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39250116 Crude Oil Emulsions a State of the Art Review

39250116 Crude Oil Emulsions a State of the Art Review

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SPE 77497 Crude Oil Emulsions: A State-Of-The-Art Review

Sunil Kokal*, SPE, Saudi Aramco

Copyright 2002, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in San Antonio, Texas, 29 September –2 October 2002. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian , SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

field emulsion treatment program is discussed, and more importantly, methods to prevent emulsion problems are highlighted. Recommendations are made for reducing and optimizing demulsifier dosage and controlling emulsion problems. Introduction Crude oil is seldom produced alone. It is generally commingled with water which creates a number of problems during oil production. Produced water occurs in two ways: some of the water may be produced as free water, i.e. water that will settle out fairly rapidly, and some of the water may be produced in the form of emulsions. Emulsions are difficult to treat and cause a number of operational problems such as tripping of separation equipment in gas-oil separating plants, production of off-spec crude oil, and creating high pressure drops in flow lines. Emulsions have to be treated to remove the dispersed water and associated inorganic salts in order to meet crude specification for transportation, storage and export and to reduce corrosion and catalyst poisoning in downstream processing facilities. Emulsions can be encountered in almost all phases of oil production and processing: inside the reservoirs, well bores and well heads, wet crude handling facilities, transportation through pipelines, crude storage and during petroleum processing. This paper provides a review of crude oil emulsions. However, the review is limited to the produced oilfield emulsions at the well head and at the wet crude handling facilities. It looks at the characteristics, occurrence, formation, stability, handling and breaking of produced oilfield emulsions. A crude oil emulsion is a dispersion of water droplets in oil. Produced oil-field emulsions can be classified into three broad groups: • Water-in-oil (W/O) • Oil-in-water (O/W) • Multiple or complex emulsions The water-in-oil emulsions consist of water droplets in a continuous oil phase and the oil-in-water emulsions consist of oil droplets in a water-continuous phase. In the oil industry water-in-oil emulsions are more common (most produced oilfield emulsions are of this kind) and therefore the oil-inwater emulsions are sometimes referred to as “reverse” emulsions. Multiple emulsions are more complex and consist of tiny droplets suspended in bigger droplets which are

Abstract Formation of emulsions during oil production is a costly problem, both in terms of chemicals used and due to production losses. This paper discusses production and operational problems related to crude oil emulsions, and present a review that will be very useful for practicing engineers. The first part of this paper presents why emulsions form during oil production, the types of emulsions encountered, and new methods for characterizing them. Crude oil emulsions are stabilized by rigid interfacial films that form a “skin” on water droplets and prevent the droplets from coalescing. The stability of these interfacial films, and hence the stability of the emulsions, depends on a number of factors including the heavy polar material in the crude oil (asphaltenes, resins, waxes, etc), solids (clays, scales, corrosion products, etc), temperature, drop size and drop size distribution, pH, oil and brine composition. These effects on emulsion stability are reviewed. The second part of this paper presents ways to tackle crude oil emulsions. The focus is on the destabilization of emulsions and the demulsification process. Emulsions are destabilized by increasing temperature and residence time, removal of solids, and controlling emulsifiers. The mechanisms involved in demulsification (flocculation, aggregation, sedimentation, creaming, and coalescence) are discussed in terms of the stability of the interfacial films. The methods involved in demulsification including thermal, mechanical, electrical, and chemical are also presented. Experience and economics determine which methods and to what degree each method is used for emulsion treatment. Finally, a section on field applications is n i cluded that should be useful for the practicing engineer who deals with emulsions, either regularly or on a limited basis. Herein the

