OILFIELD CHEMICALS

TRAINING MANUAL

PART 2

2. EMULSION BREAKING
2.1 Problem
The most important objective of any oil production facility is the separation of water and
other foreign materials from the produced crude. The breaking of these “crude oil and
water emulsions” constitutes one of the more challenging problems in today’s oil
producing industry.
During the productive life of an oil or gas well, a stage is reached when water will be co-
produced in unacceptable quantities. This water coexists with the hydrocarbons in the
reservoir and gradually infiltrates into the hydrocarbon bearing region of the formation.
Eventually water becomes part of the production from the wells regardless of the method
of recovery.
Figure 1 shows a simplified view of how water may be produced. In the early life of the
producing field some wells that are drilled close to the oil/water contact level will begin to
produce water. Other wells drilled higher in the reservoir will produce dry oil. Later, as
the oil in the reservoir becomes depleted and the water expands upward, the oil-water
interface level rises until the wells higher in the reservoir begin to produce water. In some
cases it is possible to exclude some or most of the water by plugging back the lower part
of the wellbore with cement and perforating an interval higher up in the formation. This
can at least delay water encroachment for a time.
Secondary or tertiary recovery methods are another cause of water encroachment. These
recovery methods are employed to increase the amount of oil recovered from the
reservoir, and they involve many different techniques. A number of these methods require
the injection of water or steam into the reservoir, and of course, the water is often
produced again with the oil.

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Producing
Wells

Oil

Oil - Water
Contact
Water

Figure 1

Oil leaving the producing facility has to meet a low water content specification. Too high
a level of produced water in the exported oil would severely reduce pumping and other
transport capacity. Even a small percentage of emulsified water in crude oil increases the
cost of pumping due to the larger volume and the higher viscosity of the oil. In addition,
the high salinity of the water would cause corrosion and scaling in downstream operations.
It is therefore necessary to remove the water and associated salts from the crude oil.
Production of immiscible oil and water through well head chokes and valves, along with
the simultaneous action of shear and pressure reduction, often produces stable water-in-oil
mixtures. The relative stability of these mixtures depends upon many factors such as water
cut, the nature of salts present, the viscosity of the oil, and in particular the indigenous
surfactants present in the oil.
Some of the water does not mix with the oil to give a stable mixture. This “free water”
readily separates from the oil. More often, the conditions of production are such that a
stable mixture is formed. Such a mixture is called an emulsion and must be specially
treated before separation can occur.
To appreciate the difficulties associated with the production and treatment of emulsions it
is helpful to have some basic knowledge of emulsion theory.

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2.2 Emulsion Theory

An emulsion is a mixture of two immiscible liquids, one of which is dispersed as droplets in
the other. The liquid in an emulsion that is broken into droplets is known as the dispersed
or internal phase, whereas the liquid surrounding the droplets is called the continuous or
external phase. Emulsions formed in oil producing operations are predominantly water-in-
oil

2.2.1 Types of Emulsion

Emulsions are classified according to which phase is dispersed and which phase is
continuous.
1. Water-in-Oil Emulsions (W/O)
Water is dispersed in oil; water is the dispersed or internal phase, and oil is the
continuous or external phase.
This type is often referred to as a “regular emulsion” or an oil continuous emulsion.
Water-in-oil emulsions are the type most frequently encountered when oil and water
are produced. An oil-in-water emulsion may contain from a trace to ninety plus
percent water.
Treating this type of emulsion is called dehydration.
2. Oil-in-Water Emulsion (O/W)
Oil is dispersed in water; oil is the dispersed or internal phase, water is the continuous
or external phase.
This type can also be called a “reverse emulsion” or water continuous emulsion. These
emulsions exist naturally in certain parts of the world. Oil-in-water emulsions can also
be encountered in the water which has been separated from the oil during dehydration.
Treatment of this type emulsion is sometimes referred to as de-oiling.
3. Multi-Phase Emulsions
It is not uncommon to find both oil-in-water and water-in-oil emulsions occurring
simultaneously. This is frequently encountered in slop oil systems and storage tanks
where various emulsions have mixed and been allowed to stand for a period of time. It
can also result from various secondary and tertiary recovery processes.

2.2.2 Formation of Emulsions

A stable emulsion is one that will not break down without some form of treating. Three
conditions are necessary for the formation of a stable emulsion:
1. The liquids must be immiscible.
2. There must be an emulsifying agent, or emulsifier, present.
3. There must be sufficient agitation to disperse one liquid as droplets in the other.
Many emulsions are prepared for commercial use, such as insecticides and medicines.
These are made up of two or more liquids that will not normally mix, plus the emulsifying

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 Emulsion Breaking 4

agent. A common household emulsion is mayonnaise. Mayonnaise is made of vegetable

