Reduction of Corrosion through Improvements in Desalting

by
Kenneth W. Warren PhD
NATCO
Houston, Texas
Presented to Benelux Refinery Symposium, Lanaken, Belgium, 1995.
Abstract
Historically, desalting has been used to reduce fouling in the crude distillation unit and to reduce
corrosion in the crude distillation tower overhead. For this service, desalting requirements have been
moderate and have focused on the removal of inorganic chlorides. Now emphasis is being placed on the
use of less desirable crude oils and on the conversion of low quality crude oils with new catalyst systems.
These changes have resulted in more stringent desalting requirements including not only a reduction in
permissible inorganic chlorides, but also in the reduction of alkali metal cations to very low
concentrations.
Improvements in the design and operation of desalters have been required to meet these new
requirements. These improvements include modifications of the electrostatic field configuration and
intensity, modulation of the electrostatic field, alteration of the flow patterns within the desalter, and new
ways of contacting the crude oil and the wash water. Also important are new chemical treatment
programs which reduce suspended solids entrainment in the oil. All of these changes have been made in
conjunction with environmentally mandated improvements in water discharge quality.
Introduction
Crude oil production is usually associated with the the co-production of varying amounts of water,
formation solids, and corrosion products. This water may be connate water from the oil reservoir, or it
may result from water injected in an enhanced recovery process. The water frequently contains sizeable
concentrations of dissolved salts with the chlorides, sulfates, and bicarbonates of alkali metals and
alkaline earths predominating. Separation processes are applied at the production site in order to
minimize transportation costs and to prevent corrosion in the transportation system. These result in the
removal of most of the water and the heavier formation solids. The level of field dehydration is
determined by specifications set by the oil transporter and is reflective of the relative difficulty of
dehydration. Therefore, dehydration specifications typically range from 3% bulk sediments and water
(BS&W) for heavy crudes in warm climates to 0.2% BS&W for lighter ones in cold climates. After
such processing, most field crude oils contain less than one percent bulk sediments and water. The crude
oils also may become contaminated with sea water used for ballasting during ocean transport and
additional corrosion products may be accumulated.
This residual water is normally the source of mineral salts appearing in the crude oil. The most common
of these salts are the chlorides, bicarbonates, and sulfates of sodium, calcium, and magnesium, although
other minerals may predominate in some localities. Mineral precipitates may, in some instances,
constitute a significant portion of the observed inorganic matter in oil. Iron sulfide is a particularly
troublesome example of a common mineral precipitate. This material, which results from corrosion
processes, is oil-wetted and contributes to emulsion stabilization and sludge formation within process
vessels. Other precipitates which may become dispersed in the oil result from the formation of scales,
e.g., calcium carbonate, as a result of changes in temperature or system chemistry. Finely divided scale