injected inhibitors for corrosion. multiple emulsions (water-in-oil-in-water) were observed right up to very high water concentrations (> 95%). At certain volume fraction of the water phase (watercut). As a rule of thumb. the longer the residence time required (=> larger separating plant equipment sizes). Figure 1 shows the various types of emulsions. when the volume fraction of one phase is very small compared to the other.g. sand. the stability of the emulsion and should be taken into consideration in the selection of optimum treatment protocols. Produced oil-field emulsions are classified based on their degree of kinetic stability as follows 4 : • Loose emulsions: those that will separate in a matter of a few minutes. particle interactions. viscosity decreases with increasing shear rates. droplet size. scale. their viscosity decreases. organic acids and bases. bulk and interfacial viscosities. This generally leads to a lowering of the interfacial tension (IFT) and promotes dispersion and emulsification of the droplets. to a certain extent. mineral scales and drilling muds. Naturally occurring emulsifiers in the crude oil include the higher boiling fractions. Droplet size distributions of typical petroleum emulsions are shown in Figure 2. Produced oilfield emulsions generally have droplet diameters exceeding 0. Notice the very high viscosities achieved as the watercut increases up to 80% (compare with viscosities of oil ≈80 cP and water ≈1 cP). These particles. However. The separated water is sometimes referred to as free water. Up to a watercut of 80% the emulsion is a water-in-oil emulsion. conductivities etc. a water-in-oilin-water (W/O/W) emulsion consists of water droplets suspended in larger oil droplets which in turn are suspended in a continuous water phase. The viscosity data shown in Figure 3 indicates that the emulsion exhibit Newtonian behavior up to a water content of 30% (this is indicated by constant values of viscosity for all shear rates or a slope of zero). drilling fluids. the type of emulsion that is formed depends on a number of factors 1-2 . like asphaltenes and resins.) in emulsion breakdown. an emulsion is an unstable system. aggregation or flocculation. phase inversion. then the phase which has the smaller fraction is the dispersed phase and the other will form the continuous phase. now becomes the continuous phase. • Medium emulsions: will separate in a matter of tens of minutes. Emulsion kinetic stability is attained by stabilizing agents (or emulsifiers) which could be naturally occurring in the crude oil (for example. the smaller the average size of the dispersed water droplets. In this particular case. Given the oil and water phases. presence of solids. The viscosity of emulsions depends on a number of factors: • viscosities of oil and water • volume fraction of water dispersed • droplet size distribution • temperature • shear rate • amount of solids present The relative viscosity of an emulsion is shown in Figure 4 for several different types of emulsions. Emulsions are stabilized by emulsifiers (surface active agents or surfactants) that tend to concentrate at the oil-water interface where they form interfacial films. which was the dispersed phase. an interesting phenomenon takes place. Also the non-Newtonian behavior is pseudoplastic or shear-thinning behavior i. most emulsions are stable over a period of time i. at 80% the emulsion “inverts” to an oil-in -water emulsion and the water. waxes and asphaltenes control. At approximately 80% watercut.e. Droplet size distribution in an emulsion determines. Stability of Emulsions From a purely thermodynamics point of view. Their kinetic stability is a consequence of small droplet size and the presence of an interfacial film around water droplets.2 KOKAL SPE 77497 suspended in a continuous phase. nature of emulsifying agents. Some of these properties are described below while others are described elsewhere 4 . This is because emulsions show non-Newtonian behavior1 due to droplet “crowding” or structural viscosity. collect at the oil-water interface and are wetted by both the oil and water. Emulsions are considered special liquid-in-liquid colloidal dispersions. coalescence. The droplet size distribution in an emulsion depends on a number of factors including the IFT. These compounds are believed to be the main constituents of interfacial films which form around water droplets in an oilfield emulsion. When the volume phase ratio is close to 1 (both phases in the same order of magnitude). Viscosity of emulsions can be substantially higher than the viscosity of either the oil or the water. Fine solids can also act as mechanical stabilizers. corrosion products. Viscosity of Emulsions. At watercuts above 30% the slope of the curves deviate from zero indicating nonNewtonian behavior. and • Tight emulsions: will separate (sometimes only partially) in a matter of hours or even days. basic sediment and water.e. For example.1 µ m and may be larger than 50 µ m. and the wettability of the particles 3 . shear. asphaltenes and waxes. The effectiveness of these solids in stabilizing emulsions depends on a number of factors such as particle size. This is because there is a natural tendency for a liquid-liquid system to separate and reduce its interfacial area and hence its interfacial energy. As a general rule of thumb. then other factors will determine the type of emulsion formed. which have to be much smaller than emulsion droplets. and bulk properties of oil and water. Figure 3 shows the viscosities of a very tight emulsion at different watercuts. Oilfield emulsion are characterized by a number of properties including appearance. Drop Size and Drop Size Distribution. stimulation chemicals. asphaltenes) or added during production (for example stimulating chemicals). Other surfactants that may be present are from the chemicals that are injected into the formation or well bore e. etc. they possess kinetic stability1 . oilfield emulsions behave as shear-thinning or pseudoplastic fluids: as shear rate increases. Finely divided solids found in oil production include clay particles. . These stabilizers suppress the mechanisms involved (sedimentation.

