Crude Oil Distillation

PETROLEUM
3/3/2018
 Petroleum is a complex mixture of organic liquids
called crude oil and natural gas, which occurs
naturally in the ground and was formed millions
Crude Oil Distillation

of years ago. Crude oil and natural gas are of
little use in their raw state; their value lies in
what is created from them: fuels, lubricating oils,
waxes, asphalt, petrochemicals and pipeline
quality natural gas.
1
HOW OIL WAS FORMED?
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 Oil was formed from the remains of animals and
plants that lived millions of years ago in a
marine (water) environment before the

dinosaurs. Over the years, the remains were
covered by layers of mud. Heat and pressure
from these layers helped the remains turn into
what we today call crude oil . The word
"petroleum" means "rock oil" or "oil from the
earth."
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3/3/2018 Crude Oil Distillation
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CRUDE OIL
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Crude oil is a non-uniform material. The composition depends on its location.
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The majority of crude oil is alkanes, cycloalkanes (naphthenes), aromatics,
polycyclic aromatics, S-containing compounds, etc.
Gasoline: branched alkanes
Diesel: linear alkanes
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Heavier crude contains more polycyclic aromatics
Lead to carbonaceous deposits called “coke”
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Some crudes contain a lot of sulfur, which leads to processing considerations.
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• The oil industry can be divided into three major components:
• Upstream,
• Midstream and
• Downstream.
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• The upstream industry includes exploration and production activities,
hence is also referred as the exploration and production (E&P) sector.

• The midstream industry processes, stores, markets and transports
commodities including crude oil, natural gas, natural gas liquids (NGLs)
like ethane propane and butane and sulphur.
• The downstream industry includes oil refineries, petrochemical plants,

petroleum products distributors, retail outlets and natural gas
distribution companies. The downstream industry provides consumers
thousands of products such as gasoline, diesel, jet fuel, heating oil,
asphalt, lubricants, synthetic rubber, plastics, fertilizers, antifreeze,
pesticides, pharmaceuticals, natural gas and propane. Both
internationally and within India the oil and gas sector is characterized
by existence of "integrated" companies, which are present in all these
three sectors. 9
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WHERE WE GET OİL?
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The world's top five crude oil-producing countries
are:

 Saudi Arabia
 Russia
 United States
 Iran
 China
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PETROLEUM HYDROCARBON STRUCTURES
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 Paraffins
 Hydrocarbons

 Naphthenes
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INTRODUCTION
Oil refining is a key activity.
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
 Over 600 refineries worldwide have a

total annual capacity of more than 3500
x 106 tonnes.
 Goal of oil refining is twofold:
i. production of fuels for transportation, power
generation and heating; and
ii. production of raw materials.
 Oil refineries are complex plants but are
relatively mature and highly integrated.
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REFINING OPERATIONS
Petroleum refining processes and operations can be separated into five
basic areas:
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 Fractionation (distillation) is the separation of crude oil in
atmospheric and vacuum distillation towers into groups of hydrocarbon
compounds of differing boiling-point ranges called "fractions" or "cuts."

 Conversion Processes change the size and/or structure of
hydrocarbon molecules. These processes include: :
 Decomposition (dividing) by thermal and catalytic cracking;
 Unification (combining) through alkylation and polymerization; and
 Alteration (rearranging) with isomerization and catalytic reforming.
 Treatment Processes to prepare hydrocarbon streams for additional
processing and to prepare finished products. Treatment may include
removal or separation of aromatics and naphthenes, impurities and
undesirable contaminants. Treatment may involve chemical or physical
separation e.g. dissolving, absorption, or precipitation using a variety
and combination of processes including desalting, drying,
hydrodesulfurizing, solvent refining, sweetening, solvent extraction,
and solvent dewaxing.
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 Auxiliary Operations and Facilities include:
 light steam and power generation;
 process and fire water systems;
flares and relief systems;
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
 furnaces and heaters;
 pumps and valves;

 supply of steam, air, nitrogen, and other plant gases;
 alarms and sensors;
 noise and pollution controls;
 sampling, testing, and inspecting and laboratory;
 control room;
 maintenance; and
 administrative facilities.
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History of refining process
YEARS PROCESS NAME PURPOSE BY-PRODUCTS
1862 Atm. distillation Produce kerosene Naphtha, tar, etc
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1870 Vacuum distillation Lubricants(original cracking feed Asphalt, residual
stocks(1930’s)) coker feed stocks