minerals may concentrate at phase boundaries and contribute to emulsion and sludge problems, or they
may remain dispersed in one of the phases. Another type of mineral precipitate results from the formation
of crystals of water soluble salts which then become dispersed in the oil. This effect is most frequently
observed in light oils containing high salinity dispersed water. As these light oils are stabilized to lower
pressures, gas evolution results from evaporation of light ends and precipitation of gaseous hydrocarbons
from solution. Partitioning of the water between the liquid phase and these gases results in loss of liquid
water. The salts contained in the water are then left behind as either dry crystals in the oil or as crystals
attached to drops of saturated solution. A third source of mineral matter in the oil is metal-organic
compounds such as porphyrins or salts of organic acids such as naphthenates. These are soluble or
semi-soluble in oil and account for most of the heavy metals found in crude oil.
Refiners have historically been concerned with the removal of these residual contaminants in order to
minimize salt and sediment deposition on the trays of the crude distillation tower and corrosion in the
crude column overhead. A major culprit in this corrosion is hydrogen chloride formed by the hydrolysis
of calcium and magnesium salts. Although the hydrolysis reaction also produces an equivalent quantity
of calcium and magnesium hydroxides, the volatility of hydrogen chloride results in its separation from
these basic compounds with the result that zones of condensation are bathed with hydrochloric acid
solution. Chloride ion is particularly detrimental since it promotes corrosion by depolarizing corrosion
cells and degrades precious metal catalysts by complexing and solubilizing them. Sulfur compounds and
naphthenic acids also contribute to corrosion, but usually to lesser degrees.
More recently, concerns have turned toward the effects of alkali metal cations on the life of catalysts.
Sodium ion binds to acid sites on silica/alumina catalysts and forms a eutectic whichs destroys catalytic
activity. The ecomonics of many fluid catalytic cracking and hydrodesulfurization processes are strongly
dependent upon catalyst life. The very low salt concentrations necessary for successful application of
these processes require operation of desalters close to their practical limits of efficiency.
Salts have historically been removed from crude oil by washing it with fresh water and then separating
the phases as completely as practicable. As in most liquid separation processes, the critical steps are
coagulation to destabilize the dispersion, flocculation to agglomerate the destabilized drops, and
sedimentation to separate the two liquid phases. Heat is used to both improve the reaction kinetics and
enhance the sedimentation rate. Coagulation is essential for effective separation and is accomplished by
chemical treatment. Although flocculation may be produced by thermally induced collisions or chemical
aids, the requirements for a high degree of separation and for avoidance of by-products preclude reliance
on these techniques. Therefore, electric fields have been almost universally accepted as the flocculant of
choice in desalting operations. Sedimentation is carried out in a quiescent chamber with a minimum of
flow induced or thermally induced turbulence and provision for elimination of refractory interface
sludges.
Desalting Processes
Earlier technology for electrically induced flocculation utilized alternating current (AC) fields in the
range of 16 to 23 kilovolts (KV). Although this technology grew out of work done on the electrical
precipitation of solid particles from gases which used direct current (DC) fields, the choice of AC was
made to avoid electrolysis of the aqueous phase that would result from the application of DC fields as
well as to reduce the possibility of galvanic corrosion of the pressure vessel. The rapid reversal of
polarity in an AC system (every 8.3 milliseconds with 60 hertz power) causes any electrically induced
reactions to remain reversible since the reaction products do not have time to diffuse away from the
reaction site. However, this rapid reversal of the electrical field also precludes any significant drop travel

due to electrical forces. The flocculating effect of an AC field is due to polarization of the water drops
resulting in a stretching deformation. Since adjacent ends of two water drops would be oppositely
polarized, an attractive force exists which can result in coalescence if the drops are very close together.
The attractive forces between the induced dipoles of water drops in an AC field are short range in action.
The attractive force between drops of equal size can be expressed as follows:

F'

6KE 2r 6
d4

Interdrop Attractive Force in an Electric Field

Where:
F = Force of attraction
K = Dielectric constant
E = Electric field gradient
r = Drop radius
d = Interdrop distance
Inspection of this equation illuminates both the advantages and weakness of an AC field in
electroflocculation. Note that the dipolar attractive force is highly dependent on drop size (as the sixth
power exponent testifies), with limited benefit in the coalescence of small drops. Also note the rapid
decline in dipolar force with distance. In an AC field, the efficacy of electroflocculation is dependent
upon diffusion and fluid flow to bring dispersed water drops into close proximity. The AC field is most
effective in removing large drops which are close together. Very small drops not significantly affected by
the field. Therefore, the AC field is most effective on the high water content emulsion at the inlet of a
desalter vessel and on the collection of large drops which accumulate at the oil/water interface. An
additional benefit of the oscillating elongation of the drops produced by the AC field is the rupture of any
stabilizing films which might have formed. This effect is of particular advantage in resolving slowly
condensing dispersions in the zone of hindered settling at the oil/water interface.
In a DC field the electrical forces are sustained and unidirectional. Therefore, polarized drops are able to
move along the lines of force of the field. A system was perfected in the early 1970's for combining the
freedom from electrolysis and galvanic corrosion of the AC coalescer with the advantages of drop
transport of the DC system. The electrodes in this device consist of parallel plates connected to
oppositely oriented diodes in such a manner that alternate plates are oppositely charged. Both diodes are
connected to the same end of the transformer secondary winding; therefore, the plates are charged on
alternate half cycles of the AC power supply. The other end of the secondary winding is connected to
ground, so that the electric field projected from the electrode array to the vessel is still AC. Also, the AC
field is still available at the oil/water interface to assist in condensation of the settling dispersion as well
as to provide coalescence and settling of the loosely dispersed water fraction of the incoming crude oil.
The DC field is then available to supply translational energy to the very small drops. These drops
approach the nearest plate, become charged, and are repelled toward the opposite plate on a collision
course with oppositely charged drops from that plate. Rapid coalescence ensues. Because the plates can
only charge on alternate half cycles, the current between them is limited to discharge of capacitively
stored energy and is unable to produce significant electrolysis. These plates are also operating in

