‐oil (W/O) emulsion containing to‐be‐entrapped hydrophilic molecules in the water phase and vesicle‐forming lipids in the oil phase was formulated by sonication. Second, this W/O emulsion was introduced into a microchannel emulsification device to prepare a W/O/W multiple emulsion. In this step, sodium caseinate was used as the external emulsifier. Finally, organic solvent in the oil phase was removed by simple evaporation under ambient conditions to afford lipid vesicles. The diameter of the prepared vesicles reflected the water droplet size of the primary W/O emulsions, indicating that vesicle size could be controlled by the primary W/O emulsification process. Furthermore, high entrapment yields for hydrophilic molecules (exceeding 80 % for calcein) were obtained. The resulting vesicles had a multilamellar vesicular structure, as confirmed by transmission electron microscopy.     

Dynamic behaviour of drops in oil/water/oil dispersions

The dynamic behaviour of drops of oil/water/oil (O/W/O) and water/oil (W/O) in abnormal polymer/water/surfactant systems was investigated. The size of internal oil droplets continuously decreased with time until it reached a steady-state value. Whereas the size of multiple water drops showed a minimum. After the minimum, the size of multiple water drops either reached a steady-state value or continued enlarging until phase inversion occurred. The phase inversion occurred because inclusion of oil droplets into water drops resulted in a continuous increase in effective volume fraction of dispersed phase. The time evolution of the size of multiple drops was described in terms of a balance between (a) drop break-up and escape and (b) drop coalescence and inclusion. The inclusion events retarded the initial decrease in the size of multiple water drops with time and increased the drop size after the minimum. By reducing the surfactant concentration, the ability of the dispersed phase to entrain the continuous phase decreased so that no minimum was achieved for the size of multiple drops with time, similar to conventional systems with simple drops. The size distribution of the multiple water drops initially narrowed and then widened again, whereas the size distribution of internal oil droplets continuously narrowed with time until it reached a constant value. Generally, the size distribution of drops narrowed as the average size of drops decreased. The possible mechanisms for complex drop formation were discussed and drop deformation was suggested as the main cause for inclusion at a low dispersed phase ratio.