Chapter 10: Emulsion & Oil/Water Separation: I. Oil Export Specification
Chapter 10: Emulsion & Oil/Water Separation: I. Oil Export Specification
Chapter 10: Emulsion & Oil/Water Separation: I. Oil Export Specification
10. Introduction
Oil is produced from reservoirs in association with natural formation water or mixed formation
water / injection water. This mixture is in the form of an oil and water emulsion. The separation
of water from crude is critically important to the process operation.
The process of separating water from crude oil is commonly called dehydration or demulsification
and generally involves the resolution of a water-in-oil emulsion (w/o). In refineries the related
process of removing residual salt from crude is called desalting. These processes are essential as
the refinery sets a technical specification for maximum concentrations of water and salt in the
crude oil product.
The process of removing oil residues from the separated produced water is called deoiling (o/w
emulsion). A water treatment plant is used for the separation of residual oil and residual solids.
This process is essential to meet environmental specifications or injectivity specifications.
Deoiling is covered in a later chapter.
Demulsifier chemicals, desalters and deoilers (clarifiers & reverse demulsifiers) account for
approximately 40 % (in value) of the world oilfield production chemicals market. They are
deployed at practically every crude oil processing station worldwide.
Typically the desired maximum water content will be in the range 0.2 to 0.5% and the acceptable
maximum salt content will be 10 to 25 lbs per 1000 bbl. The refinery may set tighter
specifications for water and salt than this. Water specification is sometimes specified by BS&W
(basic sediments and water) content.
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If a chemical is added that has surface activity (a surfactant emulsifier for example) it will reduce
the interfacial tension and therefore act to stabilise the system relative to the simple emulsion. If
surface active chemicals are present and adsorbed at the boundary between oil and water then
this boundary is an interfacial film.
An emulsion is a combination of two immiscible liquids, or liquids that do not mix together under
normal conditions. One of the liquids is spread out, or dispersed, throughout the other in the
form of small droplets. The droplets are termed the dispersed or internal phase whilst the liquid
surrounding the droplet is termed the continuous or external phase. Droplets can be of all sizes,
from fairly large (visible) to sub-micron in size. The majority of emulsions are not
thermodynamically stable. There is a tendency for the system to separate, reduce interfacial area
and reduce the overall interfacial energy.
Emulsions do, however, have some kinetic stability. Consequently an understanding of the likely
change of emulsion characteristic over a period of time is important when dealing with process
plant that has a fixed fluids residence time. Ultimately the stability of an emulsion relates to the
ease with which the dispersed particles are able to move and interact with each other and interact
with the continuous phase.
The emulsion may be tight (difficult to break) or loose (easy to break). It is not always obvious
from field samples if an emulsion is a w/o or an o/w type. The emulsion type can be established
by adding either water or kerosene to the sample: whichever fluid dilutes and mixes with the
emulsion is the continuous phase. Adding water to an oil continuous emulsion will not result in
dilution and the water will simply drop to the bottom as a free, uncombined phase.
Emulsions may be characterised by particle size and distribution. Size distribution by electric
properties is applicable to oil-in-water emulsions. Typically an automated (Coulter) counter is
used. A change in resistance occurs when an oil drop passes between electrodes at differing
potential: the change is proportion to the size of the particle. Many commercial instruments
depend upon light scattering and various techniques are available. Detectors are unable to
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differentiate between solids and the dispersed phase droplets. The opacity of crude oil emulsions
is problematic for many light scattering methods. X-ray and neutron scattering can determine
distributions to a smaller resolution.
Microscopy offers a definitive technique for particle size determination. Optical transmission
requires a thin sample. The wettability of the glass slide must match the continuous phase to
avoid unstable emulsions from inversion. If opacity is a problem then optical reflection
microscopy is preferred: in this case it is best to focus below the surface as air bubbles may be
tapped at the surface under the cover slip. To enhance observation of the organic phase ultra-
violet incident light is used: the returned beam is formed by fluorescence. The latter technique is
most suited to o/w emulsion observations
ii. BS&W
The term BS&W, ‘basic sediments and water’, or sometimes ‘bottom sediments and water’, is
often used to denote the dispersed water and sediments in a crude oil emulsion that settles upon
standing or separates upon centrifuging. Note that this value may contain emulsified oil from
complex emulsions. It may be determined by ASTM D96 / D4007 which are centrifuge
techniques or by D4006 which is a distillation method and potentially more accurate.
The term “basic sediment” is an old term now no longer widely used in the oil industry. It refers
to the actual solids that were present in the grind out in the free water phase. Hence the term
‘basic’, meaning alkaline sediment. Free water is not included in BS&W.
i. Agitation
Crude oil emulsions are formed as a consequence to vigorous agitation of the oil / water mix. As
the crude passes through chokes, wellhead valves etc., extreme mixing conditions are experienced
at the pressure gradient and this forms new w/o interfaces. Gas lift wells can be especially
problematic. The formation of much smaller dispersed water droplets provides temporary
(kinetic) emulsion stability. The intensity of agitation is therefore the main factor in determining
the nature of the emulsion and consequently how difficult it will be to treat. The more shearing
action (turbulent flow) is applied to the oil-water mixture, the more the water will be divided into
smaller and smaller droplets, and the more stable the emulsion.
