SPE 77497
Crude Oil Emulsions: A State-Of-The-Art Review
Sunil Kokal*, SPE, Saudi Aramco
Copyright 2002, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE Annual Technical Conference and
Exhibition held in San Antonio, Texas, 29 September –2 October 2002.
This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstract submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes without the written consent of the Society of Petroleum Engineers is
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous
acknowledgment of where and by whom the paper was presented. Write Librarian , SPE, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
Abstract
Formation of emulsions during oil production is a costly
problem, both in terms of chemicals used and due to
production losses. This paper discusses production and
operational problems related to crude oil emulsions, and
present a review that will be very useful for
practicing engineers.
The first part of this paper presents why emulsions form
during oil production, the types of emulsions encountered, and
new methods for characterizing them. Crude oil emulsions are
stabilized by rigid interfacial films that form a “skin” on water
droplets and prevent the droplets from coalescing. The
stability of these interfacial films, and hence the stability of
the emulsions, depends on a number of factors including the
heavy polar material in the crude oil (asphaltenes, resins,
waxes, etc), solids (clays, scales, corrosion products, etc),
temperature, drop size and drop size distribution, pH, oil and
brine composition. These effects on emulsion stability
are reviewed.
The second part of this paper presents ways to tackle crude
oil emulsions. The focus is on the destabilization of emulsions
and the demulsification process. Emulsions are destabilized by
increasing temperature and residence time, removal of solids,
and controlling emulsifiers. The mechanisms involved in
demulsification (flocculation, aggregation, sedimentation,
creaming, and coalescence) are discussed in terms of the
stability of the interfacial films. The methods involved in
demulsification including thermal, mechanical, electrical, and
chemical are also presented. Experience and economics
determine which methods and to what degree each method is
used for emulsion treatment.
Finally, a section on field applications is ni cluded that
should be useful for the practicing engineer who deals with
emulsions, 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. Recommendations are made for reducing and
optimizing demulsifier dosage and controlling
emulsion problems.
Introduction
Crude oil is seldom produced alone. It is generally
commingled with water which creates a number of problems
during oil production. Produced water occurs in two ways:
some of the water may be produced as free water, i.e. water
that will settle out fairly rapidly, and some of the water may be
produced in the form of emulsions. Emulsions are difficult to
treat and cause a number of operational problems such as
tripping of separation equipment in gas-oil separating plants,
production of off-spec crude oil, and creating high pressure
drops in flow lines. Emulsions have to be treated to remove
the dispersed water and associated inorganic salts in order to
meet crude specification for transportation, storage and export
and to reduce corrosion and catalyst poisoning in downstream
processing facilities.
Emulsions can be encountered in almost all phases of oil
production and processing: inside the reservoirs, well bores
and well heads, wet crude handling facilities, transportation
through pipelines, crude storage and during petroleum
processing. This paper provides a review of crude oil
emulsions. However, the review is limited to the produced
oilfield emulsions at the well head and at the wet crude
handling facilities. It looks at the characteristics, occurrence,
formation, stability, handling and breaking of produced
oilfield emulsions.
A crude oil emulsion is a dispersion of water droplets in
oil. Produced oil-field emulsions can be classified into three
broad groups:
• Water-in-oil (W/O)
• Oil-in-water (O/W)
• Multiple or complex emulsions
The water-in-oil emulsions consist of water droplets in a
continuous oil phase and the oil-in-water emulsions consist of
oil droplets in a water-continuous phase. In the oil industry
water-in-oil emulsions are more common (most produced
oilfield emulsions are of this kind) and therefore the oil-in-
water emulsions are sometimes referred to as “reverse”
emulsions. Multiple emulsions are more complex and consist
of tiny droplets suspended in bigger droplets which are
2 KOKAL
suspended 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 which in turn are suspended in
a continuous water phase. Figure 1 shows the various types
of emulsions.
Given the oil and water phases, the type of emulsion that is
formed depends on a number of factors 1-2 . As a rule of thumb,
when the volume fraction of one phase is very small compared
to the other, then the phase which has the smaller fraction is
the dispersed phase and the other will form the continuous
phase. When the volume phase ratio is close to 1 (both phases
in the same order of magnitude), then other factors will
determine the type of emulsion formed.
Emulsions are stabilized by emulsifiers (surface active
agents or surfactants) that tend to concentrate at the oil-water
interface where they form interfacial films. This generally
leads to a lowering of the interfacial tension (IFT) and
promotes dispersion and emulsification of the droplets.
Naturally occurring emulsifiers in the crude oil include the
higher boiling fractions, like asphaltenes and resins, organic
acids and bases. These compounds are believed to be the main
constituents of interfacial films which form around water
droplets in an oilfield emulsion. Other surfactants that may be
present are from the chemicals that are injected into the
formation or well bore e.g. drilling fluids, stimulation
chemicals, injected inhibitors for corrosion, scale, waxes and
asphaltenes control. Fine solids can also act as mechanical
stabilizers. These particles, which have to be much smaller
than emulsion droplets, collect at the oil-water interface and
are wetted by both the oil and water. The effectiveness of
these solids in stabilizing emulsions depends on a number of
factors such as particle size, particle interactions, and the
wettability of the particles 3 . Finely divided solids found in oil
production include clay particles, sand, asphaltenes and
waxes, corrosion products, mineral scales and drilling muds.
Oilfield emulsion are characterized by a number of
properties including appearance, basic sediment and water,
droplet size, bulk and interfacial viscosities, conductivities etc.
Some of these properties are described below while others are
described elsewhere 4 .
