INTRODUCTION

Removing water from crude oil often requires additional processing beyond
gravitational separation. In selecting a treating system, several factors should
be considered to determine the most desirable methods of treating the crude
oil to contract requirements. Some of these factors are:
1. Tightness of the emulsion.
2. Specific gravity of the oil and produced water.
3. Corrosiveness of the crude oil, produced water, and casinghead gas.
4. Scaling tendencies of the produced water.
5. Quantity of fluid to be treated and percent water in the fluid.
6. Paraffin-forming tendencies of the crude oil.
7. Desirable operating pressures for equipment.
8. Availability of a sales outlet and value of the casinghead gas produced.
A common method for separating this "water-in-oil" emulsion is to heat the
stream. Increasing the temperature of the two immiscible liquids deactivates
the emulsifying agent, allowing the dispersed water droplets to collide. As the
droplets collide they grow in size and begin to settle. If designed properly, the
water will settle to the bottom of the treating vessel due to differences in
specific gravity.
The process of coalescence requires that the water droplets have adequate
time to contact each other. It also assumes that the buoyant forces on the
coalesced droplets are sufficient to enable these droplets to settle to the
bottom of the treating vessel. Consequently, design considerations should
necessarily include temperature, time, viscous properties of oil that inhibit
settling, and the physical dimensions of the vessel, which determine the
velocity at which settling must occur.
Laboratory analysis, in conjunction with field experience, should be the basis
for specifying the configuration of treating vessels. The purpose of this chapter
is to present a rational alternative for those instances when laboratory data do
not exist or, if it is desirable, to extrapolate field experience.
EMULSION TREATING THEORY
Forming Emulsions
For an emulsion to exist there must be two mutually immiscible liquids, an
emulsifying agent, and sufficient agitation to disperse the discontinuous phase
into the continuous phase. In oil production, oil and water are the two mutually
immiscible liquids. An emulsifying agent in the form of small solid particles,
paraffins, asphaltenes, etc., is almost always present in the formation fluids,

and sufficient agitation always occurs as fluid makes its way into the well bore,
up the tubing, and through the surface choke.
The difficulty of separating the emulsified water from the oil depends on the
"stability" of the emulsion. The stability of an emulsion is dependent on several
factors:
1. The difference in density between the water and oil phases.
2. The size of dispersed water particles.
3. Viscosity.
4. Interfacial tension.
5. The presence and concentration of emulsifying agents.
The difference in density is one of the factors that determines the rate at which
water droplets drop through the continuous oil phase. The greater the
difference in density, the more quickly water droplets will settle from the oil
phase. The water particle size also affects the rate at which water particles
move through the oil phase. The larger the particle, the faster it will settle out
of the oil phase. The water particle size in an emulsion is dependent upon the
degree of agitation that the emulsion is subject to before treating. Flow through
pumps, chokes, valves, and other surface equipment will decrease water
particle sizes.
Viscosity plays two primary roles. First, as viscosity increases, more agitation is
required to shear water particles down to a smaller average size in the oil
phase. Therefore, the size of water particles that must be removed to meet
water cut specifications for a given treating system increases as viscosity
increases. Second, as viscosity increases, the rate at which water particles
move through the oil phase decreases, resulting in less coalescence and
increased difficulty in treating.
When no emulsifier is present, the interfacial tension between oil and water is
high. When interfacial tension is high, water particles coalesce easily upon
contact. When emulsifying agents are present, however, they decrease the
interfacial tension and obstruct the coalescence of water particles.
The above factors determine the "stability" of emulsions. Some stable
emulsions may take weeks or months to separate if left alone in a tank with no
treating. Other unstable emulsions may separate into relatively clean oil and
water phases in just a matter of minutes.
Normal oil field emulsions consist of an oil continuous or external phase, and a
water dispersed or internal phase. In some isolated cases, where there are high
water cuts, it is possible to form reverse emulsion with water as the continuous
phase and oil droplets the internal phase. Complex emulsions have been
reported in low gravity, viscous crudes. These mixed emulsions contain a water
external phase and have an internal water phase in the dispersed oil. The vast

majority of oil treating systems deal with normal emulsions and that is what is
discussed in this chapter.
Figure 6-1 shows a normal emulsion. The small water droplets exist within the
oil continuous phase. Figure 6-2 shows a close up of a "skin" of emulsifying
agent surrounding a water drop, and Figure 6-3 shows two drops touching, but
being prevented from coalescing due to the film of emulsifying agent around
each drop.

