Desalting of crude oil

 If the salt content of the crude oil is greater than 10 lb/1000 bbl (expressed as NaCl), the
crude requires desalting to minimize fouling and corrosion caused by salt deposition on
heat transfer surfaces and acids formed by decomposition of the chloride salts.

 In addition, some metals in inorganic compounds dissolved in water emulsified with the
crude oil, which can cause catalyst deactivation in catalytic processing units, are partially
rejected in the desalting process.
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The trend toward running heavier crude oils has increased the importance of efficient
desalting of crudes. Until recently, the criterion for desalting crude oils was 10 lb
salt/1000 bbl (expressed as NaCl) or more, but now many companies desalt all crude
oils.

Why? now many companies desalt all crude oils.

Reasons??????? Any one Know???

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When the crude oil enters the unit, it carries with it some brine in the form of very fine
water droplets emulsified in the crude oil.

The salt content of the crude measured in pounds per thousand barrels (PTB) can be
as high as 2000. Desalting of crude oil is an essential part of the refinery operation.

The salt content should be lowered to between 5.7 and 14.3 kg/1000 m3 (2 and 5
PTB)
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 Types of Salts in Crude Oil

Salts in the crude oil are mostly in the form of dissolved salts in fine water droplets
emulsified in the crude oil.

This is called a water-in-oil emulsion, where the continuous phase is the oil and the
dispersed phase is the water.

The water droplets are so small that they cannot settle by gravity. Furthermore, these
fine droplets have on their surfaces the big asphaltene molecules with the fine solid
particles coming from sediments, sands or corrosion products.
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The presence of these molecules on the surface of the droplets acts as a shield that
prevents the droplets from uniting with each other in what is called coalescence

Going back to the subject of salt types, these are mostly magnesium, calcium and
sodium chlorides with sodium chloride being the abundant(means available in large
quantities) type. These chlorides, except for NaCl, hydrolyze at high temperatures to
hydrogen chloride:
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On the other hand, NaCl does not hydrolyze. Hydrogen chloride dissolves in the
overhead system water, producing hydrochloric acid, an extremely corrosive acid.
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 Desalting Process
To remove the salts from the crude oil, the water-in oil emulsion has to be broken, thus
producing a continuous water phase that can be readily separated as a simple decanting
Process.
The process is accomplished through the following steps;
1. Water washing
2. Heating
3. Coalescence:
4. Settling
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 Water washing

Water is mixed with the incoming crude oil through a mixing valve. The water
dissolves salt crystals and the mixing distributes the salts into the water, uniformly
producing very tiny droplets. Demulsifying agents are added at this stage to aide in
breaking the emulsion by removing the asphaltenes from the surface of the droplet.

 Heating

The crude oil temperature should be in the range of 48.9–54.4 C (120–130 F) since the
water–oil separation is affected by the viscosity and density of the oil.
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 Coalescence

The water droplets are so fine in diameter in the range of 1–10 µm that they do not
settle by gravity. Coalescence produces larger drops that can be settled by gravity.
This is accomplished through an electrostatic electric field between two electrodes.
The electric field ionizes the water droplets and orients them so that they are attracted
to each other

Agitation is also produced and aides in coalescence. The force of attraction between
the water droplets is given by:
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 Settling
According to Stock’s law the settling rate of the water droplets after coalescence is
given by;
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Desalting is the removal of mineral salt from the crude in a desalter in the form of brine.

Three Methods of Desalting

1. Mechanical ×
2. Chemical ×
3. Electrical
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 Basic (Electrostatic) Desalting Unit

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 Single-Stage Desalting Unit

 Desalting is carried out by mixing the crude oil with from 3 to 10 vol% water at
temperatures from 200 to 300°F (90 to 150°C).

 Either AC or DC fields may be used and potentials from 12,000 to 35,000 V are used to
promote coalescence.

 For single-stage desalting units, 90 to 95% efficiencies are obtained.

 > 10 Ib/1000bbl and < 20 Ib/1000bbl NaCl content.

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Single-Stage Desalting Unit

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 Two-stage desalting Unit

Two-stage processes achieve 99% or better efficiency.

Two-stage desalting is used if the crude oil salt content is more than 20 lb/1000 bbl
and, in the cases where residua are catalytically processed, there are some crudes for
which three-stage desalting is used
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Two-stage desalting Unit

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 Poor desalting has the following effects:

1. Salts deposit inside the tubes of furnaces and on the tube bundles of heat
exchangers creating fouling, thus reducing the heat transfer efficiency.

2. Corrosion of overhead equipment.

3. The salts carried with the products act as catalyst poisons in catalytic cracking units.
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 Electrostatic Desalting

A typical desalter contains two metal electrodes as shown in next slide figure. A high
voltage is applied between these two electrodes. For effective desalting the electric
fields are applied as follows:

1. A high voltage field called the ‘‘secondary field’’ of about 1000 V/cm between the two
electrodes is applied. The ionization of the water droplets and coalescence takes
place here.

2. A primary field of about 600 V/cm between the water–crude interface and the lower
electrode is applied. This field helps the water droplets settle faster.
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Simplified flow diagram of an electrostatic desalter

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 Suspended solids are one of the major causes of water-in-oil emulsions. Wetting
agents are frequently added to improve the water-wetting of solids and reduce oil
carry-under in desalters.