Drop Size and Drop Size Distribution. Produced oilfield
emulsions generally have droplet diameters exceeding 0.1 µm
and may be larger than 50 µm. Droplet size distributions of
typical petroleum emulsions are shown in Figure 2. The
droplet size distribution in an emulsion depends on a number
of factors including the IFT, shear, nature of emulsifying
agents, presence of solids, and bulk properties of oil and
water. Droplet size distribution in an emulsion determines, to a
certain extent, the stability of the emulsion and should be
taken into consideration in the selection of optimum treatment
protocols. As a general rule of thumb, the smaller the average
size of the dispersed water droplets, the longer the residence
time required (=> larger separating plant equipment sizes).
Viscosity of Emulsions. Viscosity of emulsions can be
substantially higher than the viscosity of either the oil or the
water. This is because emulsions show non-Newtonian
behavior1 due to droplet “crowding” or structural viscosity. At
SPE 77497
certain volume fraction of the water phase (watercut), oilfield
emulsions behave as shear-thinning or pseudoplastic fluids: as
shear rate increases, their viscosity decreases. Figure 3 shows
the viscosities of a very tight emulsion at different watercuts.
The viscosity data shown in Figure 3 indicates that the
emulsion exhibit Newtonian behavior up to a water content of
30% (this is indicated by constant values of viscosity for all
shear rates or a slope of zero). At watercuts above 30% the
slope of the curves deviate from zero indicating non-
Newtonian behavior. Also the non-Newtonian behavior is
pseudoplastic or shear-thinning behavior i.e. viscosity
decreases with increasing shear rates. Notice the very high
viscosities achieved as the watercut increases up to 80%
(compare with viscosities of oil ≈80 cP and water ≈1 cP). At
approximately 80% watercut, an interesting phenomenon takes
place. Up to a watercut of 80% the emulsion is a water-in-oil
emulsion; at 80% the emulsion “inverts” to an oil-in -water
emulsion and the water, which was the dispersed phase, now
becomes the continuous phase. In this particular case, multiple
emulsions (water-in-oil-in-water) were observed right up to
very high water concentrations (> 95%).
The viscosity of emulsions depends on a number
of factors:
• viscosities of oil and water
• volume fraction of water dispersed
• droplet size distribution
• temperature
• shear rate
• amount of solids present
The relative viscosity of an emulsion is shown in Figure 4
for several different types of emulsions.
Stability of Emulsions
From a purely thermodynamics point of view, an emulsion is
an unstable system. This is because there is a natural tendency
for a liquid-liquid system to separate and reduce its interfacial
area and hence its interfacial energy. However, most
emulsions are stable over a period of time i.e. they possess
kinetic stability1 . Produced oil-field emulsions are classified
based on their degree of kinetic stability as follows 4 :
• Loose emulsions: those that will separate in a matter of a
few minutes. The separated water is sometimes referred to
as free water.
• Medium emulsions: will separate in a matter of tens of
minutes, and
• Tight emulsions: will separate (sometimes only partially)
in a matter of hours or even days.
Emulsions are considered special liquid-in-liquid colloidal
dispersions. Their kinetic stability is a consequence of small
droplet size and the presence of an interfacial film around
water droplets. Emulsion kinetic stability is attained by
stabilizing agents (or emulsifiers) which could be naturally
occurring in the crude oil (for example, asphaltenes) or added
during production (for example stimulating chemicals). These
stabilizers suppress the mechanisms involved (sedimentation,
aggregation or flocculation, coalescence, phase inversion, etc.)
in emulsion breakdown.
SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW
Interfacial films. As mentioned previously, produced
oilfield emulsions are stabilized by films that form around the
water droplets at the oil-water interface. These films are
believed to result from the adsorption of high molecular
weight polar molecules that are interfacially active (surfactant-
like behavior). These films enhance the stability of emulsion
by (a) reducing interfacial tension and (b) increasing the
interfacial viscosity. Highly viscous interfacial films retard the
rate of oil film drainage during the coagulation of the water
droplets by providing a mechanical barrier to coalescence.
This can lead to a reduction in the rate of
emulsion breakdown.
The characteristics of interfacial films are a function of the
crude oil type (asphaltic, paraffinic), composition and pH of
water, temperature, extent to which the adsorbed film is
compressed, contact or aging time and concentration of polar
molecules in the crude oil11,5 -7 . A good correlation exists
between the occurrence of incompressible interfacial film and
emulsion stability. These films are classified into two
categories based on their mobilities 5,6 :
Rigid or Solid Films: These are like an insoluble skin on
water droplets and are characterized by very high interfacial
viscosity. There is considerable evidence that these films are
formed by polar fractions of the oil, other emulsifiers and may
be further stabilized by fine solids. These films play a
significant role in hampering the drop coalescence process.
They provide a structural barrier to droplet coalescence and
increase emulsion stability. These films also have
viscoelastic properties.
Mobile or Liquid Films: These films, as the name implies,
are mobile and are characterized by low interfacial viscosities.
These are formed, for example, when a demulsifier is added to
an emulsion. They are inherently less stable. Coalescence of
water droplets is enhanced.
Stability of emulsions has been correlated with the
mobility of interfacial films 6 . Surfactants that modify the
rigidity of the film can considerably speed up the
demulsification process. This will be discussed further under
demulsification of emulsions.
Factors Affecting Stability. The important factors that affect
emulsion stability include5-8 :
Heavy Polar Fraction in Crude Oil. It is now well
recognized that the naturally occurring emulsifiers (or
stabilizers) are concentrated in the higher boiling, polar
fraction of the crude oil5-9 . These include asphaltenes, resins
and oil soluble organic acids (e.g. napthenic, carboxylic acids)
and bases. These compounds are the main constituents of the
interfacial films surrounding the water droplets that give the
emulsions their stability.
Asphaltenes have surface active properties 10 that make
them good emulsifiers. They hang at the oil-water interface.