Tight emulsions have mean droplet size below 10 micron and are particularly difficult to resolve.
The fact that the radius term in Stoke’s law is squared confirms the importance of minimising
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agitation during the production of crude oil. Demulsifier chemicals increase the droplet size by
particle coalescence. As crude oil w/o emulsions are concentrated (high proportion of dispersed
phase) the movement of one droplet is hindered by others and droplet size may increase by
coalescence (Stoke’s Law is not fully applicable to concentrated emulsions).
For oils having a high viscosity or high resistance to flow, a fixed amount of agitation will not
break-up the emulsion into water droplets as numerous or as small as for a lower viscosity oil. For
such high viscosity crude, more energy is required to create the emulsion. Conversely, the high
viscosity oil is able to maintain larger drops of dispersed water in suspension and small water
droplets will have an even greater resistance to settling. Viscous crude retards the movement of
both emulsifier and demulsifier. In general, it can be said that higher viscosity crude form more
stable, more difficult to treat emulsions.
The factor that is most likely to affect emulsion viscosity is the volume fraction of the dispersed
phase. When dispersed water particles are introduced into an oil phase, the flow of the oil is
disturbed and the resulting viscosity is higher than that of the oil. Dispersed phase viscosity has
almost no effect on emulsion viscosity: in real systems emulsifying agents adsorb at the interface
and the droplets behave as if they were rigid spheres.
A greater differential in specific gravity between the oil and water phases causes faster settling. A
heavy oil (high S.G.) tends to keep water droplets in suspension longer. In the same way fresh
water settles more slowly than salt water.
The surface tension of a crude oil – water interface is typically between 30 – 40 mN/m with little
stabilisation by natural emulsifiers or 20 – 30 mN/m when natural emulsifiers are present. This
indicates that the natural emulsifiers are not particularly powerful surfactants. However the
interfacial film commonly has a high interfacial shear viscosity (mechanical strength) which
increases the kinetic stability. The natural emulsifiers are the main constituent of the interfacial
films or ‘skin’ that surround water droplets. Most of these emulsifiers are oil soluble and derived
from the oil phase. They are attracted to the interface as this configuration is more energetically
favoured. In addition to stability by Marangoni effects, the interfacial film is also a mechanical
barrier to droplet coalescence. Coalescence is limited by steric and viscous film effects.
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Crudes of high TAN number contain naphthenic or fatty carboxylic acids that are oil soluble and
surface active. Precipitation of these acids by soluble calcium or sodium (from the water)
produces surface active soaps - soft deposits that concentrate at the water / oil interface and foul
process equipment
High levels of calcium or magnesium are especially likely to be troublesome. If for any reason the
fluids are produced at a lower than normal temperature (seasonal effects, heater failure), then
viscosity will be higher and the resulting emulsion will be less easy to break. Production through
long subsea lines results in cooler fluids but it is possible that the extended time that fluids are
contained within long horizontal pipelines could destabilise some emulsions.
i. Temperature Effects
As crude oil passes from the well to the processing station temperature decreases. In consequence
to the lowering of temperature,
All these factors will increase the stability of a formed emulsion. In cold producing areas or for
handling heavy crude oils, heaters may be required in flowlines to increase temperature. Heater
treaters are separator vessels that utilise heat as an aid to breaking the w/o emulsion.
Destabilisation of water-in-oil (w/o) emulsions occurs in stages and the following are usually
recognised,
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flocculation stage
creaming or dropping of water (sometimes called sedimentation).
coalescence or breaking of free water.
The flocculation stage concerns the association of droplets, including the smallest sub-micron size
drops, into clusters but without coalescence or settling. A further process, by which droplets rise
or settle by gravity but without significant coalescence is called creaming. There must be a
difference in density for creaming to occur: in a crude oil system it will be the dense brine phase
droplets that will drop towards the bottom of the vessel. The result of this process is a
concentration of disperse phase drops in an emulsion which is particularly rich in the disperse
phase. Within this zone there is considerable risk of inversion of the emulsion, for example from
90% w/o to 10% o/w.
Flocculation and creaming may occur independently of each other. However, as a result of either
of these processes, collisions between droplets are more likely.
The final stage of emulsion breaking occurs when the droplets coalesce. Drainage of the
continuous phase leads to rupture of the interfacial films between drops and an overall reduction
in free energy (lower surface area). This may take seconds or years to achieve complete
separation.
Both physical and chemical methods are employed to aid the separation of water from oil. This is
true for practically all crude oil processing stations. Enhancement of the destabilisation processes
can be achieved in a number of ways, e.g.
increased temperature
centrifugation
electrical methods
increased resonance time
chemical demulsifier treatment
By increasing the temperature, the disperse phase droplets that are in continuous Brownian
motion are encourage to strike each other more often and with greater force. There is therefore an
increased likelihood of coalescence. Heat also reduces the viscosity of the continuous phase,
liberates entrained gases and increases the solubility of many emulsifying agents in the
continuous phase. The result is higher film drainage rates. By widening the density difference of
the two phases, heat will improve 'creaming' times. Problems associated with heating are costs,
increased scale potential, increased asphaltene precipitation and increased corrosion risks.