4 .g. Lateral interactions between adsorbed molecules and the solution of the oil phase by hydrophobic groups also results in a considerable increase in the interfacial viscosity and the apparent viscosity of the oil in the film between the droplets. inter-particle interactions and the wettability of the solids3. The state of asphaltenes in the crude oil has an effect on its emulsion stability properties 4 . carboxylic acids) and bases. These compounds are the main constituents of the interfacial films surrounding the water droplets that give the emulsions their stability. lower temperatures in general enhance the emulsion forming tendencies of crude oils. But the addition of a nominal amount of asphaltenes (an amount insufficient by itself to produce emulsions) to oils containing wax can lead to the formation of stable emulsions. These films play a significant role in hampering the drop coalescence process. When such a film is formed it acts as a barrier to drop coalescence. They are inherently less stable. There is considerable evidence that these films are formed by polar fractions of the oil. Coalescence of water droplets is enhanced. The effect of waxes on emulsion stability is not clear from the literature. The primary mechanism involved in this retardation is the steric repulsion or hindrance caused by the high molecular weight materials in the film3. for example.5 -7 . the side chains can extend considerably into the oil phase. These films are believed to result from the adsorption of high molecular weight polar molecules that are interfacially active (surfactantlike behavior). Resins have a strong tendency to associate with asphaltenes and together they form a micelle. Highly viscous interfacial films retard the rate of oil film drainage during the coagulation of the water droplets by providing a mechanical barrier to coalescence. They are insoluble in acetone and dichloromethane at 30°C.12. and steric repulsion can maintain the interface at a distance sufficient to inhibit coalescence. These films also have viscoelastic properties. These films enhance the stability of emulsion by (a) reducing interfacial tension and (b) increasing the interfacial viscosity. Waxes are more apt to form a stable emulsion when they are present as fine solids in the emulsion. A good correlation exists between the occurrence of incompressible interfacial film and emulsion stability. produced oilfield emulsions are stabilized by films that form around the water droplets at the oil-water interface. Both of these effects oppose film drainage and inhibit coalescence11 .SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW 3 Interfacial films. Waxes by themselves. Solid particles stabilize emulsions by diffusing to the oil-water interface where they form rigid structures (films) that can sterically inhibit the coalescence of emulsion droplets. Surfactants that modify the rigidity of the film can considerably speed up the demulsification process. Factors Affecting Stability. The asphaltene-resin micelle plays a key role in stabilizing emulsions. It is now well recognized that the naturally occurring emulsifiers (or stabilizers) are concentrated in the higher boiling. These are formed. While asphaltenes will stabilize emulsions when they are present in a colloidal state (not yet flocculated). there is strong evidence that their emulsion stabilizing properties are significantly enhanced when they are precipitated from the crude oil and are present in the solid phase. For two drops to coalesce together. The effectiveness of these solids in stabilizing emulsions depends on factors such as the particle size. Figure 6 shows the steric repulsion produced by the interaction between the non-polar or hydrophobic groups of the surfactant molecules. polar fraction of the crude oil5-9 . The presence of the asphaltenes can naturally retard the drainage of this film. Similarly. paraffinic). resins and oil soluble organic acids (e. extent to which the adsorbed film is compressed. These include asphaltenes. Crudes that have a low cloud point generally have a higher tendency to form stable and tight emulsions than crudes with high cloud points.6 : Rigid or Solid Films: These are like an insoluble skin on water droplets and are characterized by very high interfacial viscosity. do not form stable emulsions in model oils 8 . The characteristics of interfacial films are a function of the crude oil type (asphaltic. Solids. Fine solid particles present in the crude oil are capable of effectively stabilizing emulsions. Mobile or Liquid Films: These films. The physical state of the wax in the crude oil also plays an important role in emulsion stabilization.8 . Furthermore. contact or aging time and concentration of polar molecules in the crude oil11. solid particles at the interface may be charged which may also enhance the stability of the . These films are classified into two categories based on their mobilities 5. Therefore. as the name implies. other emulsifiers and may be further stabilized by fine solids. They hang at the oil-water interface. soluble in oil and in the absence of asphaltenes. This can lead to a reduction in the rate of emulsion breakdown. The important factors that affect emulsion stability include5-8 : Heavy Polar Fraction in Crude Oil. Resins are complex high molecular weight compounds that are not soluble i n ethylacetate but are soluble in n-heptane. when a demulsifier is added to an emulsion. An asphaltene stabilized water droplet is shown in Figure 5. Asphaltenes have surface active properties 10 that make them good emulsifiers. Stability of emulsions has been correlated with the mobility of interfacial films 6 . This will be discussed further under demulsification of emulsions. waxes can interact synergistically with asphaltenes to stabilize emulsions. composition and pH of water. They provide a structural barrier to droplet coalescence and increase emulsion stability. The accumulation of asphaltenes at the interface results in the formation of the rigid film. temperature. It appears that asphaltene:resin ratio in the crude oil is responsible for the type of film formed (solid or mobile) and hence is directly linked to the stability of the emulsion6. As mentioned previously. are mobile and are characterized by low interfacial viscosities. napthenic. With surfactant molecules of the asphaltene type. Waxes are the high molecular weight paraffin substances present in the crude oil that crystallize out when the oil is cooled below its cloud point. the film has to be drained and ruptured.

