EMULSIONES

QUE ES UNA EMULSIÓN

is a stable mixture of oil and water that does not separate by gravity alone. For an emulsion
to exist there must be two mutually immiscible liquids, an emulsifying agent (stabilizer), and
sufficient agitation to disperse the discontinuous phase into the continuous phase

TIPOS DE EMULSIONES

Normal, or regular, oil-field emulsions consist of an oil continuous or external phase and a
water dispersed or internal phase.

normal water-in-oil emulsion. The small water droplets exist within the oil continuous phase.

In some cases, where there are high water cuts, such as when a water-drive field has almost
“watered out,” it is possible to form reverse emulsions with water as the continuous phase
and oil droplets as the internal phase.
Complex or “mixed” emulsions have been reported in low-gravity, viscous crude oil.

A stable or “tight” emulsion occurs when the water droplets will not settle out of the oil phase
due to their small size and surface tension. Stable emulsions always require some form of
treatment.

CÓMO SE FORMAN LAS EMULSIONES EN LA INDUSTRIA

In oil production, oil and water are the two mutually immiscible liquids. When oil and water
are produced from a well, the fluid stream also contains organic and inorganic materials.
These contaminants are preferentially absorbed at the interface between the oil and water
phases. Once the contaminants are absorbed at the interface, they form a tough film (skin)
that impedes or prevents the coalescence of water droplets. The film prevents the water
droplets from coalescing. Agitation, sufficient to disperse one liquid as fine droplets through
the other, occurs as the well fluids makes their way into the well bore, up the tubing, and
through surface chokes, down-hole pumps, and gas lift valves. Turbulence caused by the
pressure drop across the choke is the primary source of agitation for emulsion formation.

ESTABILIDAD DE UNA EMULSIÓN

Los factores de los que depende una emulsión son

● the difference in density between the water and oil phases

● the size of dispersed water particles
● viscosity, l interfacial tension
● the presence and concentration of emulsifying agents
● water salinity
● age of the emulsion
● agitation.

1. DIFERENCIAL DE DENSIDAD
one of the factors that determines the rate at which water droplets settle through the
continuous oil phase. The greater the difference in gravity, the more quickly the water
droplets will settle through the oil phase. Heavy oils (high specific gravity) tend to keep water
droplets in suspension longer. Light oils (low specific gravity) tend to allow water droplets to
settle to the bottom of the tank.

2. TAMAÑO DE GOTAS DE AGUA

. The larger the droplet, the faster it will settle out of the oil phase. The water droplet size in
an emulsion is dependent upon the degree of agitation that the emulsion is subjected to
before treating.

3. VISCOSIDAD
Juega 2 roles importantes en la estabilidad de una emulsión
- First, as oil viscosity increases, the migration of emulsifying agents to the water
droplet’s oil–water interface is retarded. This results in larger water droplets being
suspended in the oil, which in turn results in less stable emulsions in terms of
numbers of small water droplets suspended in the oil
- Second, as viscosity increases, the rate at which water droplets move through the oil
phase decreases, resulting in less coalescence and increased difficulty in treating.

4. TENSIÓN INTERFACIAL
Interfacial tension is the force that “holds together” the surfaces of the water and oil phases.
When an emulsifying agent is not present, the interfacial tension between oil and water is
low. When interfacial tension is low, water droplets coalesce easily upon contact.

5. PRESENCIA Y CANTIDAD DE AGENTE EMULSIFICANTE

Chemicals (demulsifiers) are normally used to reduce the interfacial tension. Chemical
effectiveness is enhanced by mixing, time, and temperature. Adequate mixing and sufficient
time are required to obtain intimate contact of the chemical with the dispersed phase. A
certain minimum temperature is required to ensure the chemical accomplishes its function.
Both viscosity reduction and effectiveness of chemical are dependent on the attainment of a
certain minimum temperature. It may well be that the increase in chemical effectiveness is a
result of the decrease in viscosity of the oil phase.

