Crude-Oil Emulsions:

A State-Of-The-Art Review
Sunil Kokal, SPE, Saudi Aramco
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 demulsificationincluding ther-
mal, mechanical, electrical, and chemicalare 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.
13
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
13
and website addresses
49
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.
Oilfield emulsions are characterized by a number of properties
including appearance, basic sediment and water, droplet size, bulk
Copyright 2005 Society of Petroleum Engineers
This paper (SPE 77497) was first presented at the 2002 SPE Annual Technical Conference
and Exhibition, San Antonio, 29 September2 October, and revised for publication. Original
manuscript received for review 19 April 2004. Revised manuscript received 2 November
2004. Paper peer approved 7 December 2004.
5 February 2005 SPE Production & Facilities
and interfacial viscosities, and conductivities. Some of these
properties are described below, while others are described in
other publications.
12
Droplet Size and Droplet-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 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 determinesto a certain extentthe 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 behavior
1
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.
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
Fig. 1Photomicrographs of emulsions.
Fig. 2Droplet-size distribution of petroleum emulsions. (Typi-
cal Saudi Arabian crude oil emulsions. Distributions obtained
using Nikon microscope and image-analysis software.)
Fig. 3Viscosities of very tight emulsions at 125F. (Safaniya
crude emulsions. Data obtained using Haake Rheostress RS-
150 rheometer.)
Fig. 4Relative viscosities of emulsions. (The curves are based
on typical Saudi Arabian crude emulsion viscosities measured
using Haake Rheostress RS-150 rheometer.)
6 February 2005 SPE Production & Facilities
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.
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.
11,1315
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.
1314
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.
1316
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.
1319
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.
1820
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 30C. 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 m
to several m 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
Fig. 5Mechanism of emulsion stabilization by asphaltenes.
7 February 2005 SPE Production & Facilities
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., CaCO
3
and CaSO
4
), clays, and
sand. Water-wet particles can be made oil-wet with a coating of
heavy-organic-polar compounds.
22
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
emulsionsit 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 m to more than 50 ms. 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 viscosityit 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.
1315
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.
2325
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
Fig. 6Effect of pH and demulsifier concentration on emulsion
stability.
14
8 February 2005 SPE Production & Facilities
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.
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 proposed
26
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 othereven touching at
certain pointsbut 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 methods
1,12
:
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
Fig. 7Effect of brine and pH on emulsion stability.
14
9 February 2005 SPE Production & Facilities
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 electrodesin some designsis
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 importanttoo
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 formulated
1
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 demulsifier
27
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. 2729.
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:
10 February 2005 SPE Production & Facilities
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 se-
lecting 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 12 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-
Fig. 8Typical demulsifier-molecular formulas. (EO=ethylene oxide, PO=propylene oxide)
11 February 2005 SPE Production & Facilities
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.
Recommendations
In oilfield operations, emulsion treatment and emulsion prevention
are equally important. Situations that are conducive to the forma-
tion of tight emulsions may be avoided economically. Some of the
recommendations are listed below:
1. Solids. Fine solids stabilize emulsions, and efforts should be
made to reduce solid contaminants during production. These solids
include the following:
Asphaltenes. Can be controlled by effective asphaltene man-
agement and by dispersants and other methods.
Scales. Should be reduced by scale inhibitors.
Corrosion products. Reduced by using effective corro-
sion inhibitors.
2. Acidization. Stimulation with acids can result in very tight
emulsions, so 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
concentrations, use mutual solvents, avoid commingling, and
minimize fines and precipitates during acidization.
3. Wash Water. The effect of amount, rate, and salinity of
wash water on desalter performance should be investigated.
4. Carrier Solvents. Effect of aromatic solvents used as carri-
ers on demulsifier activity should be investigated.
5. 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 re-emulsification after water separation.
6. Preheaters. An economic analysis should be performed
to investigate the applicability of heating emulsions for a
given situation.
7. Miniseparators. A small-scale portable, grid-mounted pilot
separation plant is useful in conducting dynamic emulsion-sepa-
ration tests, and it reduces the time and effort involved in testing
promising demulsifiers.
8. Operational Data. Operational data should be maintained
for each facility. Optimization of emulsion-treatment programs
should be an ongoing activity.
Acknowledgments
The material in this paper is based on 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 Ref. 12.
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SI Metric Conversion Factors
cp 1.0* E03 Pas
F (F32)/1.8 C
lbm 4.535 924 E01 kg
*Conversion factor is exact.
Sunil Kokal is a reservoir fluid property specialist at the research
and development center at Saudi Aramco in Dhahran, Saudi
Arabia. His areas of expertise include hydrocarbon phase be-
havior, crude-oil emulsions, and asphaltenes. Kokal has written
more than 70 technical papers and has authored the chapters
on Crude-Oil Emulsions and Reservoir-Fluid Sampling for
the new, revised edition of SPEs forthcoming Petroleum Engi-
neering Handbook. He holds a BS degree from the Indian Inst.
of Technology (New Delhi) and a PhD degree from the U. of
Calgary (Canada), both in chemical engineering. Kokal is a
registered professional engineer in Alberta, Canada. He has
served on many SPE committees, both at the local and inter-
national levels, and is currently a Technical Editor for SPE
Reservoir Evaluation and Engineering, as well as SPEPF. E-mail
address: Sunil.Kokal@aramco.com.
13 February 2005 SPE Production & Facilities