1913 Thermal Cracking Increase gasoline Residual, bunker
fuel
1916 Sweetening Reduce sulphur & odor Sulphur
1930 Thermal reforming Improve Octane number Residual
1932 Hydrogenation Remove sulfur sulfur
1932 Coking Produce gasoline base stocks Coke
1933 Solvent Extraction Improve lubricant viscosity index aromatics
1935 Solvent dewaxing Improve pour point Waxes
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1935 Cat. polymerization Improve gasoline yield & ON Petrochemical feed

stocks
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1937 Cat. Cracking Higher octane gasoline Petrochemical feed
stocks
1939 Visbreaking Reduce viscosity Increased distillate,

tar
1940 Alkylation Increase gasoline octane & yield High-octane aviation
gasoline
1940 Isomerization Produce alkylation feed stock Naphtha
1942 FCC Increase gasoline yield & octane Petrochemical feed

stocks
1950 Deasphalting Increase cracking feedstocks Asphalt
1952 Cat. reforming Convert low-quality naphtha aromatics
1954 Hydrodesulphurizati Remove sulfur sulfur

on
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1956 Inhibitor sweetening Remove mercaption disulfides

1957 Cat. isomerization Convert to molecules with high Alkylation
octane number feedstocks
1960 Hydrocracking Improve quality and reduce Alkylation

sulfur feedstocks
1974 Cat. dewaxing Improve pour point Wax
1975 Residual Increase gasoline yield from Heavy residual

hydrocracking residual
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Typical Approximate Characteristics and properties and of
gasoline potential of various crudes
(Representative avg. no.)
Crude Paraffins Aromatics Naphthenes Sulfur Api Naphtha. Octane no.
source (% Vol) (% Vol) (% Vol) (%Wt) gravity Yield (Typical)
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(Approx.) (% Vol)
Nigerian 37 9 54 0.2 36 28 60
-light
Saudi 63 19 18 2 34 22 40

-light
Saudi 60 15 25 2.1 28 23 35
-Heavy
Venezuela 35 12 53 2.3 30 2 60
-Heavy
Venezuela 52 14 34 1.5 24 18 50
-light
USA - - - 0.4 40 - -
-Mid cont.
sweet
USA 46 22 32 1.9 32 33 55
-W. Texas
Sour
North Sea 50 16 34 0.4 37 31 50
-Brent
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OVERVIEW OF PETROLEUM REFINING PROCESS
PROCESS ACTION METHOD PURPOSE FEEDSTOCK(S) PRODUCT(S)
NAME
FRACTIONATION PROCESSES
Atm. Separation Thermal Separate Desalted crude Gas, gasoil,
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Distillation Fractions oil distillate,
residual
Vacuum Separation Thermal Separate w/o Atmospheric Gas oil, lube
Distillation cracking tower residual stock, residual

CONVERSION PROCESSD-DECOMPOSITION
Cat. Cracking Alteration Catalytic Upgrade Gas oil, Coke Gasoline,
gasoline distillate petrochemical
feed stocks
Coking polymerize Thermal Convert Gas oil, Coke Gasoline,
vacuum distillate petrochemical
residual feed stocks
Hydro- Hydrogenate Catalytic Convert to Gas oil, Lighter,
cracking lighter HC’s cracked oil, higher-quality
residual products
*Hydrogen Decompose Thermal Produce Desulphurised Hydrogen, CO,
steam hydrogen gas, O2, steam CO2
reforming
*Steam Decompose Thermal/ Crack large Atm. Tower Cracked
cracking Catalytic molecules hvy fuel/ naphtha, coke
distillate residual
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Visbreaking Decompose Thermal Reduce Atm. Tower Distillate, tar
viscosity residual
NAME
CONVERSION PROCESES - UNIFICATION
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Alkylation Combining Catalytic Unite olefins & Tower Iso-octane
isoparaffins isobutane/ (alkylate)
cracker olefin