oil and vinegar with eggs used as the emulsifying agent. This combination would not
remain mixed if the eggs, or some other emulsifying agent, were not present. They could
be mixed by violent agitation, but they would soon separate after agitation was stopped.
Similarly, to form a stable emulsion of crude and water, an emulsifying agent must be
present.
The stability of petroleum emulsions depends upon the presence of an emulsifying agent
which is soluble, dispersible, or wettable in or by the oil or the water. If the emulsifying
agent is soluble, dispersible, or wettable more easily in or by oil than water, then the oil
will be the external phase and water the dispersed phase. Whereas, if the emulsifier is
soluble, dispersible, or wettable more readily in or by water than oil, then the opposite type
of emulsion will be formed.
The most common emulsifying agent found in petroleum emulsions include asphaltenes,
solid paraffins, resinous substances, napthenic and other oil soluble organic acids, and
finely divided materials that are more soluble, wettable, or dispersible in oil than water.
Also found are zinc, iron, and aluminum sulfates, calcium carbonate, silica and iron sulfide.
These substances are usually found at the interface between the oil and droplets of water in
the form of a film around the droplet. Other emulsifying agents may be drilling,
stimulation or production chemicals. These emulsions are referred to as “chemically
stabilized emulsions.” Care should be taken in the selection of chemicals to prevent
formation of chemically induced emulsions. For example, corrosion inhibitors should be
tested for emulsion tendency before a product is selected in order to prevent emulsification
of the well during batch treatment. Also, demulsifiers should be tested for overtreatment
during bottle testing to prevent the application of a demulsifier which may overtreat or
“burn” the oil.
The agitation necessary to form most petroleum emulsions is caused by gas bubbling
through the oil and water, or by the two liquids being forced through relatively small
openings, such as chokes, at high velocity. It is a recognized fact that emulsions are
formed rarely, if ever, in the oil reservoir, although some may be formed where the water
and oil enter the well.
Emulsification generally occurs at some stages in production. Various sources of agitation
sufficient to cause emulsification may be present between the time when the oil enters the
well and the time when they are separated at the surface. There is evidence that emulsions
are formed in wells and in the mechanical equipment used in production, or even later in
the flowlines on the surface. Undoubtedly, certain methods of production contribute to
the formation of emulsions. Naturally, flowing wells produced through chokes, and wells
produced by gas lift or air lift usually cause the most difficult emulsion problems. Most
emulsions are formed before the fluid leaves the wellhead.

2.2.3 Other Factors Affecting the Stability of Emulsions

2.2.3.1 Viscosity
The viscosity of a liquid may be thought of as its resistance to flow. The higher the
viscosity, the greater the resistance of a liquid to flow. Conversely, the lower the

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viscosity, the more readily the liquid flows. Often, if a liquid of high viscosity is heated,
the viscosity decreases so that the liquid flows more freely. Therefore, heating a crude oil
of high viscosity lowers the viscosity and makes it flow easier.
An oil of high viscosity requires more time for the water droplets to coalesce and settle out
than does an oil of low viscosity because the water droplets cannot move as rapidly
through a high viscosity oil as they can through a low viscosity oil. A common example of
this may be seen by observing the slow rate at which air bubbles rise in syrup, which has a
high viscosity, as compared to the fast rate at which they rise in water, which has a low
viscosity. Air bubble rise, whereas water droplets in oil settle, but the effect is the same.

2.2.3.2 Specific Gravity

Specific gravity should not be confused with API gravity. The specific gravity of a liquid
substance is the weight of a given amount of that liquid at a given temperature compared
to the weight of an equal volume of water at the same temperature. For example, if 1
cubic inch of water at 390F weighs 1 unit, and 1 cubic inch of another liquid at 390F
weighs 95 percent of that unit, then the specific gravity of the liquid is 0.95. On the other
hand:

1415.
degrees API = - 131.5
specific gravity

Thus, the water in the example of specific gravity above has an API gravity of 10 degrees,
while the liquid with a specific gravity of 0.95 has an API gravity of approximately 17.5
degrees.
The difference in specific gravity between the oil and water have a bearing on the stability
of the emulsion. The greater the difference, the faster the water can settle. For instance,
in a water-in-oil emulsion, a heavy oil (one with a high specific gravity and low API
gravity) tends to keep water droplets in suspension longer than an oil with low specific
gravity and high API gravity. On the other hand, a lighter water such as fresh water does
not settle out of any oil as rapidly as salt water because salt water is heavier. The fact that
heavier liquids or objects do not stay suspended in a liquid for as long as do lighter liquids
or objects can be illustrated by dropping a steel roller bearing and rubber pencil eraser of
the same size and shape into a tall glass of water. The steel bearing, which is considerably
heavier, goes directly to the bottom, but the lighter rubber eraser sinks slower.
Heating the emulsion increases the specific gravity difference between the oil and water
(lowering that of oil) in addition to lowering viscosity.

2.2.3.3 Water Percentage

A factor that influences to a certain degree the tendency of oil and water to emulsify is the
relative proportion of oil and water produced. Laboratory tests conducted to determine
the influence of oil and water concentrations in emulsions show that emulsification occurs
over a wide range of mixtures, and that maximum emulsibility is reached at some definite
ratio of water to oil.

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A small percentage of water in oil often emulsifies much more thoroughly and permanently
than a large amount. In fact, in many wells producing only small quantities of water, tight
emulsions are formed that disappear almost completely if the percentage of water is
increased beyond a certain limit. In general, the severity of an emulsion problem usually
will diminish when the quantity of water produced by a well approaches or exceeds the
quantity of oil produced.

2.2.3.4 Total Dissolved Solids

The total dissolved solids (TDS) or salinity of the water also influences settling rates. The
heavier the water, the faster the settling. Salinity also influences demulsifier or surfactant
partitioning, as high TDS brine may remain clear but relatively fresh water may become
cloudy using high RSN demulsifiers.
Fresh water emulsions are usually more difficult to treat.