Oil heaters are usually vertical vessels and are used to heat crude if the separation of phases
would otherwise be difficult. Heating to 50oC – 60oC should be sufficient to melt any paraffin
waxes that had adsorbed at the interface. However, control of light ends may be difficult if the
temperature is raised by too much and scale and corrosion may become issues.
Centrifugation is used to artificially increase the G-force and increase the concentration of the
dispersed phase in the 'creamed' emulsion layer. Breaking of the interfacial films can also occur
by this process. Centrifuges have been used for primary emulsion treatment but both centrifuges
and hydrocyclones are commonly used for deoiling (o/w emulsions).
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Electricity was used as early as 1906 by Cotterell to destabilise water in oil emulsions in the
petroleum industry. High voltage electrostatic separators are widely used to treat water in oil
emulsions in which water (the disperse phase) has a much higher permittivity than oil. The
electric grids are located near the top of the separator in the oil rich phase. The applied field
causes a dipole to form on water drops which are attracted to each other and further destabilised
by becoming elongate. If too much free water passes across the electric grid then short-circuiting
can occur.
Interaction between droplets creates forces of attraction which lead to aggregation and
coalescence. The electric fields used to resolve water in oil (crude) emulsions are high voltage ac
electric fields and produce dipoles, not electrically charged droplets. By contrast, oil in water
emulsions respond to dc current, leading to enhanced flocculation of droplets through
electrophoresis. This technique can also be applied to water in oil emulsions (electrorefining).
The action of a demulsifier is to destabilise the emulsion. In order to do this the ordered structure
of the natural surfactant / emulsion system must be disrupted allowing the disperse droplets to
approach each other. Properties that are modified as a result of demulsifier addition are.
Surfactant behaviour (oil / water interface)
Ability to flocculate dispersed phase drops
Ability to cause coalescence of dispersed phase
Wettability of solids.
Surface active molecules may be classified by the hydrophile / lipophile ratio or HLB. A series of
compounds with similar structures (a homologous series) show two stability maxima
corresponding to w/o emulsifier and o/w emulsifier properties. Between these two there is a
stability minimum where neither hydrophilic nor hydrophobic groups dominate the interfacial
region. Most demulsifiers are likely to have HLB values in the region of this stability minimum.
HLB is not easy to measure and an alternative parameter, RSN (relative solubility number) is
used by some laboratories to characterise potential demulsifiers. Useful products are those that
adsorb and partially displace the natural surfactant, then desorb again after film rupture.
Performance characteristics can be varied by product molecular weight (solubility), charge
reduction potential, flocculation behaviour etc.
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By preferentially adsorbing they also displace the pre-existing stabilising emulsifiers from
the interface. This removes the steric barrier. Interfacial tension and rheology studies
confirm that this mechanism does operate.
Modern demulsifier bases have very limited solubility in crude and initially coat the
interface of only a small portion of the water droplets. Demulsifier spreading then is
possible by hetero-droplet interaction (not via the continuous phase). This explanation
may account for the spontaneous nature of the action of demulsifiers - causing rapid
coalescence of water droplets.
Solids such as asphalts, fine silt, iron oxides or sulphides collect at the interface. The
wetting of these solids by demulsifiers will cause them to be moved into either the oil or
the water phases. It is generally more desirable to move inorganic contaminants to the
water phase and this can be achieved with a suitable wetting agent. If wax or asphalt is
the main contaminant then it would be more desirable if they were entrained in the oil
phase such that water quality is not compromised.
It would be extremely unusual for one chemical demulsifier to have all the useful properties to
optimally resolve an emulsion. The term 'demulsifier base' is used to describe an individual
product.
As a result of the wide range of crude oil types, processing conditions and the many various
stabilising agents, demulsifier selection is found to be highly specific to a given field. A typical
chemical supplier may have hundreds of potential demulsifier base concentrates that are used in
a selection procedure. Optimisation of demulsifier formulation involves treating the crude with a
formulation containing various combinations of demulsifier bases (2 or 3 components normally)
and addition of a suitable solvent.
Apart from the active components in a formulation, the solvent can play a significant role.
Alcohols can, for example increase the solubility of the indigenous crude surfactants in one or
other phase thus removing the surfactant from the interface. Aromatic solvents will lower the
interfacial activity of indigenous surfactants, reducing stability. A hydrocarbon solvent also aids
dispersion of the active components to the interfacial regions. Sjoblom discusses mechanisms and
demulsifier products.