6. SALINIDAD DEL AGUA

The salinity of the water is a measure of the total dissolved solids in the water phase. As
salinity of the water increases, the density of the water increases, which in turn increases the
differential density between the water and the oil. The increase in differential density aids in
separation of the oil and water phases. Small amounts of salt, or other dissolved solids, in
the water phase will appreciably lower the interfacial tension and thus will decrease the
difficulty of separating the two phases.

7. TIEMPO DE LA EMULSIÓN
As emulsions age they become more stable and separation of the water droplets becomes
more difficult. . Emulsions are formed during production on the fluid. The degree of
emulsification is dependent on the agitation of the two phases by pumps, chokes, etc. Before
an emulsion is produced, the emulsifying agents are evenly dispersed in the oil. As soon as
the water phase is mixed with the oil, the emulsifying agents begin to cluster around the
water droplet to form a stable emulsion. While the initial stabilization may occur in a matter of
a few seconds, the process of film development may continue for several hours. It will
continue until the film around the droplet of water is so dense that no additional stabilizer can
be attracted, or until there no stabilizer is left to be extracted from the oil. At such a time the
emulsion has reached a state of equilibrium and is said to be aged. The older the emulsion,
the more difficult it is to treat. Therefore, emulsion breaking or treating operations are often
located as close to the wellhead as possible, so that emulsions formed during flow in the
production tubing and wellhead equipment are not allowed to age before treatment.
Normally, the lower the crude viscosity and lighter the crude, the more rapid the aging
process will be.

8. AGITACIÓN
The type and severity of agitation applied to an oil–water mixture determine the water drop
size. The more turbulence and shearing action present in a production system, the smaller
the water droplets and the more stable the emulsion will be.

AGENTE EMULSIFICANTE

When studying 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. 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.”
Photomicrograph showing a close-up view of the emulsifying agent skin surrounding a water
droplet.

An emulsifying agent in the system is a material, which has a surface-active behavior. Some
elements in emulsifiers have 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 emulsifiers work to cause a dispersion
to become an emulsion.
- l It forms a viscous coating on the droplets, which keeps them from coalescing into
larger droplets when they collide. Since coalescence is prevented, it takes longer for
the small droplets, which are caused by agitation in the system, to settle out.

Photomicrograph showing two droplets touching but unable to coalesce because of

the emulsifying skin surrounding the droplets.
 - 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. (Para que 2 gotas puedan coalescer esta
fuerza debe ser mayor a la fuerza de repulsión por carga eléctrica)

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 soon after the creation of paraffins and asphaltenes, can be less stable
and easier to process if the migration of the emulsifier is incomplete.

CUALES SON LOS AGENTES EMULSIFICANTES DENTRO DE LA INDUSTRIA

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 have an immediate effect on
the emulsion’s stability.

DESEMULSIFICANTES

Emulsions can be resolved or broken thermally and/or chemically. When we chemically

resolve an emulsion, we use a demulsifier or emulsion breaker. 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. In addition, demulsifiers for water-in-oil emulsions tend to promote
oil-inwater emulsions; therefore, excessive chemical use may cause water treating
problems.

FUNCIONES DE UN DESEMULSIFICANTE

● strong attraction to the oil–water interface

● flocculation
● coalescence
● solid wetting.

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 produce an attraction for similar droplets. In this way large clusters of
droplets gather. 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 forcemay 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 opening to coalescense.

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.
As field conditions change, the chemical requirements can change. If the process is
modified, for example, very low rates on electrostatic units, the chemical requirements can
change. Seasonal changes bring paraffin-induced emulsion problems. Workovers contribute
to solids and acid/base contents, which alters the emulsion stability. So no matter how
satisfactory a demulsifier is at one point in time, it may not be satisfactory over the life of the
field.

PRUEBA DE LA BOTELLA PARA ESCOGER UN DESEMULSIFICANTE QUIMICO

Emulsion-breaking chemicals are most commonly tested with a bottle test, which involves
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 and an
estimate of the settling time required for a treating vessel.
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 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.

The best demulsifier is the compound that results in the most rapid and complete separation
of the phases at a minimum concentration. The important characteristics in the bottle test will
be dictated by the production needs and the behavior of the system.

