Chapter 3: De-Oiling Produced Water

Chapter 3: De-oiling Produced Water

3.1 Problem
Oil field produced water often contains residual quantities of oil and, in many cases, solid
particles. The oil can be either a source of revenue if removed or a source of problems if left in
the water.
Lost Revenue — Any oil left in the water wastes the time and money spent bringing it to the
surface. Even small amounts of oil removed from the water over a period of time can lead to
significant increases in revenue.
Reuse of Water — When produced water is used to supply a water-flood or steam-flood
program, it must be clean. Oil and solids can quickly foul expensive water softening resin
beads. Dirty water can also lead to costly maintenance programs for injection wells.
For both reasons many types of equipment are used to remove as much oil as possible.
Chemicals are used to improve the efficiency of equipment and reduce the cost of operation.
The solids found in produced water are commonly particles of silt, sand, and clay from the
formation, or they can be the byproducts of corrosion and scale formation. These solids are
usually removed along with the oil. They are eventually removed from the system as a waste
material or passed to the refinery with the salable oil.
In addition to the loss of revenue and the reuse of produced water, concerns for nature have
resulted in many new laws, regulations, and agencies that closely monitor the oil left in produced
water. Producers are severely penalized for discharging dirty water to the environment. Offshore
platforms have been shut down for dumping water into the ocean that leaves a visible sheen.
Chemicals increase the amount of oil a producer can sell. They help avoid costly equipment
repairs. They also protect the environment and help avoid expensive fines.
3.2 Theory
Water is almost always produced along with the crude oil. Usually when a new field is
discovered, the production is almost “dry”. The oil contains only a small percentage of water.
This soon changes. Each year the production contains more and more water, especially where the
water is pumped back into the formation. Eventually far more water is produced than oil.
Emulsions are formed, as the oil and water are co-produced. Even though the liquids are
immiscible, they become thoroughly mixed when produced to the surface and flow through the
production equipment. Additional agitation results as the liquids experience turbulence through
all the various pipes and fittings. All of this energy breaks both the oil and water into many tiny
droplets. Solids and naturally occurring surfactants often stabilize these droplets. The stabilized
droplets of water result in wet oil or regular emulsions. The stabilized droplets of oil create dirty
water or reverse emulsions.
Regular Emulsion — Wet oil, or water-in-oil mixture
Reverse Emulsion — Dirty water, or oil-in-water mixture
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Both regular and reverse emulsions exist as the production reaches the surface. A sample of the
reverse emulsion can be obtained at the wellhead. A composite of several wells can be obtained
at any convenient gathering point. For example, an automatic well testing station (AWT) is a
common sample point. When filling a five-gallon sample container with production, the two
emulsions will quickly separate. The reverse emulsion is taken from the bottom.
Continuous agitation makes it difficult for the oil and water to separate before the dehydration
system. However, the reverse emulsion can be broken and made ready to quickly separate. The
chemicals used to treat dirty water emulsions actually require agitation and, therefore, work best
as far out into the field as possible.
If the reverse emulsion is completely broken before it enters the dehydration system, most of the
oil will be efficiently removed in the free water knockout (FWKO). Some dispersed oil will still
remain in the water but is removed later in the more specialized equipment found in the water
clarification system. Water leaving the FWKO is directed to a storage tank often called a
produced water tank (PWT), CPI, precipitator, or skim tank.
Oil leaving the FWKO often requires further treatment to remove water tied up as a regular
emulsion. A heater treater (HT) supplies heat, which helps break oil emulsions. As these
emulsions are broken, additional quantities of water and solids are released from the oil. This
water joins the water from the FWKO at the produced water tank.
3.2.1 Types of Oil-in-Water Mixtures

The residual oil left in produced water is usually found as combinations of free, dispersed, and
emulsified oil.
Free oil — Produced oil that automatically separates from the water phase when agitation is
stopped or decreased.
Dispersed oil — Tiny droplets of produced oil that separate very slowly from the water phase
when agitation stops.
Emulsified oil — Tiny droplets of produced oil that is physically and chemically stabilized in
the water phase.
3.2.1.2 Soluble and Insoluble Oil
Produced water contains:
Insoluble oil, which is the oil that can be removed with conventional water clarifiers.
Soluble oil, which is not a true hydrocarbon but does show up in the IR and Gravimetric
readings as true oil.

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Soluble oil is a structure of naphtha and carboxylic acid chain that comes out of the oil phase but
does not cause sheen no matter how high the soluble oil content. Soluble oil will not cause the
water to become hazy or cloudy. The water can have a crystal clear appearance and still have an
IR reading of 200 ppm. Soluble oil is not removed from produced water with conventional water
clarifiers. Soluble oil must be treated in total fluid with an acid. Lowering of the pH will drive
the soluble oil back into the oil phase and out of the water phase. However, not all of the soluble
oil will be removed in this process. Approximately 80 to 85% of the soluble oil is removed fairly
easily and the remaining 20% will take a very high volume of acid to remove, or they may never
be removed.
Products containing phosphoric or phosphorus acid are regularly used in total fluid to remove
soluble oil. Caution needs to be exercised when using the phosphoric acid products. Phosphoric
acid will form calcium phosphate scale when used in produced waters that have significant
amounts of calcium present. Phosphorus acid will not react with calcium, and that is why it is
mostly widely used. Phosphorus acid is extremely corrosive and incompatible with 316 SS.
Hastalloy metals are recommended to be used in the injection system for any acid products.
Caution must be taken when using these products. The phosphorus acid can eat quickly through
metal if leaks are not attended to promptly. An injection quill must be used so that the acids can
be delivered directly into the produced fluids. This will keep the piping internals from corrosion
attack.
To determine if soluble oil is present in the produced water, a silica gel extraction test must be
run. This test is run with the regular Freon extraction test. After the Freon extraction, the sample
is run on the IR and is recorded as total ppm. The Freon extract is dispensed into a beaker, and
silica gel is added to the Freon extract. The sample is stirred for approximately one minute. The
sample is then allowed to sit. The silica gel will fall to the bottom of the beaker and separates
from the Freon. The Freon is filtered again and collected in the IR cuvette and placed in the IR
machine again. This reading will be insoluble oil ppm only. The insoluble oil ppm is then
subtracted from the total IR ppm, and the result is considered the soluble oil portion.
3.2.2 Water Clarification Techniques