The accumulation of asphaltenes at the interface results in the
formation of the rigid film. An asphaltene stabilized water
droplet is shown in Figure 5. When such a film is formed it
acts as a barrier to drop coalescence. For two drops to coalesce
together, the film has to be drained and ruptured. The presence
of the asphaltenes can naturally retard the drainage of this
3
film. The primary mechanism involved in this retardation is
the steric repulsion or hindrance caused by the high molecular
weight materials in the film3,4 . Figure 6 shows the steric
repulsion produced by the interaction between the non-polar
or hydrophobic groups of the surfactant molecules. With
surfactant molecules of the asphaltene type, the side chains
can extend considerably into the oil phase, and steric repulsion
can maintain the interface at a distance sufficient to inhibit
coalescence. Lateral interactions between adsorbed molecules
and the solution of the oil phase by hydrophobic groups also
results in a considerable increase in the interfacial viscosity
and the apparent viscosity of the oil in the film between the
droplets. Both of these effects oppose film drainage and
inhibit coalescence11 .
The state of asphaltenes in the crude oil has an effect on its
emulsion stability properties 4 . While asphaltenes will stabilize
emulsions when they are present in a colloidal state (not yet
flocculated), there is strong evidence that their emulsion
stabilizing properties are significantly enhanced when they are
precipitated from the crude oil and are present in the
solid phase.
Resins are complex high molecular weight compounds that
are not soluble in ethylacetate but are soluble in n-heptane.
Resins have a strong tendency to associate with asphaltenes
and together they form a micelle. The asphaltene-resin micelle
plays a key role in stabilizing emulsions. It appears that
asphaltene:resin ratio in the crude oil is responsible for the
type of film formed (solid or mobile) and hence is directly
linked to the stability of the emulsion6,8 .
Waxes are the high molecular weight paraffin substances
present in the crude oil that crystallize out when the oil is
cooled below its cloud point. They are insoluble in acetone
and dichloromethane at 30°C. The effect of waxes on
emulsion stability is not clear from the literature. Waxes by
themselves, soluble in oil and in the absence of asphaltenes,
do not form stable emulsions in model oils 8 . But the addition
of a nominal amount of asphaltenes (an amount insufficient by
itself to produce emulsions) to oils containing wax can lead to
the formation of stable emulsions. Therefore, waxes can
interact synergistically with asphaltenes to stabilize emulsions.
The physical state of the wax in the crude oil also plays an
important role in emulsion stabilization. Waxes are more apt
to form a stable emulsion when they are present as fine solids
in the emulsion. Crudes that have a low cloud point generally
have a higher tendency to form stable and tight emulsions than
crudes with high cloud points. Similarly, lower temperatures
in general enhance the emulsion forming tendencies of
crude oils.
Solids. Fine solid particles present in the crude oil are
capable of effectively stabilizing emulsions. The effectiveness
of these solids in stabilizing emulsions depends on factors
such as the particle size, inter-particle interactions and the
wettability of the solids3,12. Solid particles stabilize emulsions
by diffusing to the oil-water interface where they form rigid
structures (films) that can sterically inhibit the coalescence of
emulsion droplets. Furthermore, solid particles at the interface
may be charged which may also enhance the stability of the
4 KOKAL
emulsion. Particles must be much smaller than the size of the
emulsion droplets to act as emulsion stabilizers. Typically
these solid particles are sub-micron to a few microns in size 1
and are suspended colloidally in the liquids.
The wettability of solid particles plays an important role in
the emulsion stabilizing process 4 . If the solid remains entirely
in the oil or water phase, it will not be an emulsion stabilizer.
It must be present at the interface and must be wetted by both
the oil and water phases for it to act as an emulsion stabilizer.
When the solids are preferentially oil-wet (more of the solid in
the oil phase), then a water-in-oil emulsion will result. Oil-wet
particles will preferentially partition into the oil phase and will
prevent the coalescence of water droplets by steric hindrance.
Similarly, water-wet solids will stabilize a water-continuous or
an oil-in-water emulsion. Examples of oil-wet solids are
asphaltenes and waxes. Examples of water-wet solids are
inorganic scales (CaCO3 , CaSO4 , etc.), clays, sand, etc. Water-
wet particles can be made oil-wet by a coating of heavy
organic polar compounds13 .
When solids are wetted by both the oil and water
(intermediate wettability), they agglomerate at the interface
and retard drop-drop coalescence. These particles will have to
be relocated into either the oil or water for coalescence to take
place. This process requires additional energy and hence
provides a barrier to coalescence. The ease of formation and
stability of emulsions has been linked to asphaltene content of
the crude oil and to the pH of the water phase3,8 .
Based on experiments performed3 it was shown that the
effectiveness of colloidal particles in stabilizing emulsions
depends largely on the formation of “densely packed” layer of
solid particles (film) at the oil-water interface. This film
provides steric hindrance to the coalescence of water droplets.
The presence of solids at the interface also changes the
rheological properties of the interface which exhibits
viscoelastic behavior. This affects the rate of film drainage
between droplets and also affects the displacement of particles
at the interface.
Temperature. Temperature can affect emulsion stability
significantly. Temperature affects the physical properties of
oil, water, interfacial films, and surfactant solubilities in the
oil and water phases. These in turn affect the stability of the
emulsion. Perhaps the most important effect of temperature is
on the viscosity of emulsions: it decreases with increasing
temperatures. This decrease is mainly due to a decrease in the
oil viscosity. When waxes are present (crude below its cloud
point) and are the source of emulsion problems, application of
heat can eliminate the emulsion problem completely by
redissolving the waxes into the crude oil. Temperature
increases the thermal energy of the droplets and hence
increases the frequency of drop collisions. It also reduces the
interfacial viscosity and resulting in a faster film drainage rate
and enhanced drop coalescence.
Effect of temperature on interfacial films was studied in
some detail by Jones et al.5 . It was shown that an increase in
temperature led to a gradual destabilization of the crude
oil/water interfacial films. However, even at higher
temperatures, a kinetic barrier to drop coalescence still exists.