- Prueba en campo
Having selected a promising demulsifier candidate, a field trial should be carried out to test
the chemical’s ability to operate in a dynamic system. In the field test, the flexibility of the
demulsifier to process changes can be established. This data will be useful when the
chemical is used in full-scale operation. In most field trial situations, the demulsifier being
tested is first used in conjunction with a test separator system. This enables the supplier to
look at the response of the chemical to one or more wells and to provide the tester an idea of
the true field dosage. If this preliminary scenario is successful, the chemical can then be
dosed into the full system and optimized for different well configuration and flow rates

- Optimización
After a successful field trial, a full-scale field optimization is carried out. Here, the chemical
performance is monitored routinely as are the possible side effects of under- or overdosing,
such as separator interface build-up.

- Cambio del desemulsificante

As crude characteristics change over the life of a field, the performance of the demulsifier
chemical will change also. Typically, when fields first produce water, the emulsions formed
are difficult to break. As the field ages and the water cut increases, the stability of the
emulsion and even the emulsifying agents themselves may change. Hence, it is usual to
investigate demulsifier performance every 2–3 years.
 - Problemas del desemulsificante
The most common problem with demulsifiers is overdosing. Poor treatment, dirty water, and
interface pad build-up are all symptoms of overdosing an optimum chemical. Overdosing can
occur by a step increase in dose rate, for example, going from 5–20 ppm, or by a gradual
accumulation of chemical in the system.
Other problems with demulsifiers can be that their viscosity changes with temperature. Most
demulsifiers are viscous chemicals whose ability to be pumped can drop dramatically with
reduced temperature. If this is the case, it may be prudent to ask the chemical supplier to
produce a “winterized” version of the chemical. This is often done by reducing the
percentage of active ingredient and adding a more solvent carrier. If this is the solution, the
dose rates will need to be re-optimized for best performance.

Another common problem with demulsifiers is their apparent lack of treatment “range.” It is
not uncommon for a field demulsifier to have a different performance standard for different
wells within a field. so we can use more than one demulsifier for the field.

As there are no online analyzers for demulsifier performance, one must monitor the facilities
for changes in water or crude quality that may be attributed to poor demulsifier performance.

CONSIDERACIONES PARA LA PRUEBA DE LA BOTELLA

- Tasa de caída de las gotas de agua

In high water volume systems a chemical that creates a fast water drop-out rate is necessary
to make the system function as designed. When FWKOs are used, the speed of water
drop-out may become the most important factor.

- Sludge
When sediment and water collect without breaking to water and oil, the result is called
sludge. In some systems, non-coalesced water droplets result in a loose agglomeration that
breaks to water and oil, causing no problems. Depending upon the system and sludge
stability, interface sludge may or may not cause a problem. (No entiendo muy bien esto,
traducción: Cuando el sedimento y el agua se juntan sin romperse en agua y aceite, el
resultado se llama lodo. En algunos sistemas, las gotas de agua no coalescidas dan como
resultado una aglomeración suelta que se descompone en agua y aceite, sin causar
problemas. Según el sistema y la estabilidad del lodo, el lodo de la interfase puede o no
causar un problema)

- Interfase
The desired interface is one that has shiny oil in contact with the water (mirror interface).

- Agua turbia
The turbidity (clarity) of the water is very difficult to interpret in the bottle test and correlate to
facility behavior. When the chemical effects in the bottle are pronounced and reproducible,
some correlation can be expected. Clear water is definitely the desired result. (Segun lo que
entiendo, se espera que el agua salga clara despues de separar la emulsion)

- Color del crudo

Emulsions have a hazy appearance when compared to the bright color of treated oil. As a
crude oil emulsion separates, the color tends to brighten. Brightening of oil can be
encouraging, but it can also be deceptive if taken as the sole qualification for chemical
selection. While bright color is no guarantee of a successful chemical, lack of it assures that
the compound is not worthy of further consideration.