Grease Combining Thermal Combine soaps & Lube oil, fatty Lubricating
compounding oils acid, alkyl grease
metal
polymerizing polymerize Catalytic Unite 2 or more Cracker olefins High-octane

olefins naphtha,
petrochemical
stocks
CONVERSION PROCESS - ALTERATION OR REARRANGEMENT
Catalytic Alteration/ Catalytic Upgrade low Coker/hydro- High Oct.

reforming dehydration octane-naphtha cracker reformate/
naphtha aromatic
Isomerization Rearrange Catalytic Convert straight Butane, Isobutane/pent
chain to branch pentane, ane/hexane
hexane 23
NAME
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TREATMENT PROCESS
*Amine Treatment Absorption Remove acidic Sour gas, HCs Acid free gases

treating contaminates w/ CO2 & H2S & liq. HCs
Desalting Dehydration Absorption Remove Crude oil Desalted crude
contaminates oil
Drying & Treatment Abspt/therm Remove H2O & Liq Hcs, LPG, Sweet and dry
sweetening Sulfur-cmpds alky feed stock hydrocarbons
*Furfural Solvent ext. Absorption Upgrade mid Cycle oils & High qlty diesel
extraction distillate & lubes lube feed-stocks & lube oil
hydrodesulphu Treatment Catalytic Remove sulfur High-sulfur Desulphurised
rization contaminates residual/gas oil olefins
Hydrotreating Hydrogenation Catalytic Remove Residuals, Cracker feed,

impurities, cracked HC’s distillate, lube
saturate HC’s
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*Phenol Solvent ext. Abspt/therm. Improve visc. Lube oil base High quality
extraction Index, color stocks lube oils
Solvent Treatment Absorption Remove asphalt Vac. Tower Heavy lube oil,
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Deasphalting residual, asphalt
propane

Solvent Treatment Cool/filter Remove wax Vac. Tower lube Dewaxed lube
dewaxing from lube stocks oils basestock
Solvent Ext. Sol. Ext. Abspt/precip. Separate Gas oil, High-Octance

unsat. oils reformate, gasoline
distillate
Sweetening Treatment Catalytic Remove H2S, Untreated High-quality

Convert distillate/ distillate/
mercaption gasoline gasoline
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OİL REFİNİNG PRODUCTİON PROCESS
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 Desalting and Dewatering
 Distillation

 Reforming
 Cracking
 Alkylation
 Isomerisation
 Polymerisation
 Hydrotreating
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PHYSICAL AND CHEMICAL PROCESSES
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Chemical
Physical
Thermal Catalytic

Distillation Visbreaking Hydrotreating
Solvent extraction Delayed coking Catalytic reforming
Propane Deasphalting Flexi coking Catalytic cracking
Solvent dewaxing Hydrocracking
Blending Catalytic dewaxing
Alkylation
Polymerization
Isomerization
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IMPURITIES IN CRUDE OIL
The impurities in crude oils can be classified as
oleophobic and
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1.
2. oleophilic.
Various oleophobic impurities(insoluble in crude oil) include:

1. salts-mainly chlorides and sulphates of sodium, calcium and
magnesium,
2. sediments-such as silt, sand, drilling mud, iron oxide, iron sulphide,
etc.
3. water-presents as soluble, emulsified and/or finely dispersed water.
The oleophilic impurities (soluble in crude oils) include:

1. sulphur compounds,
2. organometallic compounds containing Ni, V, Fe, As, etc.,
3. naphthenic acids and
4. nitrogen compounds.
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Several problems caused by oleophobic impurities include:
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1. Corrosion in the atmospheric distillation overhead system caused
by HCI, which is liberated due to hydrolysis/dissociation of
chloride salts;

2. Increased consumption of ammonia to neutralize the HCI;
3. Erosion of crude oil pumps, pipelines and valves by suspended
matter through abrasive action;
4. Plugging of equipment and fouling of heat-transfer surfaces;
5. Product degradation, like high ash content in fuel oil;
6. Trace metals in distillates, which act as catalyst poisons.
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DESALTİNG AND DEWATERİNG
Crude oil is recovered from the reservoir mixed
with a variety of substances: gases water and dirt
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(minerals).
 Desalting is a water – washing operation

performed at the production field and at the
refinery site for additional crude oil cleanup. If
the petroleum from the seperators contains water
and dirt, water washing can remove much of the
water – soluble minerals and entrained solids. If
these crude oil contaminants are not removed,
they can cause operating problems during
refinery processing, such as equipment plugging
and corrosion as well as catalyst deactivation.
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DESALTING PROCESS
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FEED FROM PROCESS TYPICAL TO
STOCK PRODUCT

