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

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suspended in a continuous phase. For example, 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. Figure 1 shows the various types of emulsions. Given the oil and water phases, the type of emulsion that is formed depends on a number of factors 1-2 . As a rule of thumb, when the volume fraction of one phase is very small compared to the other, then the phase which has the smaller fraction is the dispersed phase and the other will form the continuous phase. When the volume phase ratio is close to 1 (both phases in the same order of magnitude), then other factors will determine the type of emulsion formed. Emulsions are stabilized by emulsifiers (surface active agents or surfactants) that tend to concentrate at the oil-water interface where they form interfacial films. This generally leads to a lowering of the interfacial tension (IFT) and promotes dispersion and emulsification of the droplets. Naturally occurring emulsifiers in the crude oil include the higher boiling fractions, like asphaltenes and resins, organic acids and bases. These compounds are believed to be the main constituents of interfacial films which form around water droplets in an oilfield emulsion. Other surfactants that may be present are from the chemicals that are injected into the formation or well bore e.g. drilling fluids, stimulation chemicals, injected inhibitors for corrosion, scale, waxes and asphaltenes control. Fine solids can also act as mechanical stabilizers. These particles, which have to be much smaller than emulsion droplets, collect at the oil-water interface and are wetted by both the oil and water. The effectiveness of these solids in stabilizing emulsions depends on a number of factors such as particle size, particle interactions, and the wettability of the particles 3 . Finely divided solids found in oil production include clay particles, sand, asphaltenes and waxes, corrosion products, mineral scales and drilling muds. Oilfield emulsion are characterized by a number of properties including appearance, basic sediment and water, droplet size, bulk and interfacial viscosities, conductivities etc. Some of these properties are described below while others are described elsewhere 4 . Drop Size and Drop Size Distribution. Produced oilfield emulsions generally have droplet diameters exceeding 0.1 m and may be larger than 50 m. Droplet size distributions of typical petroleum emulsions are shown in Figure 2. The droplet size distribution in an emulsion depends on a number of factors including the IFT, shear, nature of emulsifying agents, presence of solids, and bulk properties of oil and water. Droplet size distribution in an emulsion determines, to a certain extent, the stability of the emulsion and should be taken into consideration in the selection of optimum treatment protocols. As a general rule of thumb, the smaller the average size of the dispersed water droplets, the longer the residence time required (=> larger separating plant equipment sizes). Viscosity of Emulsions. Viscosity of emulsions can be substantially higher than the viscosity of either the oil or the water. This is because emulsions show non-Newtonian behavior1 due to droplet crowding or structural viscosity. At

certain volume fraction of the water phase (watercut), oilfield emulsions behave as shear-thinning or pseudoplastic fluids: as shear rate increases, their viscosity decreases. Figure 3 shows the viscosities of a very tight emulsion at different watercuts. 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). At watercuts above 30% the slope of the curves deviate from zero indicating nonNewtonian behavior. Also the non-Newtonian behavior is pseudoplastic or shear-thinning behavior i.e. viscosity decreases with increasing shear rates. Notice the very high viscosities achieved as the watercut increases up to 80% (compare with viscosities of oil 80 cP and water 1 cP). At approximately 80% watercut, an interesting phenomenon takes place. Up to a watercut of 80% the emulsion is a water-in-oil emulsion; at 80% the emulsion inverts to an oil-in -water emulsion and the water, which was the dispersed phase, now becomes the continuous phase. In this particular case, multiple emulsions (water-in-oil-in-water) were observed right up to very high water concentrations (> 95%). 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. Stability of Emulsions From a purely thermodynamics point of view, an emulsion is an unstable system. 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. However, most emulsions are stable over a period of time i.e. they possess kinetic stability1 . 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. The separated water is sometimes referred to as free water. Medium emulsions: will separate in a matter of tens of minutes, and Tight emulsions: will separate (sometimes only partially) in a matter of hours or even days. Emulsions are considered special liquid-in-liquid colloidal dispersions. Their kinetic stability is a consequence of small droplet size and the presence of an interfacial film around water droplets. Emulsion kinetic stability is attained by stabilizing agents (or emulsifiers) which could be naturally occurring in the crude oil (for example, asphaltenes) or added during production (for example stimulating chemicals). These stabilizers suppress the mechanisms involved (sedimentation, aggregation or flocculation, coalescence, phase inversion, etc.) in emulsion breakdown.