- Resultados de la centrífuga
An important quality in the final evaluation is the centrifuge results. It is always good practice
to make a centrifuge grind out to accurately determine the final amount of BS&W entrained
in the oil.

TEORIA DEL TRATAMIENTO DE EMULSIONES

Removing water from crude oil often requires additional processing beyond the normal
oil–water separation process, which relies on gravity separation. Crude oil treating
equipment is designed to break emulsions by coalescing the water droplets and then using
gravity separation to separate the oil and water. In addition, the water droplets must have
sufficient time to contact each other and coalesce. The negative buoyant forces acting on
the coalesced droplets must be sufficient to enable these droplets to settle to the bottom of
the treating vessel. Therefore, it is important when designing a crude oil treating system to
take into account temperature, time, viscosity of the oil, which may inhibit settling, and the
physical dimensions of the treating vessel, which determines the velocity at which settling
must occur.

Factores a tener en cuenta a la hora de seleccionar un metodo de tratamiento de crudo:

Stability (tightness) of the emulsion,

Specific gravity of the oil and produced water
Corrosiveness of the crude oil, produced water, and associated gas,
Scaling tendencies of the produced water
Quantity of fluid to be treated and percent water in the fluid
Paraffin-forming tendencies of the crude oil
Desirable operating pressures for equipment
Availability of a sales outlet and value of the associated 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.
TRATAMIENTOS DE EMULSIONES

The water remaining in the crude after the free water has settled out is considered to be in
an emulsified state. Emulsified oil is removed by one or more treating processes. Treating
refers to any process designed to separate crude oil from water and foreign contaminants
carried along with it from the reservoir. Emulsion treating processes require some
combination of the following: chemical addition, settling time, heat, and electrostatic
coalescing.

1. Adición química
The purpose of treating chemicals is to induce coalescence so that the oil and water will
separate rapidly. Surface-active agents are absorbed at the oil–water interface, rupture the
tough film (skin) surrounding the water droplets, and/or displace the emulsifying agent and
force the emulsifying agent back into the oil phase.

2. Cantidad de químico
The amount of chemical required cannot be predicted accurately from bottle tests. The only
reliable method of determining the amount of chemical to use is to run tests in the field. one
must make certain no other changes are being made in the facility. Temperature should
remain constant during the test; otherwise, it is impossible to determine which change,
chemical or temperature, has caused a certain effect. The amount of chemical added can
vary from 1 gallon per 150 to 1000 barrels.

Chemicals should be added continuously as possible during the entire production period and
at a rate related to the production rate. Even though some residual chemical is held in the
treater or gunbarrel, chemicals cannot be batched and be expected to do an adequate
treatment. Chemicals cannot act properly unless they are thoroughly mixed with the
emulsion. The farther upstream, a minimum of 200 ft, from a treater or gunbarrel the
chemicals are added results in better mixing and better treatment. The ideal location for
injection is at the manifold before the fluid enters a separator. In some cases an emulsion
that is difficult to treat may break quite easily if a chemical pump is set at the well.

3. Selección del quimico

A thorough understanding of the treating equipment and its contribution to the treatment are
necessary before chemical selection can be made. If little agitation is available, a fast-acting
chemical is necessary. If an FWKO vessel is used, the water drop-out rate will be very
important. If heat is unavailable, the chemical must work at ambient temperatures. Different
types of vessels require different chemical actions.

4. Tiempo de remojo
settling time is required to promote gravity settling of the coalescing water droplets.
Emulsion-treating equipment designed to provide sufficient time for free water to settle
includes three-phase separators, FWKOs, heater-treaters, and gunbarrels with an internal or
external gas boot. The time necessary for free water to settle is affected by differential
density of the oil and water, viscosity of the oil, size of the water droplets, and relative
stability of the emulsion.
 Effect of time on coalescence. Top: emulsion without chemicals. Bottom: emulsion with
demulsifier added.

