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.     

Comparison of fuel properties and emission characteristics of two- and three-phase emulsions prepared by ultrasonically vibrating and mechanically homogenizing emulsification methods

Emulsions have long been considered as an alternative fuel for combustion equipment in order to achieve better fuel economy and pollution reduction. While a mechanical homogenizing method is frequently used to prepare emulsions, the use of an ultrasonic emulsification method to do so is still rather limited, and is mostly applied to two-phase emulsions only. Hence, two-phase W/O and three-phase O/W/O emulsions, prepared by a mechanical homogenizer and an ultrasonic vibrator, respectively, were prepared and used as engine fuel. The emulsion properties, engine performance, and engine emission characteristics between these two emulsification methods were measured and compared. The potential of the ultrasonic emulsification method was also evaluated. The experimental results show that the emulsions prepared by the ultrasonic vibrator appeared to have more favorable emulsification characteristics such as smaller dispersed water droplets that were distributed more uniformly in the continuous oil phase, lower separation rate of water droplets from the continuous phase of diesel fuel and thus a lower separating rate of the dispersed water droplets from the emulsion, larger emulsion stability, and larger emulsion viscosity than the emulsions produced using a mechanical homogenizer. In addition, a larger content of water was emulsified when the emulsion was prepared using the ultrasonic vibrator than the mechanical homogenizer. The emulsions prepared by the ultrasonic vibrator also had a lower fuel consumption rate, lower bsfc, and significantly lower CO emission while at the same time having a larger black smoke opacity. When comparing the two-phase W/O and the three-phase O/W/O emulsions prepared by either the ultrasonic vibrator or the mechanical homogenizer, the two-phase W/O emulsions appeared to have a lower fuel consumption rate, bsfc, CO, and a lower black smoke opacity than the three-phase O/W/O emulsions, regardless of whether they were prepared by ultrasonic vibrator or mechanical homogenizer.     

The fuel properties of three-phase emulsions as an alternative fuel for diesel engines

Diesel engines are employed as the major propulsion power for in-land and marine transportation vehicles primarily because of their rigid structure, low breakdown rate, high thermal efficiency and high fuel economy. It is expected that diesel engines will be widely used in the foreseeable future. However, the pollutants emitted from diesel engines (in particular nitrogen oxides and particulate matter) are detrimental to the health of living beings and ecological environment have been recognized as the major air pollution source in metropolitan areas and have thus attracted much research interest. Although diesel oil emulsion has been considered as a possible approach to reduce diesel engine pollutants, previous relevant applications were restricted to two-phase emulsions. Three-phase emulsions such as oil-in-water-in-oil briefly denoted as O/W/O emulsions and water-in-oil-in-water, denoted as W/O/W, have not been used as an alternative fuel for any combustion equipment. Studies on the properties of three-phase emulsion as fuel have not been found in the literatures. The emulsification properties of an O/W/O three-phase diesel fuel emulsion were investigated in this experimental study. The results show that the mean drop size of the O/W/O emulsion was reduced significantly with increasing homogenizing machine revolution speed. An increase in inner phase proportion of the O/W/O emulsion resulted in increasing the emulsion viscosity. The viscosity of O/W/O emulsion is greater than that for water-in-oil (denoted briefly as W/O emulsion) for the same water content. More stable emulsion turbidity appeared for three-phase O/W/O diesel emulsions added with emulsifier with HLB values ranging from 6 to 8. In addition, three-phase O/W/O emulsions with greater water content will form a larger number of liquid droplets, leading to a faster formation rate and greater emulsion turbidity at the beginning but a faster descending rate of emulsion turbidity afterwards. The potential for using O/W/O emulsions as an alternative fuel for diesel engines was also evaluated.     