relatively dry oil which further limits current dissipation from them. This system, known as Dual
PolarityTM, has been widely used for both field dehydration and desalting.
A weakness of electrostatic coalescers has been the means of protecting the electrical system in the event
of excessive power requirements during short term upsets. Protection has been provided in the form of a
saturable core reactor in series with the transformer. As power demand increases in such a system, the
reactor limits the current to the transformer primary winding. Unfortunately, this has the effect of
reducing power input to the vessel at precisely the time it is most needed. To counteract this situation, an
electronic controller capable of sensing the load demand and modifying the power input to the
transformer was developed. This controller differs in action from the reactor in that power is reduced on
the basis of time rather than by variation of maximum voltage. Short bursts of high intensity energy are
applied to the emulsion with duration of the pulses limited to maintain an average power output within the
rating of the transformer. Recent work at the University of Bradford has shown that much of the
coalescing action of an electric field occurs during the rapid change of voltage with time (high dV/dt) at
the leading edge of an electrical pulse. Therefore, much of the coalescing ability of the electric field is
preserved during this pulsing action. The controller also includes provisions for programming various
electric field versus time profiles for cyclical operations.
Another limitation of electric coalescers lies in the compromise that must be drawn between field strength
required for adequate translation of small drops and field strength strength sufficient to produce
subdivision of large drops. As drop size increases and the surface-to-bulk ratio decreases, surface free
energy is no longer able to maintain rigidity of the drop, and viscous drag on the moving drop causes
deformation. As velocity or drop size increases, this deformation becomes sufficient to cause the drop to
shatter. At any given field strength there is a range of stable drop sizes limited at the lower end by the
ability of the field to transport the drop and at the upper end by drop size that can be transported without
shattering. An ideal arrangement would be a field with a high intensity zone for coalescence of very
small drops followed by gradually decreasing field strength for shifting the equilibrium drop size range to
large values. Various arrangements may be used for accomplishing this end.
Attention has so far been focused on the use of electric fields for flocculation, but an equally important
facet of desalting is achieving contact between the entrained water in the crude oil and the dilution water
used to wash the oil. Typically, the dilution water is added to the oil upstream of a valve. The water is
injected into the oil flow line through a distributor. The differential pressure across the valve is then used
to shear the water drops and mix the two phases. Typical pressures are in the 12 to 30 psi range.
Although mixing valves are generally satisfactory, they do have some disadvantages. Mixing efficiency
is generally low at extremes of phase ratio, so the use of small quantities of dilution water (less than 3%)
may not be feasible; likewise, turndown in flow rate will require adjustment of the valve to maintain
contact efficiency. More serious disadvantages include the requisite compromise between mixing
efficiency and excessive emulsification and the waste of energy expended on shear of the continuous
phase. Because very small drops act as rigid spheres following flow streamlines, it is unlikely that they
will ever achieve sufficient energy to participate in mechanically induced collisions; therefore, their
contribution to the salt content of a crude oil represents a fraction unreachable by means of mixing valves.
Mixing efficiency can be improved by adding static mixer elements downstream of the mixing valve to
achieve a more homogeneous blend of brine drops and dilution water drops. Static mixers consist of a
series of short helical baffles mounted in a pipe with adjacent baffles having reverse twists. These
devices continually blend the stream at low shear. Since increasing mixing efficiency by increasing
shear rate can result in emulsification problems, the use of low shear devices for blending the stream can
be an asset, particularly with difficult crude oils. At best, a mixing valve/desalter combination can
function only as a single stage mixer-settler.