2.2.3.5 Age of Emulsion

Crude oil emulsions are systems that are not in stable equilibrium. According to the laws
of thermodynamics, such systems change continually in an effort to attain equilibrium. As
a result, emulsions increase in stability with age, which generally increases their resistance
to dehydration. With time, the emulsifying agents can migrate to the dispersed water
droplets and coat these droplets completely. Solids (paraffin, clay, etc.) may even coat the
emulsifyed water drops. Age stabilized emulsions may require a much higher chemical rate
to treat, or even a different chemical from the fresh emulsion.

2.3 Theories of Demulsification

There are many theories that have been advanced regarding the problem of resolving crude
oil emulsions. Unfortunately, these are as diverse as the emulsions they concern and no
one theory is equally applicable in all emulsions.

2.3.1 Reverse Phase

In some cases, the breaking of emulsions has been based on the theory that the addition of
a reagent which would produce an oil-in-water emulsion will break a water-in-oil emulsion
by attempting to reverse the phases; and that in so acting, the intermediate condition of
complete demulsification will be accomplished. Though this may sometimes be true, it is
not always the case.

2.3.2 Rigid Film

There is one school of thought that the emulsion breaking reagent may have the action of
making the interfacial film rigid, or to convert it from a plastic, somewhat distensible
envelope, to a glass-like one which has a relatively low coefficient of expansion. When the
enclosed water is expanded by heating, the envelope is shattered and the emulsion is
broken. To extend this suggestion and assume that the reagent has not only the power of
rigidifying the film but actually of contracting it slightly, is to supply an explanation of the
efficacy of such reagents in the absence of heat.

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2.3.3 pH
Other schools of thought postulate that the emulsifier is rendered inactive by the addition
of the demulsifier through neutralization, change in pH or loss of solubility. Reverse
emulsions especially may be treated by charge neutralization (most reverse emulsion
breakers are cationic) or pH change. Most regular emulsions are treated with nonionics.

2.3.4 Electronic Charge

Still others believe that the emulsifying agents are polar bodies and function because of
their electronic charges, and any disturbance of these charges by electron carrying
molecules, will result in breaking the emulsion. This is especially applicable to reverse
emulsions.

2.3.5 Temperature
Another possible explanation of the great effect of small temperature increases in some
cases is that such added heat is sufficient to cause a change of state in the film, i.e.,
converts it from a solid to a liquid and thereby affects its stability greatly. Likewise, the
effects of reagents in the absence of added heat have been asserted to be dependent on
their power to cause such a change of state in the substance comprising the film, thereby
dissolving it from the interface.

2.3.6 Surface Tension

The theory that petroleum emulsion breaking is caused by a reduction in surface tension is
probably the most common. This phenomenon is often referred to without any suggestion
as to what constituent is having its surface tension lowered. It is likewise generally
predicated on a two-component system, whereas petroleum emulsions are definitely three-
component systems. The reagents used may have the incidental effect of reducing the
surface tension of either the water or the oil or both, but it is not identical with predicting
any emulsion resolution on such reduction as a cause.
In any case, the most widely accepted general explanation is that the interfacial surface
between the dispersed component and the continuous component is modified in some
manner. It is generally recognized that the liquid having the greater surface tension will
form the inner, or dispersed, phase. Hence, a change in the surface tension of either
component could result in resolution, provided that the surface tension lowering is stopped
short of the point of reversing the emulsion.

2.4 Treating Methods

The factors involved in treating water-in-oil emulsions include:
1. breaking the film surrounding the small water droplets and coalescing the droplets
to produce larger drops
2. settling the water drops during or after their coalescence
Theoretically, all emulsions separate into oil and water if allowed to settle for an unlimited
time. Much of the water produced with petroleum does separate without the assistance of

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heat, chemicals or other devices. However, the small water droplets in water-in-oil
emulsions are usually surrounded by a tough film that gives the appearance of a plastic
wrap when viewed under a microscope. This film resists being broken, and until the film is
broken, the water droplets do not merge together into coalescence (at least in any
reasonable length of time).
The higher the viscosity of a water-in-oil emulsion, the slower is the settling rate of the
water in it. Thus, if the emulsion is at a low temperature, its viscosity is high, the
separation of water from the oil is slow. Also, the smaller the water droplets are in the oil,
the longer it takes for them to separate out. In addition, if the difference in gravity
between the oil and the water in the emulsion is not great (a small gravity differential), then
their separation is slow. All the various treating practices are directed at increasing the
size of the water droplets, increasing the gravity difference between the water and oil, and
decreasing the viscosity of the oil. Therefore, heat, electricity, mechanical devices,
chemicals and various combinations of them are normally required to cause the film around
the water droplet to break and allow coalescence, resulting in improved dehydration.
It should also be emphasized that no two oil field emulsions are alike. The procedures
used to treat the emulsion produced from one field almost never work as well on an
emulsion from a different field. In fact, the emulsion produced from individual wells
within the same field sometimes varies. Further, the characteristics of the emulsion
produced by a well probably change over a long period of time in the productive life of the
well. This often means that some change in treating methods may have to be made if
treating is to remain effective. It is seldom possible to establish a specific treating program
at the beginning and expect it to be adequate throughout the life of the field. Therefore the
emulsion should be tested frequently, and changes implemented as they become necessary.
It should be noted that demulsifiers do not stop working overnight unless there is a
mechanical problem, chemical contamination such as rain water getting in the tank, or
some other change in the field such as acidizing, fracturing, batch treating for corrosion,
etc. One form of chemically induced emulsion is demulsifier overtreatment. Demulsifier
overtreatment may be indicated by an inability to break the emulsion with a slugging
compound during centrifugation (grindout). Also, the appearance of the oil will be
different (hazy and possibly showing a slight white foam). The possibility of demulsifier
overtreatment may be investigated by verifying pump rates. Demulsifier overtreatment
situations may be corrected by turning off the demulsifier pump and sending the
overtreated oil back through the system, or in some cases, by washing the overtreated oil
with brine.

