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.
Water is likely to occur in emulsion form when the crudes are naphthenic or sulfurous.

Of all the existing salts, chlorides of calcium and magnesium distinguish themselves in playing
an invincible ole in overhead corrosion.
These salts in presence of steam at 150- 200C easily hydrolise generating hydrochloric
vapours. These vapours cause corrosion to the equipment
 The most concerns of the impurities in crude oil are:
The Inorganic salts can be decomposed in the crude oil pre-heat exchangers
and heaters. As a result, hydrogen chloride gas is formed which condenses to
liquid hydrochloric acid at overhead system of distillation column, that may
causes serious corrosion of equipment.
To avoid corrosion due to salts in the crude oil, corrosion control can be used.
But the byproduct from the corrosion control of oil field equipment consists of
particulate iron sulfide and oxide. Precipitation of these materials can cause
plugging of heat exchanger trains, tower trays, heater tubes, etc. In addition,
these materials can cause corrosion to any surface they are precipitated on.
The sand or silt can cause significant damage due to abrasion or erosion to
pumps, pipelines, etc.
The calcium naphthanate compound in the crude unit residue stream, if not
removed can result in the production of lower grade coke and deactivation of
catalyst of FCC unit
Benefits of Crude Oil Desalting
Increase crude throughput

Less plugging, scaling, coking of heat exchanger and furnace tubes

Less corrosion in exchanger, fractionators, pipelines, etc.

Better corrosion control in CDU overhead

Less erosion by solids in control valves, exchanger, furnace, pumps

Saving of oil from slops from waste oil

Long standing of crudes may permit the separation of aqua phase

along with salts and other suspended impurities
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: 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 droplets
2. Heating: The crude oil temperature should be in the range of 48.954.4 oC (120130 oF) since the
wateroil separation is affected by the viscosity and density of the oil.
3. Coalescence: The water droplets are so fine in diameter in the range of 110microns 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
5. Settling: According to Stocks law the settling rate of the water droplets after coalescence is
given by
Desalter Operating Variables
Desalting temperature: The settling rate depends on the density and viscosity of
the crude. Since increasing the temperature lowers the density and viscosity, the
settling rate is increased with temperature based on the crude gravity, typical
desalting temperature can vary between 50 and 150 oC (122 and 302 oF).
Washing water ratio: Adding water to the crude oil helps in salt removal. Hence,
increasing the wash water rate increases the coalescence rate. Depending on
the desalting temperature, a minimum value should be use. For example, Kuwait
crude (31.2 API) requires 78 vol% water addition relative to the crude rate.
Water level: Raising the water level reduces the settling time for the water
droplets in the crude oil, thus improving the desalting efficiency. However, if the
water level gets too high and reaches the lower electrode, it shorts out the
desalter. Since the primary electric field depends on the distance between the
lower electrode and the watercrude interface, it is always better to keep the
level constant for stable operation.
 Washing water injection point: Usually the washing water is injected at the mixing
valve. However, if it is feared that salt deposition may occur in the preheat
exchangers, part or all of the washing water is injected right after the crude feed
pump.
Demulsifier injection rate: Demulsifiers are basic copolymers with one end being
hydrophilic (loves water and attaches to the surface of the water droplet), and the
other end being hydrophobic (loves the oil and is directed to the oil side). When these
compounds are adsorbed on the droplet surface, they stabilize the droplet. The
demulsifier is added to the crude after the feed pump or before the mixing valve at
levels between 3 and 10 ppm of the crude.
Type of washing water: Process water in addition of fresh water is used for desalting.
The water should be relatively soft in order to prevent scaling. It should be slightly
acidic with a pH in the range of 6. It should be free from hydrogen sulphide and
ammonia so as to not create more corrosion problems. Therefore, distillation overhead
condensates and process water from other units can be used after stripping.
 Pressure drop in the mixing valve: Mixing the washing water with crude
oil is necessary in order to distribute the water and dissolve any
suspended salts crystals. The pressure drop across the mixing valve
determines the mixing efficiency. On the other hand, the mixing process
produces finer (smaller diameter) droplets which tend to stabilize the
emulsion and make water separation more difficult. Therefore, there is a
compromise in selection of the appropriate pressure drop across the
mixing valve. A pressure drop between 0.5 and 1.5 bar (7.4 and 22 psi) is
used
 Hh
PETROLEUM REFINING
PROCESS
 PETROLEUM REFINERY BASICS
The fuels derived from Petroleum contribute approximately one-third to one-
half of the total world energy supply and are used for transportation fuels
(gasoline, diesel fuel, and aviation fuel, among others) and heating buildings.
Petroleum products have a wide variety of uses that vary from gaseous
and liquid fuels to near-solid machinery lubricants.
Residue of many refinery processes asphaltis now a premium value
product for highway surfaces, roofing materials, and miscellaneous
waterproofing uses.
Refining Means. . .
1. To reduce to a pure state, to remove Impurities
2. To improve or perfect
3. Salable products are made from crude.
 The combination of refining processes and operations employed
(complexity) varies from one refinery to another.
Modern refinery is highly complex, energy and capital intensive.
Role of catalytic processes, secondary processing and
hydroprocessing is increasing.
Factors deciding the complexity of a refinery.
1. Nature/source of crude oils- flexibility to process variety of crudes.

