Separation Processes 2 Emulsion Treating: Nazir Mafakheri Petroleum Engineering

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Separation processes 2

Lecture 1
Emulsion treating
Nazir mafakheri
Petroleum engineering
Introduction

• Most of the world’s oil reservoirs now produce a mixture of oil and
water.
• The liquids are subjected to shear forces through pumps or other
lifting methods, or are sheared as they pass through pressure-reducing
devices in the production line.

Lecture 1
Introduction

• The shear forces disperse one liquid into the other with variations in
drop size and stability that are related to the shear force encountered
and the physicochemical nature of the production stream. Such dispersions
commonly are referred to as emulsions, although many are not true
emulsions.

Lecture 1
Introduction

• In a true emulsion, either the drop size must be small enough


that forces from thermal collisions with molecules of the
continuous phase produce Brownian motion that prevents
settling, or the characteristics of the interfacial surfaces must be
modified by surfactants, suspended solids, or another semisoluble
material that renders the surface free energy low enough to
preclude its acting as a driving force for coalescence.

Lecture 1
Introduction

• Even in fields where there is essentially no initial water


production, water cuts eventually might increase enough to make
emulsion treatment necessary. Water content of the untreated oil
varies from < 1 to > 90 vol%.

Lecture 1
Introduction

Salt and basic-sediment-and-water (BS&W) contents are important crude-purchasing


requirements. Purchasers limit these contents in the oil they purchase, to reduce transportation
costs, water treatment and disposal costs, and equipment corrosion.

Removing water from the stream decreases the salt content, but additional steps might be
required to meet salt specifications. BS&W content limits vary according to local conditions,
practices, and contractual agreements, but typically range from 0.2 to 3.0%. BS&W usually is
predominantly water, but might contain solids, some of which are sand, silt, mud, scale, and
precipitates of dissolved solids from the producing formation. Other sources of solids are corrosion
products, bacterial debris, and precipitated petroleum fractions such as asphaltenes. Solids
are troublesome and vary widely among producing fields, zones, and wells.

Lecture 1
Introduction

• When water forms a stable emulsion with crude oil and cannot be
removed in conventional storage tanks, emulsion-treating methods
must be used.

Lecture 1
What are emulsions?
Definition of an Emulsion. Strictly speaking, an emulsion is a
heterogeneous liquid that
consists of two immiscible liquids, one of which is intimately dispersed
as droplets in the other.
In oilfield parlance, though, an emulsion is any liquid/liquid dispersion that
does not readily
separate. This latter definition is the one used in this chapter, with
apologies to the purists who
would call these fine dispersions, rather than emulsions.

Lecture 1
Emulsions

Stability of the emulsion is controlled by:

• types and amounts of surface-active agent and/or finely divided


solids

In most crude-oil/water emulsions, the water is finely dispersed in the oil. Such a water-inoil
emulsion is referred to as a “normal” emulsion. The oil can be dispersed in the water to
form an oil-in-water emulsion, which is known as an “inverse” or “reverse” emulsion.

Lecture 1
Emulsifying Agents.

Emulsifying Agents. Emulsifying agents are surface-active compounds


that attach to the water-droplet surface and lower the oil/water
interfacial tension.

• Adding energy to the mixture by agitation breaks the dispersed-


phase droplets into smaller droplets. The lower the interfacial
tension, the smaller the energy input that is required for
emulsification

Lecture 1
Emulsifying Agents.
• Some emulsifiers are asphaltic. Barely soluble in oil and strongly attracted
to water, they come out of solution and attach themselves to the
droplets of water as these droplets are dispersed in the oil.

• Asphaltic emulsifiers form thick films around the water droplets and
prevent droplet surfaces from contacting when they collide, thus
preventing coalescence.

• Oil-wet solids (e.g., sand, silt, shale particles, crystallized paraffin, iron
hydroxides, zinc compounds, aluminum sulfate, calcium carbonate, iron
sulfide, and similar materials that collect at the oil/water interface) can
act as emulsifiers. These substances usually originate in the oil formation,
but can form because of an ineffective corrosion-inhibition program

Lecture 1
Prevention of Emulsions.
• Exclude water from production - no emulsion
- But this is difficult if you have water in reservoir!
- It is nearly impossible, or nearly so, emulsion production must be
expected from many wells

- Sometimes, however, poor operating practices increase emulsification

Lecture 1
Prevention of Emulsions.
poor operating practices = what do we mean by that?
Operating practices that involve the production of excess water because of poor cementing or reservoir
management can increase emulsion-treating problems, as can a process design that subjects the oil/water mixture
to excess turbulence

Unnecessary turbulence can be caused by over pumping and poor plunger and valve maintenance in rod-
pumped wells, by use of more gas lift gas than is needed, and by pumping the fluid where gravity flow could
be used

To minimize turbulence, some operators use progressive cavity pumps, as opposed to reciprocating,
gear, or centrifugal pumps. Other operators have found that some centrifugal pumps actually can cause
coalescence if they are installed in the process without a downstream throttling valve

Wherever possible, pressure drop through chokes and control valves should be minimized before oil/water
separation

Lecture 1
Stability of Emulsions.