2.4.1 Application of Heat

Heat alone does not cause an emulsion to break down, except in rare instances. Usually
the application of heat is an auxiliary process to reduce the viscosity of the emulsion and
allow the water to fall through the oil faster. Indeed, if at all possible, heat is eliminated
entirely from the treating process. Where it is necessary to use heat, one of the many
varieties of heaters is used. All emulsion heaters fall into one of two general types:
• direct heaters

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• indirect heaters
At present, most treating plants do not employ heaters that are separate from other
treating vessels. The heater is usually an integral part of a single treating vessel in which
heating and treating are both accomplished.

2.4.1.1 Direct Heaters

In a direct heater, an emulsion comes in direct contact with the firebox, or heating element.
In general, direct heaters are used to heat non-corrosive emulsions that are under
comparatively low pressure. Direct heaters, when operating under proper conditions, are
the most efficient type of heater. The efficiency of a heater is determined by figuring out
how much gas the heater burned to heat up how many barrels of emulsion to the desired
temperature. Four basic types of direct heaters are used in the field:
1. tubular heaters
2. fluid-jacket heaters
3. internal firebox heaters
4. volume or jug-type heaters

2.4.1.2 Indirect Heaters

An indirect heater consists of three main parts
• body
• firebox
• flow-tube bundle
The firebox and flow-tube bundle may be built into the body but are usually removable for
easy cleaning, inspection and replacement. Heat from the firebox is transferred indirectly
through a water bath in the body of the vessel to the emulsion being treated in the flow-
tube bundle.
An indirect heater is less hazardous to operate than a direct heater because the fire does
not touch the flow tubes. Because the flow-tube bundle is not warmed by direct heat, the
temperature of any flow tube cannot be higher than the temperature of the water bath
surrounding it. Also, hot spots do not form in the flow-tube bundle and crack the tubes
because the temperature of the water bath is controlled by a thermostat. The relatively
low, even temperature of the water bath further minimizes salt and scale deposits. Tube
failure is not as likely as in direct heating because many deteriorating effects are held to a
minimum. Also, the oil or emulsion is not in contact with the open flame in the firebox
should a failure occur.

2.4.2 Application of Electricity

The electrical process of dehydration has been used successfully in various oil producing
areas for many years. Since the first electric dehydrator (Chem-Electric) was installed in
1909, many improvements in design and operation have been made. However, the
principle of electric dehydration has remained unchanged.

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The electric field disturbs the surface tension of each drop, probably by causing polar
molecules to reorient themselves. The reorientation weakens the film about each drop
because the polar molecules are no longer concentrated at its surface. In addition, there is
a mutual attraction of adjacent emulsion particles which are given induced charges by the
applied electrical field. This causes them to have a tendency to line up along the
electrostatic lines of force with opposite charged portions of adjacent particles in close
proximity to one another. Since the film is no longer stable, the adjacent drops can now
coalesce freely. In this way, the drops grow in size until they are large enough to settle
out of the oil by gravity.
The addition of heat and chemicals is not an actual function of the electric process of
treating emulsions. However, it is usually necessary to add these to accelerate coalescence
of the water and thus increase the capacity of the unit and also make it more efficient.
Also, demulsifiers help prevent interface pad buildup. Any significant emulsion pad in a
chem-electric is not acceptable as the emulsion pad will short out the grids resulting in
failure to dehydrate the oil (wet oil).

2.4.3 Mechanical Devices

Gravity differential is the difference in the specific gravity of water and oil. In most cases,
water weighs more than oil and therefore settles to the bottom of a tank containing both;
that is, since the specific gravity of water is higher than that of oil, water eventually settles
out. This scientific principle forms the basis for all treating procedures. All operations
involving chemicals, heat, electricity and mechanical devices are designed to prepare the
oil-water mixture for the settling step by speeding up the settling process. However, with
certain emulsions, settling alone is sufficient to separate the oil and water. In other cases,
heat and chemicals must be added prior to the settling stage.
There are four main mechanical devices used for water settling:
1. settling tanks
2. skim pits
3. gunbarrel or wash tank
4. free-water knockout

2.4.3.1 Settling Tank

In the early days of emulsion treating, the basic vessel was a settling tank (Figure 2). In
many older fields, a number of these tanks are still in use. The emulsion entering the tank
may come from the wellhead, a separator, or even some type of heater treater. The well
fluids are distributed into the bottom of the tank by means of a distributor, or spreader.
The spreader shown is simply four sections of slotted pipe radiating from a four-way tee.
The ends of the slotted pipe are plugged so that all the fluids leave the pipe through the
slots and are well dispersed over the tank bottom. This simple hookup does not provide
for conserving the light ends of the crude. Therefore, the lighter fractions of the produced
oil tend to escape, thus, decreasing the gravity and volume of the oil. Nevertheless, a
simple settling tank often proves adequate when economy is the prime factor.

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Conductor

Inlet From
Oil Outlet
Field

Water
Oil Siphon

Water

Distribution Rack
Pipe - Slotted &
Plugged on Ends

Figure 2

2.4.3.2 Skim Pits

A skim pit is simply an earthen pit (now generally lined with concrete) into which large
volumes of well fluids are produced. Only a fraction of this well fluid is oil, which rises to
the surface of the water and is skimmed off by a series of baffles as the water flows across
the pit. Although the skim pit represents a final effort to extend the economic life of wells,
significant quantities of oil are recovered in this manner. Environmental concerns and
opportunities for contamination of the produced fluids have dramatically reduced the use
of the skim pit.