Equipment used for water clarification varies greatly from field to field and often involves a
combination of techniques. The basic methods for cleaning water are outlined below. The most
frequently used are centrifugal and gas flotation. Of course the efficiency of any technique or
piece of equipment is greatly improved with the addition of chemicals.
3.2.2.1 Natural Separation
Insoluble materials will separate with time. Density differences will drive the contaminants out
of the water.
3.2.2.2 Distillation
Water can be boiled away from the contaminants. This very expensive method is only used in
special circumstances.
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3.2.2.3 Centrifuge
Spinning motion speeds up the process of natural separation by increasing the effective gravity.
3.2.2.4 Filtration
Solids and liquids can be physically trapped and removed from the water.
3.2.2.5 Coalescing
Coalescing is the action of combining droplets of oil together with the aid of a surface.
3.2.2.6 Gas Flotation
Tiny gas bubbles tend to attach themselves to solid and liquid contaminants and cause them to
float to the surface for easy removal.
3.3 Typical System and Equipment

Many types of oil and water separation equipment are seen in the oil field. Since crude oil varies
from high to low gravity and from thin to very thick, a wide variety of systems will be
encountered. Naturally, the more difficult it is to separate the oil and water, the more complex
the equipment and systems.
In the oil and water separation process, there are four basic steps. These steps can be classified as
production, dehydration, water clarification, and reuse or disposal.
3.3.1 Production
Production equipment includes everything that brings the oil and water to the surface. This
includes producing wells, headers, automatic well test equipment (AWT), and flowline. All of
this equipment is a source of agitation that thoroughly mixes the oil and water (Figure 1).
3.3.2 Dehydration
The dehydration equipment includes all the various tanks that help the oil and water separate.
Some tanks, called free water knockouts (FWKO) simply provide time for the easy, or free
water, to separate. Next, a Heater Treater (HT) is commonly used to heat the crude oil emulsion
(as described in section 3.2). Heat helps break the emulsion and lowers the percentage of water
in the oil to pipeline specifications.

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Gas Sales Oil Sales

Emulsion
2
Phase Oil
Emulsion Sep. Stock
Tank
Dry
Emulsion Oil
FWKO Heater Treater
Water
Surge
Tank
Media Filters Gas Flotation Water
To Injection/Disposal
Figure 1
3.3.3 Water Clarification

The water clarification equipment is designed to remove small residual quantities of oil and
solids from the produced water. In Figure 1, the produced water is collected from both the
FWKO and HT and is stored for additional clarification in the produced water tank. The gas
flotation unit removes the bulk of the contaminants. It is designed to mix gas bubbles with the
water. These bubbles have a tendency to stick to the contaminants. With the aid of the bubbles,
droplets of oil and solid particles are encouraged to float to the surface for easy removal.
3.3.4 Reuse or Disposal

Reuse or disposal equipment is used to send produced water to its final destination. In Figure 1,
this includes the water softeners and steam generators needed to produce steam. These are
followed by an injection well, which forces the steam back into the production zones of the
formation.
In most offshore applications the water is prepared for discharge to the ocean.

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3.4 Mechanism of Chemical Solution to Problem
3.4.1 Coagulation
The processes of coagulation and flocculation are very important ways to separate contaminants
from dirty water. Often the two terms are used interchangeably, but knowing the differences will
give a much clearer understanding of water clarification.
Coagulation is the process of encouraging small droplets of oil to merge or coalesce to form
larger droplets.
As the droplets increase in size, they separate from the water phase many times more easily. In
order to promote coagulation there are several stabilizing factors that must be overcome.
3.4.1.1 Charge Neutralization
Usually droplets of oil and particles of solids possess a natural negative charge, which is the
result of various negative ions and dissociated organic acids. These charges result in a force of
repulsion often measured as zeta potential. Crude oil contains a variety of organic acids called
napthenic acids. These not only increase zeta potential, but also increase the dispersability of oil
in water by a process known as surfactant stabilization. Until chemicals are added to neutralize
the zeta potential and decrease surfactant stabilization, coagulation is usually difficult and very
slow.
3.4.1.2 Solids Wetting
Solids can interfere with both oil dehydration and water clarification. They give rise to steric
stabilization, which simply means the solids act as a physical barrier preventing contact between
droplets. Solids often come up from the producing formation as sand, silt, and clay. Solids can
also be formed by the process of corrosion, scaling, and microbiological activity. Many of these
solids tend to coat the surfaces of the various droplets and hinder the coagulation process.
Chemicals having a degree of surfactant nature are able to remove solids from droplet surfaces
and enhance coagulation.
3.4.1.3 Surface Tension Reduction
Even after the zeta potential has been neutralized and the solids have been treated, there remains
the problem of surface tension. Surface tension acts like a skin around each droplet that must be
broken before the droplets can coalesce. Chemicals that can minimize or reduce surface tension
make collisions between adjacent droplets more likely to result in coagulation.

