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SPE Crude Oil Emulsions
SPE 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 problem, 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 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 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 crudeoil 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
(e.g., flocculation, aggregation, sedimentation, creaming, and coalescence) are discussed in terms of the stability of the interfacial
films. The methods involved in demulsificationincluding thermal, mechanical, electrical, and chemicalare also presented. Experience 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 emulsions either regularly or on a limited basis. Herein the fieldemulsion 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 (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, 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, wellbores, wellheads, 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 review is limited to the produced oilfield emulsions at the wellhead
and at the wet crude-handling facilities. It looks at the characteristics, 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 textbooks13 and website addresses49
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 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 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 approximately 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 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 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 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.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
5
Fig. 2Droplet-size distribution of petroleum emulsions. (Typical Saudi Arabian crude oil emulsions. Distributions obtained
using Nikon microscope and image-analysis software.)
Fig. 1Photomicrographs of emulsions.
Also, the non-Newtonian behavior is pseudoplastic, or shearthinning, 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 cylinder, 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
present at the interface and must be wetted by both the oil and
water phases for it to act as an emulsion stabilizer. When the solids
are preferentially oil-wet (more of the solid in the oil phase), then
a W/O emulsion will result. Oil-wet particles will preferentially
partition into the oil phase and will prevent the coalescence of
water droplets by steric hindrance. Similarly, water-wet solids will
stabilize a water-continuous or an O/W emulsion. Examples of
oil-wet solids are asphaltenes and waxes. Examples of water-wet
solids are inorganic scales (e.g., CaCO3 and CaSO4), clays, and
sand. Water-wet particles can be made oil-wet with a coating of
heavy-organic-polar compounds.22
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 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 phase.11,16
On the basis of the experiments performed,11 it was shown that
the effectiveness of colloidal particles in stabilizing emulsions depends 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 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
emulsionsit decreases with increasing temperatures. This decrease 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 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 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 compressibility 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 interfacialfilm 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, emulsions 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 stability.1315 The stabilizing, rigid-emulsion film contains organic
acids and bases, asphaltenes with ionizable groups, and solids.
8
Adding inorganic acids 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 also influences the type of emulsion formed. Low pH
(acidic) generally produces W/O emulsions (corresponding to oilwetting solid films), whereas, high pH (basic) produces O/W emulsion (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 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. 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 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 emulsionbreaking 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 stimulation.2325 In many cases, it has
been linked to formation damage, as well. Following acid treatment, 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-molecular-weight hydrocarbons. These materials are apparently precipitated 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, 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 separate in an emulsion. There are numerous methods available for determining emulsion stability.1,12 By
far, the most common method is the simple bottle test. The bottle
test involves dilution of the emulsion with a solvent, mixing in the
demulsifier, shaking to disperse the demulsifier, and observing the
phase separation as a function of time. The tests are normally done
at elevated temperatures and may involve centrifugation for enhancing 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 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, 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 demulsification 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 proposed26 for measuring the
stability of an emulsion quantitatively. The method proposed was
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% (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 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 oilfield 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 must be destroyed and the droplets
February 2005 SPE Production & Facilities
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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February 2005 SPE Production & Facilities
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13