For water separation. Addition of a demulsifier enhances demulsification after one hour and almost complete water separation is achieved after 24 hours over a wide range of pH. The stabilizing. The study suggests that for most crude oil-brine systems. When the solids are preferentially oil-wet (more of the solid in the oil phase). to between 6 -7 for the brine solution.e. Optimum pH (for water separation) changes from approximately 10 for distilled water. clays. Figure 8 shows the effect of a bicarbonate brine and distilled water on emulsion stability as a function of pH. As mentioned previously. The optimum pH for maximum emulsion stability depends on both the crude oil and brine composition. etc. However. It also influences the film compressibility by changes in the solubility of the crude oil surfactants in the bulk phase. Examples of oil-wet solids are asphaltenes and waxes. Based on experiments performed3 it was shown that the effectiveness of colloidal particles in stabilizing emulsions depends largely on the formation of “densely packed” layer of solid particles (film) at the oil-water interface. Particles must be much smaller than the size of the emulsion droplets to act as emulsion stabilizers. Brine composition also has an important effect (in relation to pH) on emulsion stability. Acid or low pH generally produces w/o emulsions (corresponding to oilwetting solid films) whereas basic or high pH produces o/w emulsion (corresponding to water-wetting mobile soap films). Oil-wet particles will preferentially partition into the oil phase and will prevent the coalescence of water droplets by steric hindrance. The pH of the water affects the rigidity of the interfacial films. they agglomerate at the interface and retard drop-drop coalescence. drops have to coalesce and the smaller the drops. Typical droplet size distributions for water-in-oil emulsions are shown in Figure 2. there exists an optimum pH range for which the interfacial film exhibits minimum emulsion stabilizing. It also reduces the interfacial viscosity and resulting in a faster film drainage rate and enhanced drop coalescence. Temperature influences the rate of build-up of interfacial films by changes in the adsorption rate and characteristics of the interface.8 . etc. When waxes are present (crude below its cloud point) and are the source of emulsion problems. Similarly. Slow degassing (removal of light ends from the crude oil) and aging leads to significant changes in the interfacial film behavior at high temperatures.5 . Frequently. water-wet solids will stabilize a water-continuous or an oil-in-water emulsion. This decrease is mainly due to a decrease in the oil viscosity. If the solid remains entirely in the oil or water phase. pH influences the type of emulsion formed. rigid emulsion film contains organic acids and bases. These particles will have to be relocated into either the oil or water for coalescence to take place. The ease of formation and stability of emulsions has been linked to asphaltene content of the crude oil and to the pH of the water phase3. emulsion droplet sizes range from less than a micron to over 50 microns. Optimum pH for demulsification is around 10 without demulsifier. Examples of water-wet solids are inorganic scales (CaCO3 . This film provides steric hindrance to the coalescence of water droplets. then a water-in-oil emulsion will result. The presence of solids at the interface also changes the rheological properties of the interface which exhibits viscoelastic behavior. Temperature affects the physical properties of oil. or maximum emulsion breaking properties. Effect of temperature on interfacial films was studied in some detail by Jones et al. . This is due to ionization effect (association/interaction of ions present in the brine with the asphaltenes). This affects the rate of film drainage between droplets and also affects the displacement of particles at the interface. In many cases it has been linked to formation damage as well. Droplet size distribution is normally represented by a histogram or by a distribution function of some sort. Temperature increases the thermal energy of the droplets and hence increases the frequency of drop collisions. Droplet Size. emulsions have a droplet size distribution rather than a fixed droplet size.). asphaltenes with ionizable groups. severe emulsion upsets occur in surface treating facilities following acid stimulation14-16 . The films generated by this process remain incompressible and non-relaxing (solid films) at high temperatures and emulsion resolution is not affected by heating. Emulsion viscosity will also be higher when the droplet size distribution is narrow i. It was shown that an increase in temperature led to a gradual destabilization of the crude oil/water interfacial films. water. Temperature can affect emulsion stability significantly. Generally emulsions that have smaller size droplets will be more stable. Generally. It must be present at the interface and must be wetted by both the oil and water phases for it to act as an emulsion stabilizer. Adding inorganic acid and bases strongly influences their ionization in the interfacial films and radically changes the physical properties of the films. it will not be an emulsion stabilizer. Perhaps the most important effect of temperature is on the viscosity of emulsions: it decreases with increasing temperatures. a kinetic barrier to drop coalescence still exists. application of heat can eliminate the emulsion problem completely by redissolving the waxes into the crude oil. Typically these solid particles are sub-micron to a few microns in size 1 and are suspended colloidally in the liquids. The latter seems to be more important. Figure 7 shows the effect of pH on emulsion stability for a Venezuelan crude6 . sand. These in turn affect the stability of the emulsion. interfacial films. the longer it will take to separate.4 KOKAL SPE 77497 emulsion. This process requires additional energy and hence provides a barrier to coalescence. Temperature. droplet size is fairly constant. and surfactant solubilities in the oil and water phases. The droplet size distribution affects emulsion viscosity: it is higher when droplets are smaller. When solids are wetted by both the oil and water (intermediate wettability). Waterwet particles can be made oil-wet by a coating of heavy organic polar compounds13 . The wettability of solid particles plays an important role in the emulsion stabilizing process 4 . CaSO4 . taken from Reference 6. even at higher temperatures. and solids. pH. pH of the water has a strong influence on emulsion stability5-7 .

As mentioned in the previous section.SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW 5 Following acid treatment. In refinery operations the primary concern is to remove inorganic salts from the crude oil before they cause corrosion or other detrimental effects in refinery equipment. or agglomeration or coagulation). During coalescence water droplets fuse or coalesce together to form a larger drop. Coalescence is the second step in the demulsification process and follows flocculation. Typically. Coalescence is enhanced by1. they may not coalesce. resins and other high molecular weight hydrocarbons. This is an irreversible process that leads to a decrease in the number of water droplets and eventually to complete demulsification. Coalescence. measurement of emulsion stability is one of the most important tests that can be performed on an emulsion. The separation index measures from zero (no separation) to 100 percent (full separation).4 . there is a standard ASTM method (ASTM 4007) available for determining the bottom sediments and water in an emulsion. being formed on contact of the crude oil with the acid. the oil shipped from a wet crude handling facility may not contain more than 0. Flocculation or Aggregation. This stability arises from the formation of interfacial films encapsulating the water droplets. viscosity of the oil. Further details are provided in the paper17 . mixing in the demulsifier. for a fixed length of time and a given demulsifier concentration. Produced oil generally has to meet company and pipeline specification. shaking to disperse the demulsifier and observing the phase separation as a function of time. The bottle test involves dilution of the emulsion with a solvent. It is a two step process. Coalescence at this stage only takes place if the interfacial film surrounding the water droplets is very weak. The first step is flocculation (or aggregation. From a process point of view. While a standard method is available for determining BS&W. To separate this emulsion into oil and water. It determines the ease with which the oil and water separates in an emulsion. During flocculation the droplets clump together forming aggregates or “floccs”. The total water separated in a regular bottle test at different demulsifier dosages is averaged to determine a separation index for the emulsion. the wells are very slow to clean up and often result in partial or complete plugging of the well. produced oil-field emulsions possess a degree of kinetic stability. emulsion can be rated on their stability by the amount of water separated in a given period of time. The first step in the demulsification process is the flocculation of water droplets. The separation index thus provides a measure of emulsion tightness (or stability): the lower the index.e. a method was proposed17 for measuring the stability of an emulsion quantitatively. no standard method is available in the literature for determining the stability of the emulsion using the bottle test. or sludges. Alternatively. the interfacial film has to be destroyed and the droplets made to coalesce. Demulsification Demulsification is the breaking of a crude oil emulsion into oil and water phases. The rate of flocculation depends on a number of factors including watercut. This low value of BS&W and salt content is required in order to reduce corrosion and deposition of salts. even touching at certain points. there is a link with the emulsion problem. The droplets are close to each other. These are among the tightest emulsions produced. There are numerous methods available for determining emulsion stability1. These precipitates are mainly asphaltenes. This plugging and formation damage generally occurs due to solid precipitates. The salts are removed by “washing” the crude oil with relatively fresh water. Therefore destabilizing or breaking emulsions is linked very intimately to the removal of this interfacial film. While there are different methods and procedures followed by various laboratories for the bottle test. The index must be quoted at the temperature of the test and the demulsifier used and is very useful for comparing the stability of emulsion from different sources (for example different wells or GOSPs). but may not lose their identity i. The tests are normally done at elevated temperature and may involve centrifugation for enhancing the separation. The factors that affect the interfacial film and consequently the stability of the emulsions were discussed earlier. The factors that enhance or speed up the emulsion breaking include: • Increasing temperature • Reducing agitation or shear • Increasing residence or retention time • Solids removal • Control of emulsifying agents Mechanisms Involved in Demulsification. By far the most common method is the simple bottle test. temperature. Demulsification is the separation of an emulsion into its component phases. the oil producer is interested in two aspects of demulsification (a) the rate or the speed at which this separation takes place and (b) the amount of water left in the crude oil after separation. They proposed the concept of an emulsion separation index to measure the tightness of an emulsion. the higher the tightness or stability. The bottle test is regularly used as a screening test for potential demulsifiers.2% basic sediment and water (BS&W) and 10 PTB (pounds of salt per thousand barrels of crude oil). While the sludges formed during an acid treatment are extremely difficult to treat (due to the high concentration of precipitated asphaltenes). Recently. and the density difference between the oil and water. The stability of the emulsion is generally related to the ease of water separation with time and demulsifier dosage. Either of these steps can be the ratedetermining step in the emulsion breaking process. Proper design of the acid treatment is necessary to avoid well productivity decline and emulsion upsets due to acidization15 . The second step is coalescence. at a given demulsifier concentration. Measurement of Stability. Destabilizing Emulsions. For example. These materials are apparently precipitated from the crude oil by the reduction in pH as a result of acid contact16 . different demulsifiers can be graded in terms of their demulsification qualities. A fast rate of separation and a low value of the residual water in the crude oil are obviously what the oil producer wants.8 a . From a practical point of view.