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3.4.2 Flocculation
To remove oil from water, we must either increase the size of the oil droplets, as we did in
coagulation, or form flocs. A floc is a network of tiny droplets and solids that are loosely
attracted to each other.
Flocculation is a process of agglomerating small droplets and solids into clusters.
Both coagulation and flocculation serve to concentrate the contaminants, which helps improve
the speed of separation from water.
3.4.2.1 Partial Charge Neutralization
If the zeta potential is not completely neutralized, there will remain a small force of repulsion
between the contaminants preventing coagulation. However, naturally occurring forces of
attraction, known as Van Der Waals forces, often become strong enough to hold the tiny
contaminants in close proximity. Thus, the zeta potential is neutralized; a point is reached where
tiny flocs begin to form. Depending on the amount of solids, the floc will float or sink, and the
contaminants will begin to separate from the water.
3.4.2.2 Polymer Bridging
Since flocs are very loose agglomerations, a small amount of agitation can easily break the floc
and redisperse the oil and solids. Fortunately, flocs can be stabilized and their size increased by
polymer bridging. Polymer bridging uses very high molecular weight molecules to physically tie
the individual and flocculated contaminants together. Once linked by polymers, the flocs are
stabilized and able to survive more vigorous agitation.
3.4.3 Adsorption
In a filter or coalescer, oil and solids are removed from water by grains of media. Media can be
sand, garnet, coal, or even ground-up walnut shells. Any of these materials will remove
contaminants by trapping them between the various grains of media. Very small contaminants
will be able to find their way through passages between the media. However, if the media is
treated with a highly cationic polymer, many of the small negatively charged contaminants will
be attracted to and adsorbed onto the media. Thus, adsorption can be used to increase the
efficiency of filters and coalescers.

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3.5 Chemical Description of Products
Water clarification products can be divided into two groups: solution polymers and latex
polymers. The division is based on whether the chemical is a water-based solution or as a two-
phased suspension called a latex. Solution polymers have low to moderately high molecular
weights, while latex polymers are extremely high molecular weight vinyl polymers.
3.5.1 Solution Polymers

A solution polymer may be a mixture of salts, solvents, and a water-soluble active ingredient.
The active material is often an organic polyamine, but a metallic salt may be used alone. Most
water clarification products are solution polymers. These products are easy to make and are easy
to use in the field.
3.5.1.1 Metal Salts
Metal salts are excellent choices for neutralizing zeta potential. Metallic ions with a multiple
positive charge are the most efficient. Zinc chloride and aluminum chloride are the most
common examples.
3.5.1.2 Polyamines
Like metallic salts, polyamines help neutralize zeta potential and speed up the coagulation
process. The significant advantages of polyamines are the abundance of positively charged
amine sites plus the surfactant and polymer bridging qualities that can be built into the polymer.
Polymers with high-charge density can be used as alternatives to metals. In filtration
applications, highly charged polyamines easily attach themselves to the filter media and still
have enough cationic charge potential to help remove oil and solids from the water. Higher
molecular weight solution polymers have the ability to help as flocculants through polymer
bridging. In all of the polyamines, there is a degree of surfactancy not found in metal salts, which
helps reduce surface tension and increases solids wetting.
3.5.1.3 Reverse Emulsion Breakers
Reverse emulsion breakers are polyamines proven especially useful for resolving oil-in-water
emulsion. These products incorporate surface-tension-reducing properties into the polyamine
chemistry and are often blended with metallic salts that speed coagulation. Other chemistries
utilized in total fluid are anionic polyacrylamides and dithiocarbamates. These are common to
production systems in the Gulf of Mexico and are used during well flow-back. These products
can also be used continuously in total fluid to improve interface and water quality in separators
with water cuts typically above 50%.

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3.5.2 Latex Polymers
3.5.2.1 Oil External
Oil external latex polymers are made from water-soluble monomers, suspended as small droplets
within a surrounding organic liquid. Droplet formation is done before polymerization. This
permits much larger polymers to be formed within the individual droplets without the problem of
long polymer chains forming very thick or solid products. Thus, for polyamines that become
more efficient as their molecular weight increases, a latex version of the chemistry is often
chosen.
Oil external latex polymers can be either anionic or cationic and have molecular weights in the
millions. When oil external latex is used, the polymer must be inverted to release the various
charged molecules. Inversion is accomplished through the use of surfactants, which disperse the
organic liquid and release the water droplets containing the desired chemical. This inversion
process requires time and agitation and is sometimes a problem for oil field applications.
However, the added efficiencies obtained with the latex products often make up for the extra
effort.
3.5.2.2 Inverted Latexes
In some applications, latex polymers are extremely efficient, and only very low dosages are
needed. Often one quart of chemical can be too much. In order to make these low dosage rates
practical from the application standpoint, the latex is actually diluted with water to make a less
concentrated product. Of course, the polymer inverts in the presence of water, and although the
product concentration is low, the viscosity is often high. The high viscosity is due to the very
high molecular weight of the polymer. Both anionic and cationic latex products can be pre-
inverted.
3.5.2.3 Water External Latexes
Water external latex polymers offer an alternative way to make high molecular weight polymers.
Water instead of oil is used as the external or continuous phase of the latex process. Water
external latex products depend on the use of surfactants to isolate the droplets. When the
polymerization process is complete, the surfactants continue to stabilize the droplets and prevent
the droplets from coalescing. This technology is less common than external latexes. However,
these polymers are easy to pump, disperse quickly in produced water, and are often preferred for
field applications.