5. Coalescencia

The process of coalescence in oil treating systems is time-dependent. In dispersions of two

immiscible liquids, immediate coalescence seldom occurs when two droplets collide.
Experiments with deep-bed gravity settlers indicate that the time to ‘grow’ a droplet size due
to coalescence can be estimated by the following equation:
The more dilute the dispersed phase, the greater the residence time needed to “grow” a
given particle size will be. That is, coalescence occurs more rapidly in concentrated
dispersions. This is the reason that oil is “water-washed” by entering the treating vessel
below the oil–water interface in most gunbarrels and treaters. Flocculation and coalescence,
therefore, occur most effectively at the interface zone between oil and water.

6. Viscosidad

The viscosity of the oil continuous phase is extremely important in sizing a treater. Stokes’
law, used to determine the settling velocity of a water droplet settling through the continuous
oil phase, includes the oil viscosity. As the oil viscosity increases, the settling velocity of a
given droplet decreases. This requires that the treater size be increased. The oil viscosity
also affects coalescence of the water droplets. As the oil viscosity increases, there is more
resistance to random motion of the water droplets. Therefore, the droplets do not move as
fast or as far.

7. Efectos del aumento de temperatura

Adding heat to the incoming oil–water stream is the traditional method of separating the
phases. The addition of heat reduces the viscosity of the oil phase, allowing more rapid
settling velocities in accordance with Stokes’ law of settling. For some emulsifying agents,
such as paraffins and asphaltenes, the addition of heat deactivates, or dissolves, the
emulsifier and thus increases its solubility in the oil phase. Treating temperatures normally
range from 100 to 160 F (38– 70 C). In treating of heavy crudes the temperature may be as
high as 300 F (150 C).

Finally, it takes fuel to provide heat, and the cost of fuelmust be considered. Thus, while
heatmay be needed to treat the crude adequately, the less heat that is used, the better.

If properly and prudently done, heating an emulsion can greatly benefit water separation.
However, if a satisfactory rate of water removal can be achieved at the minimum
temperature delivered into a process, there may be no reason to suffer the economic
penalties associated with adding heat.

8. Coalescedores electrostáticos

Coalescing of the small water drops dispersed in the crude can be accomplished by
subjecting the water-in-oil emulsion to a high-voltage electrical field. When a non-conductive
liquid (oil) containing a dispersed conductive liquid (water) is subjected to an electrostatic
field, the conductive particles or droplets are caused to combine by one of three physical
phenomena:

- Electrical attraction brings the droplets together and causes them to coalesce.
- The electric field tends to distort and thus weaken the film of the emulsifier
surrounding the water droplets. As they are relaxed during the low-voltage portion,
the surface tension will pull the droplets back toward the spherical shape. The same
effect is obtained in the next half of the alternating cycle. The weakened film is thus
more easily broken when droplets collide, making coalescence more likely.
- Droplets are attracted to an electrode due to an induced charge.
Whatever the actual mechanism, the electric field causes the droplets to move about rapidly
in random directions, which greatly increases the chances of collision with another droplet.
When droplets collide with the proper velocity, coalescence occurs. The attraction between
water droplets in an electric field is given by

This equation indicates that the greater the voltage gradient is, the greater the forces
causing coalescence will be.

9. Tamaño de la gota y tiempo de retención

The droplet diameter is the most important single parameter to control to aid in water settling
since this term is squared in Stokes’ law’s settling equation. A small increase in diameter will
create a much larger increase in settling velocity. Thus, in sizing treating equipment, it is
necessary to predict a droplet diameter, which must be separated from the oil to meet a
desired BS&W specification.
we would expect droplet size to increase with retention time in the coalescing section and
with heat input, which excites the system, leading to more collisions of small droplets.
Droplet size could be expected to decrease with oil viscosity, which inhibits the movement of
the particles and decreases the force of the collision. While it may be possible to predict the
droplet size at the inlet to the treater, the shearing that occurs at the inlet nozzle and inlet
diverter coupled with the coalescence that occurs at the oil–water interface cannot be
determined.

DISEÑO DE LOS EQUIPOS DE TRATAMIENTO

The major factors controlling the sizing of emulsion treating equipment are:

● heat input required

● gravity separation considerations
● settling equations
● retention time equations
● water droplet size.