109

Chapter 4

OIL FIELD EMULSIONS AND THEIR ELECTRICAL

RESOLUTION

L.C. WATERMAN, R.L. PETTEFER and G.V. CHILINGARIAN

INTRODUCTION

In 1850 there was a thriving industry in West Virginia and Pennsylvania based on
the evaporation of natural brines for the production of salt. An occasional trouble-
some contaminant of the brine was crude oil, which would seep from the earth with
the brine or would accompany brine produced from wells. T h s oil was skimmed off
the surface of the brine pools and discarded. The more enterprising of the salt
producers used gas that was produced from brine wells for firing the evaporating
pots. Small bottles of the oil were sold at “medicine shows”. The garish labels bore
the picture of a fierce Indian and attested to the universal curative qualities of the
“rock oil from the bowels of the earth”. Eventually a bottle of the oil was sent to
Yale University for analysis by distillation. Based on this report, a syndicate
promoted an oil well. Drilling of the Drake Well was accomplished by a group of
salt-water well drillers from West Virginia, U.S.A. Thus, from the beginning of the
petroleum industry, salt water and oil have been associated, though the roles of
contaminant and product have been reversed.
Brines reside in crude oil principally because salt water generally underlies the
crude oil in the geological formation from which it is produced. With careful
completion and production methods, it is possible to produce wells initially with no
salt water. As the producing life of a field is extended, however, increasing
proportions of salt water are produced with the oil. Salt water encroachment
normally starts at the edge of the fields and progresses until the production is
predominantly water rather than oil. The oil field waters whch are produced with
crude oils vary widely in composition and the amount of salts, which they carry in
solution, but their salinity is generally greater than that of sea water. Overall, the
total productions of oil and water from oil wells are approximately equal.
Emulsification of the water and oil, by intimate mixing, may occur in the
formations themselves, or in mechanical equipment such as pumps, chokes, gas
separators, and piping. These emulsions may comprise varying proportions of oil
and water, from 0 to loo%, but pipelines will not purchase the oil until its water
content is reduced to the 0.5-2% range, varying with the specifications prevalent for
the geographical area or dictated by the purchaser. These specifications for the
maximum water contents are dictated not by the amounts which the pipeline
operator would prefer to have, i.e., no water at all, but rather by the difficulties of
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reducing commercially the water contents in specific crude oils to lower values by
even the best dehydration methods.
The emulsified water exists predominantly in the form of dispersed particles
(water-in-oil type of emulsion), which will vary in size from large drops down to
small ones of about 1 pm (0.00004 in.) in diameter. Character of the water and of
the oil (gravity, surface tension, chemical constituents, etc.) and production methods
will determine the size distribution and stability of emulsion particles.
Chlorides, sulfates, and carbonates of sodium, magnesium, and calcium are
generally present in the water in decreasing order. The mineralogy and petrology of
geologic formations (e.g., clayey sands, limestones, and dolomites) from which the
oil is produced and diagenetic and catagenetic processes influence the composition
and concentration of brines. Concentration of salts in the brine varies widely from
field to field.
As the ratio of water to oil increases to predominantly water, there is a tendency
for inverse emulsions (oil-in-water) to be formed, particularly if the pumping
equipment is worn and wire-drawing of the mixture occurs. The O/W emulsions
have the viscosity of water and may be milky or coffee-colored. Indeed, milk is an
oil-in-water emulsion. Particle size is of the order mentioned above. Treatment of
inverse emulsions is done by chemical methods, but prevention of emulsification by
good mechanical maintenance is often helpful. These emulsions may be stabilized
by organic acid salts of monovalent metals.

THEORY OF EMULSIONS

A discussion of the theory of emulsion formation involves a study at molecular

level of the individual groups and their environment. The formation of a drop and
its interface between oil and water requires energy. It is a rule of nature that all
energetic systems tend to seek the lowest level of free energy. Thus, an elevated
object tends to fall, a pressure tends to relieve itself, and a hot object cools to the
temperature of its environment. The energy of drop formation causes the drops to
be spherical, because this shape represents the least area and free energy for a given
volume. Drop formation by agitation is beautifully demonstrated by Dr. Edgerton’s
famous flash photograph “Coronet” of a drop of milk falling into a saucer of milk
(Fig. 4-1). The energy also tends to cause the drops to coalesce and to settle to bulk
water. Impurities in the system, however, will interfere with coalescence and reduce
the free energy.
In the case of a molecule internal to a liquid system, it is attracted equally in all
directions toward all of its neighboring molecules, which is a characteristic of liquids
(see Fig. 4-2). If the liquid is divided in a horizontal plane and separated into two
parts, the molecules at the new surfaces are attracted by equal forces in the
horizontal plane and to the adjoining molecules beneath in the lower portion and,
similarly, upward for the upper section. The separation of the molecules at the plane
of cleavage was accomplished by a force necessary to overcome the intermolecular
 111

Fig. 4-1. “Coronet”, formation of drops.