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A new technology that has entered the market is the dispersion polymer. Dispersion polymer
technology has eliminated the use of the former latex polymers in treating overboard water in the
Gulf of Mexico. It is very effective in most of the production in the Gulf of Mexico. Some areas
require very little volume of this product to be effective and can overtreat and create a very
polymerized floc. In other areas, the products can be used from low to high concentrations with
little or no side effects from the floc. The dispersion polymer does exist in a diluted form and is
somewhat viscous but is pumpable.
3.6 Product Selection Testing

There are three commonly used water clarification tests used for product selection and dosage
recommendation: Bottle Test, Jar Test, Gas Flotation Test. They differ mainly in the amount of
agitation applied to the water sample. One simply chooses the test which best matches the
agitation of the system.
The following is a brief evaluation guide, intended to help in the selection of water clarifiers for
oil field systems. An outline of methods of selection for various systems, such as Wemco’s, gas
floatation cells, corrugated plate interceptors, and Vortols are included, along with some useful
tips taken from experienced experts in the field. (These methods should be noted and used in
conjunction with present system practices to reach the best conditions for chemical screening.)
3.6.1 Bottle Testing

Bottle testing is the most widely used water clarification test. Clear calibrated 6-ounce
prescription bottles conveniently hold 100 ml of produced water. Dosages are often from 10 to
50 ppm but in some situations can be as high as 1,000 ppm. Usually higher dosages are
uneconomical.
After the chemicals have been applied, the samples are agitated followed by visual observation.
Agitation can be applied as slow rolls, medium shakes, or hard shakes to simulate a wide variety
of system conditions. Usually three or more sets of agitation are applied with observations taken
after each set. This permits identification of chemicals that work with a minimum of agitation as
well as those that work well after complete agitation. It is most efficient to grade bottles after
each agitation on a scale of 1 to 10 with 10 being best. After the final agitation, comments on
clarity or flocculation can be added.
Results are recorded on the Bottle Test (REB & Coagulant) report form.
The basic bench top test is used in water clarifier selection.

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3.6.1.1 Test Equipment
6 oz. (200 ml) clear prescription bottles

10 micrometer dispenser (for concentrated, full strength additives)
Disposal syringe, when using dilute solutions (1, 5, 10 ml sizes)
10 ml graduated test tubes (for diluting standard solutions)
Dilution solvent, water
Clean-up solvent, water
3.6.1.2 Procedure
Add 100 mls of water to be tested directly into sample bottles. Always try to avoid collecting a
large volume of water at the sample source and filling bottles later.
Usually the water contains iron that is observed to come out of solution readily. It is advisable to
inject test chemicals into empty bottles and then fill bottles with produced water and cap
immediately. This reduces oxidation and helps in the selection of the most effective compound.
Add neat test chemicals to the bottles. Usually a low treat rate is used (1 to 50 ppm), however
treating rates as high as 1,000 ppm may be necessary. The undiluted chemicals can be added at
these low levels using a 10 micro liter dispenser.
1.0 μl of neat chemical in 100 mls of water = 10 ppm treat rate.
Guard against variations in water quality by including a standard in each set of tests. A standard
can be a blank (no chemical added) or any chemical that shows promise.
Agitate. The amount of agitation to use is hard to determine, usually 50 to 100 shakes (by hand)
is used, unless the distance between the chemical injection point and the treating vessel is
unusually short.
After running a treatment performance curve with the incumbent product, select the most
effective dosage rate and begin comparisons of chemicals in your kit. Best candidates are then
subjected to decreasingly lower injection rates. Some compounds, while highly priced, may be
active at a lower dose; allow for these differences in bench testing.
3.6.1.3 Evaluation
Results of the test are taken by visual observation. Observe the water clarity of each bottle by
looking through the bottle at a printed surface such as a paint pen. Also consider the consistency
of the floc produced. A very fine floc that easily disperses throughout the water will not perform
well in most systems. A very thick sticky floc can form a pad in the vessel that the oil skimmings
return to. Observe the bottles within the first five minutes, as oxidation will rapidly occur.
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The following number system can be used to describe performance.
1 Excellent Clear aqueous phase, stable floc

2 Good Slight haze, good stable floc
3 Fair Turbidity present, unstable floc
4 Poor Little oil breakout, little or no floc
5 Bad No treatment, same as untreated water
Adding a “+” can be used to distinguish between slight variations in performance.
The above are comparable within one set of readings and should not be compared with those
taken at other times.
It is also important to note the appearance at the interface. Note if there is a clean oil layer
floating on the water or whether there is a floc present. A brisk twist or tilting of the bottle is
used to disturb the water, and an observation should be made as to whether a floc is thrown down
or not. Some water clarifiers containing metallic salts may cause a floc problem that is
undesirable in the system. Amines and quaternary compounds tend to be less troublesome.
Polyacrylates and dithiocarbamates can often help with interface and water quality in turbulent
under-designed vessels. Inject these products into total fluid at 5 to 15 ppm before initial
separation to improve the water quality leaving the vessel. This ultimately makes for easier
treatment by sending cleaner water to the CPI, DGF, and IGF cells. Bottle Test these chemicals
using produced fluids before initial separation (total fluids).
3.6.2 Jar Testing