Emulsifying Agent
When thinking about emulsion stability, it may be helpful to realize that in a
pure oil and pure water mixture, without an emulsifying agent, no amount of
agitation will create an emulsion. If the pure oil and water are mixed and
placed in a container, they quickly separate. The natural state is for the
immiscible liquids to establish the least contact or smallest surface area. The
water dispersed in the oil forms spherical drops. Smaller drops will coalesce
into larger drops and this will create a smaller interface area for a given
volume. If no emulsifier is present, the droplets will eventually settle to the
bottom causing the smallest interface area.
This type of mixture is a true "dispersion." An emulsifying agent has a surface
active behavior. Some element in the emulsifier has a preference for the oil,
and other elements are more attracted to the water. An emulsifier tends to be
insoluble in one of the liquid phases. It thus concentrates at the interface.
There are several ways an emulsifier changes a dispersion into an emulsion.
The action of the emulsifier can be visualized as one or more of the following:
1. It decreases the interfacial tension of the water droplet, thus causing smaller
droplets to form. The smaller droplets take longer to coalesce into larger
droplets, which can settle quickly.
2. If forms a viscous coating on the droplets that keeps them from coalescing
into larger droplets when they collide. Since coalescence is prevented, it takes
longer for the small droplets created by agitation to settle out.
3. The emulsifiers may be polar molecules, which align themselves in such a
manner as to cause an electrical charge on the surface of the droplets. Since
like electrical charges repel, two droplets must collide with sufficient force to
overcome this repulsion before coalescence can occur.
Naturally-occurring surface active materials normally found in crude oil serve
as emulsifiers. Paraffins, resins, organic acids, metallic salts, colloidal silts and
clay, and asphaltenes (a general term for material with chemical compositions
containing sulfur, nitrogen, and oxygen) are common emulsifiers in oil fields.
Workover fluids and drilling mud are also sources of emulsifying agents.
The type and amount of emulsifying agent has an immediate effect on the
emulsion's stability. It has been shown that the temperature history of the
emulsion is also important as it effects the formation of paraffins and
asphaltenes. The speed of migration of the emulsifying agent to the oil/water
interface and the behavior in terms of the strength of the interface bond are
important factors. An emulsion treated soon after agitation or the creation of
paraffins and asphaltenes can be less stable and easier to process if the
migration of the emulsifler is incomplete. An aged emulsion may become more
difficult to treat. Normally, the lower the crude viscosity and lighter the crude
the more rapid the aging process. Therefore, early treatment may be a lesser
factor in treating low-viscosity, high-API-gravity crudes.

Demulsifiers
Chemical demulsifiers sold under various trade names, such as Tretolite,
Visco, and Breaxit, are highly useful in resolving emulsions. Demulsifiers
act to neutralize the effect of emulsifying agents. Typically, they are surface
active agents and thus their excessive use can decrease the surface tension of
water droplets and actually create more stable emulsions.
There are four important actions required of a demulsifier:
1. Strong attraction to the oil-water interface.
2. Flocculation.
3. Coalescence.
4. Solid wetting.
When these actions are present, they promote the separation of oil and water.
The demulsifier must have the ability to migrate rapidly through the oil phase
to the droplet interface, where it must compete with the more concentrated
emulsifying agent. The demulsifier must also have an attraction for droplets
with a similar condition. In this way large clusters of droplets gather which,
under a microscope, appear like bunches of fish eggs. The oil will take on a
bright appearance since small droplets are no longer present to scatter the
light rays. At this point the emulsifier film is still continuous. If the emulsifier is
weak, the flocculation force may be enough to cause coalescence. This is not
true in most cases and the demulsifier must therefore neutralize the emulsifier
and promote a rupture of the droplet interface film. This is the opener that
causes coalescence. With the emulsion in a flocculated condition the film
rupture results in rapid growth of water-drop size.
The manner in which the demulsifier neutralizes the emulsifier depends upon
the type of emulsifiers. Iron sulfides, clays, and drilling muds can be water wet
causing them to leave the interface and be diffused into the water droplet.
Paraffins and asphaltenes could be dissolved or altered to make their films less
viscous so they will flow out of the way on collision or could be made oil wet so
they will be dispersed in the oil.
It would be unusual if one chemical structure could produce all four desirable
actions. A blend of compounds is therefore used to achieve the right balance of
activity. The demulsifier selection should be made with the process system in
mind. If the treating process is a settling tank, a relatively slow-acting
compound can be applied with good results. On the other hand, if the system is
a chemelectric process where some of the flocculation and coalescing action is
accomplished by an electric field, there is need for a quick-acting compound,
but not one that must complete the dropletbuilding action.
Emulsion-breaking chemicals are most commonly tested with bottle tests,
which involve mixing various chemicals with samples of the emulsion and
observing the results. Such tests are effective in eliminating some chemicals

and selecting those that appear to be more efficient. Bottle tests also provide
an estimate of the amount of chemical required. Bottle tests should be
performed on a representative sample as soon as the sample is obtained
because of the possible detrimental effects of aging. These tests should also be
performed at conditions that are as close to field treating conditions as
possible. Synthetic water should not be used in place of produced water in
bottle tests because the produced water may have very different properties,
and it may contain impurities that are not present in the synthetic water.
While candidate chemicals and approximate dosages can be determined in
bottle tests, the dynamic nature of the actual flowing system requires that
several candidates be field-tested. In actual conditions, the emulsion
undergoes shearing through control valves, coalescence in flow through pipes,
and changes to the emulsion that occur inside the treating vessel as a result of
inlet diverters, water wash sections, etc. Static bottle tests cannot model these
dynamic conditions.
As field conditions change, the chemical requirements can change. If the
process is modified, e.g., very low rates on electrostatic units, the chemical
requirement can change. Seasonal changes bring paraffin induced emulsion
problems. Workovers contribute to solids content, which alters emulsion
stability. So, no matter how satisfactory a demulsifier is at one point in time, it
cannot be assumed that it will always be satisfactory over the life of the field.