+.-
attraction in the vertical direction. The product of the vertical force times the short
distance through which the forces are significant is the work done in forming the
surfaces. This is the “free energy” of the system. It is proportional to the area of the
surfaces formed. Numerically, the “free energy” per unit area is equal to the
“surface tension”, which is, at least, a convenient mathematical concept. The work
done in increasing a surface area is that which is necessary to move a molecule to

t -0-I
c f
Molecule at the
interlace
Molecule internal to
the liquid

Fig. 4-2. Forces of attraction between molecules.

112

the unbalanced forces at the surface from the interior of the liquid where the forces
are balanced. The foregoing is true whether the material at the new surface is in
contact with a gas, such as air, or another immiscible liquid, as is the case with oil
and water. In the latter case, “interfacial tension” is the expression used. The
surface tension of water at 20°C is 73 dynes/cm, whereas that of most organic
liquids is about 28 dynes/cm. Interfacial tension between crude oil and water varies
from about 20 dynes/cm to 32 dynes/cm. When oil and water are vigorously
mixed, both types of emulsion are formed, but primarily the minor phase tends to
become dispersed. Both types of emulsion tend to resolve and the surviving type
(O/W or W/O) depends largely on the nature of the stabilizer and the phase ratio.
Further reference to “emufsions” in this chapter implies water-in-oil type emulsions,
which is the predominant type in crude oil production.
The formation of an emulsion involves the creation of enormous areas of
interface with attendant free energy that is supplied by agitation in pumps, friction
in lines, or pressure drop through valves. For example, in half a gallon of oil, a 1%
emulsion consists of about one cubic inch of water. If the water is divided into
drops 0.0001 in. in diameter, there will be about 2 trillion of them. The total area of
interface formed would be 400 ft2, almost equal to the surface of two 9 X 12 ft rugs
on both sides. This area can gather a considerable amount of stabilizer or dust. The
free energy tends to subside and will do so in pure systems of distilled water and a
pure hydrocarbon, such as hexane: the drops coalesce to form free water.
In impure systems, however, another form of energy degradation may precede
and prevent coalescence. Polar molecules (i.e., molecules which have external
electrical fields) or groups of molecules in the oil, that are least similar to the most
prevalent oil molecular species, will be subject to somewhat lower intermolecular
forces. Being less attracted to the internal body of the oil and by virtue of its polar
nature, some material will be adsorbed to the oil-water interface, water itself being
highly polar. Such materials include asphalt, asphaltenes, resins, oxygenated sulfur
and nitrogen compounds, porphyrins, waxes, metallo-organic salts, organic acids,
and sediments. Of these, asphaltenes are most prominent. If present, impurities
from the water side may be adsorbed to the interface. Interfacial adsorption of these
surface-active materials results in a reduction of free energy. Such surface-active
materials are called stabilizers or emulsifying agents. Stabilizers constitute the third
essential component of stable emulsions of oil and water. They give rise to a
physical barrier that prevents water drops from getting close enough for the
intermolecular forces (water-to-water attraction) to be of sufficient strength to bring
about coalescence. Stabilization of the interface begins at the instant a drop is
formed. The process is called “aging”. It may proceed rapidly or extend over a
period of days. Emulsion that has been held in storage may have been “aged”,
thereby increasing the dehydration problem. When concentrated, the extraneous
molecules (similar in kind) have a mutual attraction, which results in an elastic,
sometimes tough and viscous, film around the drop. When molecules are present
that are attracted and enveloped by the water on one end and the oil on the other,
such as is the case with the soaps (e.g., calcium naphthenate), the interface becomes
 113

indistinct, the free surface energy may become very low, and the emulsion will be
very resistant to treatment.