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Interfacial films. As mentioned previously, produced oilfield emulsions are stabilized by films that form around the water droplets at the oil-water interface. These films are believed to result from the adsorption of high molecular weight polar molecules that are interfacially active (surfactantlike behavior). These films enhance the stability of emulsion by (a) reducing interfacial tension and (b) increasing the interfacial viscosity. 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. This can lead to a reduction in the rate of emulsion breakdown. The characteristics of interfacial films are a function of the crude oil type (asphaltic, paraffinic), composition and pH of water, temperature, extent to which the adsorbed film is compressed, contact or aging time and concentration of polar molecules in the crude oil11,5 -7 . A good correlation exists between the occurrence of incompressible interfacial film and emulsion stability. These films are classified into two categories based on their mobilities 5,6 : Rigid or Solid Films: These are like an insoluble skin on water droplets and are characterized by very high interfacial viscosity. There is considerable evidence that these films are formed by polar fractions of the oil, other emulsifiers and may be further stabilized by fine solids. These films play a significant role in hampering the drop coalescence process. They provide a structural barrier to droplet coalescence and increase emulsion stability. These films also have viscoelastic properties. Mobile or Liquid Films: These films, as the name implies, are mobile and are characterized by low interfacial viscosities. These are formed, for example, when a demulsifier is added to an emulsion. They are inherently less stable. Coalescence of water droplets is enhanced. Stability of emulsions has been correlated with the mobility of interfacial films 6 . Surfactants that modify the rigidity of the film can considerably speed up the demulsification process. This will be discussed further under demulsification of emulsions. Factors Affecting Stability. The important factors that affect emulsion stability include5-8 : Heavy Polar Fraction in Crude Oil. It is now well recognized that the naturally occurring emulsifiers (or stabilizers) are concentrated in the higher boiling, polar fraction of the crude oil5-9 . These include asphaltenes, resins and oil soluble organic acids (e.g. napthenic, carboxylic acids) and bases. These compounds are the main constituents of the interfacial films surrounding the water droplets that give the emulsions their stability. Asphaltenes have surface active properties 10 that make them good emulsifiers. They hang at the oil-water interface. The accumulation of asphaltenes at the interface results in the formation of the rigid film. An asphaltene stabilized water droplet is shown in Figure 5. When such a film is formed it acts as a barrier to drop coalescence. For two drops to coalesce together, the film has to be drained and ruptured. The presence of the asphaltenes can naturally retard the drainage of this

film. The primary mechanism involved in this retardation is the steric repulsion or hindrance caused by the high molecular weight materials in the film3,4 . Figure 6 shows the steric repulsion produced by the interaction between the non-polar or hydrophobic groups of the surfactant molecules. With surfactant molecules of the asphaltene type, the side chains can extend considerably into the oil phase, and steric repulsion can maintain the interface at a distance sufficient to inhibit coalescence. 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. Both of these effects oppose film drainage and inhibit coalescence11 . The state of asphaltenes in the crude oil has an effect on its emulsion stability properties 4 . 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. Resins are complex high molecular weight compounds that are not soluble i n ethylacetate but are soluble in n-heptane. Resins have a strong tendency to associate with asphaltenes and together they form a micelle. The asphaltene-resin micelle plays a key role in stabilizing emulsions. 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 emulsion6,8 . 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. They are insoluble in acetone and dichloromethane at 30C. The effect of waxes on emulsion stability is not clear from the literature. Waxes by themselves, soluble in oil and in the absence of asphaltenes, do not form stable emulsions in model oils 8 . 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. Therefore, waxes can interact synergistically with asphaltenes to stabilize emulsions. The physical state of the wax in the crude oil also plays an important role in emulsion stabilization. Waxes are more apt to form a stable emulsion when they are present as fine solids in the emulsion. Crudes that have a low cloud point generally have a higher tendency to form stable and tight emulsions than crudes with high cloud points. Similarly, lower temperatures in general enhance the emulsion forming tendencies of crude oils. Solids. Fine solid particles present in the crude oil are capable of effectively stabilizing emulsions. The effectiveness of these solids in stabilizing emulsions depends on factors such as the particle size, inter-particle interactions and the wettability of the solids3,12. 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. Furthermore, solid particles at the interface may be charged which may also enhance the stability of the