• High API = tends to form less emulsions


• Low API = more emulsions

• High viscosity = forms more stable emulsions


• Low viscosity = forms less stable emulsions

• In addition, high-viscosity/high-density oils usually contain more emulsifiers


than do lighter oils.

Lecture 1
How to destabilize Emulsions?

Lecture 1
Emulsion treating.
• Heating.

• Using heat to treat crude-oil emulsions has four basic benefits:


Heat reduces the viscosity of the oil, which allows the water droplets to
collide with Greater force and to settle more rapidly.

Heat also might increase the density difference between the oil and the
water, thus accelerating settling. In general, at temperatures below 180°F,
adding heat will increase the density difference.
• Because most light oils are treated below 80°C (, the effect of heat on
gravity is beneficial. For heavy crudes ( < 20°API), which normally are
treated above 80°C, heat might have a negative effect on the density
difference

Lecture 1
Emulsion treating.
• Heating.

Lecture 1
Emulsion treating.
• Chemical Demulsifiers

Dehydration chemicals, or demulsifiers, are chemical compounds that


are widely used to destabilize, and assist in coalescence of, crude-oil
emulsions

This treatment method is popular because the chemicals are easily


applied, usually are reasonable in cost, and usually minimize the amount
of heat and settling time required.

Lecture 1
Emulsion treating.
• Chemical Demulsifiers

The chemical counteracts the emulsifying agent, allowing the dispersed


droplets of the emulsion to coalesce into larger drops and settle out of the
matrix. To work, demulsifiers must be injected into the emulsion; must mix
intimately with the emulsion and migrate to all the protective films
surrounding all the dispersed droplets;

Lecture 1
Emulsion treating.
• Chemical Demulsifiers

and dispersed droplets must displace or nullify the effect of the


emulsifying agent at the interface. For the oil and water to separate, there
must also be a period of continual, moderate agitation of the treated
emulsion to produce contact between and coalescence of the dispersed
droplets, as well as a quiet settling period.

Lecture 1
Emulsion treating.
• Chemical Demulsifiers
Four actions are required of a chemical demulsifier:

• Strong attraction to the oil/water interface. The demulsifier must be able to


migrate rapidly through the oil phase to reach the droplet interface where it
must counteract the emulsifying
agent.

• Flocculation. The demulsifier must have an attraction for water droplets with
a similar charge and bring them together. In this way, large clusters of water
droplets gather, which under a microscope look like bunches of fish eggs.

Lecture 1
Emulsion treating.
• Chemical Demulsifiers
Four actions are required of a chemical demulsifier:

• Coalescence. After flocculation, the emulsifier film remains continuous. If the


emulsifier is weak, the flocculation force might be enough to cause
coalescence; however, this usually is not true, and the demulsifier must enable
coalescence by neutralizing the emulsifier and promoting rupture of the droplet
interface film. In the flocculated emulsion, the film rupture causes increasing
water-drop size

Lecture 1
Emulsion treating.
• Chemical Demulsifiers
Four actions are required of a chemical demulsifier:

• Solids wetting. Iron sulfides, clays, and drilling muds can be made water-wet,
which causes them to leave the interface and be diffused into the water
droplets. Paraffins and asphaltenes can be dissolved or altered by the
demulsifier to make their films less viscous, or they can be
made oil-wet so that they will be dispersed in the oil.

Lecture 1
Emulsion treating.
• Chemical Demulsifiers
The demulsifier should be selected with all functions of the treating system
in mind. If the process is a settling tank, a relatively slow-acting demulsifier
can be applied with good results.
As field conditions change and/or the treating process is modified, the
chemical requirements might change
Applying heat to an emulsion after a demulsifier has been mixed with it
increases the chemical’s effectiveness by reducing the emulsion viscosity and
facilitating more intimate chemical/emulsion mixing. Chemical reaction at
the oil/water interface happens more rapidly at higher temperatures

Lecture 1
Emulsion treating.
• Agitation.

Agitation or turbulence is necessary to form a crude-oil emulsion. When


turbulence is controlled, however, it can assist in resolving the emulsion.
Agitation increases the number of collisions of dispersed particles of water
and increases the probability that they will coalesce and settle from the
emulsion. Be careful to prevent excessive agitation that will cause
further emulsification instead of resolving the emulsion

Lecture 1
Emulsion treating.
• Coalescing Plates.