By manipulating the relation of drop size to field strength, the electric field can be used to both mix and
separate. Drops of dilution water subjected to high field strength can be sheared to very small sizes by
the combination of translational shear and shattering due to charge density instability, and then as the
field strength is lowered, they coalesce with the entrained brine and settle out. It is worth noting that most
of the contact between the brine and the dilution water occurs as the two are coalesced together.
Therefore, multiple coalescence events contribute much more to contact efficiency than does greater shear
in a mechanical device. By cycling the field strength, the process can be repeated many times during the
retention time of the drops within the electric field. As a result, the contact efficiency of a multi-stage
mixer-settler can be realized in a single vessel. Since the electrical force is concentrated on the dispersed
phase, loss of energy due to shear of the continuous phase is reduced. Turndown and low dilution water
flow rates are readily accommodated.
The electrostatic mixing system operates with countercurrent contact between the dilution water and the
crude oil. This is in contrast to conventional systems which are restricted to concurrent flow by the nature
of the mixing device. Countercurrent flow results in contact between the freshest water and the cleanest
oil. This ensures maximum effectiveness of the dilution water. This flow pattern also has the effect of
placing fresh water near the outlet so that any inadvertent carry-over will be free of salt.
Efficient mixing combined with effective electrical flocculation and sedimentation can achieve a high
degree of removal of dissolved salts. However, the other two classes of mineral matter, precipitates and
oil soluble compounds, are not as well handled. Oil soluble compounds cannot be removed by water
washing unless the chemistry of the system can be manipulated to alter their solubility characteristics.
Precipitates, particularly soluble salt crystals, present a difficult challenge, but one that must be faced if
exotic catalysts are to be protected. Crystalline salt in oil is not driven toward coalescence by strong
interfacial tension nor is it accelerated by electrical forces. Contact between the salt crystal and a drop of
dilution water depends upon imparting sufficient kinetic energy to the water drop alone to produce a
collision capable of penetrating any surrounding film and wetting the crystal surface. Contact efficiency
is limited at best, and a combination of high intensity mechanical mixing with electrostatic mixing will
give better results than either by itself.
There are several conditions which should serve as danger signals or "red flags" to desalting process
engineers. These are for the most part things that can be handled if considered early in the design
process, but which can be problematical or fatal otherwise. The presence of wax can lead to solid
stabilized emulsions which are very difficult to resolve. Wax precipitates from solution at a temperature
known as the cloud point. Operating near or below the cloud point of a waxy crude oil should definitely
be avoided. Another temperature related problem is viscosity, particularly with heavy oils. Viscosities of
approximately 50 SSU (Saybolt Seconds Universal) or less are preferred for desalter operation. Also of
concern is the bubble point which is the pressure at which gas is evolved at the operating temperature. If
the gas partial pressure exceeds the bubble point, gas bubbles will form in the vessel and will cause the
liquid to be stirred and "back mixed" with resulting loss of extraction efficiency.
The presence of crystalline salt is always a "red flag." Salt crystals can become coated with a film of
impurities or semisolid hydrocarbons and be exceedingly difficult to reach with the dilution water. The
mechanisms of attraction and acceleration which produce drop/drop coalescence are not operative in the
case of salt crystals; therefore, contact is not readily obtained.
Other conditions of which the designer should be wary are the presence of suspended solids, particularly
iron sulfide, which can lead to stabilized emulsions. Iron sulfide, being heavy and oil wetted, can rob the
sedimentation process of its driving force -- density differential. Dilution water quality can also be a

