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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.
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.
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
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.
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.
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.
2.3.3 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.
2.3.5 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.
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.
• 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.
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).
Conductor
Inlet From
Oil Outlet
Field
Water
Oil Siphon
Water
Distribution Rack
Pipe - Slotted &
Plugged on Ends
Figure 2
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.
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
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.
Gas
Out
Baffles Emulsion
Inlet
Emulsion
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.
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.
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.
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.
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.
Observations:
Figure 2A-1