2.4.3.3 Gun Barrel or Wash Tank

A wash tank, or “gun barrel” as it is more commonly known, is a settling tank that is fitted
with an internal or external boot, or flume. Although gun barrels are not employed to the
extent now that they once were, many are still in use. They are worth studying in part
because certain principles of breaking emulsions can be observed by a description of gun
barrels.
In general, gun barrels are composed of five principle parts, each of which serves one or
more specific purposes (Figure 3).

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Gas Equalizer

Gas
Emulsion Out
From Field

Oil
Out

Clean
Oil

Emulsion
Conductor
Pipe
(Downcomer)
Water
Water

Water
Out
Spreader

Figure 3

1. The inlet line is the pipe that conducts the emulsion (water and oil) from the oil and
gas separator to the gun barrel.
2. The conductor pipe (also known as the boot, flume, downcomer or stack) is the
large pipe through which the emulsion passes before entering the bottom of the gun
barrel. The boot may be mounted either inside or outside the tank, and serves
three main purposes.
a. Gas separates from the emulsion inside the boot, and thus turbulence is reduced
within the body of the gun barrel.
b. It serves as a surge tank to prevent slugs of emulsion from being injected into
the gun barrel.

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c. It spreads the emulsion more evenly throughout the water wash by means of a
spreader, or apron, which is attached to the bottom of the boot.
3. The body, or tank, holds the water wash (or water layer), emulsion and clean oil
layers and allows time for the oil and water to separate.
4. The water outlet (also called the “water leg”, outside siphon, or “grasshopper”)
serves two purposes.
a. It provides an outlet for the water that has separated from the emulsion.
b. It is used to regulate the amount of water held in the gun barrel.
5. The oil outlet line conducts the clean oil from the gun barrel to the storage tanks.
The majority of gun barrels have several other part, such as gas equalizers between the
tank and conductor pipes, gas lines, bleeder line, and gauge glasses. The oil and water
interface may be seen through the gauge glass.
The principles on which the gun barrel operates are best seen by tracing the path of the
emulsion through it and describing what happens in each step (refer to Figure 3). Assume
that settling is being used as the sole means of separation of the water and oil and that no
heat or chemical is added, although often chemicals are injected and a heater is installed in
the system before the emulsion reaches the gun barrel. As the emulsion enters the
conductor pipe from the inlet, it is subjected only to atmospheric pressure. Since it is
necessary to exert pressure on the oil and gas separator, which is located in the emulsion
stream ahead of the gun barrel, some gas comes out of solution with the decrease in
pressure as the emulsion enters the gun barrel. This gas is carried out through a gas outlet
line to be vented, or to a gas gathering system. Only liquid flows down the conductor pipe
to enter the gun barrel near the bottom.
A spreader is placed on the bottom of the conductor pipe to spread the emulsion out so
that it is distributed through the water wash. If the spreader was not there, the emulsion
would channel through the free water held in the gun barrel in one large column. The
spreader is usually placed about 2 feet off the bottom of the vessel. This depth immerses
the spreader as deeply as possible in the water, yet keeps it above the sludge that may
accumulate in the bottom of the tank. The diameter of the spreader depends on the size of
the gun barrel; it is usually from about 40 to 70 percent of the diameter of the tank, but
some are smaller.
Some emulsion breaking occurs as the emulsion comes in contact with the surface of the
spreader and flows from the center to the outside rim of the spreader. Spreaders are
designed so that the emulsion emerges from them in very small streams. As the streams of
emulsion rise through the free water, some emulsion breaking occurs by the close contact
of the emulsion and free water. Many of the water droplets are washed out of the oil,
allowing clean oil to continue to rise.
Above the free water held in the gun barrel are two liquid layers, the top layer containing
clean oil and the next layer containing emulsion. These layers are not clearly defined, but
blend into each other. As the emulsion rises fairly rapidly through the free water due to
the difference in specific gravity of the two liquids (oil being lighter than water), it goes
into the layer of emulsion already present above the free water layer. In the emulsion layer

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the rate of travel is slower, and the remaining water and solids settle out. Oil, being lighter
than emulsion, rises to the top and exits through the oil outlet to the storage tanks.
In summary, the action that occurs in the gun barrel to separate oil and water is divided
into two main parts:
1. Washing
The washing is done in the free water layer.
2. Settling
Settling occurs in the emulsion layer.
Since not all emulsions are alike, no set pattern on the amount of free water that should be
held in a gun barrel can be established. For instance, washing has little or no effect on
certain emulsions; therefore, in such cases a very small amount of free water in the tank is
all that is necessary. On the other hand, some emulsions completely break down by
washing; therefore, it is advantageous to have a large amount of free water in the gun
barrel.
When selecting a demulsifier for a gun barrel system, it is especially important to select the
product which shows the lowest BS in the grindout. This will reduce the potential for
accumulation of an interface pad.