problem due to high pH, the presence of surfactants, or other conditions which can lead to increased
emulsion stability. It is obvious that in order to remove salt, the dilution water must be sufficiently low in
salt content to achieve the required equilibrium concentration in the residual entrained water. However,
not as obvious is the need for dilution water quality sufficient to avoid contributing to an emulsification
process. Streams containing considerable amounts of coke particles, suspended solids, iron sulfide, or
emulsified oil should not be used. Neither should streams containing traces of surfactant chemicals or
caustic soda. Ammonia should be limited to less than 200 ppm to avoid fouling and corrosion in the
crude distillation unit overhead as well as to limit pH excursions. Ammonia also tends to form volatile
salts which can contribute to salt carry-over. The pH of the water should be preferably below 9.0 and
provision for acid injection for pH control should be made if higher values are expected. High values of
pH may enhance the formation of stable emulsions. The water should contain less than 0.02 ppm oxygen,
less than 1 ppm fluoride, and should be low in sodium salts, suspended solids, and total hardness.
Desalting Equipment
A desalting system consists of a means of mixing fresh water with an oil stream and a means of separating
the water and oil. The oldest desalter designs used pressure drop across a valve to mix the dilution water
with the oil and an AC field to enhance separation. Special globe valves were favored as mixing devices
in these systems. Later, laboratory tests showed that the Sauter mean diameter of the drop dispersions
were directly related to differential pressure across the valve and not highly dependent on valve type. As
a result of these tests, less expensive valves may be employed.
Desalter vessels are usually equipped with some type of spreader to distribute inlet flow and an oil outlet
collector. Interface drains and sand jets are frequently provided for removal of solids and sludge, and
sample taps arranged for sampling above, below, and several points within the interface zone are
included.
AC Desalters
AC desalters most commonly use an
arrangement of charged horizontal bar gratings
or grids for establishing the electric field within
the vessel. A two grid system uses a lower
charged grid and an upper grounded grid with a
separation of six to eight inches (sometimes
adjustable) between them. The incoming oil is
introduced near the oil/water interface and
flows upward through the grids to an outlet
collector. The water layer is also grounded
through the shell of the vessel. AC fields are
then established between the water and the
charged grid and between the charged grid and
the grounded grid. Oil flows across both of
these fields as it transits the vessel. Newer
designs use a multiplicity of charged grids in
an effort to improve efficiency and throughput.
Also employed is a technique for spreading the
incoming emulsion between the energized
electrodes. All of these variations are aimed at

increasing the retention time of the dispersion within the most intense zone of the electric field in order
for polarized drops to have time to achieve approach distances within the range of action by the dipolar
forces.
Transformers for AC desalting are usually built with 16KV and 23KV secondary taps. Single phase
transformers are most commonly used with multiple transformers wired for load balancing on large
installations. In some cases, three phase transformers are employed with multiple grids wired to accept
different phases. In order to protect the transformers during process upsets, an internal reactor equal to
100% of the transformer reactance is placed in series with the primary winding. As the load on the
transformer increases, the voltage drop across the inductor increases thereby limiting the current to the
transformer. A transformer with 100% reactance can tolerate a short circuit on its secondary output
without overheating. An unfortunate side effect of this protection scheme is that when the process is most
in need of power, the reactor prevents the transformer from delivering it.
Dual PolarityTM Desalters
Dual PolarityTM desalters also use mixing valves
for phase dispersion and contact. However, the
electric field is established with a horizontal
array of vertically hung parallel plates.
Alternate plates are charged positive and
negative through connection to diodes. The two
sets of diodes are connected to the same end of
the transformer winding with the other end
connected to ground. This arrangement gives a
DC plate-to-plate field and an AC plate-toground field. In this way, the advantages of
drop movement and drop charge in a DC field
are combined with the film rupturing capability
and corrosion resistance of an AC field.
Transformers for Dual PolarityTM desalters are
identical to those used for AC desalters with the
addition of an oil filled secondary junction box
which houses the diode packs.
Load Responsive ControllerTM
Dual PolarityTM desalters may also be fitted with a power supply known as a Load Responsive
ControllerTM (LRC). The LRC consists of a 30% reactance transformer in combination with an electronic
device which senses the load being drawn and adjusts the power to the transformer accordingly. The
power adjustment is accomplished by silicon controlled rectifiers (SCRs) which switch the power on and
off rapidly so the very short bursts of high power are interspersed with off periods so the transformer does
not exceed its average heat dissipation rating. This allows power to be delivered to the process under
upset conditions without compromising the integrity of the power supply. The LRC may also be
programmed to modulate power to the process.