Properly designed and placed baffle plates can assist demulsification


by evenly distributing emulsion in a vessel and causing gentle agitation
that helps to coalesce the droplets by causing dispersed water particles to
collide

Lecture 1
Emulsion treating.
• Coalescing Plates.

Corrugated-plate pack, a special coalescing medium for crude-oil


emulsions.

Lecture 1
Emulsion treating.
• Coalescing Plates.

The serpentine-pipe
coalescing pack grows a
larger drop size on the
inlet separator of a
gravity settler

Lecture 1
Emulsion treating.
• Coalescing Plates.

Kinetic (static) mixer for mixing chemical demulsifier with emulsion

Lecture 1
Emulsion treating.
• Water Washing.
In some emulsion-treating vessels, separation of liquids and vapors
takes place in the inlet diverter, flume, or gas boot that is located at the top of the vessel. The
liquids flow by gravity through a large conduit to the bottom of the vessel.

Filtering. A filtering material with the proper pore-space size and the proper ratio of
pore space to total area can be used to filter out the dispersed water droplets of a crude-oil
emulsion by preferentially wetting the filtering material with oil and keeping it submerged in
oil

Fibrous Packing. Fibrous coalescing packs are not commonly used in oil treating, but
are discussed here for completeness and to differentiate between filtering and coalescence

Lecture 1
Emulsion treating.
• Gravity Settling.

Gravity settling is the oldest, simplest, and most widely used method for treating
crude-oil emulsions. The density difference between the oil and the water causes the
water to settle through and out of the oil by gravity. The gravitational force is resisted
by a drag force from their downward movement through the oil.

v = the downward velocity of the water droplet relative to the oil, ft/sec; d = the diameter of the water droplet, μm;
Δγow = the specific-gravity difference between the water and the
oil (water/oil); and μo = dynamic viscosity of the oil, cp

Lecture 1
Emulsion treating.
• Gravity Settling.

• The larger the water droplet is, the greater is its downward velocity (i.e., the larger the
droplet, the less time it takes to settle to the bottom of the vessel, and thus the easier it is to
treat the oil).

• The greater the density difference between the water droplet and the oil, the greater is the
downward velocity (i.e., the lighter the oil, the easier it is to treat the oil). For example, if the
oil gravity is 10°API and the water is fresh, the settling velocity will be zero because there is
no gravity difference.

• The higher the temperature, the lower the oil viscosity, and thus the greater the downward
velocity of the water droplets. It is easier to treat the oil at high temperatures than at low temperatures
(assuming a small effect on gravity difference because of increased temperature).

Lecture 1
Emulsion treating.
• Gravity Settling.

Gravity settling is the oldest, simplest, and most widely used method for treating
crude-oil emulsions. The density difference between the oil and the water causes the
water to settle through and out of the oil by gravity. The gravitational force is resisted
by a drag force from their downward movement through the oil.

Q = heat input, Btu/hr, ΔT = temperature increase, °F, qo = oil flow rate,


qw = water flow rate, γo = specific gravity of oil, and γw = specific gravity of water.

Lecture 1
Emulsion treating.
• Gravity Settling.

gravity loss vs. temperature for 33°API crude oil

Lecture 1
Emulsion treating.
• Gravity Settling.

Percent loss by volume vs. temperature for 33°API crude oil

Lecture 1
Emulsion treating.
Retention Time.

In a gravity settler (e.g., an oil-treating tank or the coalescing section


of an oil-treating vessel), coalescence will occur, but because of the small
forces at work, the rate of contact between water droplets is low, and colliding
droplets seldom coalesce immediately . Thus, the coalescence process occurs
over time, but it follows a steep exponential curve in which successive doubling
of retention time yields small, incremental increases in droplet size.

Lecture 1
Emulsion treating.
Centrifugation.

Because of the density difference between oil and water, centrifugal


force can be used to break an emulsion and separate it into oil and water. Small
centrifuges are used to determine the BS&W content of crude-oil emulsion
samples. A few centrifuges have
been installed in oil fields to process emulsions, but centrifuges have not been
widely used for treating emulsions because of high initial cost, high operating
and maintenance costs, low capacity, and their tendency to foul.

Lecture 1
Emulsion treating.
Distillation.

Distillation can be used to remove water from crude-oil emulsions. Along


with lighter oil fractions, the water can be distilled by heating and then
separated by appropriate means. The lighter oil fractions usually are returned
to the crude oil. The only current use of distillation is in the “flash system” that
is used in 15°API and lower oil.

Lecture 1
Emulsion treating.
Distillation.

Typical flash-distillation system for dehydrating


emulsions of heavy viscous crude oils.