 Oxyalkylated alkylphenols and sulfates are the most frequently used wetting agents
Group Assignment (4 marks)

The following analytical methods are used to determine the salt content of crude oils:

1. HACH titration with mercuric nitrate after water extraction of the salt

2. Potentiometric titration after water extraction

3. Mohr titration with silver nitrate after water extraction

4. Potentiometric titration in a mixed solvent

5. Conductivity
Problems/Calculations

 Calculate the S in Straight run product . The S in raw crude is 1 % and B.P is 240
degree C. ( in Venezuela ).
ANSWER:
0.027 %
Summary of the Crude oil Desalting Unit
Introduction to Atmospheric Distillation Unit.
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 ATM Distillation Unit

Purpose; to get the lightest products/ use for light products.

After desalting, the crude oil is pumped through a series of heat exchangers and its
temperature raised to about 550°F (288°C) by heat exchange with product and reflux
streams.

It is then further heated to about 750°F (399°C) in a furnace (i.e., direct-fired heater or
“pipe still”) and charged to the flash zone of the atmospheric fractionator
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 The furnace discharge temperature is sufficiently high [650 to 750°F (343 to 399°C)] to
cause vaporization of all products withdrawn above the flash zone plus about 10 to
20% of the bottoms product.

 This 10 to 20% “over-flash” allows some fractionation to occur on the trays just above
the flash zone by providing internal reflux in excess of the sidestream withdrawals.
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The atmospheric fractionator normally contains 30 to 50 fractionation trays. Separation

of the complex mixture in crude oils is relatively easy, and generally five to eight trays
are needed for each sidestream product plus the same number above and below the
feed plate. Thus, a crude oil atmospheric fractionation tower with four liquid sidestream
drawoffs will require from 30 to 42 trays .
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The liquid sidestream withdrawn from the tower will contain lower-boiling components
that lower the flash point, because the lighter products pass through the heavier
products and are in equilibrium with them on every tray. These “light ends” are stripped
from each sidestream in a separate small stripping tower containing four to ten trays
with steam introduced under the bottom tray. The steam and stripped light ends are
vented back into the vapor zone of the atmospheric fractionator above the
corresponding side-draw tray
How the atmospheric Distillation Trays Work?
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 Reflux drum

Large-scale distillation towers use a reflux system to achieve a more complete product
separation. Reflux is that portion of a tower’s condensed overhead liquid product that
is cycled back to the top of the tower where it flows downward to provide cooling and
condensation of the up flowing vapors.

Reflux is a technique involving the condensation of vapors and the return of this
condensate to the system from which it originated.
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Reflux is provided by condensing the tower overhead vapors and returning a portion of
the liquid to the top of the tower, and by pump-around and pumpback streams lower in
the tower. Each of the sidestream products removed from the tower decreases the
amount of reflux below the point of drawoff. Maximum reflux and fractionation are
obtained by removing all heat at the top of the tower, but this results in an inverted
cone-type liquid loading, which requires a very large diameter at the top of the tower..
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To reduce the top diameter of the tower and even the liquid loading over the length of
the tower as well as to improve energy efficiency, intermediate heat-removal streams
are used to generate reflux below the sidestream removal points. To accomplish this,
liquid is removed from the tower, cooled by a heat exchanger, and returned to the
tower or, alternatively, a portion of the cooled sidestream may be returned to the tower.
This cold stream condenses more of the vapors coming up the tower and thereby
increases the reflux below that point
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Flash zone vapor rises up through the column, where it is contacted by condensing
liquid flowing down due to gravity from the top trays of the column. At every stage, the
liquid and vapor are in equilibrium. The highest boiling point liquid condenses on the
tray just above the bottom flash zone, and the lowest boiling point liquid condenses at
the top of the column.
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 Side Cut Strippers

The lightest side drew off from the fractionating column is a fraction called kersoene,
boiling in the range of 150 to 280 degree C which flows in to smaller column called
side stripper.

The Purpose of the side stripper is to remove some light HCs by using steam injection
or external heater called reboiler.
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The energy efficiency of the distillation operation is also improved by using pump-
around reflux. If sufficient reflux was produced in the overhead condenser to provide
for all sidestream drawoffs as well as the required reflux, all of the heat energy would
be exchanged at the bubble-point temperature of the overhead stream. By using
pump-around reflux at lower points in the column, the heat transfer temperatures are
higher, and a higher fraction of the heat energy can be recovered by preheating the
feed.
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Although crude towers do not normally use reboilers, several trays are generally
incorporated below the flash zone, and steam is introduced below the bottom tray to
strip any remaining gas oil from the liquid in the flash zone and to produce a high-
flash-point bottoms. The steam reduces the partial pressure of the hydrocarbons and
lowers the required vaporization temperature.
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The overhead condenser on the atmospheric tower condenses the pentane-and

heavier fraction of the vapors that passes out of the top of the tower. This is the light
gasoline portion of the overhead, containing some propane and butanes and
essentially all of the higher-boiling components in the tower overhead vapor.

Some of this condensate is returned to the top of the tower as reflux, and the
remainder is sent to the stabilization section of the refinery gas plant, where the
butanes and propane are separated from the C5–180°F (C5–82°C) LSR gasoline.