Mechanical Entrainment in W/O/W Emulsion Liquid Membrane

Abstract

An experimental study of mechanical entrainment in W/O/W emulsions is conducted. W/O/W emulsions are stirred for various stirring times under the conditions that mechanical entrainment solely occurs, and changes in volume of the W/O emulsions and size distribution of the internal water droplets are measured. The rate of change in number of the water droplets entrained is found to be proportional to the volume fraction of W/O emulsions. Based on this result, a new model for mechanical entrainment is developed. The calculated change in W/O emulsion volume with time agrees with the observed ones except in the region near phase inversion. Then, phase inversion is discussed.     

Interfacial Crystallization of Diacylglycerols Rich in Medium‐ and Long‐Chain Fatty Acids in Water‐in‐Oil Emulsions

The effects of diacylglycerols rich in medium‐ and long‐chain fatty acids (MLCD) on the crystallization of hydrogenated palm oil (HPO) and formation of 10% water‐in‐oil (W/O) emulsion are studied, and compared with the common surfactants monostearoylglycerol (MSG) and polyglycerol polyricinoleate (PGPR). Polarized light microscopy reveals that emulsions made with MLCD form crystals around dispersed water droplets and promotes HPO crystallization at the oil‐water interface. Similar behavior is also observed in MSG‐stabilized emulsions, but is absent from emulsions made with PGPR. The large deformation yield value of the test W/O emulsion is increased four‐fold versus those stabilized via PGPR due to interfacial crystallization of HPO. However, there are no large differences in droplet size, solid fat content (SFC), thermal behavior or polymorphism to account for these substantial changes, implying that the spatial distribution of the HPO crystals within the crystal network is the driving factor responsible for the observed textural differences. MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals to enhance the rigidity of emulsion. This study provides new insights regarding the use of MLCD in W/O emulsions as template for interfacial crystallization and the possibility of tailoring their large deformation behavior. Practical Applications: MLCD is applied in preparing W/O emulsion. It is found that MLCD forms unique interfacial Pickering crystals around water droplets, which promote the surface‐inactive HPO nucleation at the oil‐water interface. Thus MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals, which can greatly enhance the rigidity of emulsion. This observation would provide a theoretical reference and practical basis for the application of the MLCD with appreciable nutritional properties in lipid‐rich products such as whipped cream, shortenings margarine, butter and ice cream, so as to substitute hydrogenated oil. MLCD‐stabilized emulsions can also be explored for the development of novel confectionery products, lipsticks, or controlled release matrices.     

Poly(methyl methacrylate) multihollow particles by water in oil in water emulsion polymerization

Multihollow‐structured poly(methyl methacrylate) (PMMA) particles were produced employing the water in oil in water (W/O/W) emulsion polymerization technique where sorbitan monooleate was used as a primary surfactant and sodium laurylsulfate and Glucopen, a polypeptide derivative, were used as secondary surfactants. Vinyl acetate was copolymerized to improve the wettability of the particles. The agitation speed and concentration of the urethane acrylate employed as a reactive viscosity enhancer played a crucial role in determining the morphology and average size of the PMMA multihollow particles. In high agitation speed the multihollow particles displayed a small size and narrow size distribution resulting from efficient droplet breakup. Especially when the urethane acrylate was incorporated, PMMA multihollow particles with a smooth and clear surface were achieved. This was believed to be because the urethane acrylate increased the viscosity of the monomer mixture and helped to form the stable W/O/W emulsion droplets that restricted droplet coalescence during polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 38–44, 2000     

The effect of shear and oil/water ratio on the required hydrophile-lipophile balance for emulsification

Required hydrophile-lipophile balance (HLB) values were examined in terms of the nature of kerosene-water, both oil-in-water (O/W) and water-in-oil (W/O), emulsions formed using Span 80/Tween 80 surfactant blends. Both the nature of the emulsification method and the oil/water ratio were critical in determining the resulting emulsion type. Both high- and low-shear conditions were investigated. Under high shear, low internal phase emulsions formed using the surfactant mixtures that corresponded to the required HLB values for emulsification involving kerosene (6 for W/O and 14 for O/W). However, at low shear, high internal phase (concentrated) emulsions resulted. Furthermore, depending on the oil/water ratio, some of the high internal phase emulsions were opposite to the type expected, given the HLB of the surfactant blend used. From these results, it appears that the emulsification technique (applied shear and oil/water ratio) used can be of greater importance in determining the final emulsion type than the HLB values of the surfactants themselves.     