DEHYDRATION

Dehydration is concerned with reduction, removal, rupture, or counteraction of

the stabilizing films, coalescence of the droplets, and gravitational separation of the
oil and water phases in a relatively brief residence time, e.g., 20 min. According to
Stokes’ law, velocity of settling of a water drop is proportional to the cross-sectional
area, difference between the gravity of oil and that of water, and the viscosity of the
oil. Thus, the most favorable combination for separation exists when the oil has high
API gravity and low viscosity, and water consists of large, unstabilized drops of
salty water.
By good production practice, the encroachment of water may be delayed,
whereas the degree of emulsification may be mitigated by good equipment mainte-
nance. Consequently, to some extent, produced water may be unemulsified (or “free
water”) and will separate rapidly unassisted. Nonetheless, a large proportion of oil
that is produced must be treated.
The means of treatment are: (1) heat, (2) chemical destabilization, (3) electrical
coalescence, and (4) gravitational settling.

Heat

Heat increases the solvency of the bulk oil for the stabilizer and the rate of
diffusion of the stabilizer into the bulk oil; it decreases the viscosity, thickness, and
cohesion of the film. Heat also reduces viscosity of the oil. Heating the oil to
promote dehydration has been used from the earliest days of oil industry. Like
many tools that have served well in terms of effectiveness, however, its use has
decreased in favor of more efficient means or their combinations. Evaporation
losses from heat result not only in a loss of oil volume, but a reduction in price
because of a decrease in the API gravity. Decrease in the API gravity of one degree
corresponds to a volume loss of about 2.5%. In some instances, even a slight loss of
API gravity may lower the price into the next lower bracket. Furthermore, fuel gas,
that was formerly wasted, is now a valuable product. Thus, the penalty for
inefficient heating is multiplied and treatment by heat is fast becoming obsolete or
an accessory to other methods.
The most effective and efficient source of heat is that of the producing formation.
By treating oil on the flowline as close to the well as other considerations permit,
loss of connate heat is avoided. Furthermore, “aging” of the emulsion and emulsifi-
cation by surface equipment is held to a minimum. Such “flowline treatment”,
therefore, is highly desirable. Frequently no additional heat is required for such
treatment and maximum efficiency is gained at minimum cost.
114

Fig. 4-3. Rupture of emulsion film by chemical destabilizer.

Chemical additives

The emulsion can be further modified by addition of chemical destabilizers.

These surface-active agents adsorb to the water-oil interface, rupturing the skin
and/or displacing the stabilizer back into the oil. Figure 4-3 shows the effect of
additions of destabilizer to an oil-water interfacial film. The motivation derives
from a still further lowering of the interfacial tension of the drop. The added
molecules, however, are of such dimension, in such limited concentration, and of
such arrangement at the interface that the film quality and thickness are drastically
changed. Time and turbulence aid diffusion of the treating chemical through the oil
to the interface; therefore, it is usually added to the oil at the wellhead. The
synthetic interfacial material, having caused the natural skin to recede from part or
all of the interface, comprises a thin film susceptible to rupture by the attractive
intermolecular forces of water-to-water at very close distances. Inasmuch as these
forces vary inversely as the seventh power of the distance between molecules, the
remaining problem is bringing the drops into very close contact quickly and without
such severe turbulence that could cause the drops to redisperse.
William S . Barnickel discovered and pioneered the use of treating chemicals
about sixty-eight years ago. Thousands of his “Tret-0-Lite”* demulsifier com-
pounds have been used wherever oil is produced. Selection of a compound is
ordinarily accomplished by actual test on a sample of emulsion. The mechanism of
the chemical process is not explicable by any simple theory.

* Registered Trademark, Petrolite Corporation.

 115

( C )

Fig. 4-4. Effect of electric field on water drops in oil.

Electrical treatment

The application of electric field is a powerful tool for causing dispersed drops to
rapidly collide with one another and for overcoming the resistance of stabilizing
films. The collision and coalescence of drops is accomplished by an induced dipole
attraction between them. After coalescence, separation of the phases is due to
gravity.
The interaction of a field and induced dipoles is illustrated in the drawings and
photomicrographs of Fig. 4-4. Figure 4-4.a shows a suspended uncharged particle,
whereas Fig. 4-4.b exhibits the displacement of charges on a single drop (induced
dipole) by an applied field. Full-line drawing in Fig. 4-4.c represents the effect of an
applied field upon adjacent particles separated by a distance equal to a few radii.
The broken-line drawing and photo are explained later.
In Fig. 4-4.b, a single water drop is shown in an alternating electric field. There is
a displacement of electric charges induced on it. The field and the induced charges
shown in this figure reverse 120 times per second, but the relationship holds at any
116

instant. The electrodes establish the electric field to whch the drop is responsive.
The left end is electrically attracted to the left by the field and the right end is
pulled to the right. The drop is an induced dipole. Inasmuch as the forces are equal
and opposite in direction, the drop remains in place and merely elongates. If the
field is disconnected, the drop resumes its spherical shape and there is no residual
change as a result of the electric field application. While the drop is distorted and
under the influence of the field, however, the highly-polar stabilizing film will be
responsive, and coalescence can more readily occur when the drops come in contact.
The attractive coalescing force, F, between the aligned drops of equal size is
equal to:

6KE2a6
F= - (4-1)
d4

where K is the dielectric constant of the oil, E is the potential gradient, a is the
drop radius, and d is the distance between centers. Accordingly, the force increases
very rapidly as drop size increases and as the distance between particles decreases.
Action is almost instantaneous.
There is a limitation of the size to which the drops may coalesce for a given field
strength and a maximum voltage that may be applied to a given system. This is due
to a tendency for electrically charged drops to disperse. The condition necessary for
stability in undisturbed drops is given by the following relationship:

where E, is the critical dispersing gradient at the surface of the drop, C is a

proportionality constant, T is the interfacial tension, and a is the drop radius. For
any effective coalescing gradient in a given system, there is a corresponding
maximum size beyond which drops discharge small droplets. Broken-line drawing
and photo in Fig. 4-4.c show a large drop dispersing toward a smaller stable drop.
Conductance between drops reduces attraction.
Optimum gradients and electrode configuration have been determined by 70
years of worldwide practical application, since Dr. F.G. Cottrell invented electrical
dehydration. The principles have been extended to other applications of which
electrical desalting of crude oil is the most important.
Desalting is the removal of contaminants (salts and sediments) that reside in
crude oil after normal dehydration has reduced the BSW to pipeline specification.
In the process, salt particles in the residual BSW are dissolved and dispersed by
added fresh water (about 5%), after which brine droplets are electrically coalesced
and separated by gravity. The final contaminant content of the crude oil may be a
few parts per million. Though desalting equipment is a normal part of all refineries,
salt specifications are being imposed on oil moved by pipelines and tankers in many
Fig. 4-5. Pictorial assembly of Petreco” electric dehydrator.
‘I
118

parts of the world. “Petreco”* desalters, first used about 1935, have been applied to
streams of a few hundred barrels per day to up to 300,000 bpd (bbl/D) in a single
unit, meeting specifications as low as about one part per million chloride content.

ELECTRIC DEHYDRATORS

Through the years, design of dehydrators has progressed steadily from the early
models treating a few hundred barrels per day and delivering oil with a few per cent
of BSW up to the current dehydrator models delivering from 1000 to 182,000 bbl/D
containing less than 0.5% BSW.
Design features of dehydrators of all sizes are essentially similar. These features
are shown in Fig. 4-5. Size ranges from 6 ft in diameter by 12 ft long to 14 ft in
diameter by 140 ft long. Normally, operating voltages are 480 V at switchboard and

Fig. 4-6. Equipment (10x21 ft Petreco dehydrator: first floor) for handling production at Lake
Maracaibo. Venezuela.

* Registered Trademark, Petrolite Corporation.

 119

16,500 V at electrode. Optionally, both electrodes may be electrified with opposing

polarity, thereby impressing the sum of the two voltages upon the field. All electrical
equipment is enclosed and protected against overload, and meets all safety require-
ments.
Electric power consumption varies according to the conductivity of the crude oil.
Ordinarily, the least conductive crude oils have high API gravity for whxh the load
is about 0.5 kW for each 1000 bbl/D capacity. For heavy crude oils the load may be
2 kW per 1000 bbl/D capacity.
An important feature of the design is to combine the dual function of electrical
coalescence with optimum settling in a single vessel. The internal piping and
electrode arrangement is directed to this end. Residence time of the crude oil in the
dehydrator is about 20 min.
Cost of dehydrators varies inversely with the size and the API gravity of the
crude oil. Large units treating high-API-gravity crude oils are most economical in
cost.
Electrical dehydrators are adaptable to special situations. Figure 4-6 shows an
installation in Lake Maracaibo, Venezuela. The operation of a large number of wells
is controlled at these “stations”. The electrical dehydrators operate at a well
temperature ( = 130°F), to conform with the restriction that no fire is permitted.
“Tret-0-Lite” demulsifier, in the amount of about 6 ppm is added to the oil prior to
electrical treatment. The 10 x 12 ft “Petreco” dehydrator reduces the water content
of 12,000 bbl of oil per day from 50%to 0.3%.

Fig. 4-7. Typical “Petreco” electric dehydrator.