reduced problems with scale and corrosion formation and reduced light-ends loss. Electrical Methods. Heating the emulsion enhances its breaking or separation. High voltage electricity (electric grids) is often an effective means of breaking emulsions. The selection process for chemicals is still viewed as an art rather than a science. There are hundreds of commercial demulsifier .6 KOKAL SPE 77497 high rate of flocculation. separation equipment. Electrostatic dehydration is rarely used alone as a method of breaking emulsions. they migrate to the oil-water interface and rupture or weaken the rigid film and enhance coalescence of water droplets. The electrical system consists of a transformer and electrodes that provide high voltage alternating-current. xylene. Second. and high temperatures. Optimum emulsion breaking with a demulsifier requires: • A properly selected chemical for the given emulsion • Adequate quantity of this chemical • Adequate mixing of the chemical in the emulsion. Lower temperatures result in fuel economy. • Applying electrical fields that promote coalescence. It reduces the viscosity of the oil and increases the water settling rates. These vessels separate the free water and break emulsions. Mechanical Methods. However. The distance between the electrodes. Application of heat for emulsion breaking should be based on an overall economic analysis of the treatment facility. heat accelerates the emulsion breaking process. Due to the wide variety of crude oils. In the oil industry crude oil emulsions must be separated almost completely before the oil can be transported and processed further. Chemical Methods. settling tanks. • Sufficient retention time in emulsion treaters to settle water droplets • Addition of heat. These include free water knock out drums. short-chain alcohols. Emulsion separation into oil and water necessarily involves the destabilization of emulsifying films around water droplets. Cost effectiveness of adding heat should be balanced against longer treatment time (larger separator). thus enhancing destabilization. These tests include bottle tests. In other words. demulsification methods are very application specific. Testing procedures are available to select appropriate chemicals 4.17. Furthermore. high watercuts. loss of light ends and a resultant oil-product price. the use of electrostatic dehydration will result in a reduction of heat addition. brines (and hence emulsions). This process is accomplished by any or combination of the following methods1. It is generally theorized that water droplets have a charge associated and when an electric field is applied. In some cases the chemicals (demulsifiers) act as a wetting agent and alter the wettability of the stabilizing particles which leads to a breakup of the emulsion film. The most common methods of emulsion treatment have been the application of heat and an appropriate chemical demulsifier to pro mote destabilization followed by a settling time to allow gravitational separation to occur. water (and gas). toluene. By far the most common method of emulsion treatment is by adding chemicals called demulsifiers. Demulsifiers are chemicals that contain solvents (benzene. This displacement also brings about a change in properties like interfacial viscosity or elasticity of the protecting film. Demulsification Methods. in some designs. • Increasing the temperature of the emulsion. increasing the temperature leads to an increased tendency towards scale deposition and an increased potential for corrosion in treating vessels. it costs money to heat the emulsion stream. chemical costs and the costs of installation of electrostatic grids or retrofitting. etc to facilitate or completely resolve the emulsions. Increasing the temperature has some negative effects. with an ever increasing understanding of the emulsion breaking process. Electrostatic grids can also lead to a reduction in the use of emulsion breaking chemicals. the coalescence frequency between water droplets is increased due to the higher thermal energy of the droplets. very rarely does it resolve the emulsion problem alone. Selection of the right demulsifier is very crucial in the emulsion breaking process. high interfacial tensions. coalescers. This is generally accomplished in large volume separators and desalters. it can result in the loss of light ends from the crude oil reducing its API gravity and the treated oil volume. chemical demulsifiers and product specifications. The electric field also disturbs the interfacial rigid film by rearranging the polar molecules thereby weakening the tight film and enhancing coalescence. flocculants and wetting agents. the availability of new and improved chemicals. emulsions and conditions change over time and add to the complexity of the treatment process. new technology and R&D efforts. absence of mechanically strong films. Finally. There is a wide variety of mechanical equipment available in the breaking of oil-field produced emulsions. Demulsifiers are surface active compounds and when added to the emulsion. • Adding chemical demulsifiers. desalters. The demulsifiers act by total or partial displacement of the indigenous stabilizing interfacial film components (polar materials) around the emulsion droplets. is adjustable so that the voltage can be varied to meet the requirement of the emulsion being treated. the droplets move about rapidly and collide with each other and coalesce. two and three phase separators (low and high pressure traps). First. low oil and interfacial viscosities. Selection of Chemicals. Furthermore. The electrodes are placed in such a way to provide an electric field that is perpendicular to the direction of flow. surfactants. Invariably.4 : • Reducing the flow velocity that allows gravitational separation of oil. It is generally used in conjunction with chemical and heat addition. However. A detailed description is provided in Reference 4. selection of the right chemical is becoming easier and more organized and many of the failures have been eliminated. • Changing the physical characteristics of the emulsion. These chemicals are designed to neutralize the effect of emulsifying agents that stabilize emulsions. Increased temperatures also result in the destabilization of the rigid films due to reduced interfacial viscosity. heavy aromatic naptha). All test procedures have limitations. Thermal Methods. dynamic simulators and actual plant tests. electric grids.

