FRACTIONATION OF

PETROLEUM

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Product from Petroleum and their uses

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 Crude Oil refinery
• Crude oil is a multicomponent mixture
consisting of many compounds.
• Petroleum refining refers to the separation as
well as reactive processes to yield various
valuable products.
• Therefore, a key issue in the petroleum refining
is to deal with multicomponent feed streams
and multicomponent product streams.

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 Cont.
• Refinery process can be viewed upon as a combination of
both physical and chemical processes or unit operations and
unit processes respectively.
• Physical process in a refinery is the distillation process that
enables the separation of lighter components from the
heavier components.
• The separation process occurs in large distillation towers,
where the oil is exposed to extreme heat, causing it to
separate into gases and liquids. The products separate
based on the temperature differences between the bottom
and top of the tower.
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 Cont.
• The products range from propane gas near the
top, diesel in the middle and lubricants near
the bottom.
• Chemical processes such as alkylation and
isomerization enable the reactive
transformation of various functional groups to
desired functional groups in the product
streams.

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Cont.

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 DEHYDRATION AND DESALTING
• The purpose of desalting is to remove
undesirable impurities, especially salts and
water, from the crude oil prior to distillation.
• Removing of salt reduces corrosion in
exchanger, fractionators, pipelines. Less
erosion by solids in control valves, exchanger,
furnace, pumps.

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 Cont.
• Salt dissolved in water (brine) enters the crude
stream as a contaminant during the production
or transportation of oil to refineries.
• If salt is not removed from crude oil, serious
damage can result, especially in the heater
tubes, due to corrosion caused by the presence
of Cl
• Salt in crude oil also causes reduction in heat
transfer rates in heat exchangers and furnaces.
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 Cont.
• If the salt content of the crude 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 Desalting and fractional
distillation of crude oil chloride salts.(<1000
lb/bbl).

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Cont.

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 Cont.
• Most typical methods of crude-oil desalting are:
Chemical and Electrostatic separation:
Washing of the salt from crude oil with water oil
and water phases are separated in a settling tank
by adding chemicals to assist in breaking up
emulsion or by the application of electrostatic
field to collapse the droplets of saltwater more
rapidly.

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 Cont.
Chemical desalting
Water and chemical surfactant (demulsifiers) are
added to the crude, heated so that salts and other
impurities dissolve into the water or attach to the
water, and then held in a tank where they settle out.
Electric desalting
Under charge condition polar molecules get
oriented and get separated. More than 90% of salt
can be removed in just less than half an hour.
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 Cont.
Wash water and T requirement in Desalter
• (3-4vol%, T 240-260oF (API >30), to 7-10vol%, T 280-
300oF for API<30)
• For single-stage desalting units 90 to 95% efficiencies
are obtained and two-stage processes achieve 99% or
better efficiency.
• Efficiencies of up to 99% water removal in a single
stage are claimed for the dual field process.
• Heavy naphthenic crudes form more stable emulsions
than other crudes. Higher temperature is required.
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Cont.

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 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
- 160°C (methane) to +1000°C 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.
• 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. 15
 Cont.
• A country like the USA is deeply involved in production of
more gasoline; frequently converting 70% of crude to
gasoline.
• 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 Atmospheric 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).
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 Boiling Points

• Boiling point largely determines the molecules destination

• Overlap in boiling ranges provides flexibility in production 17
 Cont.
• 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
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 Cont.
• The naphtha cut has a carbon number range between 5
and 6. 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. 19
 Cont.
• 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

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 Cont.
• 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
360°C at the bottom of the column.
• From this VDU, we obtain distillates, as bases for
lube oils and paraffin. Lube oils are used for the
lubrication of car and truck engines, as well as
for the lubrication of equipment in industry.
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 Cont.

• 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
paving roads and motorways.

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 Blending of Gasoline
• Refining processes do not generally produce commercially usable
products directly, but rather semi-finished products which must be
blended in order to meet the specifications of the demanded
products.
• The main purpose of product blending is to find the best way of
mixing different intermediate products available from the refinery
and some additives in order to adjust the product specifications.
• For example, gasoline is produced by blending a number of
components that include alkylate reformate, FCC gasoline and an
oxygenated additive such as methyl tertiary butyl ether (MTBE) to
increase the octane number.