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emulsion. Particles must be much smaller than the size of the emulsion droplets to act as emulsion stabilizers. Typically these solid particles are sub-micron to a few microns in size 1 and are suspended colloidally in the liquids. The wettability of solid particles plays an important role in the emulsion stabilizing process 4 . If the solid remains entirely in the oil or water phase, it will not be an emulsion stabilizer. 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. When the solids are preferentially oil-wet (more of the solid in the oil phase), then a water-in-oil emulsion will result. Oil-wet particles will preferentially partition into the oil phase and will prevent the coalescence of water droplets by steric hindrance. Similarly, water-wet solids will stabilize a water-continuous or an oil-in-water emulsion. Examples of oil-wet solids are asphaltenes and waxes. Examples of water-wet solids are inorganic scales (CaCO3 , CaSO4 , etc.), clays, sand, etc. Waterwet particles can be made oil-wet by a coating of heavy organic polar compounds13 . When solids are wetted by both the oil and water (intermediate wettability), they agglomerate at the interface and retard drop-drop coalescence. These particles will have to be relocated into either the oil or water for coalescence to take place. This process requires additional energy and hence provides a barrier to coalescence. 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 phase3,8 . 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. This film provides steric hindrance to the coalescence of water droplets. The presence of solids at the interface also changes the rheological properties of the interface which exhibits viscoelastic behavior. This affects the rate of film drainage between droplets and also affects the displacement of particles at the interface. Temperature. Temperature can affect emulsion stability significantly. Temperature affects the physical properties of oil, water, interfacial films, and surfactant solubilities in the oil and water phases. These in turn affect the stability of the emulsion. Perhaps the most important effect of temperature is on the viscosity of emulsions: it decreases with increasing temperatures. This decrease is mainly due to a decrease in the oil viscosity. When waxes are present (crude below its cloud point) and are the source of emulsion problems, application of heat can eliminate the emulsion problem completely by redissolving the waxes into the crude oil. Temperature increases the thermal energy of the droplets and hence increases the frequency of drop collisions. It also reduces the interfacial viscosity and resulting in a faster film drainage rate and enhanced drop coalescence. Effect of temperature on interfacial films was studied in some detail by Jones et al.5 . It was shown that an increase in temperature led to a gradual destabilization of the crude oil/water interfacial films. However, even at higher temperatures, a kinetic barrier to drop coalescence still exists.

Temperature influences the rate of build-up of interfacial films by changes in the adsorption rate and characteristics of the interface. It also influences the film compressibility by changes in the solubility of the crude oil surfactants in the bulk phase. Slow degassing (removal of light ends from the crude oil) and aging leads to significant changes in the interfacial film behavior at high temperatures. The films generated by this process remain incompressible and non-relaxing (solid films) at high temperatures and emulsion resolution is not affected by heating. Droplet Size. As mentioned previously, emulsion droplet sizes range from less than a micron to over 50 microns. Generally, emulsions have a droplet size distribution rather than a fixed droplet size. Typical droplet size distributions for water-in-oil emulsions are shown in Figure 2. Droplet size distribution is normally represented by a histogram or by a distribution function of some sort. Generally emulsions that have smaller size droplets will be more stable. For water separation, drops have to coalesce and the smaller the drops, the longer it will take to separate. The droplet size distribution affects emulsion viscosity: it is higher when droplets are smaller. Emulsion viscosity will also be higher when the droplet size distribution is narrow i.e. droplet size is fairly constant. pH. pH of the water has a strong influence on emulsion stability5-7 . The stabilizing, rigid emulsion film contains organic acids and bases, asphaltenes with ionizable groups, and solids. Adding inorganic acid and bases strongly influences their ionization in the interfacial films and radically changes the physical properties of the films. The pH of the water affects the rigidity of the interfacial films. pH influences the type of emulsion formed. 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). Figure 7 shows the effect of pH on emulsion stability for a Venezuelan crude6 . Optimum pH for demulsification is around 10 without demulsifier. 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. Brine composition also has an important effect (in relation to pH) on emulsion stability. Figure 8 shows the effect of a bicarbonate brine and distilled water on emulsion stability as a function of pH, taken from Reference 6. Optimum pH (for water separation) changes from approximately 10 for distilled water, to between 6 -7 for the brine solution. This is due to ionization effect (association/interaction of ions present in the brine with the asphaltenes). The study suggests that for most crude oil-brine systems, there exists an optimum pH range for which the interfacial film exhibits minimum emulsion stabilizing, or maximum emulsion breaking properties. The optimum pH for maximum emulsion stability depends on both the crude oil and brine composition. The latter seems to be more important. Frequently, severe emulsion upsets occur in surface treating facilities following acid stimulation14-16 . In many cases it has been linked to formation damage as well.