Alkylphenol ethoxylate resins and polyethers are good for water dropping and coalescing of water
droplets. Variation of alkyl group, degree of ethoxylation or propoxylation and the formation of
cyclic (calixarenes) forms modify performance of the resins. There are acid catalysed and base
catalysed resins and each has specific advantages and disadvantages. Acid catalysed resins are
effective at causing good dropping or creaming of the flocculated disperse phase and thereby
affecting coalescence. Good residence time is needed to achieve good water quality. Higher
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molecular weight products are also good wetting agents. Best water drop properties can be
achieved from the lower molecular weight types. The typical range of molecular weight is 500 to
20000.
The known endocrine disrupting behaviour of alkylphenols limits all future use of these products.
Di-epoxides are one of the most important and useful classes of demulsifier, providing excellent
emulsion breaking. They are often slow to separate water as single components, but can produce
a superb finished product when blended with resins and/or polyamines. These could be described
as oil cleaners as they promote low BS&W and salt content. Due to their universal nature, many
commercial demulsifier formulations contain a di-epoxide base. As an example, polyethylene
glycol (PEG) of different molecular weights is reacted with bisphenol A to form compounds
having different hydrophile-lipophile balances and hence different surface activities.
Polyamines bases are now commonly used. They are similar to di-epoxides in some respects, as
they give low BS&W and very good desalting. They blend well with resins and can give fast water
separation of specific crude oils. The most significant disadvantage of this type is that they will
prefer systems with a considerable amount of initial mixing and long contact time.
Wetting Agents, e.g. some ethoxylates, sulphonates, amine ethoxylates, are extremely useful for
treating emulsions stabilised by inorganic solids. By selectively wetting the surfaces of inorganic
species such as clays, sulphide minerals or iron hydroxides, it is possible for the solids to be
displaced from the emulsion interface layer and become associated with the free aqueous phase.
Similarly by careful choice of wetting agent it may be possible to displace organic solids such as
waxes and asphaltene, effectively re-solubilising them in the organic phase. Sulphonated oils were
amongst the earliest chemical demulsifiers used on crudes (1940’s) and exhibit fair to good
wetting and water drop properties, with some ability to brighten oil. They do not normally
overtreat especially in high gravity crudes.
It is extremely rare that a single product would be cost effective for resolving a crude emulsion.
Synergism of performance from more than one component is likely: that is the overall
performance from a multi-component mix is greater than the sum of the individual product
performances. The characteristics of water-in-oil emulsions in produced oil operations are so
varied that crude oil from each field is treated as a specific case, demanding an individual
solution.
Solvent: The role of the solvent is to solubilise the selected combination of bases into a stable
solution and once injected, to enable those bases to be quickly distributed throughout the crude
emulsion. The solvent itself can have a significant effect on the overall performance and this
should be taken into account during the evaluation procedure. Performance can improve by
dilution with solvent: the lower viscosity formulation is able to transport to the interface quickly.
Solvents are often a mix of a hydrocarbon and an alcohol.
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i. Toxicity Concerns
Chemicals that can interfere with the normal function of the endocrine system are termed
endocrine disruptors. They demonstrate hormone-like activity. Numerous chemicals have been
implicated as possible endocrine disruptors including alkylphenols and alkylphenol ethoxylates.
Concerns about the safety of persons handling demulsifiers based on simple alkylphenol
ethoxylates has led to a ban on their use. However, alkylphenol ethoxylate resins are not
implicated as they have a much higher molecular weight and could not pass a biological
membrane. Despite the apparent safety of these resins some countries, including Norway, have
enforsed a ban based on the very low concentrations of unreacted ethoxylate that may remain in
the product. A general review on endocrine disruptors is presented by Cooper.
Alternative demulsifiers based upon modified silicones are claimed to be environmentally clean –
but expensive. The study showed that silicones were capable of breaking both asphaltic and wax
stabilised crudes. There are claims that synergistic blends of silicone products plus conventional
bases are cost effective.
It is possible to sample a crude oil line from a simple probe fitted flush to internal surface. This
arrangement is satisfactory for low pressure systems if the point of sampling is immediately
downstream of a choke valve, for example, where there is much agitation. Alternatively a probe
may be used that extends to the centreline.
For horizontal pipes any sample points that are removed from points of agitation are unlikely to
provide assurance that the sample is representative. If the sample is required for w/o emulsion
bottle tests then that sample should be taken from a point on a horizontal pipe which corresponds
to the emulsion (above the mid-point). Sample points on a vertically inclined pipe recover
product that is more representative of the total fluids.
If the system is a high pressure system (more than 1000 psi, for example) then a high pressure
sample receiver should be used (see later) as a safety precaution. Note that the removal of a
sample under high pressure can stabilise emulsions by reducing droplet size. The sample point
should also have an isolation valve.
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None of these simple sampling options provide truly representative samples. The reason for this
is that the velocity of the fluids across the sample orifice and within the probe is not the same as
the velocity of the fluids generally in the pipe.
To have a true representative sample an iso-kinetic probe is required: this enables the withdrawn
sample to have the correct proportions of oil, water and contaminants as present in the pipeline.
When this is done correctly the sample can be used to determine the quality of the oil, the basic
sediments and water (BS&W), the chemical composition, or the API gravity or it can be used to
perform advanced emulsion studies. Iso-kinetic sampling would not normally be used for
demulsifier testing.