Influence of Coagulant Salt Addition on the Treatment of Oil‐in‐Water Emulsions by Centrifugation,Ultrafiltration, and Vacuum Evaporation

Abstract

Droplet size is a key factor in the treatment of oil‐in‐water (O/W) emulsions, because of its influence on emulsion properties. The addition of a coagulant salt generally causes emulsion destabilization, increasing the droplet size, and enhancing coalescence between oil droplets, which helps its further treatment. The influence of CaCl₂ addition on droplet size distribution of a commercial O/W emulsion used in machining processes was studied in order to facilitate oil removal and to improve its further treatment by centrifugation, ultrafiltration (UF) and vacuum evaporation. The critical coagulation concentration (CCC) was observed at a CaCl₂ concentration of 0.05 M. The quality of the final aqueous effluent, expressed as its chemical oxygen demand (COD) value, was compared for all treatments. The highest COD values were obtained for centrifugation, while the COD of the UF permeate was approximately constant for all UF trials. The best effluent quality was obtained by vacuum evaporation. A combination of these techniques should be appropriate for most industrial treatments of O/W emulsions, depending on the subsequent use of the resulting aqueous effluent.     

Preparation of monodisperse water-in-oil-in-water emulsions using microfluidization and straight-through microchannel emulsification

Water-in-soybean oil-in-water (W/O/W) emulsions with an internal water phase content of 10–30% (vol/vol) were prepared by a two-step emulsification method using microfluidization and straight-through microchannel (MC) emulsification. A straight-through MC is a silicon array of micrometer-sized through-holes running through the plate. Microfluidization produced water-in-oil (W/O) emulsions with submicron water droplets of 0.15–0.26 μm in average diameter (d _av,w/o) and 42–53% in CV (CV_w/o) using tetraglycerin monolaurate condensed ricinoleic acid esters (TGCR) and polyglycerin polycondensed ricinoleic acid esters (PGPR) as surfactants dissolved in the oil phase. The d _av,w/o and viscosity of the W/O emulsions increased with an increase in internal water phase content. Straight-through MC emulsification was performed using the W/O emulsions as the to-be-dispersed phase and polyoxyethylene (20) sorbitan monooleate (Tween^® 80) as a surfactant dissolved in the external water phase. Monodisperse W/O/W emulsions with d _av,w/o/w of 39.0–41.0 μm and CV_w/o/w below 5% were successfully formed from a straight-through MC with an oblong section (42.8×13.3 μm), using the TGCR-containing systems. The d _av,w/o/w of the monodisperse W/O/W emulsions decreased as the internal water phase content increased because of the increase in viscosity of the to-be-dispersed phase. Little leakage of the internal water droplets and no droplet coalescence or droplet break-down were observed during straight-through MC emulsification.     

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.     

The effects of ethanol content and emulsifying agent concentration on the stability of vegetable oil-ethanol emulsions