120

GAS GAS
OUT [RELIEF INLET

FIRE
TUBE

AA
WATER DRAIN WATER DRAIN
OUT OUT

Fig. 4-8. Diagram of “chemelectric” treater.

Fig. 4-9.Facilities for Gulf Coast, U.S.A., offshore production.

 121

Figure 4-7 shows a typical 10 X 41 ft “Petreco” dehydrator installed in the Linda

Field, Indonesia. This dehydrator is treating 35,000 bbl of 17” API crude oil per
day.

AUTOMATED DEHYDRATION

The Petreco “chemelectric”* dehydrator is a combination unit for oil-gas sep-

aration, heating, chemical destabilization, and electrical dehydration of oil as it is
produced from the wells. The “chemelectric” dehydrator is ideally adapted for lease
automation and flowline installation. Thus, the oil is treated with a minimum of
handling and “aging”, which is an ideal arrangement.
Aside from the convenience, a substantial saving in investment, piping, real
estate, pumping, heat, chemicals, vapor losses, and labor has resulted from coordi-
nation of the several treating elements to produce the best end result for the least
cost. The combination of treating elements makes it possible to proportion them for

Fig. 4-10. “ Chemelectric” treater for Colombia, South America, production.

* Registered Trademark, Petrolite Corporation.

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Fig. 4-11. LACT operation treaters in Oklahoma, U.S.A.

best operation, such as increasing content of chemicals and reducing heat, or to

increase the throughput capacity by adjustment of both. This unit is especially
useful in dehydrating the very stable emulsions produced by secondary recovery
operations, such as flooding by water, steam, or fire. Figure 4-8shows diagrammati-
cally the operation of a “chemelectric” unit.
Figure 4-9 is an aerial view of an automated installation for handling offshore
production, in the Gulf Coast. Oil is received from offshore in the high-pressure gas
separators at lower left. Then it flows through the two “chemelectric” treaters at
right center and, finally, through meters on platform at center to transfer to storage
tank at upper left.
In Fig. 4-10,a 10 x 25 ft “chemelectric” treater is being installed in Colombia,
South America. The unit will degass and dehydrate 10,000 bbl/D of 20” API crude
oil containing up to 20%water and 3 MMscf of gas per day.
Figure 4-11 shows 6 x 15 ft and 10 x 20 f t “chemelectric” treaters installed on a
LACT lease at County Line, Oklahoma.
The highly simplified enclosed electrical gear of the “chemelectric” treater is
presented in Fig. 4-12. The conduit between the 16,500V transformer and the vessel
contains the high-voltage cable.
 123

Fig. 4-12. Electrical equipment on “chemelectric” treater.

It must be remembered that the gravity, viscosity, and asphaltic content of the
crude oil together with the gas pressure and the methods of production will
influence both the equipment cost and the cost of operation. The latter may vary
from a few tenths of a cent per barrel to a few cents per barrel.
Whatever the situation, the combination of heat to modify the oil, chemicals to
modify the emulsion, and electricity to consummate the operation will provide
versatility, reliability, and economy.

SAMPLE QUESTIONS

(1) Draw a schematic vertical cross section through an electrical dehydrator.

(2) Describe the two steps involved in dehydration by electrical method.
(3) List different types of electric dehydrators.
(4) Illustrate method of arranging electric dehydrator equipment.
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ACKNOWLEDGEMENTS

The help extended by D.L. Kraft, G.C.Hardwicke, and F.D. Watson is greatly
appreciated by the authors.

REFERENCES

Blair, C.M., 1960.Interfacial films affecting the stability of petroleum emulsions. Chem. Ind., May 14:
538-544.
Greenlee, R.W., 1960. Factors in the Stability of Petroleum Emulsions. Prepr. Pap. Div. Pet. Chem., Am.
Chem. Soc., Sept. 11-16.
Monson, L.T. and Stenzel, R.W., 1946.The technology of resolving emulsions. In: J. Alexander (Editor),
Colloid Chemistty, Vol. VI. Rheinhold, New York, N.Y., pp. 535-552.
Roberts, C.H.M., 1932.A new theory of emulsions. J. Phys. Chem., 36: 3087-3107.
Shea, G.B., 1937. Practices and Methoah of Preventing and Treating Crude Oil Emulsions. Bur. Mines
Bull., 417: 106 pp.
Swigart, T.E., 1961. Histoty of Petroleum Engineering. Am. Pet. Inst., Div. Prod., Dallas, Tex., pp.
925-931.
Waterman, L.C., 1965. Electrical coalescers, theory and practice. Chem. Eng. Progr., 61(10): 51-57.