Some crude oils age quickly – within one hour - whereas others are hardly changed after several
days. Ageing should not affect the relative performance of demulsifiers but it will affect the
optimum application rate. Background, blank emulsion tests are repeated several times during
one day to observe any drift due to ageing.
Some researchers have used high-pressure rigs to attempt to simulate the conditions in a field
separator. However in order to screen large numbers of potential demulsifier surfactants a more
rapid technique is essential. Selection of the optimum chemical normally is made by "bottle tests"
and experienced technicians conduct a series of optimisation experiments using the large number
of surfactant bases individually and in combination. It is most important that testing is
conducted on representative fresh samples of emulsion, as aged (oxidised) oils will not give the
same result.
The preferred product will have been chosen because of many factors such as the brightness of
the oil, clarity of the water, interface quality between the oil and water, required operating
temperature, settling time, salt content, the BS&W (Bottom Sediments and Water) specification
of the export crude, and cost. Laboratory results on fresh crude are a good indication to field
performance.
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The first task is to establish the basic test protocol and this is selected to represent the field
conditions, for example, residence times and temperature, as closely as possible. A good sample
of fresh emulsion is collected from an appropriate point on the produced fluid stream and is then
divided into several test bottles (sometimes pre calibrated). Chemical ratios are usually critical.
The amount and severity of cold agitation, temperature employed, amount and severity of hot
agitation and settling time all affect the end result.
Demulsifiers are diluted before use to ensure accurate dosing. These solutions should be prepared
fresh and stoppered during use. All solution bottles, syringes, test tubes should be cleaned with
suitable solvent before use (75%xylene, 25%IPA). All glassware such as pipettes must also be kept
clean to prevent cross contamination.
1. Fresh emulsion should ideally be used. In any event, a representative sample of crude
should be removed from a sealed container.
2. Prepare solutions of all demulsifier samples to be examined (2% in solvent, xylene/IPA is
suggested). Check that solutions are clear. Label accordingly with demulsifier code.
3. Determine the approximate chemical concentration if unknown. Select a demulsifier
believed to be effective (use the incumbent if possible). Add 0.2ml to 3.0 ml of diluted
demulsifier (from 2) and follow steps 4, 6 through 18. The smallest amount of demulsifier
that gives satisfactory results is the chemical concentration that forms the basis of
subsequent work.
4. Fill an appropriate number of 200ml graduated, 'prescription' bottles with emulsion
(100ml). Substitute 150ml 'milk' test bottles if graduated bottles unavailable.
5. Measure by pipette, aliquots of demulsifier solutions (from 2) into a corresponding sample
of emulsion. The amount used should correspond to that determined from 3. Label
accordingly.
6. Seal each bottle with a screw cap and agitate by hand for 50 or 100 coalescence shakes at
ambient temperature. Attempt to treat each bottle equally.
7. Allow the sample bottles to settle. It may be possible to separate the oil / water at ambient
temperature. Bright oil and good water separation indicates a satisfactory result.
8. If step 7 does not indicate satisfactory results, loosen caps, place bottles in a heated water
bath at a temperature representative of dehydration plant.
9. Remove bottles from bath, tighten caps and agitate by hand for 25 shakes. Again treat all
sample equally.
10. Observe appearance after several minutes. Clear oil is a good sign. Cloudy, dull oil still
contains water and is less good.
11. Return sample bottles to water bath and allow to stand for a longer period. Viscous crudes
may require several hours before some separation occurs.
12. Observe and record the amount of water separation in each bottle. This result is only an
indicator of performance and cannot be used alone to compare products. If possible
photograph the bottles.
13. Fill small (15ml) graduated centrifuge tubes (graduation marks in %) with gasoline.
(100ml tubes are preferred for accurate laboratory work but the 15ml tubes are better for
field use).
14. Carefully pipette samples from the oil phase of each sample and add to the half filled
centrifuge tubes. All the oil samples must be extracted from the same height within the oil
phase and care should be taken to avoid extracting the water interface.
15. Mildly agitate the oil / solvent mix by hand for 15 shakes to ensure thorough mixing.
Centrifuge samples for 2/3 minutes at approximately 1750 revs /min. Treat all equally
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16. Read and record the basic sediment content (unresolved emulsion), water content and the
sum of basic sediment and water. Photograph if possible.
17. Add 2/3 drops of a dilute (2%) solution of a slugging demulsifier (Baker’s DMO80046 is
an example) to each centrifuge tube, agitate by hand for a few minutes, heat to required
temperature in a bath and re-centrifuge for 2 minutes.
18. Read and record the total basic sediment and water content. Normally this will be all
water. Compare with value from step 16.
19. At least one of the tested samples should have shown an acceptable result. If not longer
temperature incubation, agitation or settling time may be necessary and tests will
therefore be repeated. Alternative chemical may be examined.
20. In some instances, demulsifiers will show a sludging effect at the interface. Even 'good'
products may do this if overdosed. Sludge should no longer be present by stage 18.