2. Demand pattern in the markets.

3. Product quality - current/ future.
4. Production of feedstocks for downstream units.

5. Inter-fuel substitution.
Year Process Name Purpose By Product

1862 Atmospheric Distillation Produce Kerosene Naphtha,Cracked Residuum

1870 Vacuum Distillation Lubricants Asphalt,Residua

1913 Thermal Cracking Increase Gasoline Yield Residua,Fuel Oil

1916 Sweetening Reduce Sulfur Sulfur

1930 Thermal Reforming Improve Octane Number Residua

1932 Hydrogenation Remove Sulfur Sulfur

1932 Coking Produce Gasoline Coke

Improve Lubricant Viscosity

1933 Solvent Extraction Aromatics
Index

1935 Solvent Dewaxing Improve Pour Point Wax

1935 Catalytic Polymerization Improve Octane Number Petrochemical Feedstocks

1937 Catalytic Cracking Higher Octane Gasoline Petrochemical Feedstocks

1940 Alkylation Increase Octane Number High-Octane aviation Fuel

Year Process Name Purpose By Product
Produce Alkylation
1940 Isomerization Naphtha
Feedstock

1942 Fluid Catalytic Cracking Increase Gasoline Yield Petrochemical Feedstocks

Increase Cracker
1950 Deasphalting Asphalt
Feedstock
Convert Low-Quality
1952 Catalytic Reforming Aromatics
Naphtha
1954 Hydrodesulfurization Remove Sulfur Sulfur

1956 Inhibitor Sweetening Remove Mercaptans Disulfides and Sulfur

Convert To High Octane
1957 Catalytic Isomerization Alkylation Feedstocks
Products
Improve Quality And
1960 HydroCracking Alkylation Feedstocks
Reduce Sulfur
1974 Catalytic Dewaxing Improve Pour Point Wax

1975 Resid HydroCracking Increase Gasoline Yield Cracked Residua

Produce Alkylation
1940 Isomerization Naphtha
Feedstock
 DISTILLATION OF PETROLEUM
Distillation is a separation technique used for separation of soluble liquid mixtures into
individual components.
Petroleum being a mixture of hydrocarbons has a boiling range of - 160C (methane) to
+1000C or more (pitch) i.e. to say a mixture of gas, liquid and solid, requires an
effective and economic distillation to process into a number of cuts of small boiling
range.
These cuts are later processed and tailored to suit the requirements of consumers.

Modern refinery techniques have meticulously lad the way to recover as many
fractions as possible from crude, discarding the least possible in view of the binding
situation i.e. dearness of crude
The fractions in demand are in fact the property of a country; (although most of the
fractions are common and in good demand, though not to same extent), hence a
refinery should have the facilities for such fractions; this in turn makes each refinery
a complete entity. 16
 A country like the USA is deeply involved in production of more gasoline; frequently
converting 70% of crude to gasoline.
Whereas in a country like India, the picture is different, the accent being on middle distillates.

This necessity has made Indian refineries to exalt the production of more middle distillates

The basis of refinery distillation design rests completely on TBP tests.

Distillation of crude mainly takes place in two stages.