2.4.3.4 Free-Water Knockouts (FWKO)

Free water is produced with oil that settles within five minutes while the well fluids are
stationary in a settling space within a vessel. Free water, then, is not part of the emulsion
and may be readily separated by the force of gravity alone. Free water removal prevents
overloading the heating and treating plant. For instance, consider that it takes about three
and one half times more heat to raise the temperature of water than oil. Therefore, if most
or all of the free water is removed first, then substantial savings in the fuel needed to fire
the heater can be made. A “free-water knockout” is a vessel that is used to remove
excessive amounts of free water in the flowlines ahead of the treating plant.
While there are many different configurations, free-water knockouts are either two-phase
or three-phase in design. A two-phase FWKO is designed such that only the free water
separates from the oil or emulsion. A three-phase FWKO separates free-water and gas
from the oil or emulsion (Figure 4).
In general, a free-water knockout is simply a vessel that provides a space for free water to
settle out of an emulsion. Sometimes filter material is installed in the FWKO to aid in
removing tiny droplets of oil or emulsion that may be entrained in the water as it passes
through the filter. The free water is drawn off the bottom of the unit, and the emulsion or
oil passes out the top to the treating system. Thus, all free water is removed, and only the
emulsion is handled by the heating or treating system.

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 Emulsion Breaking 15

Gas
Out
Baffles Emulsion

Inlet

Emulsion
Out

Water Water Out

Figure 4

2.4.4 Chemicals
Under proper conditions, emulsions are resolved quickly and effectively by chemicals
synthesized to have demulsifying properties. To break an emulsion chemically, the
chemical must be carried to the interface of the emulsified water and the surrounding oil.
In this action, it is believed that the chemical powers the interfacial tension of the oil and
water, allowing the dispersed particles to coalesce into larger drops which then separate
from the oil.
The resolution of emulsions by chemical means has a wide range of application; it is
equally adaptable to either large or small scale operations and has a high degree of
flexibility. Moreover, chemical treatment permits facilities to be proportioned to the
volume of oil treated so that the installation of a large capacity plant during the period of
flush production does not penalize the operator unduly by increasing his treating costs later
when the quantity of emulsion to be treated has declined. Chemical dehydration requires
only a low initial investment in plant equipment and operating costs are not high.
The success of treating emulsified oil depends upon:
• An adequate quantity of the most effective chemical.
• Sufficient agitation to cause thorough mixing of the chemical with the emulsion.
• Where necessary, the addition of heat to facilitate breaking of the emulsion. “Cold
treating” may be possible if ambient temperature is above the paraffin cloud point, or if
working with a frozen or icy emulsion, the emulsion is first melted. Cold treating
usually requires considerably more demulsifier than treating with heat. There is usually
an economically effective ratio of chemical to heat, as well as a practical one.
• Proper handling and separation of the gas before settling.
• Sufficient time to permit settling of the released water.

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 Emulsion Breaking 16

2.4.4.1 Chemical Injection Points

To obtain uniform distribution of the demulsifier and maximum chemical action with
minimum chemical consumption, the demulsifier should be introduced where the
subsequent flow through the system will provide optimum agitation.
In general, best treating results are obtained by introducing chemical before the well fluid
enters the gas separator, preferably at the wellhead or into the flow line as close to the
wellhead as possible. In this way, use is made of the agitation in the flowline and the
equipment between the well and the separation equipment. Injecting the treating chemical
into the well fluid after it has passed through the separator usually results in excessive use
of chemical because the amount of agitation in the system beyond the separator is
insufficient to be fully effective. Where flowlines from several wells are manifolded into a
header and the emulsion from the different wells are relatively uniform, it is desirable to
introduce the chemical directly into the header. Where one well is producing most of the
emulsified oil, it is often practical to inject the chemical necessary for all the wells into the
flowline near the wellhead of the offending well. Of coarse, other provisions for injecting
chemical must be made if the well producing most of the emulsion is shut-in.

2.4.4.2 Selection of Chemicals - The Bottle Test

The bottle test is performed to assist in the selection of the treating compound which will
most effectively break the emulsions from any given well, lease or field. The bottle test
results may also be used as an indication of the ratio of treating compound to emulsion
which will be required to achieve salable oil.
There are some basic rules which need to be followed in carrying out a proper and
informative bottle test.
• The sample used for the bottle test must be chemical free and representative of the
emulsion to be treated. If possible, always use a composite sample.
• The sample should be as fresh as possible because rapid aging of some emulsions
affects their susceptibility to treating.
• The same conditions of agitation, heat, dosage and retention time as are found on
the lease should be simulated as closely as possible. The system survey should also
note any recent changes in the field, chemicals, workovers, etc.

Bottle Test Procedure

The bottle test is performed in three separate functions, which are: Ratio Test, Elimination
Test, and the Confirmation Test. While a detailed bottle test procedure is provided in your
REDIFAX, the following is a basic description.
1. Obtain a chemical free, representative sample of the emulsion to be treated.
2. Drain off the free water, mix residual crude oil, and centrifuge a sample to obtain the
BS&W (basic sediment and water) content. Record on the bottle test report form.
Important: It may be necessary to use the amount of free water in your test that
the emulsion sees in the system (water levels in the FWKO and
treating vessels). Water may have to be added back to the bottles to