21. As a precaution, pipette all coalesced water from bottles deemed to be 'acceptable'. Shake
very gently 10 times and quickly pour into centrifuge tubes half filled with gasoline, agitate
and centrifuge for 2 minutes.
22. Record water and basic sediment content. Demulsifiers giving lowest basic sediment
content are to be preferred.
23. Step 17 may be repeated on centrifuged sample from 21. Optional.
24. It is normal to screen many demulsifiers. Several test series will be undertaken to cover
the full range. The better products are then subject to a final selection test. If there is a
demulsifier currently in use in the field then this will be used for comparison.
An experienced engineer will be able to vary the above procedure to reduce total test time.
Optimum formulations will generally contain two and possibly three active bases. Once the
technician has completed his task, it is normal for the oil company to conduct a small-scale field
test, usually in one typical well or in a section of the production system for a period of several
days. At this stage the preferred laboratory product can be optimised for final acceptance and full
field application. The final water quality and oil quality is monitored. Demulsifier concentrations
found by test will normally exceed that required within the plant. Final optimisation is therefore
always made on the plant itself.
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The optimum concentration of demulsifier formulation will vary between 5 mg/l and about 200
mg/l but is commonly between 10 and 60 mg/l. The point of injection is important. Demulsifier is
injected into the emulsion in such a way that rapid mixing is achieved. This could be hindered if
the dose rate is low and in this situation it can be advantageous to dilute the demulsifier further
with the same solvent that is used in the formulation.
As demulsifier dose is critical it is clear that the chemical must be added in a continuous manner
with dose being adjusted for flow variance. Addition upstream of a point of turbulence is good,
unless the intensity of the turbulence is so great that re-emulsification can occur.
Rapid acting demulsifiers are required in plant with limited capacity or short residence time. It
may be appropriate to use this type if there is a free water knock out in the production or if the
emulsion is to be treated in a heater-treater or chemelectric unit. These demulsifiers will often be
used for processing on offshore platforms. A characteristic of this type is that they do not produce
very low concentrations of residual water.
Slow acting demulsifiers do produce lower residual water (BS&W) content. They can be used in a
settling tank, a wash tank as the residence time may be 8 – 24 hours. It also follows that
demulsifiers that act in this way can also produce oil with lower salt content.
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are very large with long residence times. Demulsifier chemicals will be optimised for these
systems.
Offshore and on boats there is a limit to available space and the weight of dehydration equipment.
Vessel design is optimised for short residence time. Demulsifier chemicals are developed that
work much quicker although this frequently results in less good water-in-oil quality
It is normal for more than one item of plant to be used in series to treat crude emulsions. For
example in a high pressure offshore field there may be two or three separators in series (to allow
gradual reduction in system pressure) followed by an electrostatic coalescer to remove residual
water from the oil phase.
Figure 10.1
Figure 10.2
xii. Continuous Operation – Upstream Vessels – FWKO, Wash tanks, Gun Barrels.
A free water knockout vessel (FWKO) is essentially a horizontal tank for the separation of free,
uncombined water. It is a simple long-residence time vessel for low gas content crudes and is may
be used to remove free water, thus preventing overloading other downstream dehydration
equipment. This is particularly important where the crude requires heating, as it takes nearly four
times more heat energy to achieve the same temperature in water as in oil. It is common for
knockout drums to contain filter material to help remove entrained oil from the water.
The simple tanks rely on gravity and demulsifiers to settle to oil from water. A wash tank vessel is
basically a large gravity settling tank fitted with an internal or external boot. The former is known
as a Gun barrel and the latter as a Wash tank. These units are found in onshore locations,
particularly in older fields and provide a relatively long residence time for separation. They are
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common onshore in the USA as a preliminary upstream treatment of the emulsion. Gun-barrel
vessels range in size from 500 barrels to 10000 barrels and are usually made from steel or
fibreglass.
The barrel or inlet pipe acts as a gas separator and anti surge device, thus reducing turbulence in
the main tank. The spreader plate allows the slowly moving emulsion to be distributed evenly into
the water phase allowing it to be washed, and encouraging the water particles to increase in size.
The settling time is important to allow time for the water droplets to increase in size can fall by
gravity. These large tanks offer the most economic method of settling for many onshore field
locations.
These vessels are widely used equipment in offshore locations but are also used onshore. They can
be horizontal or vertical orientated.
In a two-phase separator, crude enters the equipment and hits a diverter plate causing a
reduction in momentum. Liquids (oil and water) fall by gravity into a liquid collection system and
pass to the second stage of treatment. The residence time allows dissolved gases to be released.
The gas passes through mist extractors, wire mesh plates or other plates to allow the residual
liquid droplets to coalesce.
The purpose of the common 3-phase separator is to remove gas from the liquids and remove oil
from water. The separator will have some arrangement of weirs to enable the separation of water
and oil (see diagram below). The internal configuration of plates, baffles and demisters can be
quite complex. The vertical arrangement is more stable on offshore installations which are liable
to movement. Four functional operations occur within the 3-phase vessels,
Inlet momentum reduction: various devices absorb the momentum of the fluids entering
the vessel.