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Following acid treatment, the wells are very slow to clean up and often result in partial or complete plugging of the well. This plugging and formation damage generally occurs due to solid precipitates, or sludges, being formed on contact of the crude oil with the acid. These precipitates are mainly asphaltenes, resins and other high molecular weight hydrocarbons. These materials are apparently precipitated from the crude oil by the reduction in pH as a result of acid contact16 . While the sludges formed during an acid treatment are extremely difficult to treat (due to the high concentration of precipitated asphaltenes), there is a link with the emulsion problem. These are among the tightest emulsions produced. Proper design of the acid treatment is necessary to avoid well productivity decline and emulsion upsets due to acidization15 . Measurement of Stability. From a practical point of view, measurement of emulsion stability is one of the most important tests that can be performed on an emulsion. It determines the ease with which the oil and water separates in an emulsion. There are numerous methods available for determining emulsion stability1,4 . By far the most common method is the simple bottle test. The bottle test involves dilution of the emulsion with a solvent, mixing in the demulsifier, shaking to disperse the demulsifier and observing the phase separation as a function of time. The tests are normally done at elevated temperature and may involve centrifugation for enhancing the separation. While there are different methods and procedures followed by various laboratories for the bottle test, there is a standard ASTM method (ASTM 4007) available for determining the bottom sediments and water in an emulsion. The stability of the emulsion is generally related to the ease of water separation with time and demulsifier dosage. For example, at a given demulsifier concentration, emulsion can be rated on their stability by the amount of water separated in a given period of time. Alternatively, for a fixed length of time and a given demulsifier concentration, different demulsifiers can be graded in terms of their demulsification qualities. The bottle test is regularly used as a screening test for potential demulsifiers. While a standard method is available for determining BS&W, no standard method is available in the literature for determining the stability of the emulsion using the bottle test. Recently, a method was proposed17 for measuring the stability of an emulsion quantitatively. They proposed the concept of an emulsion separation index to measure the tightness of an emulsion. The total water separated in a regular bottle test at different demulsifier dosages is averaged to determine a separation index for the emulsion. The separation index measures from zero (no separation) to 100 percent (full separation). The separation index thus provides a measure of emulsion tightness (or stability): the lower the index, the higher the tightness or stability. 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). Further details are provided in the paper17 .

Demulsification Demulsification is the breaking of a crude oil emulsion into oil and water phases. From a process point of view, 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. A fast rate of separation and a low value of the residual water in the crude oil are obviously what the oil producer wants. Produced oil generally has to meet company and pipeline specification. Typically, the oil shipped from a wet crude handling facility may not contain more than 0.2% basic sediment and water (BS&W) and 10 PTB (pounds of salt per thousand barrels of crude oil). This low value of BS&W and salt content is required in order to reduce corrosion and deposition of salts. 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. The salts are removed by washing the crude oil with relatively fresh water. Destabilizing Emulsions. As mentioned in the previous section, produced oil-field emulsions possess a degree of kinetic stability. This stability arises from the formation of interfacial films encapsulating the water droplets. To separate this emulsion into oil and water, the interfacial film has to be destroyed and the droplets made to coalesce. Therefore destabilizing or breaking emulsions is linked very intimately to the removal of this interfacial film. 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. Demulsification is the separation of an emulsion into its component phases. It is a two step process. The first step is flocculation (or aggregation, or agglomeration or coagulation). The second step is coalescence. Either of these steps can be the ratedetermining step in the emulsion breaking process. Flocculation or Aggregation. The first step in the demulsification process is the flocculation of water droplets. During flocculation the droplets clump together forming aggregates or floccs. The droplets are close to each other, even touching at certain points, but may not lose their identity i.e. they may not coalesce. Coalescence at this stage only takes place if the interfacial film surrounding the water droplets is very weak. The rate of flocculation depends on a number of factors including watercut, temperature, viscosity of the oil, and the density difference between the oil and water. Coalescence. Coalescence is the second step in the demulsification process and follows flocculation. During coalescence water droplets fuse or coalesce together to form a larger drop. This is an irreversible process that leads to a decrease in the number of water droplets and eventually to complete demulsification. Coalescence is enhanced by1,8 a

