Crude Oil Emulsions:

A State Of The Art Review

Summary
The formation of emulsions during oil production is a costly prob- lem, both in terms of chemicals used and production lost. This paper
discusses production and operational problems related to crude-oil emulsions and presents a review that will be useful for practicing
engineers.
The first part of this paper presents why emulsions form during oil production, the types of emulsions encountered, and new meth- ods
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 inter- facial films, and hence, the stability of the emulsions, depends on a number of
factors, including the heavy material in the crude oil (e.g., asphaltenes, resins, and waxes), solids (e.g., clays, scales, and corrosion
products), temperature, droplet size and droplet-size distribution, pH, and oil and brine composition. The effects of these factors on
emulsion stability are reviewed within this paper. The second part of this paper presents methods to tackle crude-
oil emulsions. The focus is on the destabilization of emulsions and the demulsification process. Emulsions are destabilized by increas- ing
temperature and residence time, removal of solids, and con- trolling emulsifiers. The mechanisms involved in demulsification (e.g.,
flocculation, aggregation, sedimentation, creaming, and co- alescence) are discussed in terms of the stability of the interfacial films. The
methods involved in demulsification—including ther- mal, mechanical, electrical, and chemical—are also presented. Ex- perience and
economics determine which methods are used, and to what degree, for emulsion treatment.
Finally, a section on field applications also is included that should be useful for the practicing engineer who deals with emul- sions
either regularly or on a limited basis. Herein the field- emulsion treatment program is discussed, and more importantly, methods to prevent
emulsion problems are highlighted. Recom- mendations are made for reducing and optimizing demulsifier dos- age 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 pro- duction.
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 (GOSPs), production of off-specification crude oil, and creating high
pressure drops in flowlines. Emulsions have to be treated to remove the dispersed water and associated inorganic salts to meet crude
specification for transportation, stor- age, and export and to reduce corrosion and catalyst poisoning in downstream-processing facilities.
Emulsions can be encountered in almost all phases of oil pro- duction and processing: inside the reservoirs, wellbores, well- heads, and
wet crude-handling facilities; transportation through pipelines and crude storage; and during petroleum processing. This paper provides a
review of crude-oil emulsions; however, the re- view is limited to the produced oilfield emulsions at the wellhead and at the wet crude-
handling facilities. It looks at the character- istics, occurrence, formation, stability, handling, and breaking of produced oilfield emulsions.
Crude-oil emulsions is a broad area and several books have been written on the subject. 1–3 This paper provides an overview that is
primarily targeted towards the practicing engineers with the objective of familiarizing them with the most important issues. For in-depth
details and further reading on the subject matter, the reader is directed to the textbooks 1–3 and website addresses4–9 provided in the
references.

Definitions. A crude-oil emulsion is a dispersion of water droplets in oil. Produced oilfield emulsions can be classified into three broad
groups:
• Water-in-oil (W/O) emulsions.
• Oil-in-water (O/W) emulsions.
• Multiple or complex emulsions.
The W/O emulsions consist of water droplets in a continuous oil phase, and the O/W emulsions consist of oil droplets in a continuous
water phase. In the oil industry, W/O emulsions are more common (most produced oilfield emulsions are of this kind), and therefore, the
O/W emulsions are sometimes referred to as “reverse” emulsions. Multiple emulsions are more complex and consist of tiny droplets
suspended in bigger droplets that are sus- pended in a continuous phase. For example, a water-in-oil-in-water (W/O/W) emulsion consists
of water droplets suspended in larger oil droplets that in turn are suspended in a continuous water phase. Fig. 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.1,2,10 As a rule of thumb, when the
volume fraction of one phase is very small compared with the other, then the phase that has the smaller fraction is the dispersed phase
and the other will form the continuous phase. When the phase-volume ratio is close to 1 (both phases of approxi- mately the same
magnitude), then other factors will determine the type of emulsion formed.
Emulsions are stabilized by emulsifiers (i.e., surface-active agents, or surfactants) that tend to concentrate at the oil/water interface
where they form interfacial films. This generally leads to a reduction of interfacial tension (IFT) and promotes dispersion and
emulsification of the droplets. Naturally occurring emulsifiers in the crude oil include higher boiling-point fractions, such as asphaltenes
and resins, and organic acids and bases. These com- pounds 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 chemicals that are injected into the formation
or wellbore (e.g., drilling fluids; stimulation chemicals; and injected inhibitors for corrosion, scale, waxes, and asphaltenes control). Fine
solids can also act as mechanical stabi- lizers. These particles, which have to be much smaller than emul- sion droplets, collect at the
oil/water interface and are wetted by both the oil and water. The effectiveness of these solids in stabi- lizing emulsions depends on a
number of factors, such as particle size, particle interactions, and the wettability of the particles. 11 Finely divided solids found in oil
production include clay particles, sand, asphaltenes and waxes, corrosion products, mineral scales, and drilling muds.