SPE 77497
Temperature influences the rate of build-up of interfacial films
by changes in the adsorption rate and characteristics of the
interface. It also influences the film compressibility by
changes in the solubility of the crude oil surfactants in the bulk
phase. Slow degassing (removal of light ends from the crude
oil) and aging leads to significant changes in the interfacial
film behavior at high temperatures. The films generated by
this process remain incompressible and non-relaxing (solid
films) at high temperatures and emulsion resolution is not
affected by heating.
Droplet Size. As mentioned previously, emulsion droplet
sizes range from less than a micron to over 50 microns.
Generally, emulsions have a droplet size distribution rather
than a fixed droplet size. Typical droplet size distributions for
water-in-oil emulsions are shown in Figure 2. Droplet size
distribution is normally represented by a histogram or by a
distribution function of some sort.
Generally emulsions that have smaller size droplets will be
more stable. For water separation, drops have to coalesce and
the smaller the drops, the longer it will take to separate. The
droplet size distribution affects emulsion viscosity: it is higher
when droplets are smaller. Emulsion viscosity will also be
higher when the droplet size distribution is narrow i.e. droplet
size is fairly constant.
pH. pH of the water has a strong influence on emulsion
stability5-7 . The stabilizing, rigid emulsion film contains
organic acids and bases, asphaltenes with ionizable groups,
and solids. Adding inorganic acid and bases strongly
influences their ionization in the interfacial films and radically
changes the physical properties of the films. The pH of the
water affects the rigidity of the interfacial films.
pH influences the type of emulsion formed. Acid or low
pH generally produces w/o emulsions (corresponding to oil-
wetting solid films) whereas basic or high pH produces o/w
emulsion (corresponding to water-wetting mobile soap films).
Figure 7 shows the effect of pH on emulsion stability for a
Venezuelan crude6 . Optimum pH for demulsification is around
10 without demulsifier. Addition of a demulsifier enhances
demulsification after one hour and almost complete water
separation is achieved after 24 hours over a wide range of pH.
Brine composition also has an important effect (in relation
to pH) on emulsion stability. Figure 8 shows the effect of a
bicarbonate brine and distilled water on emulsion stability as a
function of pH, taken from Reference 6. Optimum pH (for
water separation) changes from approximately 10 for distilled
water, to between 6-7 for the brine solution. This is due to
ionization effect (association/interaction of ions present in the
brine with the asphaltenes). The study suggests that for most
crude oil-brine systems, there exists an optimum pH range for
which the interfacial film exhibits minimum emulsion
stabilizing, or maximum emulsion breaking properties. The
optimum pH for maximum emulsion stability depends on both
the crude oil and brine composition. The latter seems to be
more important.
Frequently, severe emulsion upsets occur in surface
treating facilities following acid stimulation14-16 . In many
cases it has been linked to formation damage as well.
SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW
Following acid treatment, the wells are very slow to clean up
and often result in partial or complete plugging of the well.
This plugging and formation damage generally occurs due to
solid precipitates, or sludges, being formed on contact of the
crude oil with the acid. These precipitates are mainly
asphaltenes, resins and other high molecular weight
hydrocarbons. These materials are apparently precipitated
from the crude oil by the reduction in pH as a result of acid
contact16 . While the sludges formed during an acid treatment
are extremely difficult to treat (due to the high concentration
of precipitated asphaltenes), there is a link with the emulsion
problem. These are among the tightest emulsions produced.
Proper design of the acid treatment is necessary to avoid well
productivity decline and emulsion upsets due to acidization15 .
Measurement of Stability. From a practical point of view,
measurement of emulsion stability is one of the most
important tests that can be performed on an emulsion. It
determines the ease with which the oil and water separates in
an emulsion. There are numerous methods available for
determining emulsion stability1,4 . By far the most common
method is the simple bottle test. The bottle test involves
dilution of the emulsion with a solvent, mixing in the
demulsifier, shaking to disperse the demulsifier and observing
the phase separation as a function of time. The tests are
normally done at elevated temperature and may involve
centrifugation for enhancing the separation. While there are
different methods and procedures followed by various
laboratories for the bottle test, there is a standard ASTM
method (ASTM 4007) available for determining the bottom
sediments and water in an emulsion. The stability of the
emulsion is generally related to the ease of water separation
with time and demulsifier dosage. For example, at a given
demulsifier concentration, emulsion can be rated on their
stability by the amount of water separated in a given period of
time. Alternatively, for a fixed length of time and a given
demulsifier concentration, different demulsifiers can be graded
in terms of their demulsification qualities. The bottle test is
regularly used as a screening test for potential demulsifiers.
While a standard method is available for determining
BS&W, no standard method is available in the literature for
determining the stability of the emulsion using the bottle test.
Recently, a method was proposed17 for measuring the stability
of an emulsion quantitatively. They proposed the concept of
an emulsion separation index to measure the tightness of an
emulsion. The total water separated in a regular bottle test at
different demulsifier dosages is averaged to determine a
separation index for the emulsion. The separation index
measures from zero (no separation) to 100 percent (full
separation). The separation index thus provides a measure of
emulsion tightness (or stability): the lower the index, the
higher the tightness or stability. The index must be quoted at
the temperature of the test and the demulsifier used and is very
useful for comparing the stability of emulsion from different
sources (for example different wells or GOSPs). Further
details are provided in the paper17 .
5
Demulsification
Demulsification is the breaking of a crude oil emulsion into oil
and water phases. From a process point of view, the oil
producer is interested in two aspects of demulsification (a) the
rate or the speed at which this separation takes place and (b)
the amount of water left in the crude oil after separation. A
fast rate of separation and a low value of the residual water in
the crude oil are obviously what the oil producer wants.