Lecture 1
Emulsion treating.
Desalting

. Most produced water contains salts that can cause problems in production and refining,
when solids precipitate to form scale on process equipment. The salts also accelerate
corrosion in piping and equipment

The salt content of crude oil almost always consists of salt dissolved in small droplets of
water that are dispersed in the crude. Sometimes the produced oil contains crystalline salt,
which forms because of pressure and temperature changes and because of stripping of
water vapor as the fluid flows up the wellbore and through the production equipment.
The salinity of produced brine varies widely, but for most produced water, it ranges from
5,000 to 250,000 ppm of equivalent NaCl.

Lecture 1
Emulsion treating.
Water solubility

Lecture 1
Emulsion-Treating Equipment

Designing equipment or a system for treating crude-oil emulsions and sizing


each piece of equipment for a specific application requires experience and
engineering judgment

Lecture 1
Emulsion-Treating Equipment

Free Water
Knockout (FWKOs)
. Where large quantities of water
are produced, it usually is desirable
to separate the free water before
attempting to treat the emulsion.
This is done using a separator
known as an FWKO.

FWKOs are designed as either


horizontal or vertical pressure
vessels, but predominantly
horizontal.

Lecture 1
Lecture 1
Emulsion-Treating Equipment
• Storage Tanks. Oil generally should be water-free before it is flowed
into lease-storage tanks; however, if the oil contains only a small
percentage of water and/or if the water and oil are loosely emulsified,
the water could be allowed to settle to the bottom of the oil-storage
tank and then be drawn off before oil shipment.

• This practice generally is not recommended or


followed, but for small volumes of free or loosely emulsified water on
small leases or for low volume marginal wells, it might be a practical
and economical procedure.

Lecture 1
Emulsion-Treating Equipment
• When a storage tank is used for dehydration, the oil is flowed into the
tank and allowed to settle. When the tank is full of liquid, flow into
the tank is stopped or switched to another tank, and the full tank
remains idle while water settles out of the oil.

• When the water has separated, it is drained from the bottom of the
tank and the oil is gauged, sampled, and pumped or drained to a
truck or pipeline.

Lecture 1
Emulsion-Treating Equipment
• Settling Tanks - Settling
tanks that are used to
treat oil go by various
names.
Some of the most common
names are gun barrel
(named for the protrusion
of its central flume), wash
tank, and dehydration tank.

Lecture 1
Emulsion-Treating Equipment
• Settling Tanks - spreader – most important part of the settling tank design
• There are many types of spreader design

Lecture 1
Emulsion-Treating Equipment
• Settling Tanks

Lecture 1
Emulsion-Treating Equipment
• Settling Tanks

Many settling tanks help the


treatment process by adding
heat to the liquid using a direct
heater, an indirect heater, or a
type of heat exchanger.

Lecture 1
Emulsion-Treating Equipment
• Settling Tanks

Heaters

Lecture 1
Emulsion-Treating Equipment

• Settling Tanks - Heaters

Lecture 1
Emulsion-Treating Equipment

• Settling Tanks - Heaters

Lecture 1
Emulsion-Treating Equipment

• Desalting
• Most produced water contains salts that can cause problems in production and refining,
when solids precipitate to form scale on process equipment. The salts also accelerate
corrosion in piping and equipment. The salt content of crude oil almost always consists of
salt dissolved in small droplets of water that are dispersed in the crude. Sometimes the
produced oil contains crystalline salt, which forms because of pressure and temperature
changes and because of stripping of water vapor as the fluid flows up the wellbore and
through the production equipment

Lecture 1
Emulsion-Treating Equipment

• Desalting
• Most produced water contains salts that can cause problems in production and refining,
when solids precipitate to form scale on process equipment. The salts also accelerate
corrosion in piping and equipment. The salt content of crude oil almost always consists of
salt dissolved in small droplets of water that are dispersed in the crude. Sometimes the
produced oil contains crystalline salt, which forms because of pressure and temperature
changes and because of stripping of water vapor as the fluid flows up the wellbore and
through the production equipment

Lecture 1
Emulsion-Treating
Equipment
• Desalting

Lecture 1
Emulsion-Treating Equipment
Salinity of produced brine
• The salinity of produced brine varies widely, but for most produced water, it ranges from
5,000 to 250,000 ppm of equivalent NaCl. Crude oil that contains only 1.0% water with a
15,000-ppm salt content has 55 lbm of salt per 1,000 bbl of water-free crude. The chemical
composition of these salts varies, but nearly always is mostly NaCl, with lesser amounts of
calcium and magnesium chloride. Salt content limits might be by either of the following:
• transportation requirements in the production field or shipping terminal
• concerns over corrosion, fouling, or catalyst degradation in the refinery

Purpose of a desalting system


• The purpose of a desalting system is to reduce the salt content of the treated oil to
acceptable levels. When the salinity of the produced brine is not too high, merely ensuring
that there is a low fraction of water in the oil can reduce salt content. In that case, the
terms desalting and emulsion treating effectively have the same meaning, and the concepts
and equipment can be used.

Lecture 1

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