IMAGEN 1
 Oilfield emulsions are characterized by a number of properties including appearance, basic sediment and water, droplet size, bulk and
interfacial viscosities, and conductivities. Some of these properties are described below, while others are described in other publications.

Droplet Size and Droplet-Size Distribution. Produced oilfield emulsions generally have droplet diameters exceeding 0.1 µm and may be
larger than 50 µm. Droplet-size distributions of typical petroleum emulsions are shown in Fig. 2. The droplet-size distri- bution 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 (which implies larger separating-plant equipment sizes).

Viscosity of Emulsions. Viscosity of emulsions can be substan- tially higher than the viscosity of either the oil or the water. This is because
emulsions show non-Newtonian behavior1 caused by droplet “crowding” or structural viscosity. At certain volume frac- tions of the water
phase (water cut), oilfield emulsions behave as shear-thinning, or pseudoplastic, fluids; as shear rate increases, their viscosity decreases.
Fig. 3 shows the viscosities of a very tight emulsion at different water cuts. The viscosity data shown in Fig. 3 (for Saudi Arabian crude
emulsions) indicate that the emul- sions 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 water cuts above 30%, the slopes of the curves deviate from zero, indicating
non-Newtonian behavior.

IMAGEN 2

Also, the non-Newtonian behavior is pseudoplastic, or shear- thinning, behavior (i.e., viscosity decreases with increasing shear rates).
Fig. 3 shows the very high viscosities achieved as the water cut increases up to 80% (compare with viscosities of oil 20 cp and water 1
cp). At approximately 80% water cut, an interesting phenomenon takes place. Up to a water cut of 80%, the emulsion is a W/O emulsion;
at 80%, the emulsion “inverts” to an O/W emulsion, and the water, which was the dispersed phase, now becomes the continuous phase.
In this particular case, multiple emulsions (W/O/W) were observed right up to very high water concentrations (greater than 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 Fig. 4 for several different types of emulsions. While these data are for Saudi Arabian
crude emulsions, such plots can be generated easily for any crude-oil emulsion. Emulsion viscosity depends on several factors, and Fig.
4 provides only an estimate. For more precise values, experimental data must be used. Emulsion viscosity is measured by standard
viscometers and rheometers, such as capillary-tube and rotational viscometers (e.g., concentric cylin- der, cone and plate, and parallel
plate). It is important that the temperature is constant and quoted with the viscosity data. Special procedures must be adopted for
measuring the rheology of emulsions.1

Stability of Emulsions
From a purely thermodynamic 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 stability). 1 Pro- duced oilfield emulsions are classified on the basis of their degree of kinetic
stability as follows:
• Loose emulsions. Those that separate in a few minutes. The separated water is sometimes referred to as free water.
• Medium emulsions. Will separate in ten minutes or more.
• Tight emulsions. Will separate (sometimes only partially) in a matter of hours or even days.
Emulsions are considered special liquid-in-liquid colloidal dis- persions. Their kinetic stability is a consequence of a small droplet size
and the presence of an interfacial film around the water drop- lets. Emulsion kinetic stability is attained by stabilizing agents (or emulsifiers)
that could be naturally occurring in the crude oil (as- phaltenes, for example) or added during production (stimulating chemicals, for
example). These stabilizers suppress the mecha- nisms involved (i.e., sedimentation, aggregation or flocculation, coalescence, and phase
inversion) in emulsion breakdown.