Produced oil generally has to meet company and pipeline
specification. Typically, the oil shipped from a wet crude
handling facility may not contain more than 0.2% basic
sediment and water (BS&W) and 10 PTB (pounds of salt per
thousand barrels of crude oil). This low value of BS&W and
salt content is required in order to reduce corrosion and
deposition of salts. In refinery operations the primary concern
is to remove inorganic salts from the crude oil before they
cause corrosion or other detrimental effects in refinery
equipment. The salts are removed by “washing” the crude oil
with relatively fresh water.
Destabilizing Emulsions. As mentioned in the previous
section, produced oil-field emulsions possess a degree of
kinetic stability. This stability arises from the formation of
interfacial films encapsulating the water droplets. To separate
this emulsion into oil and water, the interfacial film has to be
destroyed and the droplets made to coalesce. Therefore
destabilizing or breaking emulsions is linked very intimately
to the removal of this interfacial film. The factors that affect
the interfacial film and consequently the stability of the
emulsions were discussed earlier. The factors that enhance or
speed up the emulsion breaking include:
• Increasing temperature
• Reducing agitation or shear
• Increasing residence or retention time
• Solids removal
• Control of emulsifying agents
Mechanisms Involved in Demulsification. Demulsification
is the separation of an emulsion into its component phases. It
is a two step process. The first step is flocculation (or
aggregation, or agglomeration or coagulation). The second
step is coalescence. Either of these steps can be the rate-
determining step in the emulsion breaking process.
Flocculation or Aggregation. The first step in the
demulsification process is the flocculation of water droplets.
During flocculation the droplets clump together forming
aggregates or “floccs”. The droplets are close to each other,
even touching at certain points, but may not lose their identity
i.e. they may not coalesce. Coalescence at this stage only takes
place if the interfacial film surrounding the water droplets is
very weak. The rate of flocculation depends on a number of
factors including watercut, temperature, viscosity of the oil,
and the density difference between the oil and water.
Coalescence. Coalescence is the second step in the
demulsification process and follows flocculation. During
coalescence water droplets fuse or coalesce together to form a
larger drop. This is an irreversible process that leads to a
decrease in the number of water droplets and eventually to
complete demulsification. Coalescence is enhanced by1,8 a
6 KOKAL
high rate of flocculation, absence of mechanically strong
films, high interfacial tensions, low oil and interfacial
viscosities, high watercuts, and high temperatures.
Demulsification Methods. In the oil industry crude oil
emulsions must be separated almost completely before the oil
can be transported and processed further. Emulsion separation
into oil and water necessarily involves the destabilization of
emulsifying films around water droplets. This process is
accomplished by any or combination of the following
methods1,4 :
• Reducing the flow velocity that allows gravitational
separation of oil, water (and gas). This is generally
accomplished in large volume separators and desalters.
• Adding chemical demulsifiers.
• Increasing the temperature of the emulsion.
• Applying electrical fields that promote coalescence.
• Changing the physical characteristics of the emulsion.
Due to the wide variety of crude oils, brines (and hence
emulsions), separation equipment, chemical demulsifiers and
product specifications, demulsification methods are very
application specific. Furthermore, emulsions and conditions
change over time and add to the complexity of the treatment
process. The most common methods of emulsion treatment
have been the application of heat and an appropriate chemical
demulsifier to pro mote destabilization followed by a settling
time to allow gravitational separation to occur.
Thermal Methods. Heating the emulsion enhances its
breaking or separation. It reduces the viscosity of the oil and
increases the water settling rates. Increased temperatures also
result in the destabilization of the rigid films due to reduced
interfacial viscosity. Furthermore, the coalescence frequency
between water droplets is increased due to the higher thermal
energy of the droplets. In other words, heat accelerates the
emulsion breaking process. However, very rarely does it
resolve the emulsion problem alone. Increasing the
temperature has some negative effects. First, it costs money to
heat the emulsion stream. Second, it can result in the loss of
light ends from the crude oil reducing its API gravity and the
treated oil volume. Finally, increasing the temperature leads to
an increased tendency towards scale deposition and an
increased potential for corrosion in treating vessels.
Application of heat for emulsion breaking should be based
on an overall economic analysis of the treatment facility. Cost
effectiveness of adding heat should be balanced against longer
treatment time (larger separator), loss of light ends and a
resultant oil-product price, chemical costs and the costs of
installation of electrostatic grids or retrofitting.
Mechanical Methods. There is a wide variety of
mechanical equipment available in the breaking of oil-field
produced emulsions. These include free water knock out
drums, two and three phase separators (low and high pressure
traps), desalters, settling tanks. These vessels separate the free
water and break emulsions. A detailed description is provided
in Reference 4.
Electrical Methods. High voltage electricity (electric
grids) is often an effective means of breaking emulsions. It is
generally theorized that water droplets have a charge
SPE 77497
associated and when an electric field is applied, the droplets
move about rapidly and collide with each other and coalesce.
The electric field also disturbs the interfacial rigid film by
rearranging the polar molecules thereby weakening the tight
film and enhancing coalescence. The electrical system consists
of a transformer and electrodes that provide high voltage
alternating-current. The electrodes are placed in such a way to
provide an electric field that is perpendicular to the direction
of flow. The distance between the electrodes, in some designs,
is adjustable so that the voltage can be varied to meet the
requirement of the emulsion being treated.
Electrostatic dehydration is rarely used alone as a method
of breaking emulsions. It is generally used in conjunction with
chemical and heat addition. Invariably, the use of electrostatic
dehydration will result in a reduction of heat addition. Lower
temperatures result in fuel economy, reduced problems with
scale and corrosion formation and reduced light-ends loss.
Electrostatic grids can also lead to a reduction in the use of
emulsion breaking chemicals.
Chemical Methods. By far the most common method of
emulsion treatment is by adding chemicals called demulsifiers.
These chemicals are designed to neutralize the effect of
emulsifying agents that stabilize emulsions. Demulsifiers are
surface active compounds and when added to the emulsion,
they migrate to the oil-water interface and rupture or weaken
the rigid film and enhance coalescence of water droplets.