for example. ethoxylated resins. Add to this the changing conditions at the separation facilities. Other factors include internal packing vs. laboratory testing is excellent for screening different emulsion samples for relative tightness. During tertiary oil recovery (especially during surfactant or micellar flooding). salt content and temperature. the demulsifier rates quoted vary from less than 10 ppm to more than 100 ppm (based on total production rates). On the other hand. For example. influences the coalescence of water droplets through enhanced film drainage. Demulsification using chemicals is a very complex phenomenon. The best demulsifiers are those that readily displace preformed rigid films and leave a mobile film (films that exhibit little resistance to coalescence) in its place. a high dosage of demulsifier (an overtreat condition) may be detrimental to the treatment process.SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW 7 products available that may be tested. The amount or dosage of demulsifier required is very site specific and depends on a number of factors. Demulsifier displace the natural stabilizers (emulsifier) present in the interfacial film around the water droplets. costs. ethoxylated nonylphenols. In general. Demulsifiers are typically formulated1 with polymeric chains of ethylene oxides and polypropylene oxides of alcohol. Based on an evaluation of the literature. ethoxylated alcohols and amines. solidswetting characteristics and of course. molecular weight and structure of the ethylene or propylene oxides can be changed giving a complete range of solubilities. it is difficult to prescribe “standard” or typical dosage rates for treating emulsions. HLBs. the different types of crude being handled. Mechanism of Demulsification Using Demulsifiers. This results in a very slow selection process especially at larger facilities. the laboratory bottle tests are done under static conditions and the field usage is dynamic. This displacement. some of the chemicals come in different concentrations (active ingredient in a carrier solvent). charge neutralization tendencies. polyhydric alcohols and sulphonic acid salts. The efficiency of the demulsifier is dependent on its adsorption at the oil-water or droplet surface. economic analysis dictates the type and size of equipment used and the balance between the amount of chemical and heating requirements. The amount of chemical added is also important. The only clear generalization regarding demulsifiers is that they are high molecular weight (comparable to natural surfactants) and when used as emulsifying agents. The indigenous surfactants (like asphaltenes) present in the crude oil are only weakly adsorbed and are readily displaced by the demulsifier. the amount of chemical and heat to resolve emulsions. Demulsifier Chemistries. occurring at the oil-water interface. Too little demulsifier will leave the emulsion unresolved. However. In this case the demulsifier simply replaces t he natural emulsifiers at the interface. Since demulsifiers are also surface active agents like the emulsifiers. crude oil specifications may decide the system to be used for emulsion treatment. Due to the wide variety of chemicals available as demulsifiers. This displacement is brought about by the adsorption of the demulsifier at the interface. it should 4 : • Dissolve in the continuous oil phase • Concentration of the demulsifier should be high enough to diffuse to the oil-water interface. There is no ‘standard’ solution available for striking a balance between. evaluating prospective . There are a host of hypotheses/theories regarding the physico-chemical mechanism for the action of a chemical demulsifier11 in emulsion breaking process. In some cases. Laboratory bottle tests can provide an estimate of treating temperatures and retention times that can be used for design and operation. the lower the amount of demulsifier needed. However. it should not be higher than a critical concentration (critical aggregate concentration). the size of the equipment: the savings in equipment cost must be balanced against the increased capital and operating costs of the packing or coalescing grids. and depend on experience. There is a wide variation within the intermediate type as well. The film drainage process is shown schematically in Figure 10 taken from Reference 18. Commercial demulsifiers may contain one type of active ingredient or a mixture of several of these intermediates. It is therefore important at such facilities to maintain a record of operational data and testing procedures as an on-going activity. Due to the large variety of components present in the crude oil. The greater the treatment temperature. These numbers are provided for primary or secondary oil recovery emulsions. To ensure good overall demulsifier performance. Demulsifiers are generally specific for a given emulsion and may be completely ineffective for another emulsion. it is not surprising that the effectiveness of a given demulsifier is sensitive to the crude oil type. Demulsifier selection and optimization are described in detail in Reference 4. Typical demulsifier chemistries are shown in Figure 9. the adsorption and displacement process (and hence the demulsifier effectiveness) is also dependent on pH. • Partition into the water phase (partitioning coefficient close to unity) • Possess a high rate of adsorption at the interface • The interfacial activity should be high enough to suppress the interfacial tension gradient thus accelerating the rate of film drainage and promoting coalescence. There is a competition for adsorption when other surface active species are present. for example. The engineer must rely on laboratory data and data from nearby wells or fields. ethoxylated phenols. an excess quantity of demulsifier may also produce very stable emulsions. However. they tend to establish an emulsion opposite in type to that which is stabilized by natural surfactants. Demulsifier dosages. generally are much greater in the static bottle tests than during field conditions. Dosage. the choice of separation equipment and the variations in product qualities. demulsifier rates can be typically in the thousands of ppm and higher in extreme cases. Field Applications The design of emulsion treating equipment and procedures for a given field or application requires experience and engineering judgment. In addition. Furthermore.