IMAGEN 3 Y 4

Interfacial Films. As mentioned previously, produced oilfield emulsions are stabilized by films that form around the water drop- lets at
the oil/water interface. These films are believed to result from the adsorption of high-molecular-weight polar molecules that are interfacially
active (i.e., exhibit surfactant-like behavior). These films enhance the stability of emulsion by (a) reducing IFT and (b) increasing the
interfacial viscosity. Highly viscous inter- facial films retard the rate of oil-film drainage during the coagu- lation of the water droplets by
providing a mechanical barrier to coalescence. This can lead to a reduction in the rate of emul- sion breakdown.
The characteristics of interfacial films are a function of the crude-oil type (e.g., asphaltic and paraffinic), composition and pH of water,
temperature, the extent to which the adsorbed film is compressed, contact or aging time, and concentration of polar molecules in the crude
oil.11,13–15 A good correlation exists be- tween the occurrence of incompressible interfacial film and emul- sion stability. These films are
classified into two categories on the basis of their mobilities.13–14
Rigid, or Solid, Films. These are like an insoluble skin on water droplets and are characterized by very-high interfacial vis- cosity.
There is considerable evidence that these films are formed by polar fractions of the oil and other emulsifiers and may be further stabilized
by fine solids. These films play a significant role in hampering the droplet-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 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. 14 Surfactants that modify the rigidity of the film
can considerably speed up the demulsification process. This will be discussed further under the section “Demulsification of Emulsions.”

Factors Affecting Stability. The important factors that affect emulsion stability include the following.13–16
Heavy Fraction in Crude Oil. It is now well recognized that the naturally occurring emulsifiers (or stabilizers) are concentrated in the
higher-boiling-point, polar fraction of the crude oil.13–19 These include asphaltenes, resins, and oil-soluble organic acids (e.g., naphthenic
and carboxylic acids) and bases. These com- pounds are the main constituents of the interfacial films surround- ing the water droplets that
give the emulsions their stability.
While it is well established that the heavy asphaltenic material stabilizes oil-continuous emulsions, there is considerable debate on the
precise mechanism of stabilization. The asphaltenes reside at the oil/water interface because of their surface-active proper- ties.18–20 The
accumulation of asphaltenes at the interface results in the formation of a rigid film. An asphaltene-stabilized water droplet is shown in
Fig. 5. When such a film is formed, it acts as a barrier to droplet coalescence. For two drops to coalesce to- gether, the film has to be
drained and ruptured. The presence of the asphaltenes can naturally retard the drainage of this film. Refer- ence 18 provides an excellent
discussion on the mechanism of asphaltene-stabilized emulsions.
The state of asphaltenes in the crude oil also has an effect on its emulsion-stabilizing properties. While asphaltenes will stabilize
emulsions when they are present in a colloidal state (not yet floc- culated), 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 in ethylacetate, but are soluble in n-heptane. The role of
resins in stabilizing emulsions has also been debated in litera- ture. Some researchers believe that resins have a tendency to as- sociate
with asphaltenes and, together form a micelle. The result- ing asphaltene/resin micelle plays a key role in stabilizing emul- sions. It
appears that the 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 emulsion.14,16 How- ever, there remains considerable debate on this topic.
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 dichlo- romethane at 30°C. The effect of waxes on emulsion stability is not clear from the
literature. Waxes by themselves are soluble in oil and, in the absence of asphaltenes, do not form stable emulsions in model oils.16
However, the addition of a nominal amount (an amount insufficient by itself to produce emulsions) of asphaltenes to oils containing wax
can lead to the formation of stable emul- sions. Therefore, waxes can interact synergistically with asphalt- enes 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 greater 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 such factors as the particle size, interparticle interactions, and the wettability of the solids. 11,21 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. Further- more, solid particles at the interface may be charged, which may also enhance the stability of
the emulsion. Particles must be much smaller than the size of the emulsion droplets to act as emulsion stabilizers. These particles typically
range from smaller than 1 µm to several µm in size,1 and they are suspended colloidally in the liquids.
The wettability of solid particles plays an important role in the emulsion-stabilizing process. 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 W/O 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 O/W emulsion. Examples of oil-wet solids are asphaltenes and waxes.
Examples of water-wet solids are inorganic scales (e.g., CaCO3 and CaSO4), clays, and sand. Water-wet particles can be made oil-wet with
a coating of heavy-organic-polar compounds.22