Optimum emulsion breaking with a demulsifier requires:
• A properly selected chemical for the given emulsion
• Adequate quantity of this chemical
• Adequate mixing of the chemical in the emulsion.
• Sufficient retention time in emulsion treaters to settle
water droplets
• Addition of heat, electric grids, coalescers, etc to facilitate
or completely resolve the emulsions.
Selection of Chemicals. Selection of the right demulsifier
is very crucial in the emulsion breaking process. The selection
process for chemicals is still viewed as an art rather than a
science. However, with an ever increasing understanding of
the emulsion breaking process, the availability of new and
improved chemicals, new technology and R&D efforts,
selection of the right chemical is becoming easier and more
organized and many of the failures have been eliminated.
Demulsifiers are chemicals that contain solvents (benzene,
toluene, xylene, short-chain alcohols, heavy aromatic naptha),
surfactants, flocculants and wetting agents. The demulsifiers
act by total or partial displacement of the indigenous
stabilizing interfacial film components (polar materials)
around the emulsion droplets. This displacement also brings
about a change in properties like interfacial viscosity or
elasticity of the protecting film, thus enhancing
destabilization. In some cases the chemicals (demulsifiers) act
as a wetting agent and alter the wettability of the stabilizing
particles which leads to a breakup of the emulsion film.
Testing procedures are available to select appropriate
chemicals 4,17. These tests include bottle tests, dynamic
simulators and actual plant tests. All test procedures have
limitations. There are hundreds of commercial demulsifier
SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW
products available that may be tested. Add to this the changing
conditions at the separation facilities. This results in a very
slow selection process especially at larger facilities. It is
therefore important at such facilities to maintain a record of
operational data and testing procedures as an
on-going activity.
Dosage. The amount of chemical added is also important.
Too little demulsifier will leave the emulsion unresolved. On
the other hand, a high dosage of demulsifier (an overtreat
condition) may be detrimental to the treatment process. Since
demulsifiers are also surface active agents like the emulsifiers,
an excess quantity of demulsifier may also produce very stable
emulsions. In this case the demulsifier simply replaces the
natural emulsifiers at the interface.
Due to the wide variety of chemicals available as
demulsifiers, the different types of crude being handled, the
choice of separation equipment and the variations in product
qualities, it is difficult to prescribe “standard” or typical
dosage rates for treating emulsions. Furthermore, some of the
chemicals come in different concentrations (active ingredient
in a carrier solvent). The amount or dosage of demulsifier
required is very site specific and depends on a number of
factors. Based on an evaluation of the literature, the
demulsifier rates quoted vary from less than 10 ppm to more
than 100 ppm (based on total production rates). These
numbers are provided for primary or secondary oil recovery
emulsions. During tertiary oil recovery (especially during
surfactant or micellar flooding), demulsifier rates can be
typically in the thousands of ppm and higher in extreme cases.
Demulsifier Chemistries. Demulsifiers are generally
specific for a given emulsion and may be completely
ineffective for another emulsion. Demulsifiers are typically
formulated1 with polymeric chains of ethylene oxides and
polypropylene oxides of alcohol, ethoxylated phenols,
ethoxylated alcohols and amines, ethoxylated resins,
ethoxylated nonylphenols, polyhydric alcohols and sulphonic
acid salts. Typical demulsifier chemistries are shown in Figure
9. Commercial demulsifiers may contain one type of active
ingredient or a mixture of several of these intermediates.
There is a wide variation within the intermediate type as well.
For example, molecular weight and structure of the ethylene
or propylene oxides can be changed giving a complete range
of solubilities, HLBs, charge neutralization tendencies, solids-
wetting characteristics and of course, costs.
Mechanism of Demulsification Using Demulsifiers.
Demulsification using chemicals is a very complex
phenomenon. There are a host of hypotheses/theories
regarding the physico-chemical mechanism for the action of a
chemical demulsifier11 in emulsion breaking process. The only
clear generalization regarding demulsifiers is that they are
high molecular weight (comparable to natural surfactants) and
when used as emulsifying agents, they tend to establish an
emulsion opposite in type to that which is stabilized by natural
surfactants. Demulsifier displace the natural stabilizers
(emulsifier) present in the interfacial film around the water
droplets. This displacement is brought about by the adsorption
of the demulsifier at the interface. This displacement,
7
occurring at the oil-water interface, influences the coalescence
of water droplets through enhanced film drainage. The film
drainage process is shown schematically in Figure 10 taken
from Reference 18. The efficiency of the demulsifier is
dependent on its adsorption at the oil-water or droplet surface.
There is a competition for adsorption when other surface
active species are present. The indigenous surfactants (like
asphaltenes) present in the crude oil are only weakly adsorbed
and are readily displaced by the demulsifier.
Due to the large variety of components present in the crude
oil, it is not surprising that the effectiveness of a given
demulsifier is sensitive to the crude oil type. In addition, the
adsorption and displacement process (and hence the
demulsifier effectiveness) is also dependent on pH, salt
content and temperature. The best demulsifiers are those that
readily displace preformed rigid films and leave a mobile film
(films that exhibit little resistance to coalescence) in its place.
To ensure good overall demulsifier performance, it should 4 :
• Dissolve in the continuous oil phase
• Concentration of the demulsifier should be high enough to
diffuse to the oil-water interface. However, it should not
be higher than a critical concentration (critical aggregate
concentration).
• Partition into the water phase (partitioning coefficient
close to unity)
• Possess a high rate of adsorption at the interface
• The interfacial activity should be high enough to suppress
the interfacial tension gradient thus accelerating the rate
of film drainage and promoting coalescence.
Demulsifier selection and optimization are described in
detail in Reference 4.