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 Emulsion Breaking 17

facilitate demulsification of some emulsions with low levels of

dispersed water (2-3%) in order to provide a water wash.
3. Fill 6 oz. prescription bottles to the 100 ml. mark, cap, and invert to coat the glass with
an emulsion film.
4. Add proper dosage of 10% solutions of compounds to be tested. 1% or 2% solutions
may be needed for better dispersion of the demulsifier in heavy crude to duplicate
results in the system.
5. Agitate the bottles to disperse the chemical into the emulsion.
6. If the emulsion requires heat for treatment, place the bottles in a water bath at the
system temperature.
7. After agitation, observe and record the water drop, interface, and water quality data
during periodic time intervals (Figure 2A-1 found in the Appendix).
8. After maximum water drop and/or clean oil is achieved in one or several bottles,
perform the thief (oil layer only) grindouts and composite (oil and emulsion
layer)grindouts. Record the results. In general, thief after residence time in the system
is reached. If the best water drop sample is still higher in BS&W than the system,
continue to run the test and thief the best sample at intervals until pipeline specification
is reached.
a) Fill the centrifuge tubes to the 50% mark with a suitable hydrocarbon solvent. DO
NOT USE GASOLINE as it often contains emulsion breaking compounds.
Xylene is a good solvent as it is a good paraffin solvent and helps differentiate
paraffin from emulsion.
b) Set the thief pipette approximately 15-20 ml. above the oil/water interface of the
bottle with the maximum water drop.
c) Draw oil from a bottle and fill the centrifuge tube to the 100% mark. Mix the
contents of the tube by shaking and place in the centrifuge. Continue this process
until all bottles have been sampled. Centrifuge and record the results.
d) After all the tubes have been centrifuged, an excess chemical or “slug” grindout
should be performed on all the tubes. Add 2-3 drops of a suitable emulsion
breaker to each tube, mix thoroughly, and heat to 1500 if appropriate. Centrifuge
and record the results. The lowest BS&W is the goal. If two grindouts show the
same total BS&W, the product which shows the lowest BS (higher water) is the
best choice, as an interface pad will be minimized.
e) Next, a composite grindout should be performed. The lower water layer of each
bottle should be removed.
f) The bottle is then mixed by hand and steps a) through d) are repeated. In step b),
it is not necessary to use a pipette. The sample may simply be mixed and poured
into the centrifuge tubes.
Ratio Test
The Ratio Test is the first function of the bottle test. Normally, the compound in use for
the emulsion is dosed at different levels to determine the proper dosage for treatment. A
general rule of thumb is to dose the compound at three levels below and three levels above

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 Emulsion Breaking 18

the existing rate. The ratio test prevents wasting time in the Elimination Test by dosing
too low (resulting in no treatment), or dosing too high (resulting in too many compounds
giving good results and possibly resulting in overtreatment). The Ratio Test is also where
the parameters of the bottle test are defined. This is where, based on system information,
agitation, dosage, heat and retention time are determined to produce salable oil with the
compound in use.
An overtreat ratio (3 to 5 times the normal treating rate) indicates if overtreating is a
problem. If at all possible, avoid products which overtreat. The low ratio, below the
treating rate, exaggerates treating differences and helps select the best product.

Elimination Test
The second function of the bottle test is the Elimination Test. After the test parameters
have been determined, the bulk of the testing will be accomplished during the Elimination
Test. Instead of dosing one compound at several ratios, many compounds will be dosed at
the same ratio. Sometimes, many compounds are dosed at several ratios. The ratio to use
will be based on the results of the Ratio Test. The Elimination Test is completed when all
the desired compounds have been screened and several promising ones have been
identified.

Re-emulsification Test
After grindouts have been obtained, re-mix the separated emulsions of the best chemical
candidates to determine which do not re-emulsify.

Confirmation Test
The Confirmation Test is the last function of the bottle test. The Confirmation Test is
nothing more than a Ratio Test with the best compounds identified during the Elimination
Test. Several ratios below and several ratios above the dosage that gives salable oil should
be run. The results of the Confirmation Test should determine the best compound that
treats this emulsion to pipeline oil, and indicate the optimum and range of the dosage.

Bottle Test Results

During the bottle test, compounds are evaluated and observations are made on several
criteria. These observations are recorded on a bottle test report form for comparison
study and as a permanent record of knowledge. Below are the main criteria recorded on
the bottle test report for the evaluation of emulsion breakers.
1. Water Drop - Water drop is defined to be the water which coalesces and settles to the
bottom of the prescription bottle. The relative speed of the breaking of an emulsion is
usually indicated by the speed of water drop. The speed of water drop can be
misleading. Sometimes a compound will show rapid initial water drop and then stop
before all the water is released. The best water drop is both fast and complete. The
importance of the speed of water drop depends on the system treating the emulsion.
As a general rule, as the retention time is increased, the importance of speed is
decreased. It is generally advisable not to select a product which drops water much
faster than the system residence time.