Vapour demisting: oil droplets are removed from the gas by demisting pads, vanes or wire
mesh
Liquid retention for oil / water separation: separation occurs within this section. The
retention time is influenced by crude oil gravity, temperature and the required BS&W.
Liquid outlet control: various configurations of weirs, buckets, spill-overs, vortex breakers
etc are available to ensure there is no re-combination of separated phases.
The use of a vertical separator system (compare horizontal) enables the efficient operation of high
GOR crudes and also enables crude processing to work better offshore or on FPSO.
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In the case of a 3-phase separator the gas volume needs to be adequate to ensure that the
demisting pads work efficiently. Oil is usually withdrawn from a surge compartment downstream
of a weir placed about 1 metre from the end of a vessel. Alarms are used to alert to high and low
levels and for oil-water interface control.
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Electrostatic coalescers are capable of achieving very low water-in-oil concentrations. They are
frequently deployed at refinery sites for removal of residual water to achieve the required feed
specification. They are also commonly used at oilfield processing stations (onshore and offshore)
where the term chemelectric treater is often used. Coalescers can be fitted with heated fire tubes
(electrostatic heater treaters).
These treaters are now the most widely used systems to mechanically treat emulsions. Like the
heater treater they are fully automatic, available in various sizes but normally arranged
horizontally. In the first stage of operation, the principle is the same as the heater treater: gas
leaving the heater end, avoiding breakout later in the process. The hot wet oil enters the electrical
coalescing section via an emulsion spreader to give uniform flow. A high voltage AC electrical field
causes the dispersed water droplets to become elongate with a charge dipole. This enhances
attraction between droplets and accelerates coalescence. The electrodes are placed towards the
top of the vessel to minimise short-circuiting by free water. The voltage is adjusted according to
the requirements.
The feed to these units should be of relatively low water cut (maximum about 30%, typically 15%
or less) to retain efficiency and prevent short-circuiting. A large voltage (10 – 20 kilovolts) is
supplied by a transformer unit (usually mounted on top of the vessel) but the energy consumed
overall is relatively low. The power unit and high voltage connections are certified for use in
hazardous areas. Oil leaving a conventional coalescer will have water content of 0.1 to 0.5% by
volume. Dual polarity vessels do not use a conventional AC current supply. This is replaced by a
system with both AC and DC current fields.
Compact systems do not rely on gravity as the primary settling mechanism. Cyclone systems use
vortex flow to provide very high g-forces to enhance density differences and accelerate separation.
The technology may be applied as inlet devices to separators, axial flow and multicyclones for gas
scrubbing and deoilers and desanders for oily water treatment.
Centrifuges are becoming increasingly popular. The application of energy to rotating elements
increases separation efficiency when compared to cyclones as the static wall or boundary layer
effects are eliminated. Equipment is complex but offers high efficiencies plus low weight and
small footprint requirements. In common with cyclones, centrifuges may be applied to water in
oil emulsions and to oil in water emulsions. Compact separation systems have a low demand for
chemicals compared to conventional equipment but a disadvantage is their sensitivity to flow
variations and slug-flow conditions. They are useful for heavy crudes.
An Auger is a simple device for separating bulk gas: multiphase fluids enter axially and stationary
helical vanes force the liquids to the outer surface. It can be configured for downhole use. A split-
level separator system and other centrifugal force separators use related technologies to produce
high quality gas. Several gas-liquid cyclones are commercially available.
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The advantages of separating water downhole, within the wellbore, and reinjection to an aquifer
zone are obvious. Downhole oil-water separation (DOWS) systems have been developed and
trialled. If proven the technology will enable a high proportion of the water to be removed,
reducing the load on downstream equipment but it is unlikely to replace the need for
conventional surface separation facilities.
The downhole separation system is achieved either by (1) gravity separation, using the annulus
space and perforations in the lower annulus above the packer for re-injection of water, or (2) a
hydrocyclone separation system in which the heavier water is forced downward into an isolated
zone for reinjection.
The pumping (injection) options include electric submersible pumps, progressing gravity pumps
and sucker rod pumps. All these options may be considered for the hydrocyclone separator but
gravity separator systems use sucker rods for reinjection.
The potential for full scale sea floor (subsea) separation is being evaluated by Statoil in the Tordis
field (from 2007, shown opposite). The Troll pilot (Norsk
Hydro) and the VASP system operated by Petrobras have
proven the feasibility of phase separation subsea. When
fully operational the Tordis system will handle 200000 b/d
fluids and re-inject 150000 b/d water. Gas will be removed
by a cyclone on the inlet side of the main vessel which is
designed to enable separation of oil and water by gravity
settling. The separated gas will be recombined with the
separated oil for export. It is the use of a bypass loop for the
gas which is novel and made possible the construction of a
compact system
Figure 10.4
10.14 Refinery Desalting
Refineries are complex expensive chemical plants with sensitive catalyst systems that can only
operate effectively with low contaminant levels in the crude oil feed stock. Crude oils contain
traces of impurities such as iron sulphide, sand, silt and water. Entrained water normally contains
salts in the form of chlorides, which when heated to high temperatures (average distillation
temperature 650oF) can hydrolyse, releasing hydrochloric acid. This acid along with others
present in the crude (naphthenic) can cause serious corrosion problems within the refinery
pipework.