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 Cont.
• The octane number is a characteristic of spark
engine fuels such as gasoline.
• Octane number is a measure of a fuel’s tendency
to knock in a test engine compared to other
fuels.
• Knock resistance is a fuel’s ability not to self-
ignite and burn in an uncontrolled way while the
fuel is being compressed. This means that the
air-fuel mixture in the engine is not ignited only
by the ignition spark, but also by compression. 24
 Cont.
• The octane number, posted octane number (PON)
commercially used for gasoline (referred to as the road
octane number), is the average of its research octane
number (RON) and motor octane number (MON).
• The difference between RON and MON is known as
fuel sensitivity (S).
• The research octane number (RON) describes the
behavior of the fuel in the engine at lower
temperatures and speeds
• The motor octane number (MON) describes the
behavior of the fuel in the engine at high
temperatures and speeds 25
 Cont.
• There are a number of additives, such as
oxygenated ethers or alcohols, that can enhance a
gasoline octane number.
• Tetra-ethyl lead (TEL) which was used for
enhancing octane number, has now been phased
out and replaced by the oxygenates listed in Table
below with their octane numbers

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Cont.

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Pipe-still Heaters

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 Cont.
• Tube-still heaters are used in petroleum and petrochemical
plants for various purposes, such as crude distillation
(atmospheric and vacuum), reboiling, and preheating of oil
stocks, where heating is carried out for vaporization purposes
only
• These are low temperature furnaces (as compared to furnaces
used in metallurgical, ceramic, or cement plants), Where heat
duty of burners vary from 0.5 to 100 million kcal/hr and
temperature goes up to 1200°C.
• The pressure may be allowed as high as 10 MPa (100 atm,
approximately).

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 Cont.
• These furnaces are commonly housed in a cylindrical or
rectangular box type refractory-lined steel casing
supported on a steel structure above ground.
• The heater has a radiant section and a convection section.
• Feed flowing through the pipes in the radiant section
receives heat from the flames of the burning fuel from
the burners.
• In the convection section, feed entering the furnace
recovers heat from the hot flue gas leaving the radiant
section.

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 Cont.
• Various designs of such furnaces are available, such as
helical coil type, vertical cylindrical, box type, twin cell
type, terrace wall type, multi-section pyrolysis type, etc.
• A small duty furnace (<2 million kcal/h) uses a pipe
arranged in the form of a helical coil having only a
radiant section.
• These furnaces are low efficiency furnaces as no
convection zone is present.
• However, they are easy to clean and maintain, but are
costly and occupy a large space.

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Cont.

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 Pipe-still Furnace Elements
• The common elements of pipe furnaces consist of pipes
or tubes, supports of the pipes, refractories, burners, still
shell and structural elements.
• The furnaces have got separate radiation section and
convection section.
• The most universal classification is based on direction of
tubes as well as shape of furnace and mode of
application of heat.
• In most of the furnaces, the direction of tubes is
horizontal as in all box type heaters and vertical in
cylindrical stills.
• Radiant walls also use horizontal tubes, however tubes
can be placed vertically also. 33
 Heater Pipes or Tubes
• Steel pipes are used for normal heating operations with
nominal bore diameters varying from 2 to 6 in and a thickness
varying in the range of 40–80 schedule.
• For certain cases, the diameter may be as high as 8 in or more,
especially for vacuum services.
• Tubes are vertically arranged in single or multiple rows
surrounding an equally spaced burner on the bottom cross
section of the furnace.
• The material of construction of the tubes is selected based on
the flue gas composition, the nature of the feed hydrocarbons,
and the temperature and pressure of the operation.

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 Cont.
• Alloys of steel containing chromium, molybdenum,
and nickel are widely used as the material for tubes
in the furnace
• The presence of chromium resists corrosion from
hydrogen sulfide, mercaptans, organic acids, high
temperature oxide corrosion, etc.
• A typical distillation furnace in a refinery contains
5% chromium and 0.5% molybdenum in steel.

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