In vegetable oil-ethanol emulsions ethanol is the polar phase and vegetable oil is the nonpolar phase. The primary advantage of vegetable oil-ethanol emulsions over conventional water-oil emulsions is that they enable the incorporation of water-and oil-insoluble or poorly soluble functional compounds and/or drugs into emulsions. A number of nonionic surfactants were used to select appropriate stabilizers for stable vegetable oil-ethanol emulsions. We found decaglycerol mono-oleate (MO750) to be the best stabilizer for ethanol-in-oil (E/O) emulsions. The effects of ethanol content and of emulsifying agent concentration on the stability of vegetable oil-ethanol emulsions were examined with MO750. After emulsification, two turbid layers formed simultaneously when ethanol content exceeded 20 wt%. The top layers (oil-in-ethanol emulsions; O/E emulsions) were very unstable, whereas the stability of the bottom layers (E/O emulsions) depended on the ethanol content. The stability of E/O emulsions is closely related to the effective concentration of MO750 aggregates, which play an important role in the film thickness stability of interfacial films formed by surfactant aggregates. Instability of E/O emulsion at 5 wt% MO750 is probably due to the polydispersity (i.e., nonuniform size and shape) of MO750 aggregates at high MO750 concentration. E/O emulsions prepared with 0.1, 0.5, and 1 wt% MO750 were stable, suggesting that the interfacial films formed were effective in protecting the droplets against coalescence and Ostwald ripening.     

Destabilization‐Enhanced Centrifugation of Metalworking Oil‐in‐Water Emulsions: Effect of Demulsifying Agents

The effect of a commercial flocculant (Alpacon® WS009) and two coagulant salts (CaCl₂ and AlCl₃) on the stability of metalworking oil‐in‐water (O/W) emulsions was examined. Two O/W emulsions were tested: a fresh emulsion, prepared in the laboratory from a commercial concentrate, and a waste metalworking emulsion, provided by a local waste management company, with initial oil concentrations of 32900 and 16900 mg/L, respectively. The emulsion stability was studied at different demulsifier concentrations, temperatures and pH through centrifugation tests, zeta potential and multiple light scattering measurements. Emulsion breakdown is explained by electrostatic repulsion of oil droplets and steric interactions. The former was observed for the laboratory emulsion, while the latter was observed for the waste emulsion. Aluminum chloride was the only effective agent for demulsifying both emulsions.     

Emulsification characteristics of three- and two-phase emulsions prepared by the ultrasonic emulsification method

Diesel engines exhausting gaseous emission and particulate matter have long been regarded as one of the major air pollution sources, particularly in metropolitan areas, and have been a source of serious public concern for a long time. The emulsification method is one of the potentially effective techniques to reduce emission pollution from diesel engines. Ultrasonic waves are a kind of sound waves with a frequency larger than 20 kHz, and they cannot be detected by the human ear. The phenomena of cavitation and hot spots produced by the rather violent action of ultrasonic waves can cause rapid chemical and physical reactions. This allows immiscible liquids to be well stirred with each other by means of ultrasonics. An ultrasonically vibrating machine that provides ultrasonic waves of a 40-kHz frequency was employed to prepare two- and three- phase emulsions in this experimental study. The fuel properties and the emulsion stability of the diesel emulsions were measured and analyzed. Experimental results show that the ultrasonic emulsification method successfully prepared two- and three-phase emulsions with tiny dispersed-phase droplets that are very evenly distributed in the outer oil or water phase. The ultrasonic processing time, quantity and HLB of the emulsifying agent were noted to have determinative influences on the formation of the emulsion and the fuel properties. A longer ultrasonic processing time caused less un-emulsified diesel fuel, smaller sizes and a more even distribution of dispersed-phase droplets in the outer oil phase and larger emulsion viscosity. However, a longer ultrasonic processing time also produced a larger temperature rise in the emulsion, leading to the deterioration of the emulsion stability. The O/W emulsion was found to have the lowest percentage of separation and thus the highest emulsion stability among the O/W/O, O/W and W/O emulsions. In addition, in comparison with the W/O emulsion, the O/W emulsion was shown to have a smaller size and a more even distribution of the dispersed-phase droplets. It also had a lesser rise in emulsion temperature when the ultrasonic processing time increased. The control of the ultrasonic processing time is important to successfully prepare the three-phase O/W/O emulsion. Too long a vibration time at the second-stage of emulsification is shown to cause the dispersed-phase pellets to contract and congregate with the inner-phase droplets. The three-phase emulsion structure then finally disappears and transforms into a two-phase emulsion. The addition of 2% by volume of the emulsifier mixture of Span80 and Tween80 with a HLB = 8, as suggested by this study for the preparation of stable two- and three-phase emulsions, were observed to have the lowest percentage of separation of the W/O and O/W/O emulsions. For preparing a stable O/W emulsion, the proportion of the emulsifier could be as low as 1.5% by volume. The percentage of separation of the O/W/O emulsion was lower and less influenced by the change in emulsion temperature than was the W/O emulsion with the same water content. However, the O/W/O emulsion was found to have a larger viscosity and a more significant variation of its viscosity, depending on the ultrasonic processing time, than the W/O emulsion.     