To overcome these problems modern refineries desalt the crude by means of a fresh water wash.
A desalter is therefore a dehydration vessel with facility to introduce clean water. The desalter
may be located at the field site (upstream of main export) or near to the refinery.
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Within refineries there is often a good supply of clean fresh water, or steam condensate, which is
ideal for addition to the crude for washing. The mixture is then processed using equipment very
similar to that described in the dehydration section of this document. The produced effluent
water should be free of oil, and the produced oil should be low in solids, salt etc. (within the
refinery specification).
Salt content is measured in lb per 1000 barrels (PTB) or g per m3 (or ppm). Crude containing up
to 10 PTB (36.5 g/m3) is normally acceptable to refinery operation although some refineries
demand <5PTB. Crude between 10 PTB and 20 PTB (73 g/m3) could be accepted if the refinery
fractionators are completed in corrosion resistant metallurgy. Crude containing more than 20
PTB is likely to need treatment to reduce the salt content.
Parameters such as crude temperature, composition of the wash water, the degree of mixing,
system settling time are variables that determine the quantity and type of demulsifier (desalter)
used.
Potential water problems include high calcium and iron sulphide content (increased stabilisation
of emulsions). Refinery chemelectric treaters do not need heaters as the crude has already been
heated as part of the wash water process.
To ensure optimum efficiency desalting chemicals are added after the heater trains. Chemical
demulsifier residues will remain from the primary dehydration stages. However supplementary
demulsifier added to the desalter upstream of the mixing valve is common. Addition of acids or
alkalis to the dilution water may be necessary if the water requires pH modification. Hydrolysis of
chlorides in the refinery produces hydrochloric acid which reduces pH. Ammonia or filming
inhibitors can be added to reduce corrosivity.
The combined crude plus wash water stream passes through the electrical treaters slowly
(typically having a residence time of 30 minutes) to assist separation. Separated oil is pumped to
the refinery and separated water is treated in the effluent plant prior to disposal. The desalter
effluent is a major source of contaminated wastewater: the water contains variable amounts of
chloride, sulphide, bicarbonate, phenols, benzene, PAH and other hydrocarbons.
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Further Reading
‘Emulsions – fundamentals and applications in the Petroleum industry’ Ed: Laurier L Schramm,
Advances in Chemistry Series 231, American Chemical Society, 1992. ISBN 0-8412-2006-9.
Sjoblom, Johan, et.al, ‘Demulsifiers in the Oil Industry’, in ‘Encyclopedic Handbook of Emulsion
Technology’, publ. Marcel Dekker, March 2001.
References
1. Arnold, E.A., and Koszela, P.J., ‘Droplet Settling vs. Retention-Time Theories for Sizing Oil
/Water Separator, SPE Prod. Engineering, Feb 1990, p59.
2. Kokal, S., ‘Crude-Oil Emulsions: A State-of-the-Art Review’, SPE 77497, SPE Prod & Facilities
Feb 2005, p5-13.
3. Kokal, S. And Al-Ghamdi, A., ‘Performance Appraisals of Gas-Oil Separation Plants’, SPE
102854, SPE Prod & Facilities, May 2008, p287-296
4. Ogunsina, O.O., and Wiggins, M.L., ‘A Review of Downhole Separation Equipment’, SPE
94276, SPE Prod and Operations Symp., Oklahoma, April 2005.
5. Aveyard, R, et.al, ‘The Resolution of Water in Crude Oil Emulsions by the Addition of Low
Molar Mass Demulsifiers, J. Colloid and Interface Science, Vol 139, 1, Oct 1990, p128.
6. Dalmazzone, C.,and Noik, C, ‘Development of New Green Demulsifiers for Oil Production’,
SPE 65041, Intn. Symposium Oilfield Chemistry, Houston, February 2001.
7. Poindexter, M.K., et.al., ‘The Key to Predicting Emulsion Stability: Solids Content’, SPE
93008, SPE Prod & Facilities, Aug 2006, p357-364.
8. Cooper, R.L., and Kavlock, R.J. ‘Endocrine disruptors and reproductive development: a
weight of evidence review, J Endocrinology, 152, p 159-166m 1997.
9. Crook, G., ‘Subsea separation first for Tordis’, Petroleum Review, May 2006, p12-14.
10. Agrell, J and Faucher, M., ‘Heavy Oil and Bitumen Dehydration – A Comparison Between
Disc Stack Centrifuges and Conventional Separation Technology’, SPE 97913, SPE Prod &
Facilities, May 2007, p 156-160
11. Balson, T, ‘Something Old,Something New: A Discussion about Demulsifiers’ Royal Soc.
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