IMAGEN 5

When solids are wetted by both the oil and water (intermediate wettability), they agglomerate at the interface and retard droplet/ droplet
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 coales- cence. 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 phase.11,16
On the basis of the experiments performed,11 it was shown that the effectiveness of colloidal particles in stabilizing emulsions de- pends
largely on the formation of a “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 that
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 sig- nificantly. Temperature affects the physical properties of oil, wa- ter,
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 de- crease is mainly
caused by 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 emul- sion problem completely by redissolving the waxes into the crude oil. Temperature increases
the thermal energy of the droplets and, hence, increases the frequency of droplet collisions. It also reduces the interfacial viscosity and
results in a faster film-drainage rate and enhanced droplet coalescence.
Effect of temperature on interfacial films was studied in some detail by Jones et al.13 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 droplet
coalescence still exists. Temperature influences the rate of buildup of interfacial films by changing the adsorption rate and characteristics
of the interface. It also influences the film com- pressibility by changing 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 nonrelaxing (solid films) at high temperatures, and emulsion
resolution may not be affected by heating.
Droplet Size. As mentioned previously, emulsion droplet sizes range from less than 1 µm to more than 50 µms. Generally, emul- sions
have a droplet-size distribution rather than a fixed-droplet size. Typical droplet-size distributions for W/O emulsions are shown in Fig. 2.
Droplet-size distribution is normally represented by a histogram or a distribution function of some sort.
Generally, emulsions that have smaller-sized droplets will be more stable. For water separation, droplets have to coalesce, and the
smaller the droplets, 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. Water-phase pH has a strong influence on emulsion sta- bility.13–15 The stabilizing, rigid-emulsion film contains organic acids and
bases, asphaltenes with ionizable groups, and solids.

Adding inorganic acids and bases strongly influences their ioniza- tion 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 also influences the type of emulsion formed. Low pH (acidic) generally produces W/O emulsions (corresponding to oil- wetting
solid films), whereas, high pH (basic) produces O/W emul- sion (corresponding to water-wetting mobile soap films). Fig. 6 shows the effect
of pH on emulsion stability for a Venezuelan crude.14 Optimum pH for demulsification is approximately 10, without demulsifier. An
addition of a demulsifier enhances demul- sification 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. Fig. 7 shows the effect of a bicarbonate brine
and distilled water on emulsion stability as a function of pH, taken from Ref. 14. Optimum pH (for water separation) changes from
approximately 10 for distilled water to between 6 and 7 for the brine solution. This is because of the ionization effect (i.e.,
association/interaction of ions present in the brine with the asphalt- enes). 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 sta- bility 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 stimulation.23–25 In many cases, it has been linked
to formation damage, as well. Following acid treat- ment, the wells are very slow to clean up and partial or complete plugging of the well
often results. This plugging and formation damage generally occurs because of solid precipitates (or sludges) being formed on contact of
the crude oil with the acid. These precipitates are mainly asphaltenes, resins, and other high-molec- ular-weight hydrocarbons. These
materials are apparently precipi- tated from the crude oil by the reduction in pH as a result of acid contact. 25 While the sludges formed
during an acid treatment are extremely difficult to treat (because of the high concentration of precipitated asphaltenes), there is a link to
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 caused by acidization.24