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high rate of flocculation, absence of mechanically strong films, high interfacial tensions, low oil and interfacial viscosities, high watercuts, and high temperatures. Demulsification Methods. In the oil industry crude oil emulsions must be separated almost completely before the oil can be transported and processed further. Emulsion separation into oil and water necessarily involves the destabilization of emulsifying films around water droplets. This process is accomplished by any or combination of the following methods1,4 : Reducing the flow velocity that allows gravitational separation of oil, water (and gas). This is generally accomplished in large volume separators and desalters. Adding chemical demulsifiers. Increasing the temperature of the emulsion. Applying electrical fields that promote coalescence. Changing the physical characteristics of the emulsion. Due to the wide variety of crude oils, brines (and hence emulsions), separation equipment, chemical demulsifiers and product specifications, demulsification methods are very application specific. Furthermore, emulsions and conditions change over time and add to the complexity of the treatment process. 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. Thermal Methods. Heating the emulsion enhances its breaking or separation. It reduces the viscosity of the oil and increases the water settling rates. Increased temperatures also result in the destabilization of the rigid films due to reduced interfacial viscosity. Furthermore, the coalescence frequency between water droplets is increased due to the higher thermal energy of the droplets. In other words, heat accelerates the emulsion breaking process. However, very rarely does it resolve the emulsion problem alone. Increasing the temperature has some negative effects. First, it costs money to heat the emulsion stream. Second, it can result in the loss of light ends from the crude oil reducing its API gravity and the treated oil volume. Finally, increasing the temperature leads to an increased tendency towards scale deposition and an increased potential for corrosion in treating vessels. Application of heat for emulsion breaking should be based on an overall economic analysis of the treatment facility. Cost effectiveness of adding heat should be balanced against longer treatment time (larger separator), loss of light ends and a resultant oil-product price, chemical costs and the costs of installation of electrostatic grids or retrofitting. Mechanical Methods. There is a wide variety of mechanical equipment available in the breaking of oil-field produced emulsions. These include free water knock out drums, two and three phase separators (low and high pressure traps), desalters, settling tanks. These vessels separate the free water and break emulsions. A detailed description is provided in Reference 4. Electrical Methods. High voltage electricity (electric grids) is often an effective means of breaking emulsions. It is generally theorized that water droplets have a charge

associated and when an electric field is applied, the droplets move about rapidly and collide with each other and coalesce. The electric field also disturbs the interfacial rigid film by rearranging the polar molecules thereby weakening the tight film and enhancing coalescence. The electrical system consists of a transformer and electrodes that provide high voltage alternating-current. The electrodes are placed in such a way to provide an electric field that is perpendicular to the direction of flow. The distance between the electrodes, in some designs, is adjustable so that the voltage can be varied to meet the requirement of the emulsion being treated. Electrostatic dehydration is rarely used alone as a method of breaking emulsions. It is generally used in conjunction with chemical and heat addition. Invariably, the use of electrostatic dehydration will result in a reduction of heat addition. Lower temperatures result in fuel economy, reduced problems with scale and corrosion formation and reduced light-ends loss. Electrostatic grids can also lead to a reduction in the use of emulsion breaking chemicals. Chemical Methods. By far the most common method of emulsion treatment is by adding chemicals called demulsifiers. These chemicals are designed to neutralize the effect of emulsifying agents that stabilize emulsions. Demulsifiers are surface active compounds and when added to the emulsion, they migrate to the oil-water interface and rupture or weaken the rigid film and enhance coalescence of water droplets. 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. Sufficient retention time in emulsion treaters to settle water droplets Addition of heat, electric grids, coalescers, etc to facilitate or completely resolve the emulsions. Selection of Chemicals. Selection of the right demulsifier is very crucial in the emulsion breaking process. The selection process for chemicals is still viewed as an art rather than a science. However, with an ever increasing understanding of the emulsion breaking process, the availability of new and improved chemicals, new technology and R&D efforts, selection of the right chemical is becoming easier and more organized and many of the failures have been eliminated. Demulsifiers are chemicals that contain solvents (benzene, toluene, xylene, short-chain alcohols, heavy aromatic naptha), surfactants, flocculants and wetting agents. The demulsifiers act by total or partial displacement of the indigenous stabilizing interfacial film components (polar materials) around the emulsion droplets. This displacement also brings about a change in properties like interfacial viscosity or elasticity of the protecting film, thus enhancing destabilization. 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. Testing procedures are available to select appropriate chemicals 4,17. These tests include bottle tests, dynamic simulators and actual plant tests. All test procedures have limitations. There are hundreds of commercial demulsifier