• For existing systems record demu lsifier and other relevant operational data (production rates. watercuts. appropriate measures should be taken in the design phase for increased water handling. temperatures. These factors can provide information that may be important during demulsifier selection. sediments in the water. clarity of the water. drop size and drop size distribution. and loose solids hanging at the interface. bulk viscosity and interfacial viscosity. Several field studies related to emulsion problems have been described in the literature 4. temperature. removal of solids. within a few minutes of sampling) as aging of samples has a significant effect on demulsifier dosages. • Operational experience and laboratory work are necessary to substantiate emulsion concerns and identify solutions. BS&W. etc. For example. • The mechanisms involved in demulsification are (a) flocculation and aggregation. solids (clays. • Produced oil-field emulsions are stabilized by rigid interfacial films that form a “skin” on water droplets and prevent the droplets from coalescing. and. Situations that are conducive to the formation of tight emulsions may be avoided economically. and hence the stability of the emulsions. o Scales: should be reduced by scale inhibitors o Corrosion products: reduced by using effective corrosion inhibitors. The frequency of evaluation depends on many factors including the relative cost of the demulsifier usage. During the field trials. if possible) to evaluate the performance and compare with the incumbent chemical performance.e. • Review the emulsion treatment program periodically as conditions change. electrical. and ultimately followed by (c) coalescence. settling times. • Treatment capacities can be increased for existing separator trains by re-engineering and retrofitting.17 . Experience and economics determine which methods and to what degree each method is used for emulsion treatment. These data are also very useful for optimization of emulsion treatment programs. heating costs. • The most common method of measuring the stability of an emulsion is by the bottle test. cleanest separation at the lowest possible cost per unit barrel of crude. (b) sedimentation and creaming. and evaluating the effects of different variables on emulsion resolution4. These solids include o Asphaltenes: can be controlled by effective asphaltene management. unit demulsifier costs. Bottle tests have limitations in determining dosage but are good for screening and trend analysis. mechanical. temperatures. and manpower requirements. Some of the recommendations are listed below: • Solids: Fine solids stabilize emulsions and efforts should be made to reduce solid contaminants during production. • There are very few reported field case studies on emulsion treatment. waxes. etc). and can pinpoint certain activities that may be responsible for emulsion upsets and underlying problems. Representative emulsion samples are taken and transferred into several centrifuge tubes.13. internal packing can be installed in the separator for improving emulsion resolution. oil and brine composition. dispersants. Laboratory tests with actual samples are recommended. the amount of water and salt remaining in the produced crude.19 . and controlling emulsifiers. most importantly. depends on a number of factors including the heavy polar material in the crude oil (asphaltenes. etc). o/w or multiple). Several demulsifiers (generally from different demulsifier vendors) are added to the centrifuge tubes in various amounts and water dropout data are collected and analyzed to determine the best demulsifier. • Emulsions are destabilized by increasing temperature. operating temperatures. To select a demulsifier for a given system one generally starts with the bottle tests. For selecting the best demu lsifier several sets of tests may be necessary at different concentrations. • The stability of these interfacial films. two or three promising demulsifiers are selected for field testing. Pilot and plant tests should determine the actual treatment requirements. scales. The best demulsifier is the one that produces the fastest. and chemical. nature of emulsifying agents present. It is also a good idea to test the chemicals over a period of time (minimum of 1-2 days and longer. the screened chemicals should be tested at various concentrations. resins. Concluding Remarks • Emulsions are characterized by the type of emulsions (w/o. • During the early design of the separation facility the planning for future emulsion treatment should begin. emulsion treatment and emulsion prevention are equally important. etc. clarity of separated water. During the bottle tests. These data can be useful for analyzing demulsifier dosages (for example during the summer and winter). Recommendations In oil-field operations. costs) over a period of time. moderate agitation followed by gentle settling (residence time). It is highly recommended that the bottle test be c onducted with ‘fresh’ emulsions (i. • The methods involved in emulsion breaking or demulsification are thermal. pH. many other factors should also be noted: color and appearance of the emulsion. if watercuts are anticipated to increase. The demulsifier dosages obtained in the lab are generally greater than will be needed in the field. However. capacity limitations. For example. watercuts. Some of the general guidelines for an emulsion treatment programs include: • Each producing stream is unique and must be evaluated individually to determine the best separation strategy.17.. Typical dosages of demulsifier range from less than 10 to over 100 ppm for oil recovery during primary and secondary (waterflooding) recovery and significantly higher for tertiary recovery operations. corrosion products. drop size and drop size distribution. After the bottle tests.8 KOKAL SPE 77497 demulsifiers. data from nearby wells and/or fields can be used as estimates. presence of a ‘rag’ layer. .