Measurement of Stability. From a practical point of view, mea- surement 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 separate in an emulsion. There are numer- ous
methods available for determining emulsion stability.1,12 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 temperatures and may involve centrifugation for en- hancing the separation. While there are different methods and procedures
followed by various laboratories for the bottle test, there is a standard American Society for Testing Materials (ASTM) method (ASTM
4007) available for determining the bot- tom 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, emulsions 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 demulsifica- tion qualities. The bottle test is regularly used as a
screening test for potential demulsifiers.

IMAGEN 6 Y 7

While a standard method is available for determining basic sediment and water (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 proposed26 for measuring the stability of an
emulsion quantitatively. The method proposed was the concept of an emulsion separation index to measure the tight- ness 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% (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 it is very useful for comparing the stability of emulsions from different sources (e.g., different wells
or GOSPs). Further details are provided in the paper.26

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: the rate or speed at which this separation takes place and 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% BS&W or 10 lbm of salt per thousand barrels of crude oil. This low value of BS&W and salt content is required
to reduce corrosion and depo- sition of salts. In refinery operations, the primary concern is to remove inorganic salts from the crude oil
before they cause cor- rosion 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 oilfield emulsions possess a degree of kinetic stability. This
stability arises from the formation of interfacial films encap- sulating the water droplets. To separate this emulsion into oil and water, the
interfacial film must 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 sta- bility 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, agglomeration, or coagulation). The second step is coalescence. Either of these
steps can be the rate-determining step in the emul- sion-breaking process.
Flocculation or Aggregation. The first step in the demulsifi- cation process is the flocculation of water droplets. During floc- culation,
the droplets clump together forming aggregates, or “flocs.” 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 takes place only if the inter- facial film surrounding the
water droplets is very weak. The rate of flocculation depends on a number of factors, including water cut, temperature, viscosity of the
oil, and the density difference be- tween the oil and water.
Coalescence. Coalescence is the second step in the demulsifi- cation process and follows flocculation. During coalescence, water
droplets fuse, or coalesce, to form a larger droplet. This is an irreversible process that leads to a decrease in the number of water droplets,
and eventually to complete demulsification. Coalescence is enhanced by a high rate of flocculation, 1,16 absence of mechani- cally strong
films, high IFTs, low oil and interfacial viscosities, high water cuts, and high temperatures.