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products available that may be tested. Add to this the changing conditions at the separation facilities. This results in a very slow selection process especially at larger facilities. It is therefore important at such facilities to maintain a record of operational data and testing procedures as an on-going activity. Dosage. The amount of chemical added is also important. Too little demulsifier will leave the emulsion unresolved. On the other hand, a high dosage of demulsifier (an overtreat condition) may be detrimental to the treatment process. Since demulsifiers are also surface active agents like the emulsifiers, an excess quantity of demulsifier may also produce very stable emulsions. In this case the demulsifier simply replaces t he natural emulsifiers at the interface. Due to the wide variety of chemicals available as demulsifiers, the different types of crude being handled, the choice of separation equipment and the variations in product qualities, it is difficult to prescribe standard or typical dosage rates for treating emulsions. Furthermore, some of the chemicals come in different concentrations (active ingredient in a carrier solvent). The amount or dosage of demulsifier required is very site specific and depends on a number of factors. Based on an evaluation of the literature, the demulsifier rates quoted vary from less than 10 ppm to more than 100 ppm (based on total production rates). These numbers are provided for primary or secondary oil recovery emulsions. During tertiary oil recovery (especially during surfactant or micellar flooding), demulsifier rates can be typically in the thousands of ppm and higher in extreme cases. Demulsifier Chemistries. Demulsifiers are generally specific for a given emulsion and may be completely ineffective for another emulsion. Demulsifiers are typically formulated1 with polymeric chains of ethylene oxides and polypropylene oxides of alcohol, ethoxylated phenols, ethoxylated alcohols and amines, ethoxylated resins, ethoxylated nonylphenols, polyhydric alcohols and sulphonic acid salts. Typical demulsifier chemistries are shown in Figure 9. Commercial demulsifiers may contain one type of active ingredient or a mixture of several of these intermediates. There is a wide variation within the intermediate type as well. For example, molecular weight and structure of the ethylene or propylene oxides can be changed giving a complete range of solubilities, HLBs, charge neutralization tendencies, solidswetting characteristics and of course, costs. Mechanism of Demulsification Using Demulsifiers. Demulsification using chemicals is a very complex phenomenon. There are a host of hypotheses/theories regarding the physico-chemical mechanism for the action of a chemical demulsifier11 in emulsion breaking process. The only clear generalization regarding demulsifiers is that they are high molecular weight (comparable to natural surfactants) and when used as emulsifying agents, they tend to establish an emulsion opposite in type to that which is stabilized by natural surfactants. Demulsifier displace the natural stabilizers (emulsifier) present in the interfacial film around the water droplets. This displacement is brought about by the adsorption of the demulsifier at the interface. This displacement,

occurring at the oil-water interface, influences the coalescence of water droplets through enhanced film drainage. The film drainage process is shown schematically in Figure 10 taken from Reference 18. The efficiency of the demulsifier is dependent on its adsorption at the oil-water or droplet surface. There is a competition for adsorption when other surface active species are present. The indigenous surfactants (like asphaltenes) present in the crude oil are only weakly adsorbed and are readily displaced by the demulsifier. Due to the large variety of components present in the crude oil, it is not surprising that the effectiveness of a given demulsifier is sensitive to the crude oil type. In addition, the adsorption and displacement process (and hence the demulsifier effectiveness) is also dependent on pH, salt content and temperature. 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. To ensure good overall demulsifier performance, it should 4 : Dissolve in the continuous oil phase Concentration of the demulsifier should be high enough to diffuse to the oil-water interface. However, it should not be higher than a critical concentration (critical aggregate concentration). 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. Demulsifier selection and optimization are described in detail in Reference 4. Field Applications The design of emulsion treating equipment and procedures for a given field or application requires experience and engineering judgment. The engineer must rely on laboratory data and data from nearby wells or fields, and depend on experience. There is no standard solution available for striking a balance between, for example, the amount of chemical and heat to resolve emulsions. The greater the treatment temperature, the lower the amount of demulsifier needed. In general, economic analysis dictates the type and size of equipment used and the balance between the amount of chemical and heating requirements. In some cases, crude oil specifications may decide the system to be used for emulsion treatment. Other factors include internal packing vs. 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. Laboratory bottle tests can provide an estimate of treating temperatures and retention times that can be used for design and operation. However, the laboratory bottle tests are done under static conditions and the field usage is dynamic. Demulsifier dosages, for example, generally are much greater in the static bottle tests than during field conditions. However, laboratory testing is excellent for screening different emulsion samples for relative tightness, evaluating prospective