When water enters a large system like a pit or wash tank, the fluids experience only a slight
amount of agitation. These larger systems are actually designed to minimize agitation to
encourage the natural separation of oil and solids from the water. Jar testing is simply a way to
test chemicals for use in these low agitation systems.
A Jar Test permits several beakers of water to be stirred simultaneously at very low rpm. Usually
the sample is between 500 and 1,000 ml. Chemicals can be added neat or as 1% solutions in
water. After chemicals have been added, agitation is turned to a high rpm for 15 seconds to
disperse the chemical. However, the agitation is quickly reduced to a low rpm value. This
simulates adding the chemical to the flowline in front of a wash tank and then entering the
quietness of the large system. Observations are made at regular intervals. Coagulation and
flocculation properties are easily seen because they develop slowly. Tests usually run from 5 to
20 minutes.
Record the results on the Jar Testing Report form.

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3.6.3 Gas Flotation Testing
Many systems employ the action of gas bubbles to float both oil and solid contaminants out of
the water phase. These systems usually have high amounts of agitation and create foam or froth
above the water phase. There are two types of of float cells. The rotor type is commonly called a
WEMCO or PETROLITE float cell. It generates a liquid vortex resulting in a gas /liquid
interface which extends through the interior of the rotor to a point just above the bottom of the
cell. The gas cavity within the vortex is at sub atmospheric pressure resulting in the flow of gas
from the vapor space in the cell through the rotor where it is mixed with the water. The eductor
type, commonly called a MONOSEP, VERISEP or UNICELL, uses clean water pumped from
the discharge of the cell through an eductor. This causes a localized low-pressure area at the
nozzle. Natural gas flows from the vapor space into the eductor where it mixes with the water as
it leaves the nozzle. Gas flotation testing is usually done with a unit called a bench Wemco to
simulate these systems.
Agitation is usually for one minute at 1,800 rpm using air. However, nitrogen or regulated gas
can be supplied in place of air to avoid oxidation effects, i.e., the formation of iron precipitates.
At the end of the agitation, we wait 15 to 30 seconds to permit air bubbles to surface. Then a
sample of water is taken from below the water surface and placed in a clean prescription bottle.
Bottles containing treated water can be graded visually using a scale from 1 to 10. To obtain
actual oil ppm readings, the water samples can be extracted with a solvent such as Freon and
compared to a known extraction curve using a visual or IR Spectrometer.
Citric acid can be added to the water at 50 ppm to reduce oxidation during the test period. At the
end of the test, allow the water to settle for 30 seconds prior to pulling a sample for oil-in-water
content. Actual effective treatment dosage, found in this manner, should closely correlate with
that required in the system. (Test volume of water required with the bench model is 3 liters; for
example, 45 μl of straight chemical would be required for a dosage rate of 15 ppm.) Products
that produce a stable form of oil immediately and continue to lift oil over the test period would
normally be in the final selection group.
Record your results on the Gas Flotation Testing Report form.
3.6.4 For Vortols (Hydorcyclones)

Produced water from the separators is introduced tangentially through a rectangular port in a
conically shaped chamber. As the water rotates rapidly around the chamber, and moves
downward, the decreasing diameter causes high centrifical acceleration of the water to the
outside wall and lighter oil droplets to move to the center of the cone. The oil rises to the top and
flows out and the water exits the bottom of the cone.
Products selected should work very quickly to break any reverse emulsion that may be present in
the produced water. Vortols are very effective when all oil present is free and oil droplets are
above a critical particle size. Vortols are ineffective on oily waters that contain untreated reverse

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emulsions. Vortols are usually ineffective on oil particles of 5 micron or less in size. Products,
which tend to work, are carbamate types and polyacrylamides.
3.6.5 For Corrugated Plate Interceptors (CPIs)

A CPI is a corrugated plate interceptor. It works when oily water passes between plates and free
oil particles rise until they collect and coalesce on the underside of a plate. The coalesced oil
travels upstream along the plate until it reaches the water surface where it is skimmed off and
collected.
When selecting a product for use in CPIs or similar systems, remember the turbulence, which in
most cases is minimal. In a Bottle Test, little agitation, at times 50 slow rolls or less, may be
appropriate in an attempt to simulate system turbulence. Products such as polyacrylates,
carbonates and those containing salts, such as aluminum sulfate or aluminum chloride, may be
very useful.
3.7 Field Application of Chemicals

For most oil field systems, water clarification means removing oil from the produced water.
Removing solids is also important, but oil is usually the major contaminant. Treating produced
water as soon as possible usually improves cost efficiency and leads to the best water quality.
3.7.1 Production System Applications

Reverse emulsions are usually treated as far out in the field as possible, thus taking advantage of
all the mixing available through the production equipment and flowlines. This is done because
reverse emulsion breakers require lots of agitation to be effective.
In systems with difficult reverse emulsions, the water reaching the dehydration system is light to
dark brown. However, when the right reverse emulsion breaker is applied, the water will be
clear, containing only large dispersed droplets of oil that easily separate.
3.7.2 Dehydration System Applications

Relatively few applications are made directly in front of dehydration systems. Frequently reverse
emulsion breakers cannot be used in the field and, therefore, will have to be used very close to
the dehydration system. With less available agitation, there is often a tendency to over treat. This
can possibly lead to oil treating and water treating problems.
In some systems, latex polymer flocculants have been applied with the aid of water and static
mixers. High molecular weight cationic polymers have the ability to polymer bridge droplets of
oil. This reduces the amount of oil leaving with the discharged water. Experience has shown that
latex polymers appear to help oil dehydration and interface control. However, care must be taken
because the opposite has been true in some systems.