Analysis of droplet expulsion in stagnant single water-in-oil-in-water double emulsion globules

Double emulsions created by phase inversion can be used for fast liquid–liquid separation; therefore, the coalescence behaviors of these types of multiple emulsions need to be predictable for different physical properties and drop size ratios. The aim of this study is to determine the influence of the effective overall drop diameter and the internal droplet size on the coalescence time and the coalescence behavior. Experimental investigations on the physical stability of single stagnant water-in-oil-in-water (W₁/O/W₂) double emulsion globules are performed. For this investigation, a formation device to inject one water droplet into an oil drop inside a water bulk phase is developed. The coalescence process of the sole internal water droplet floating on the O/W₂ interface with the water bulk phase, often termed droplet expulsion or external coalescence, is recorded with a high speed camera. Based on image analysis, the diameters of the effective overall drop D, containing the oil and entrapped water volume, and the internal water droplet d are determined. Additionally, the coalescence time τ, including the time from the first contact of the internal droplet and the drop-bulk interface to the film rupture is measured. A large increase in coalescence time with increasing water droplet diameters is found. For the investigated paraffin oil–water system and initial drop sizes, partial coalescence occurs. In this case, the diameter ratio of daughter-to-mother droplet ψ is determined.     

Influence of Processing on the Physical Stability of Multiple Emulsions Containing a Green Solvent

The influence of the emulsification process on the microstructure and physical stability of model water‐in‐oil‐in‐water (W/O/W) emulsions formulated with a green solvent and a mixture of amphiphilic copolymers as emulsifiers was investigated. Emulsions were prepared by applying a homogenization step with a rotor‐stator device followed by high‐pressure homogenization. Viscous flow tests, transmitted light optical microscopy, globule size distribution (GSD), and multiple light scattering (MLS) measurements were carried out. The GSDs obtained were the result of a recoalescence due to overprocessing and the coalescence of inner droplets with the outer water phase. MLS detected a main destabilization mechanism by creaming. The passing of the emulsion through a high‐pressure homogenizer (HPH) significantly delayed the creaming process.     

A novel method for preparing oil-in-water-in-oil type multiple emulsions using organophilic montmorillonite clay mineral

A stable formula using oil-in-water-in-oil (O/W/O) type multiple emulsions was investigated. The components consisted of hydrophilic nonionic surfactant (HCO-60), organophilic montmorillonite, and lipophilic nonionic surfactant (DIS-14). O/W/O emulsions were prepared by a double-step procedure in which an O/W emulsion was prepared in the first step, and then the O/W emulsion was “re-emulsified” in an oil phase with organophilic montmorillonite. The diameter of the innermost oil droplets decreased with increasing HCO-60 content (0.1–3%), while the viscosity showed a maximum at 1% of HCO-60, indicating that the yiel of re-emulsification is highest at this condition. Viscosity of the O/W/O emulsion increased with increasing organophilic montmorillonite and DIS-14. According to the results of a phase ratio study, viscosity and stability of the O/W/O emulsion decreased at high weight fraction of inner oil phase (0.4–0.5), indicating that the excess amount of inner oil phase is absorbed by the outer oil phase. These results revealed that the weight fraction of inner oil phase should be kept below 0.3 for a stable O/W/O emulsion. A similar study on the weight fraction of O/W phase [фO/W)/O] suggested that the O/W/O emulsion is stable at ϕ(O/W)/O=0.65–0.70.     