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demulsifiers, and evaluating the effects of different variables on emulsion resolution4,17 . To select a demulsifier for a given system one generally starts with the bottle tests. Representative emulsion samples are taken and transferred into several centrifuge tubes. 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. For selecting the best demu lsifier several sets of tests may be necessary at different concentrations, temperatures, watercuts, etc. The demulsifier dosages obtained in the lab are generally greater than will be needed in the field. It is highly recommended that the bottle test be c onducted with fresh emulsions (i.e., within a few minutes of sampling) as aging of samples has a significant effect on demulsifier dosages. During the bottle tests, many other factors should also be noted: color and appearance of the emulsion, clarity of the water, sediments in the water, presence of a rag layer, and loose solids hanging at the interface. These factors can provide information that may be important during demulsifier selection. After the bottle tests, two or three promising demulsifiers are selected for field testing. During the field trials, the screened chemicals should be tested at various concentrations, operating temperatures, settling times, clarity of separated water, and, most importantly, the amount of water and salt remaining in the produced crude. It is also a good idea to test the chemicals over a period of time (minimum of 1-2 days and longer, if possible) to evaluate the performance and compare with the incumbent chemical performance. The best demulsifier is the one that produces the fastest, cleanest separation at the lowest possible cost per unit barrel of crude. Several field studies related to emulsion problems have been described in the literature 4,13,17,19 . 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. Laboratory tests with actual samples are recommended. However, data from nearby wells and/or fields can be used as estimates. During the early design of the separation facility the planning for future emulsion treatment should begin. For example, if watercuts are anticipated to increase, appropriate measures should be taken in the design phase for increased water handling. Operational experience and laboratory work are necessary to substantiate emulsion concerns and identify solutions. Pilot and plant tests should determine the actual treatment requirements. Bottle tests have limitations in determining dosage but are good for screening and trend analysis. Treatment capacities can be increased for existing separator trains by re-engineering and retrofitting. For example, internal packing can be installed in the separator for improving emulsion resolution. For existing systems record demu lsifier and other relevant operational data (production rates, watercuts, temperatures, costs) over a period of time. These data can

be useful for analyzing demulsifier dosages (for example during the summer and winter), unit demulsifier costs, and can pinpoint certain activities that may be responsible for emulsion upsets and underlying problems. These data are also very useful for optimization of emulsion treatment programs. Review the emulsion treatment program periodically as conditions change. The frequency of evaluation depends on many factors including the relative cost of the demulsifier usage, heating costs, capacity limitations, and manpower requirements. Concluding Remarks Emulsions are characterized by the type of emulsions (w/o, o/w or multiple), nature of emulsifying agents present, BS&W, drop size and drop size distribution, bulk viscosity and interfacial viscosity. Produced oil-field 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. The most common method of measuring the stability of an emulsion is by the bottle test. Emulsions are destabilized by increasing temperature, moderate agitation followed by gentle settling (residence time), removal of solids, and controlling emulsifiers. The mechanisms involved in demulsification are (a) flocculation and aggregation, (b) sedimentation and creaming, and ultimately followed by (c) coalescence. The methods involved in emulsion breaking or demulsification are thermal, mechanical, electrical, and chemical. Experience and economics determine which methods and to what degree each method is used for emulsion treatment. There are very few reported field case studies on emulsion treatment. 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. Recommendations In oil-field operations, emulsion treatment and emulsion prevention are equally important. Situations that are conducive to the formation of tight emulsions may be avoided economically. Some of the recommendations are listed below: Solids: Fine solids stabilize emulsions and efforts should be made to reduce solid contaminants during production. These solids include o Asphaltenes: can be controlled by effective asphaltene management, dispersants, etc. o Scales: should be reduced by scale inhibitors o Corrosion products: reduced by using effective corrosion inhibitors.

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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. To avoid emulsion upsets, the acid design should incorporate effective demulsifiers at high concentration, use of mutual solvents, avoid commingling, and minimize fines and precipitates during acidization. Wash water: The effect of amount, rate and salinity of wash water on desalter performance should be investigated. Carrier solvents: Effect of carrier aromatic solvent on demulsifier activity should be investigated. Mixing intensity: Chokes and other mixing devices should be controlled to optimize shear and mixing. While a moderate amount of mixing is necessary and beneficial, severe mixing leads to tight emulsions or even reemulsification after water separation. Preheaters: An economic analysis should be performed to investigate the applicability of heating emulsions for a given situation. Mini-separators: A portable, grid-mounted, pilot miniseparation plant is useful in conducting dynamic emulsion separation tests and reduces the time and effort involved in testing promising demulsifiers. Operational data: Operational data should be maintained for each facility. Optimization of emulsion treatment program should be an on-going activity.