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In offshore facilities mostly polyacrylamides and dithiocarbamates would be recommended in
total fluid applications and generally do not need as much agitation to be effective.
3.7.3 Water Clarification System Applications

Most of the chemicals in the water clarification product line are applied directly into the water
clarification system. Chemicals are used to help specialized pieces of equipment run more
efficiently by promoting coagulation and flocculation.
3.7.3.1 Natural Separation
Directing produced water into a pit or large vessel permits contaminants to separate naturally.
Solids will sink and organic liquids will float when the amount of agitation or turbulence is
reduced.
The speed of separation is greatly enhanced by a variety of chemicals. In most systems, a

cationic material such as metals, solution polymers, and latex flocculants are effective. In some
systems, often where high quantities of corrosion inhibitors are used, anionic latex flocculants
are effective. In many systems, a cationic metal or solution polymer is used to destabilize the oil
and form a larger stabilized floc that will speed the separation process.
3.7.3.2 Gas Flotation
Gas flotation systems, especially induced and dispersed systems, are becoming very common.
They are fast and very efficient.
The most commonly used chemicals are dispersion polymers and copolymers. When these
dispersion polymers are applied correctly, achieving complete inversion, they are able to remove
oil very efficiently. They help form stabilized floc and help create a lasting froth on top of the
water. As the contaminants begin to ride on top of the foam, they can be quickly and easily
removed.
In some systems, reverse emulsions or heavy amounts of dispersion enter the water clarification
system. These systems are frequently old and in poor repair. Metallic ions or highly charged
polyamines are frequently used in combination with dispersion polymers and polyacrylamides.
The cationic coagulants destabilize the contaminants and improve the speed of oil removal by the
flocculant.
Systems with high concentrations of brine frequently have high amounts of dissolved iron. This
iron can precipitate as it comes in contact with oxygen. Precipitated iron plugs injection wells
and can cause a sheen when water is discharged from offshore platforms. For these systems,
oxidizers or dithiocarbamates are used to precipitate the iron before the water leaves the
clarification equipment.

3-16
3.7.3.3 Filtration and Coalescing
Many systems improve water quality by forcing water through beds of sand. In these systems
highly charged epi/DMA/NH3 and aniline formaldehyde polymers are used. Cationic charged
polymers help charge the sand filter media and attract the negatively charged contaminants.
Adding the chemical directly in front of the filter or coalescer does this most efficiently. By
putting the chemical as close to the media as possible, the interaction of the chemical with the
media is maximized.
3.8 Monitoring
When chemicals are applied to the customer’s system, water quality must be tested and
compared to previous or desired performance. The following techniques are commonly used to
help quantify the benefits of a new water clarifier product.
3.8.1 Oil Parts per Million (ppm) in Water Curve

An oil ppm curve is set up to determine the amount of oil left in a sample of water. A solvent
such as Hexane, 1,1,1-trichloroethane, or Freon is used to extract the oil from the water sample.
This solvent extraction can be tested by a visible or IR spectrometer and compared to known
dilution of oil in solvent. A standard curve can be drawn of the known concentrations versus
readings, and unknown concentrations can easily be interpolated from the graph.
In the gravimetric method, a Freon extraction is evaporated, and the residual oil and grease is
weighed.
In the infrared method, the Freon is extracted, and the infrared absorption is measured at a
wavelength of the carbon hydrogen bond.
You must be very careful to not overfill a sample collected for an Oil and Water Analysis. Oil
tends to adhere to the bottle wall and separate from the water. If the bottle is filled more than
once, oil from each filling is likely to stay in the bottle, giving erroneously high results.
Alternately, free oil may be carried out of the bottle by overflowing, giving low results.
3.8.2 Turbidity
Turbidity meters are fairly common in water clarification plants. Testing samples is fairly easy.
A water sample is put in a glass cuvette and a NTU reading is taken. Readings start at zero for
distilled water and rise as the sample contains higher and higher quantities of light-scattering
impurities.
3.8.3 Infrared
Infrared spectrometers are sometimes preferred to visible spectrometers for determining oil ppm.
This is because some oils have very little visible color or darkness. Especially in the analysis of
soluble organics, an IR spectrometer is very useful. This testing uses Freon or hexane solvent to

3-17
extract the dispersed oil. Hydrochloric acid (HCl) is added to lower the pH to 1 to extract soluble
organics.
3.8.4 Membrane Filter Analysis

Information about water quality can be obtained by filtering impurities onto a 0.45 micron filter.
Passing water, acid, and chloroform through the membrane and weighting the impurities left on
the membrane after each extraction gain information about the types of impurities. The
membrane can also be charred to distinguish sand from non-extractable organics. The major
drawback to this method is that the lab extraction usually requires two weeks for completion.
We can determine the concentration of the suspended solids in water by passing a known
quantity of water through a membrane filter and determining the weight of solids collected on
the filter (Millipore).
3.8.5 Deposit Analysis

Often deposits of oil, sand, and scale coat the inside of equipment and pipes. Taking samples of
these deposits and having them analyzed can often help determine sources of water problems.
3.8.6 Particle Size Analysis

Various particle size analyzers are available. The Nalco OFC Research Department uses a
Coulter Counter, which on occasion, has been used to determine the size of water contaminants.
Some customers are interested in removing all contaminants above a certain size to ensure
injection wells will not be plugged too quickly.
In the Coulter Counter method, a fixed volume of water containing suspended solid particles is
forced through an orifice. As each particle passes through the orifice, the increased resistance
results in a voltage pulse that is proportional to particle volume. The pulses produced by a series
of particles passing through the orifice are electronically scaled and counted, yielding a particle-
size distribution.