Demulsification Methods. In the oil industry, crude-oil emulsions must be separated almost completely before the oil can be trans- ported
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 one or a combination of the following methods1,12:
• Reducing the flow velocity that allows gravitational separa- tion 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. Because of the wide variety of crude oils, brines (and, hence,
emulsions), separation equipment, chemical demulsifiers, and product specifications, demulsification methods are very applica- tion
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 appropriate chemical demulsifiers to promote destabi- lization,
followed by a settling time to allow gravitational separa- tion 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 de- stabilization of the rigid films caused by reduced interfacial vis- cosity.
Furthermore, the coalescence frequency between water droplets is increased because of the higher thermal energy of the droplets. In other
words, heat accelerates the emulsion-breaking process. However, very rarely does it resolve the emulsion prob- lem 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 American Petroleum Inst. (API) gravity and the treated-oil volume. Finally, increasing the temperature leads
to an increased tendency toward 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. The cost
effectiveness of adding heat should be balanced against longer treatment time (larger separator), loss of light ends and a resultant reduced
oil-product price, chemical costs, and the costs of instal- lation of electrostatic grids, or retrofitting.
Mechanical Methods. There is a wide variety of mechani- cal equipment available in the breaking of oilfield produced emulsions.
These include free-water knockout drums, two- and three- phase separators (low- and high-pressure traps), desalters, and settling tanks. These
vessels separate the free water and break emulsions.
Electrical Methods. High-voltage electricity (electric grids) is often an effective means of breaking emulsions. It is generally theorized
that water droplets have an associated charge and, when an electric field is applied, the droplets move about rapidly, collide with each other,
and coalesce. The electric field also disturbs the rigid interfacial 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 as 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 chemi- cal and
heat requirements. Invariably, the use of electrostatic de- hydration will result in a reduction of heat addition. Lower tem- peratures result
in fuel economy, reduced problems with scale and corrosion formation, and reduced light-ends loss. Electrostatic grids also can lead to a
reduction in the use of emulsion-break- ing chemicals.
Chemical Methods. By far, the most common method of emul- sion treatment is 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, 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 wa- ter droplets.
• Addition of heat, electric grids, coalescers, or other methods to facilitate or completely resolve the emulsions.
Selection of Chemicals. Selection of the right demulsifier is 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 tech- nology, and research and development 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 (e.g., benzene, toluene, xylene, short-chain alcohols, and heavy aromatic naph- tha),
surfactants, flocculants, and wetting agents. The demulsifiers act by total or partial displacement of the indigenous stabilizing components
(polar materials) of the interfacial film surrounding the emulsion droplets. This displacement also brings about a change in properties such
as 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 wet- tability of the stabilizing particles, which leads to a breakup of the emulsion film.
Testing procedures are available to select appropriate chemi- cals.12,26 These tests include bottle tests, dynamic simulators, and actual plant
tests. All test procedures have limitations. There are hundreds of commercial demulsifier products available that may be tested; add to
this the changing conditions at the separation facilities, and the result is 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 ongoing 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. Because 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 the natural emulsifiers at the interface.
Because of the wide variety of chemicals available as demul- sifiers, 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 (some active ingredients are in a carrier solvent). The amount, or
dosage, of demulsifier required is very site specific and depends on a number of factors. On the basis of evaluated 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 surfac- tant or micellar flooding), demulsifier rates
can typically be in the thousands of ppm, higher in extreme cases.
Demulsifier Chemistries. Demulsifiers are generally specific for a given emulsion and may be completely ineffective for an- other
emulsion. Demulsifiers are typically formulated1 with poly- meric chains of ethylene oxides and polypropylene oxides of al- cohol,
ethoxylated phenols, ethoxylated alcohols and amines, ethoxylated resins, ethoxylated nonylphenols, polyhydric alcohols, and sulphonic
acid salts. Typical demulsifier chemistries are shown in Fig. 8. Commercial demulsifiers may contain one type of active ingredient or a
mixture of several of these intermediates. There is a wide variation within the intermediates as well. For example, molecular weight and
structure of the ethylene or pro- pylene oxides can be changed, giving a complete range of solu- bilities, hydrophile/lipophile balances,
charge-neutralization ten- dencies, solids-wetting characteristics and, of course, costs.
Mechanism of Demulsification by Use of Demulsifiers. Demulsification by use of chemicals is a very complex phenom- enon.
There are hosts of hypotheses/theories regarding the physi- cochemical mechanism for the action of a chemical demulsifier27 in the
emulsion-breaking process. The only clear generalization regarding demulsifiers is that they are high in molecular weight (comparable
with natural surfactants), and when used as emulsi- fying agents, they tend to establish an emulsion opposite in type to those stabilized
by natural surfactants. Demulsifiers 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 displace- ment, occurring at the oil/water
interface, influences the coales- cence of water droplets through enhanced film drainage. The ef- ficiency 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 sur- factants (like asphaltenes) present in the crude oil are only weakly adsorbed and are readily displaced by the
demulsifier. The mecha- nisms of emulsion breaking by demulsifiers are discussed in Refs. 27–29.

Because of 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 (i.e., films that exhibit little resistance to coalescence) in its place. To ensure good overall demulsifier per- formance, the
demulsifier should do the following:

IMAGEN 8

• Dissolve in the continuous oil phase.