First stage distillation is carried out at atmospheric pressure, hence named Atmospheic Distillation
unit (ADU)
The undistillated portion of crude, called reduced crude is further distilled under reduced pressure in
a second unit known Vacuum distillation unit (VDU).
The maximum pressure in an atmospheric column rarely reaches 2atm and at the top of the
column the pressure is only few centimetres of mercury above atmospheric pressure.
When the crude contains a good amount of soluble gases, to avoid load on ADU, a prelashing or
topping column is employed.
Prelashing is also useful when crude has to be transported to a long distance.
 The first unit of a refinery is
called the Crude Distillation Unit
or CDU.
This unit is operated at high
temperatures, at the bottom, and
at a pressure of 2 barg.
This first unit divides the crude
oil into different smaller
petroleum cuts, used as bases for
everyday commercial products.
At the top of the crude column,
we have the lighter compounds,
with the lowest carbon number,
and the lowest boiling
temperature.
 The naphtha cut has a carbon number range
between five and six. This cut is the raw material
used in the petrochemical industry, to produce
different types of plastics with different
properties.
Next, the gasoline cut, is composed of hydrocarbons
with seven to eleven carbon numbers.This cut is
the base of the gasoline fuels, used for spark
ignition engines.
The Kerosene cut, is the main base used to
produce jet fuel - called Jet A1 - delivered to all
international airports. Typically, the carbon
number of this cut is between eleven and thirteen.
The next cut, is the Diesel cut, which is the base
of diesel fuel, for diesel engines of cars and trucks.
The hydrocarbon chains contain between thirteen
and twenty five carbon numbers.
This cut is also the base for heating oil, used to
heat buildings, houses and offices.
 The atmospheric residue, obtained at the bottom
of the CDU, is treated in a second distillation
column called the Vacuum Distillation Unit or VDU.
This column is operated under vacuum (80 mm
Hg), and at a temperature of 360C at the bottom
of the column.
From this VDU, we obtain distillates, as bases for
lube oils and paraffins. Lube oils are used for the
lubrication of car and truck engines, as well as
for the lubrication of equipment in industry.
Finally, at the bottom of the vacuum distillation
column, we have the vacuum residue. This cut
contains all the heavy hydrocarbons from the
crude oil with carbon numbers higher than 50 .
This cut is used to produce Heavy fuels, for
example, for boats or power plants.
It is also the base used to produce bitumen, for
roads and motorways.
VACUUM DISTILLATION COLUMN (VDU)
Hydrocarbons should not be heated to too high temperature due to cracking
reactions that take place above about 400 C.
Coke deposits on piping and equipment increase maintenance costs and reduce
process unit run-time.
Therefore crude distillation bottom (residue) is further processed in a vacuum
column to recover additional distillates, light and heavy vacuum gas oils as
feedstock to cracking units or lube-oil processing.
Distillation is carried out with absolute pressures in the tower flash zone area of
25 to 40 mmHg.
To improve vaporization, the effective pressure is lowered even further by the
addition of steam to the furnace inlet and at the bottom of the vacuum tower.
The amount of stripping steam used is a function of the boiling range of the feed
and the fraction vaporized as well as furnace outlet temperatures (380 420 C).
 Vacuum towers are much larger in diameter than atmospheric towers, usually
12 15 meters.
The operating pressure is maintained by using steam ejectors and condensers.
The size and number of vacuum device is determined by the vacuum needed
and the quality of vapors handled, for 25 mmHg, three ejector stages are
usually required.
A few millimetres decrease in pressure drop between the vacuum-inducing
device and the flash zone will save operating costs.
 The yield we can obtain from crude oil depends on the origin of the crude.

For instance, for an Arabian Light crude, from Saudi Arabia, we have, at the outlet of
the Crude Distillation Unit, 5% of gas, 20% of gasoline, 30% of Kerosene and diesel and
45% of heavy cuts.
But, these yields obtained at the outlet of the CDU do not correspond to the market
demand for final products.
 The idea is to transform the heavy products recovered at the bottom of the
CDU into lighter products, according to the market demand.
For that, we feed the Vacuum Distillation Unit (VDU) with the atmospheric
residue.
By doing that, we recover a vacuum distillate, with a carbon number between
25 and 50, and, at the bottom, a vacuum residue, with a carbon number higher
than 50.
The vacuum distillate is treated in a Fluid Catalytic Cracker called FCC, or in
a Distillate hydrocracker, called DHC.
The vacuum residue will be treated in a delayed coker.
The whole idea is to transform heavy cuts into diesel, kerosene, gasoline, as
needed by the market, in order to balance the offer and the demand.