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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, Bob Hintermeier and Edward Chen. A detailed version of the paper is also being published in Reference 4. REFERENCES 1. Schramm, L.L. (Ed.), Emulsions: Fundamentals and Applications in the Petroleum Industry, , Adv. Chem. Ser. Monograph Series 231, Am. Chem. Soc., Washington DC (1992). 2. Schubert, H. and Armbroster, H., Principles of Formation and Stability of Emulsions, Int. Chem. Engg., vol. 32 # 1, pp 14-28 (1992). 3. Tambe, D.E. and Sharma, M.M., Factors Controlling the Stability of Colloid-Stabilized Emulsions, J. Coll. Int. Sci., vol 157, pp 244-253 (1993). 4. Kokal, S.L., Crude Oil Emulsions in Petroleum Engineers Handbook, SPE (2003). 5. Jones, T.J., Neustadter, E.L., and Wittingham, K.P., Water-in-Crude Oil Emulsion Stability and Emulsion Destabilization by Chemical Demulsifiers, J. Petrol. Can. Technol., pp 100-108, April-June (1978). 6. Strassner, J.E., Effect of pH on Interfacial Films and Stability of Crude Oil-Water Emulsions, J. Petrol. Technol., pp 303-312, March (1968). 7. Kimbler, O.K., Reed, R.L., and Silberberg, I.H.,

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Physical Characteristics of Natural Films Formed at the Crude Oil-Water Interfaces, J. Petrol. Technol., pp 153-165, June (1966). Bobra, M., A Study of the Formation of Water-in-Oil Emulsions, Proc. of the 1990 Arctic and Marine Oil Spill Program Tech. Seminar, Edmonton, Canada (1990). Eley., D.D., Hey, M.J., and Symonds, J.D., Emulsions of Water in Asphaltene Containing Oils, Coll. & Surf., vol 32, pp 87-103 (1988). Kokal, S.L. and Sayegh, S.G., Asphaltenes: The Cholesterol of Petroleum, SPE 29787 paper presented at the 6th Middle East Oil Show, Bahrain, March (1995). Salager, J.L., The Fundamental Basis for the Action of a Chemical Dehydrant: Influence of Physical and Chemical Formulation on the Stability of an Emulsion, Int. Chem. Engg., vol 30, # 1, pp 103-116 (1990). Levine, S. and Sanford, E., Stabilization of Emulsion Droplets by Fine Powders, Can. J. Chem. Engg., vol 62, pp 258-268 (1985). Kokal, S.L. and Al-Juraid, J.I., Reducing Emulsion Problems By Controlling Asphaltene Solubility and Precipitation, paper SPE 48995 presented at the 1998 SPE Annual Technical Conference and Exhibition, New Orleans (1998). Coppel, C.P., Factors Causing Emulsion Upsets in Surface Facilities Following Acid Stimulation, J. Petrol. Technol., pp 1060-1066 (1975). Ali, S.A., Durham, D.K. and Elphingstone, E.A., Test Identifies Acidizing Fluid/Crude Compatibility Problems, Oil Gas J., pp 47-51, March (1994). Moore, E.W., Crowe, L.W., and H endrickson, A.R., Formation, Effects and Prevention of Asphaltene Sludges During Stimulation Treatments, J. Petrol. Technol., pp 1023-1028 (1965). Kokal, S.L. and Wingrove, M.D., Emulsion Separation Index: From Laboratory to Field Case Studies SPE 63165 paper presented at the Annual Tech. Conf. and Exh., Dallas (2000) Bhardwaj, A. and Hartland, S., Dynamics of Emulsification and Demulsification of Water-in-Crude Oil Emulsions, Ind. Engg. Chem. Res. , vol 33, pp 1271-1279 (1994). Kokal, S.L. and Juraid, J.I., Quantification of Various Factors Affecting Emulsion Stability: Watercut, Temperature, Shear, Asphaltene Content, Demulsifier Dosage and Mixing Different Crudes, SPE 56641 paper presented at the Annual Tech. Conf. and Exh., Houston Texas (1999).

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