• Diffuse the oil/water interface on the basis that the con- centration of the demulsifier is high enough; however, it should not be higher
than a critical concentration (i.e., critical aggre- gate concentration).
• Partition into the water phase (partitioning coefficient close to unity).
• Possess a high rate of adsorption at the interface.
• Suppress the IFT gradient, thus accelerating the rate of film drainage and promoting coalescence on the basis that the interfa- cial
activity is high enough.
Demulsifier selection and optimization are described in detail in Ref. 12.

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 speci- fications may decide the system to
be used for emulsion treatment. Other factors include internal packing vs. the size of the equip- ment; the savings in equipment cost must
be balanced against the increased capital and operating costs of the packing or coalesc- ing grids.
Laboratory bottle tests can provide an estimate of treating tem- peratures 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 dos- ages, for example,
generally are much greater in the static bottle tests than under field conditions. However, laboratory testing is excellent for screening
different emulsion samples for relative tightness, evaluating prospective demulsifiers, and evaluating the effects of different variables on
emulsion resolution.12,26
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
demulsifier, several sets of tests may be necessary at different values of concentration, temperature, water cut, and other factors The
demulsifier dosages obtained in the laboratory are generally greater than those needed in the field. It is highly recommended that the
bottle test be conducted with fresh emul- sions (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 appear- ance 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 dur- ing 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, degrees of 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
(a minimum of 1–2 days or longer, if possible) to evaluate the performance and compare with the incumbent- chemical performance.
The best demulsifier is the one that pro- duces the fastest, cleanest separation at the lowest possible cost per barrel of crude.
Several field studies related to emulsion problems have been described in the literature. 12,22,26,30 Some of the general guidelines for an
emulsion-treatment program include the following:
• Each producing stream is unique and must be evaluated in- dividually 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.
• The planning for future emulsion treatment should begin dur- ing the early design of the separation facility. For example, if water
cuts 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 demulsifier and other relevant operational data (e.g., production rates, water cuts, temperatures, and costs)
over a period of time. These data can be useful for analyzing demulsifier dosages (e.g., during the summer and win ter) and unit-demulsifier
costs, and can pinpoint certain activities that may be responsible for emulsion upsets and underlying prob- lems. These data are also very
useful for optimizing emulsion- treatment programs.
• Review the emulsion-treatment program periodically as con- ditions change. The frequency of evaluation depends on many factors,
including the relative cost of the demulsifier usage, heating costs, capacity limitations, and manpower requirements.

Conclusions
1. Emulsions are characterized by the type of emulsion (W/O, O/W, or multiple), nature of emulsifying agents present, BS&W, droplet
size and droplet-size distribution, bulk viscos- ity, and interfacial viscosity.
2. Produced oilfield emulsions are stabilized by rigid interfacial films that form a skin on water droplets and prevent the droplets from
coalescing.
3. The stability of these interfacial films, and, hence, the stability of the emulsions, depends on a number of factors, including the heavy
material in the crude oil (e.g., asphaltenes, resins, and waxes), solids (e.g., clays, scales, and corrosion products), tem- perature, droplet
size and droplet-size distribution, pH, and oil and brine composition.
4. The most common method of measuring the stability of an emulsion is with the bottle test.
5. Emulsions are destabilized by increasing temperature, moderate agitation followed by gentle settling (i.e., residence time), re- moving
solids, and controlling emulsifiers.
6. The mechanisms involved in demulsification are flocculation, aggregation, and coalescence.
7. The methods involved in emulsion breaking or demulsification are thermal, mechanical, electrical, and chemical. Experience and
economics determine which methods are used, and to what degree, for emulsion treatment.
8. There are very few reported field case studies on emulsion treat- ment. Typical dosages of demulsifier range from less than 10 to more
than 100 ppm for oil recovery during primary and sec- ondary (i.e., waterflooding) recovery and are significantly higher for tertiary-
recovery operations.