3-18
3.9 Troubleshooting Water Treating Problems
Deepwater and shelf platforms can have their share of water treating problems. We will be
discussing some of the basic issues around some of the most frequently occurring water treating
problems. Usually, it is not the water clarifier that has stopped working in the system. Often, a
type of system upset, mechanical problem, or something foreign has entered the system to cause
the water clarifier to be ineffective. In most cases, finding the source of the problem is the key to
solving the water-treating problem. Below are some of the key things to keep in mind when
troubleshooting a water clarifier problem.
Excessive oil — One of the first things to check in the system is the water outlet of the three
phase vessels. Samples should be taken and visually compared to what is normally coming
out of the vessels. It may be necessary to run IRs on some of the outlets. A sample with
excessive oil or excessively oily water could be an indication that the particular vessel is
experiencing some sort of upset and needs to be corrected. Check the vessel for dump valve
operation and interface pads. Demulsifiers can also dirty the water when more water-soluble
chemistries are blended together. Sending excessive oil out with the water will overload the
water treating system and cause an upset. Some separators have an isolated water section that
can trap oil on the surface. This accumulation of oil will have to be skimmed over and
removed before the water coming out of the vessel will improve.
Lack of floatation — Check the floatation cell and determine if the gas dispersion is
sufficient. Mechanical troubleshooting of the vessel will require checking the motors for
proper rotation and rpm of the impellers. Also the depurators must be free of any solids or
sludge buildup to ensure proper gas bubble dispersion. Salt buildup around the shaft is an
indication that oxygen is entering the vessel. For water circulation models, check the
eductors for plugging that would reduce proper floatation by not inducing sufficient
dispersed gas into the unit. Circulation pumps that have leaking seals are a sign of oxygen
intrusion into the float cell. Significant amounts of solids in the water as well as chemical
interference can also kill the foam in a float cell.
Gas blanket — Having the proper gas blanket is very critical to the efficient operation of a
float cell or any water treating vessel or tank A proper ounce gauge must be used to ensure
that a two- to four-ounce gas blanket is maintained at all times. On some vessels, the gas
blanket can fluctuate and allow oxygen to get in on the down cycle. All seals and hatches on
the water treating should be maintained and no leakage allowed. If gas can escape from a
hatch, it can also be an avenue for oxygen introduction. Some operators are under the false
impression that an oil blanket on top of water will prevent oxygen intrusion. However,
oxygen is much more soluble in oil than in water and will rapidly diffuse through an oil
layer. Water circulation or injection pumps are also sources of oxygen intrusion in a system.
Oxygen can be drawn into leaking pump suctions and seals. If a pump is leaking water, no
matter what the injection pressure, oxygen is being induced in the system If oxygen should
enter a vessel, it will react with the iron that is present in the water and cause iron oxide
formation. Oxidizing iron is one of the most frequently found problems in poor water quality.
The oxidized iron begins to form a solid. Oil can attach to it and make it difficult for the
water clarifier to lift out the iron-oxide oil-covered particle. Also iron oxide alone can make a

3-19
dull sheen on the water when it goes overboard even if sufficient oil is removed from the
overboard water. The hatches of a float cell should be kept sealed shut and should not be
routinely opened unless poor performance requires visual inspection.
Excessive gas — In some cases, certain floatation vessels can have too much gas introduced
into the eductors and actually cause a rolling or boiling effect in the vessel. This rolling of the
cell will cause oil to be reintroduced back into the cell instead of being skimmed off. The gas
should be regulated to provide a small uniform gas pattern in the floatation vessel. This will
help lift the small oil particles and solids out of the water.
Oil removal— It is very important to remove oil skimmings ( floc) from each cell of the
flotation unit as it floats to the surface. If this oil is allowed to remain on top of the cell, it
will be dispersed into the water and make it very difficult to remove. At no time should a
layer of oil be allowed to accumulate on the water surface. Skim rates should be set so that
continuous oil removal and a minimum of water carryover are maintained. If skim rates are
set to high excessive water will be recirculated back through the system. Adjusting the entire
water level of the vessel and adjusting the heights of weir bars or weir gates on individual
cells sets skimming rates.
Outside interference’s — A majority of the time, water-treating problems will be caused by
something other than just the improper water clarifier in use. Usually, outside interference
from something introduced to the system or mechanical problems are the actual sources of
the problem. Therefore, just looking to change out the water clarifier may not be the proper
thing to do. Most of the time finding the route cause to the problem will be beneficial to a
long-term solution. Some of the most common problems that may occur will be looked at in
this section.
Wet oil tank — The wet oil tank can be a collection vessel of many different contaminants
on the platform. Some of the contaminants that go to the wet oil tank can be glycol, VRU oil,
compressor oils, sumps, and heavy floc from the water treating vessels. These types of
contaminants can accumulate in the wet oil tank, be circulated back through the system, and
have detrimental effects in the water treating system. Usually the water clarifier selected
works very well on the produced water from the platform. However, when one or more of
these contaminants are sent into the system from the wet oil pump, it will change the treating
characteristics of the produced water and render the water clarifier ineffective.
Finding the source of the contamination and preventing it from getting into the wet oil tank is
the best way to clear up the problem. If this is not possible, treating the wet oil tank with acid
or some other chemistry may clean up the problem. In some cases, changing the water
clarifier to one that can handle the contamination can be utilized. Care needs to be taken
when selecting a clarifier to handle contamination so that it does not create severe floc
problems. Other things to look for are corrosion inhibitors that petition into the water phase,
soaps from washing down the deck, work-over fluids from wells recently completed or
acidized, pads and interfaces in vessels pulling under, and solids from a particular well or
vessel that are feeding into the system. In all cases, a total systems approach is always the
best way to begin to attack a water-treating problem.