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 Emulsion Breaking 19

2. BS&W Content of Oil - BS&W stands for basic sediment and water. Basic sediment is
usually unresolved emulsion but can also include organic and inorganic solids. BS&W
can be distinguished in crude oil by a trained and experienced bottle tester using the
naked eye. As the BS&W content decreases, the deeper the color and brighter, or
polished looking, the oil layer becomes. The best and most accurate way to measure
BS&W content is to perform a thief grindout and slug grindout on the oil. The thief
grindout measurement tells how well the emulsion is resolving, and how complete is
the water release, or dehydration. The slug grindout tells if there is any secondary
emulsion in the oil. Secondary emulsion is a new term that will be defined and
distinguished from normal, or primary emulsion, as follows:
a). Primary Emulsion - The BS which is thrown down on centrifuging a sample of
crude oil without the addition of an excess (slug) amount of treating chemical.
Primary emulsion is thrown down as a more or less well defined layer.
b) Secondary Emulsion - The additional amount of BS which is present in the
grindout tube which did not pack down on centrifuging and which on treatment
with an excess (slug) of chemical is broken down to oil and water. The presence of
secondary emulsion results in the water reading of the slug grindout to be larger
than the sum of the BS and water readings of the unslugged grindout.
Generally, the best compound will be the one which has the lowest slug grindout with
the least amount of BS in the unslugged grindout.
If there is a question whether the sediment is paraffin or emulsion, the centrifuge tube
may be heated. If the sediment separates with heating to show water and oil, it is
emulsion. If the sediment melts and no water appears, tilt the tube. Paraffin will re-
solidify along the side of the tube.
3. Interface - In the ideal treatment of crude oil emulsions, the oil-water interface should
be a sharp, clean line without any web or sludge. Presence of a considerable amount
of sludge or web is undesirable. In a treating plant, this foreign material will eventually
go to stock and be reported as BS. Trace amounts of web or sludge seen in the bottle
test, however, may disappear or treat out in the treating plant. Foreign materials at the
interface can often be seen through visual observations and are recorded for reference.
Sometimes, the condition of the interface is not easily seen and needs a more accurate
method of evaluation. The composite grindout is the tool used to determine the
quality of the oil contained between the oil-water line and the level at which the thief
grindout was taken. Some compounds are referred to as “sludgers”. This means that
they give good thief grindouts, but make sludge of water, BS, or both at the interface.
These compounds may yield clean oil for a time, but eventually a pad will build and
grow at the interface, spilling over to stock and causing bad oil. The composite
grindout will reveal this potential problem.
4. Water Quality - During bottle tests, water quality is noted and recorded for reference.
Concern for the environment, injection well plugging, formation damage, and increased
treating cost are a few reasons why water quality is important in treating regular
emulsions. Although most production facilities have water treatment systems, it is
important not to add to or create water problems with regular emulsion breakers.

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 Emulsion Breaking 20

Selecting an emulsion breaker compound which produces clean oil and clean water is
the ultimate goal.
High RSN demulsifiers or wetting agents (surfactants) can cause cloudy water by
dispersing oil in the water phase, especially in fresh water. In high TDS water, higher
RSN products may be used without oil-in-water problems.
5. Treating Range - Compounds with the widest treating range which yields good
emulsion treatment are preferred, but not always the best for a certain application.
Wide treating range products are better able to handle fluctuations in product rates,
system upsets, temperature changes, and are easier to introduce into a treating plant.
Wide treating range compounds also help overcome the tendency of field operators to
increase dosages when system upsets occur. If this happens and the compound goes
into an overtreat condition, this attempted solution can make the problem worse than
the original problem.
Testing on a composite sample over several days is recommended to insure consistent
demulsification. If you select an emulsion breaker based on samples from one well,
there is a chance the product may not be effective for the entire field.
The treating system may dictate the importance of one factor to be weighted more heavily
than another; but all of these criteria should be considered when evaluating emulsion
breakers by the bottle test. The bottle test is not an exact science, only a tool to aid in the
selection of emulsion breaker compounds. It is a static test performed on a dynamic
system and cannot duplicate the true fluids. Nevertheless, the bottle test remains the
industry standard for emulsion breaker evaluation.

2.4.4.3 Plant Testing an Emulsion Breaker

Once a chemical has been selected from the bottle test results, it is time to plant test the
product. If the bottle test was run carefully and the chemical selected properly, the plant
test should be successful. During the plant test, there are many observations which should
be made. These observations should be recorded on the Plant Test Report for use in
presentation to the customer, or for future reference. Listed below are some of the
observations that should be made:
1. The actual test begins several days before the chemical is changed. All the data listed
in 2 through 9 should be taken while the present chemical is still being used to treat the
system. Gathering this data will insure that you have a good comparison of the
performance of the product to be tested.
2. Chemical consumption and injection points - all chemicals being used, not just the
emulsion breaker.
3. Daily production.
4. Temperature in the treating vessels.
5. Condition of oil coming to the treating vessels.
6. Condition of oil going to stock.
7. Obtain some idea of the size of the emulsion pad in the vessels.
8. Height of the water level and depth of the oil in the vessels.

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 Emulsion Breaking 21

9. Obtain a thorough knowledge of the operation of the lease or system. This should
include such things as the frequency of bad tank bottoms, the average shipping cuts,
the well treating schedule, and the BS&W allowable for the wells involved.

August 25, 1997 Nalco/Exxon Energy Chemicals, L.P.

 APPENDIX

Bottle Test Report

Company: Field: Lease:
Wells: Current Chemical: Rate:
Gravity: Type System:
District: Oil / Water Production: Page: of

Testing Data Water Drop ( minutes) Thief Grindout Composite Grindout

Line Product ppm B.S. W Slug B.S. W Slug
Agitation 1st 2nd 1
Time 2
Amount 3
Temp. 4
Bath Temp. 5
Time of Thief 6
Test Length 7
Samp. Size 8
Soln. Conc. 9
10
Grindout B.S. Water 11
Straight 12
50/50 13
Slug 14
Codes for Observation 15
Condition of Water 16
Post Treatment 17
18
CW - Clean Water 19
H - Hazy 20
D - Dirty 21
22
Condition of O/W Interface 23
24
V - Very 25
S - Slight 26
W - Webby 27
R - Rag 28
B - Bag 29
GI - Good Interface 30
FE - Fish Eggs 31
32
33
34
35
36
37
38
39
40

Observations:

Tested by: Date:

Figure 2A-1

August 25, 1997 Nalco/Exxon Energy Chemicals, L.P.