Double emulsions of water-in-oil-in-water stabilized by α-form fat microcrystals. Part 1: Selection of emulsifiers and fat microcrystalline particles

Double emulsions are commonly stabilized by monomeric and/or polymeric emulsifiers. Pickering stabilization by solid particles such as colloidal microcrystalline cellulose has been mentioned only once as a possible technique to stabilize the external interface of the water-in-oil-in-water emulsion. No further work was carried out exploring this option. The present study shows that solid microcrystalline fat particles of α-form are capable of adsorbing at the water-oil interface and, together with other hydrophobic emulsifiers, can stabilize water-in-oil (W/O) emulsions. The crystals must be submicron in size in order to effectively adsorb and arrange at the interface. Large crystals do not fit and were found to flocculate as free crystals in the continuous oil phase. The α-form crystals can be obtained by flash-cooling saturated triglycerides in vegetable oils in the presence of emulsifiers, such as polyglycerol polyricinoleate (PGPR), that stabilize the dispersion and serve as α-tending crystal structure modifiers. It was assumed that PGPR also serves as a cross-linker or bridge between the crystalline fat particles and the water, and facilitates the anchoring of the fat particles in the oil phase in one direction while dangling itself in the water phase. The double emulsion droplets prepared with these W/O emulsions are relatively large in size (6–18 μm), but stable to coalescence. The marker (NaCl) does not seem to release with time, suggesting that the fat particles form microcapsules on the water interface, totally sealing the water from releasing its addenda. The systems seem to have a significant potential for food emulsions.     

Spherical‐particle generation by phase change materials: Near‐monosize particles from emulsions

The solidification behavior of water‐in‐oil (W/O) emulsion droplets in stagnant pure water was investigated. The droplets were formed from a single capillary tube when the emulsion was pumped by a syringe pump. Different experimental parameters, like surfactant concentration in the preparation of the emulsion, water content in the W/O emulsions, and flow rate, were investigated. The surfactant concentrations were varied from 0.2 to 5 % by volume at different flow rates. The water contents were increased from 5 to 25 % also by volume. The investigation focused on the formation of droplets from a capillary tip. The solidification phenomena of the emulsion drops in the coolant were observed. With higher flow rates, a change from dripping to jetting phenomena was observed. The solid emulsion particles of different sizes were obtained depending on the parameters of the operation. The solid particles were not completely spherical in shape but somewhat ellipsoid.     

玉米油W1/O/W2型多重乳状液稳定性的研究

高脂食品严重危害着人类健康,这引起人们对低脂食品的的不断追求,因此脂肪替代品的开发越来越受到人们重视。本试验以玉米油和生物高聚物为主要原料通过两步乳化法制备W1/O/W2多重乳状液作为脂肪替代品(FS),以离心稳定性为衡量标准,用显微镜直接观察,探讨了初复乳乳化工艺、各相相对体积比对玉米油W1/O/W2型多重乳状液体系稳定性的影响。结果表明:1.影响玉米油多重乳状液稳定性的主要因素有:复乳的乳化工艺,内水相与油相体积之比等。2.两步乳化工艺中第二步乳化工艺对复乳稳定性影响较大,其规律是随着乳化强度的提高,粒径减小,稳定性呈上升趋势,适宜的乳化条件为7200 r.min.1,13 min,而第一步乳化工艺对复乳稳定性几乎没有影响。3.内水相与油相、初乳与外水相均是影响复乳稳定性的主要因素,前者主要是依靠改变初乳黏度来影响复乳稳定性,后者主要是乳滴间范德华力与电排斥力共同作用的结果,适宜的体积比分别为1:4和1:1。     

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.