R. “Quantification of Various Factors Affecting Emulsion Stability: Watercut. Kimbler.L. J. Sci.L. Optimization of emulsion treatment program should be an on-going activity... Jones. Int. “Physical Characteristics of Natural Films Formed at the Crude Oil-Water Interfaces”.J. REFERENCES 1. severe mixing leads to tight emulsions or even reemulsification after water separation. “Factors Causing Emulsion Upsets in Surface Facilities Following Acid Stimulation”. pp 153-165. Demulsifier Dosage and Mixing Different Crudes”. J. R. D. 17. # 1. “Water-in-Crude Oil Emulsion Stability and Emulsion Destabilization by Chemical Demulsifiers”. “Asphaltenes: The Cholesterol of Petroleum”. Int. Hey. Can.. S. paper SPE 48995 presented at the 1998 SPE Annual Technical Conference and Exhibition. D.L. 13. pp 244-253 (1993). Edmonton.L. Durham. “Dynamics of Emulsification and Demulsification of Water-in-Crude Oil Emulsions”. and Sanford. .J. 6.P. March (1995). J. Proc. Preheaters: An economic analysis should be performed to investigate the applicability of heating emulsions for a given situation. and minimize fines and precipitates during acidization. pp 47-51.. Soc.. Ser. Strassner. Wash water: The effect of amount. Carrier solvents: Effect of carrier aromatic solvent on demulsifier activity should be investigated. 14. April-June (1978). O. M.E. D. Coll. 18. Ind. S. Int.. Dallas (2000) Bhardwaj.. 12. S. S. pp 100-108. L. Temperature. Schubert.). Engg. 16. Crowe. Mini-separators: A portable. J. 4.I. 8. pp 1060-1066 (1975). vol 62. T. M.L.SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW 9 • • • • • • • Acidization: Stimulation with acids can result in very tight emulsions and acid jobs should be designed with care and their field performance should be reviewed. H. Ali. Seminar. avoid commingling. H. Petrol.A. J.M. L.. pp 1023-1028 (1965).W. Coll. “Crude Oil Emulsions” in Petroleum Engineers Handbook.. SPE (2003). 9... Technol. Chem. Chem. Kokal. New Orleans (1998). Chem. Acknowledgements The material in this paper is based on an a literature review report conducted at Saudi Aramco as part of a Ghawar Emulsion Study Team with contributions from Mohammad Abdulmoghini.. pp 103-116 (1990). use of mutual solvents. SPE 29787 paper presented at the 6th Middle East Oil Show.K. and Armbroster.... J.. SPE 56641 paper presented at the Annual Tech.. “Emulsion Separation Index: From Laboratory to Field Case Studies” SPE 63165 paper presented at the Annual Tech.. . vol 32. vol 33. and Juraid. “Principles of Formation and Stability of Emulsions”. E. pp 258-268 (1985). S. 15. J.E. . S. 5. Levine. Canada (1990)... Washington DC (1992).P. 19. I. Effects and Prevention of Asphaltene Sludges During Stimulation Treatments”. Technol.. Technol. 11. A detailed version of the paper is also being published in Reference 4.. Engg.L. and Al-Juraid. E. E. Bobra. S.L. Technol. March (1994). vol.. 10. 7. Kokal. Engg..D. Petrol. Moore. While a moderate amount of mixing is necessary and beneficial.. & Surf. and Elphingstone.. pp 1271-1279 (1994). and Sharma.L.. K.. Kokal. Coppel. Adv. S. and Exh. Chem. “A Study of the Formation of Water-in-Oil Emulsions”. Bahrain.. 32 # 1. Reed. and Symonds..K. Eley. Schramm.. pp 303-312. “Reducing Emulsion Problems By Controlling Asphaltene Solubility and Precipitation”. C. Res.. and Wingrove.D. Neustadter. of the 1990 Arctic and Marine Oil Spill Program Tech. Petrol.. J. and Hartland.L. Petrol. Kokal. and Wittingham. E. Petrol. Salager. Asphaltene Content.D.W... vol 157.. rate and salinity of wash water on desalter performance should be investigated. J. Engg. Chem. pp 14-28 (1992). “Stabilization of Emulsion Droplets by Fine Powders”.. March (1968). Bob Hintermeier and Edward Chen. A. Chem. To avoid emulsion upsets. S. J. vol 30.H. the acid design should incorporate effective demulsifiers at high concentration. pilot miniseparation plant is useful in conducting dynamic emulsion separation tests and reduces the time and effort involved in testing promising demulsifiers. “Factors Controlling the Stability of Colloid-Stabilized Emulsions”. June (1966). Conf. A. and Exh. Emulsions: Fundamentals and Applications in the Petroleum Industry. grid-mounted. and Sayegh. “Effect of pH on Interfacial Films and Stability of Crude Oil-Water Emulsions”.A. Mixing intensity: Chokes and other mixing devices should be controlled to optimize shear and mixing. and Silberberg. Kokal. J. Am. M. Houston Texas (1999). Tambe. 3.I. M. 2. (Ed. “Test Identifies Acidizing Fluid/Crude Compatibility Problems”. Shear. Conf. “Formation. J.. Oil Gas J..G. “Emulsions of Water in Asphaltene Containing Oils”. Technol. and H endrickson. Operational data: Operational data should be maintained for each facility. Monograph Series 231.. “The Fundamental Basis for the Action of a Chemical Dehydrant: Influence of Physical and Chemical Formulation on the Stability of an Emulsion”. Can.. pp 87-103 (1988)..

10 KOKAL SPE 77497 .


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