Electro-DynamicTM Desalters

The Electro-DynamicTM Desalter is a new design incorporating the principles of field strength control,
electrostatic mixing, and countercurrent flow. Field strength control can be accomplished in several ways.
The most obvious of these is by variable electrode spacing. Although this arrangement functions well, its
mechanical implementation is difficult, especially with regard to large vessels. A more practical approach
is the use of electrodes of varying conductivity. High field strength exists across zones of high
conductivity, and reduced field strength is found in the regions of lower conductivity. The desired
conductivity patterns can be produced by using electrodes constructed of composite materials whose
surface composition can be adjusted in manufacture to provide these patterns. Such electrode plates have
the advantage of maintaining a tapered field strength under a range of operating conditions. They are also
"self healing" under arcing. A metal grid array will be completely discharged by an arc with loss of field
in the entire vessel. Because an arc on a composite grid must be fed through a surface resistance, it is
quickly quenched, and only the plate area in the immediate vicinity of the arc is discharged. Slippage due
to temporary loss of field is largely eliminated.
A third method of controlling field strength is to vary the transformer output voltage to create a time
based field decay rather than a spatial variation in strength. Since this method is based on time, it can
easily be tailored to the kinetic needs of the process. It also can be used to eliminate excessive "hold-up"
of small drops in the zones of high field intensity which could lead to arcing if unchecked. The
electrostatic mixing process can be applied most successfully when both the composite plate technology
and the modulating controller are employed. Four distinct stages have been identified in the mixing and
coalescing process with unique field strength requirements for optimum performance of each stage.
These are as follows:
Dispersal: A fast ramp-up of
voltage to the mixing voltage.
Provides rapid reduction of the
large drop population.
Mixing: Sustained high intensity
field for maximum drop
subdivision.
Coalescing: Voltage ramp-down
to permit optimum drop growth.
It is in this stage that most of the
contact between the dilution water
and the entrained brine occurs.
Settling: Sustained low intensity
field for drop growth and
sedimentation.

Each of these stages can be adjusted for optimum intensity and duration using the Load Responsive
ControllerTM (LRC). Often it will be found necessary to effect a small compromise between dehydration
(coalescing and settling) and contact efficiency (dispersal and mixing). The compromise is small
because in the presence of countercurrent flow the water carry-over produced by intense mixing is mostly
fresh water; therefore, desalting efficiency is not diminished.
Countercurrent flow is essential for realization of
the full potential to be gained by multiple stages
of mixing and coalescence. To achieve this
benefit it is necessary to introduce dilution water
above the electrodes in the zone of dry oil. The
water must remain as coarse drops in this area to
prevent carry-over. Uniform distribution is
desired, although the electric field produces
some amount of distribution and will overcome
mild maldistribution. The simplest way of
spreading the dilution water above the electrodes
is through a system of laterals with orifices sized
to produce a slight pressure drop at design flow
rates. Because of increased contact efficiency,
less dilution water is usually required in this
system. Sometimes other benefits may accrue in
injecting any excess water into the feed stream, e.g., reduced upstream heat exchanger fouling or
crystalline salt removal. The Electro-Dynamic DesalterTM is a system consisting of electrostatic mixing,
the Load Responsive ControllerTM, composite electrodes, and countercurrent flow of the dilution water.
Both the composite electrodes and the LRC have been applied in oilfield dehydration systems for many
years and have proven to be reliable and effective.
Laboratory Tests
Laboratory tests on prospective crude oil feedstocks have proven quite effective in assisting in desalter
design. Laboratory evaluation of crude oil desalting is done with a combination of static and dynamic test
methods. Samples are routinely checked for viscosity as a function of temperature, API gravity, BS&W
content, suspended solids content, and salt content. Microscopic examination for the presence of
crystalline salt may also be performed. If desired, foam indices may also be determined.
After physical and chemical characterization, a small aliquot of the sample is subjected to static
electrostatic testing. The power consumption as a function of time is plotted and the shape of the curve is
used to draw conclusions regarding the treatability of the sample. Static testing also serves as a useful
screening tool for optimizing chemical selection.
Dynamic testing is then performed using a pilot plant capable of 300o F, 100 psi operation. It is designed
as a vertical section through a full scale desalter with a liquid depth of eight feet. Variable parameters
include flow rate, pressure, temperature, chemical dosage, countercurrent or concurrent flow, dilution
water rate, AC or DC field, conventional or electrostatic mixing, and a full range of modulated electric
field profiles. This unit has been used for desalting studies on a number of crude oils from both domestic
and international sources.