Field Applications
The design of emulsion treating equipment and procedures
for a given field or application requires experience and
engineering judgment. The engineer must rely on laboratory
data and data from nearby wells or fields, and depend on
experience. There is no ‘standard’ solution available for
striking a balance between, for example, the amount of
chemical and heat to resolve emulsions. The greater the
treatment temperature, the lower the amount of demulsifier
needed. In general, economic analysis dictates the type and
size of equipment used and the balance between the amount of
chemical and heating requirements. In some cases, crude oil
specifications may decide the system to be used for emulsion
treatment. Other factors include internal packing vs. the size of
the equipment: the savings in equipment cost must be
balanced against the increased capital and operating costs of
the packing or coalescing grids.
Laboratory bottle tests can provide an estimate of treating
temperatures and retention times that can be used for design
and operation. However, the laboratory bottle tests are done
under static conditions and the field usage is dynamic.
Demulsifier dosages, for example, generally are much greater
in the static bottle tests than during field conditions. However,
laboratory testing is excellent for screening different emulsion
samples for relative tightness, evaluating prospective
8 KOKAL
demulsifiers, and evaluating the effects of different variables
on emulsion resolution4,17 .
To select a demulsifier for a given system one generally
starts with the bottle tests. Representative emulsion samples
are taken and transferred into several centrifuge tubes. Several
demulsifiers (generally from different demulsifier vendors) are
added to the centrifuge tubes in various amounts and water
dropout data are collected and analyzed to determine the best
demulsifier. For selecting the best demu lsifier several sets of
tests may be necessary at different concentrations,
temperatures, watercuts, etc. The demulsifier dosages obtained
in the lab are generally greater than will be needed in the field.
It is highly recommended that the bottle test be conducted
with ‘fresh’ emulsions (i.e., within a few minutes of sampling)
as aging of samples has a significant effect on demulsifier
dosages. During the bottle tests, many other factors should
also be noted: color and appearance of the emulsion, clarity of
the water, sediments in the water, presence of a ‘rag’ layer,
and loose solids hanging at the interface. These factors can
provide information that may be important during
demulsifier selection.
After the bottle tests, two or three promising demulsifiers
are selected for field testing. During the field trials, the
screened chemicals should be tested at various concentrations,
operating temperatures, settling times, clarity of separated
water, and, most importantly, the amount of water and salt
remaining in the produced crude. It is also a good idea to test
the chemicals over a period of time (minimum of 1-2 days and
longer, if possible) to evaluate the performance and compare
with the incumbent chemical performance. The best
demulsifier is the one that produces the fastest, cleanest
separation at the lowest possible cost per unit barrel of crude.
Several field studies related to emulsion problems have
been described in the literature 4,13,17,19 . Some of the general
guidelines for an emulsion treatment programs include:
• Each producing stream is unique and must be evaluated
individually to determine the best separation strategy.
Laboratory tests with actual samples are recommended.
However, data from nearby wells and/or fields can be
used as estimates.
• During the early design of the separation facility the
planning for future emulsion treatment should begin. For
example, if watercuts are anticipated to increase,
appropriate measures should be taken in the design phase
for increased water handling.
• Operational experience and laboratory work are necessary
to substantiate emulsion concerns and identify solutions.
Pilot and plant tests should determine the actual treatment
requirements. Bottle tests have limitations in determining
dosage but are good for screening and trend analysis.
• Treatment capacities can be increased for existing
separator trains by re-engineering and retrofitting. For
example, internal packing can be installed in the separator
for improving emulsion resolution.
• For existing systems record demu lsifier and other relevant
operational data (production rates, watercuts,
temperatures, costs) over a period of time. These data can
SPE 77497
be useful for analyzing demulsifier dosages (for example
during the summer and winter), unit demulsifier costs,
and can pinpoint certain activities that may be responsible
for emulsion upsets and underlying problems. These data
are also very useful for optimization of emulsion
treatment programs.
• Review the emulsion treatment program periodically as
conditions change. The frequency of evaluation depends
on many factors including the relative cost of the
demulsifier usage, heating costs, capacity limitations, and
manpower requirements.
Concluding Remarks
• Emulsions are characterized by the type of emulsions
(w/o, o/w or multiple), nature of emulsifying agents
present, BS&W, drop size and drop size distribution, bulk
viscosity and interfacial viscosity.
• Produced oil-field emulsions are stabilized by rigid
interfacial films that form a “skin” on water droplets and
prevent the droplets from coalescing.
• The stability of these interfacial films, and hence the
stability of the emulsions, depends on a number of factors
including the heavy polar material in the crude oil
(asphaltenes, resins, waxes, etc), solids (clays, scales,
corrosion products, etc), temperature, drop size and drop
size distribution, pH, oil and brine composition.
• The most common method of measuring the stability of
an emulsion is by the bottle test.
• Emulsions are destabilized by increasing temperature,
moderate agitation followed by gentle settling (residence
time), removal of solids, and controlling emulsifiers.
• The mechanisms involved in demulsification are (a)
flocculation and aggregation, (b) sedimentation and
creaming, and ultimately followed by (c) coalescence.
• The methods involved in emulsion breaking or
demulsification are thermal, mechanical, electrical, and
chemical. Experience and economics determine which
methods and to what degree each method is used for
emulsion treatment.
• There are very few reported field case studies on
emulsion treatment. Typical dosages of demulsifier range
from less than 10 to over 100 ppm for oil recovery during
primary and secondary (waterflooding) recovery and
significantly higher for tertiary recovery operations.
Recommendations
In oil-field operations, emulsion treatment and emulsion
prevention are equally important. Situations that are conducive
to the formation of tight emulsions may be avoided
economically. Some of the recommendations are listed below:
• Solids: Fine solids stabilize emulsions and efforts should
be made to reduce solid contaminants during production.
These solids include
o Asphaltenes: can be controlled by effective
asphaltene management, dispersants, etc.
o Scales: should be reduced by scale inhibitors
o Corrosion products: reduced by using effective
corrosion inhibitors.
SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW
• Acidization: Stimulation with acids can result in very
tight emulsions and acid jobs should be designed with
care and their field performance should be reviewed. To
avoid emulsion upsets, the acid design should incorporate
effective demulsifiers at high concentration, use of mutual
solvents, avoid commingling, and minimize fines and
precipitates during acidization.
• Wash water: The effect of amount, rate and salinity of
wash water on desalter performance should be
investigated.
• Carrier solvents: Effect of carrier aromatic solvent on
demulsifier activity should be investigated.
• Mixing intensity: Chokes and other mixing devices
should be controlled to optimize shear and mixing. While
a moderate amount of mixing is necessary and beneficial,
severe mixing leads to tight emulsions or even re-
emulsification after water separation.
• Preheaters: An economic analysis should be performed to
investigate the applicability of heating emulsions for a
given situation.
• Mini-separators: A portable, grid-mounted, pilot mini-
separation plant is useful in conducting dynamic emulsion
separation tests and reduces the time and effort involved
in testing promising demulsifiers.
• Operational data: Operational data should be maintained
for each facility. Optimization of emulsion treatment
program should be an on-going activity.
Acknowledgements
The material in this paper is based on an a literature review
report conducted at Saudi Aramco as part of a Ghawar
Emulsion Study Team with contributions from Mohammad
Abdulmoghini, Bob Hintermeier and Edward Chen. A detailed
version of the paper is also being published in Reference 4.
REFERENCES
1. Schramm, L.L. (Ed.), Emulsions: Fundamentals and
Applications in the Petroleum Industry, , Adv. Chem.
Ser. Monograph Series 231, Am. Chem. Soc.,
Washington DC (1992).
2. Schubert, H. and Armbroster, H., “Principles of
Formation and Stability of Emulsions”, Int. Chem.
Engg., vol. 32 # 1, pp 14-28 (1992).
3. Tambe, D.E. and Sharma, M.M., “Factors Controlling
the Stability of Colloid-Stabilized Emulsions”, J. Coll.
Int. Sci., vol 157, pp 244-253 (1993).
4. Kokal, S.L., “Crude Oil Emulsions” in Petroleum
Engineers Handbook, SPE (2003).
5. Jones, T.J., Neustadter, E.L., and Wittingham, K.P.,
“Water-in-Crude Oil Emulsion Stability and Emulsion
Destabilization by Chemical Demulsifiers”, J. Petrol.
Can. Technol., pp 100-108, April-June (1978).
6. Strassner, J.E., “Effect of pH on Interfacial Films and
Stability of Crude Oil-Water Emulsions”, J. Petrol.
Technol., pp 303-312, March (1968).
7. Kimbler, O.K., Reed, R.L., and Silberberg, I.H.,
9
“Physical Characteristics of Natural Films Formed at
the Crude Oil-Water Interfaces”, J. Petrol. Technol., pp
153-165, June (1966).
8. Bobra, M., “A Study of the Formation of Water-in-Oil
Emulsions”, Proc. of the 1990 Arctic and Marine Oil
Spill Program Tech. Seminar, Edmonton, Canada
(1990).
9. Eley., D.D., Hey, M.J., and Symonds, J.D., “Emulsions
of Water in Asphaltene Containing Oils”, Coll. & Surf.,
vol 32, pp 87-103 (1988).
10. Kokal, S.L. and Sayegh, S.G., “Asphaltenes: The
Cholesterol of Petroleum”, SPE 29787 paper presented
at the 6th Middle East Oil Show, Bahrain, March
(1995).
11. Salager, J.L., “The Fundamental Basis for the Action of
a Chemical Dehydrant: Influence of Physical and
Chemical Formulation on the Stability of an Emulsion”,
Int. Chem. Engg., vol 30, # 1, pp 103-116 (1990).
12. Levine, S. and Sanford, E., “Stabilization of Emulsion
Droplets by Fine Powders”, Can. J. Chem. Engg., vol
62, pp 258-268 (1985).
13. Kokal, S.L. and Al-Juraid, J.I., “Reducing Emulsion
Problems By Controlling Asphaltene Solubility and
Precipitation”, paper SPE 48995 presented at the 1998
SPE Annual Technical Conference and Exhibition,
New Orleans (1998).
14. Coppel, C.P., “Factors Causing Emulsion Upsets in
Surface Facilities Following Acid Stimulation”, J.
Petrol. Technol., pp 1060-1066 (1975).
15. Ali, S.A., Durham, D.K. and Elphingstone, E.A., “Test
Identifies Acidizing Fluid/Crude Compatibility
Problems”, Oil Gas J., pp 47-51, March (1994).
16. Moore, E.W., Crowe, L.W., and Hendrickson, A.R.,
“Formation, Effects and Prevention of Asphaltene
Sludges During Stimulation Treatments”, J. Petrol.
Technol., pp 1023-1028 (1965).
17. Kokal, S.L. and Wingrove, M.D., “Emulsion
Separation Index: From Laboratory to Field Case
Studies” SPE 63165 paper presented at the Annual
Tech. Conf. and Exh., Dallas (2000)
18. Bhardwaj, A. and Hartland, S., “Dynamics of
Emulsification and Demulsification of Water-in-Crude
Oil Emulsions”, Ind. Engg. Chem. Res. , vol 33, pp
1271-1279 (1994).
19. Kokal, S.L. and Juraid, J.I., “Quantification of Various
Factors Affecting Emulsion Stability: Watercut,
Temperature, Shear, Asphaltene Content, Demulsifier
Dosage and Mixing Different Crudes”, SPE 56641
paper presented at the Annual Tech. Conf. and Exh.,
Houston Texas (1999).
10 KOKAL SPE 77497
SPE 77497 CRUDE OIL EMULSIONS: A STATE-OF-THE-ART REVIEW 11