3-20
Deepwater water system start-ups — After the initial start-up and well unloading of a new
deepwater project, the production is normally 100% oil for the first year or so. This can vary
but is true in most cases. After some time of producing pure oil, the field will begin to
experience water breakthrough. In the very beginning, water breakthrough may not require
that the water system be commissioned. As long as oil production is high and the Lact unit is
below 1% BS&W, the water system is not utilized. However, some high-producing oil wells
can bring in significantly high water production rates in a very short time, and
commissioning the water system quickly is necessary.
The suggested process to commission the water treating system is to utilize a filtration
company like Cetco filtration. They can be set up on the Wemco or last treating vessel outlet
and filter the water before it goes overboard. This gives you time to select the proper
demulsifier and water clarifier to treat the system. After implementing the water clarifier
program and obtaining sufficient water quality going overboard, the filtration equipment can
be disconnected and sent in. This process ensures no out-of-compliance water ever goes
overboard during the start-up of the water system.
If the filtration company is not an option for start-up of the water treating system, the
chemical program may need to be started up before the oil sales is above the 1% BS&W
level. If you begin to experience water quality problems, the water system can still be shut in
for a short time, and the platform will not have to be shut in due to high BS&W at the Lact
unit. During the initial start-up and unloading of the wells, some of the completion waters
and solids may have accumulated in some of the vessels and still be lying in the bottom.
When the water dumps are opened for the first time, the water and solids will enter the water
system and make the water harder to treat than normal and may cause upsets. This is why
filtration is preferred. However, if this is not available, you will need to open these vessels
slowly and feed them into the water system carefully.
Start-up of the water treating system needs to be thought through and planned beforehand.
This ensures that water treating will have no negative impact on the environment or the
whole treating system. It also ensures uptime on the platform.

3-21

Chapter 3: De-Oiling Produced Water

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Chapter 3: De-oiling Produced Water

Chapter 3: De-oiling Produced Water

Oil Field Chemicals Training Manual

3.2.1 Types of Oil-in-Water Mixtures

Produced water contains:

Oil Field Chemicals Training Manual

3.2.2 Water Clarification Techniques

3.2.2.6 Gas Flotation

3.3 Typical System and Equipment

Oil Field Chemicals Training Manual

Gas Sales Oil Sales

3.3.3 Water Clarification

3.3.4 Reuse or Disposal

Oil Field Chemicals Training Manual

3.4.1.1 Charge Neutralization

3.4.1.2 Solids Wetting

3.4.1.3 Surface Tension Reduction

Oil Field Chemicals Training Manual

3.4.2.1 Partial Charge Neutralization

3.4.2.2 Polymer Bridging

Oil Field Chemicals Training Manual

3.5.1 Solution Polymers

3.5.1.1 Metal Salts

3.5.1.3 Reverse Emulsion Breakers

Oil Field Chemicals Training Manual

3.5.2.2 Inverted Latexes

3.5.2.3 Water External Latexes

Oil Field Chemicals Training Manual

3.6 Product Selection Testing

3.6.1 Bottle Testing

The basic bench top test is used in water clarifier selection.

Oil Field Chemicals Training Manual

6 oz. (200 ml) clear prescription bottles

1.0 μl of neat chemical in 100 mls of water = 10 ppm treat rate.

The following number system can be used to describe performance.

1 Excellent Clear aqueous phase, stable floc

Adding a “+” can be used to distinguish between slight variations in performance.

3.6.2 Jar Testing

Oil Field Chemicals Training Manual

Record your results on the Gas Flotation Testing Report form.

3.6.4 For Vortols (Hydorcyclones)

Oil Field Chemicals Training Manual

3.6.5 For Corrugated Plate Interceptors (CPIs)

3.7 Field Application of Chemicals

3.7.1 Production System Applications

3.7.2 Dehydration System Applications

Oil Field Chemicals Training Manual

3.7.3 Water Clarification System Applications

3.7.3.1 Natural Separation

The speed of separation is greatly enhanced by a variety of chemicals. In most systems, a

3.7.3.2 Gas Flotation

Oil Field Chemicals Training Manual

3.8.1 Oil Parts per Million (ppm) in Water Curve

Oil Field Chemicals Training Manual

3.8.4 Membrane Filter Analysis

3.8.5 Deposit Analysis

3.8.6 Particle Size Analysis

Oil Field Chemicals Training Manual

Oil Field Chemicals Training Manual

Oil Field Chemicals Training Manual

Oil Field Chemicals Training Manual

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