Chemical requirements are relative, but the pilot unit historically requires more chemical than field
installations due to mixing and retention time characteristics. Inlet BS&W has little relation to outlet salt
since much of the water in high BS&W crude oils is easily removed. Therefore, meaningful performance
comparisons must consider absolute outlet values rather than percentage removal. Desalter flux,
expressed as barrels per day per square foot of longitudinal vessel cross section, affects both the retention
time of the liquid in the electric field and the net sedimentation velocity of water drops settling against the
rising oil. Since net sedimentation velocity is related to drop size, increasing flux increases the minimum
size of drops which can be settled. This results in increased carry-over at high flux. This carry-over
includes dispersed brine and produces high effluent salt as contrasted to the fresh water carry-over
resulting from excess mixing voltage.
Analytical Procedures
Laboratory results are obtained by analysis of total chloride ion followed by conversion to equivalent
sodium chloride and reported as pounds of salt per thousand barrels of oil (PTB). At salt levels of 2 PTB
and below, great care is required in order to achieve meaningful and reproducible results. Although
several analytical schemes are available for salt analysis, extraction and analysis of soluble salts has
proven to be the most reliable method for use with the least interference from other constituents.
The procedure involves diluting an oil sample with xylene and extracting the mixture with boiling
deionized water. The extraction funnels are then placed in a water bath at 140 to 160oF for phase
separation to occur. If necessary, acidification or chloride-free emulsion breaker may be used to enhance
separation. The aqueous layer is removed and filtered if it is still cloudy or if entrained oil is present. It
is then titrated with dilute silver nitrate (0.01N) using chromate indicator under incandescent lighting.
The titration procedure is known as the Mohr Method and is more fully described in American Petroleum
Institute Recommended Practice RP 45. Endpoint recognition requires a practiced eye when using dilute
titrant. Alternately, ion chromatography may be used for chloride determination if available. This
technique is extremely accurate for determination of small quantities of chloride, but the equipment is
more expensive. Care must be taken to avoid contamination of the sample during handling due to the
widespread occurrence of chloride in nature and the very small quantity being measured.
Another method in common use is the spectrophotometric determination of the metals - sodium, calcium,
and magnesium. These techniques, using atomic absorption or inductively coupled plasma, are accurate
and highly automated. However, they do not distinguish between soluble salts and those which exist
primarily in the oil phase such as metal-organic compounds or mineral precipitates. Therefore, the results
obtained with these methods may be poorly related to desalter performance.
Analysis by conductivity, as described in ASTM D-3230, is a widely used technique for process
monitoring and quality control. At low salt levels, oil conductivity becomes a function of water content
and pH as well as salt content. Since the ions responsible for pH changes are from 2.6 to 4.6 times as
conductive as chloride, minor pH changes far outweigh the effects of changes in chloride concentration.
Other problems such as variation in the composition of the salt mix in oils also help to preclude the use of
this method as a reliable indicator of absolute desalter performance at low effluent salt contents.
Summary

In any process designed to approach theoretical limits, attention to detail becomes critical -- in
analysis, design, operating conditions, and control of feedstream quality. In order to minimize
10

corrosion and maximize catalyst life while processing heavy or low quality crude oils, it is
essential that refinery desalters be operated at maximum efficiency. Electric field control,
countercurrent desalting, and multi-stage contact provide means of increasing desalter efficiency
to meet these needs.

11