Crude Storage Treating Desalted crude Atm. Distillation tower
Waste waters Treatment
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DESALTING OF CRUDE OILS
The desalting process consist of diluting this high salt content brine with incoming
fresh water to produce low salt content water. Salt content is measured as
NaCl/thousand barrels of oil and its range varies from 10 to 200 PTB. Crude oil
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contaminated by salt water when shipped in tankers.
1. Primary settling.
2. Heating the oil before settling.

3. Sometimes the addition of chemicals to the mixture before
settling gave further improvements.
4. To get consistently good result practically all refiners now use
electrical desalting equipment.
ELECTRICAL DESALTING OF CRUDE OILS
Electrical desalting process consists of two steps.

1. forming an emulsion of crude oil and water.
2. demulsification process in which the emulsion of crude oil and water
formed in the first step is broken by means of an electrical field.
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Crude oil desalting
 The two most typical methods of crude-oil desalting are chemical and
electrostatic separation, and both use hot water as the extraction
agent.
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 In chemical desalting, water and chemical surfactant (demulsifies) are
added to the crude, which is heated so that salts and other impurities
dissolve or attach to the water, then held in a tank to settle out.

 Electrical desalting is the application of high-voltage electrostatic
charges to concentrate suspended water globules in the bottom of
the settling tank. Surfactants are added only when the crude has a
large amount of suspended solids.
 A third (and rare) process filters hot crude using diatomaceous earth.
 The crude oil feedstock is heated to 65-180°C to reduce viscosity and
surface tension for easier mixing and separation of the water. The
temperature is limited by the vapor pressure of the crude-oil
feedstock.
 In both methods other chemicals may be added. Ammonia is often
used to reduce corrosion. Caustic or acid may be added to adjust the
pH of the water wash. 35
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Desalting
Chemical
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20000 to 24000 volts

95% salt is removed
Electrical desalting
120-130oC
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 a controlled pressure drop is maintained using
mixing valve
 The flow enters the vessel under conditions of low
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velocity (Laminar)
 multiple stages (desalter) is offset by reduced

corrosion, plugging and catalyst poisoning in
downstream equipments subjected to lower salt
content
 The rate at which the water is injected into the
crude is depending primarily upon the salt
 If sufficient mixing across the valve alone is not
obtained, heat exchanger train as a means of
emulsification may be used
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PROCESS VARIBLES IN DESALTER PROCESS
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1. Pressure drop through mixing valve: optimum operation pressure 0.3
kgf/cm2 of the maximum
2. Chemical addition: not required

3. Water injection rate: 3-8 volume %
4. Conductivity: to maintain good conductivity there must be no voltage
drop
5. Temperature: must be as high as 140oC
6. Desalter pressure : It must be high enough to prevent vaporization
7. pH value: 6.5 to 8.5
8. Solids at water-oil interface: Sludge formed reaches upto electrode and
cause trouble
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Typical operating conditions
Process variables Haldia refinery Gujarat refinery
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Desalting temperature, oC 125-130 126-130
Desalting pressure, kgf/cm2 8.3-8.5 10

Pressure drop across mixing valve, kgf/cm2 1.35 1.3-1.5
Water injection rate, vol.% of crude 1.3-1.9 4.5-6.0

Salt content, ppm
Inlet salt content, ppm 20-30 -
PTB - 6-20
Outlet salt content, ppm 4-8 -
PTB - 2-4
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CRUDE OIL DISTILLATION
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 Crude oil consists of hydrocarbons varying in boiling range from
methane to asphalt.
 The aim of crude oil distillation is to fractionate the crude oil into
 light hydrocarbons (C1 through C4),
 gasoline components and
 middle distillates (kerosene/ATF, gas oil) which can be marketed directly or
with a minimum of further processing.
42
43
44
DİSTİLLATİON
 Distillation separates chemicals by the difference
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in how easily they vaporize
 The two major types of classical distillation

include
 continuous distillation and
 batch distillation
 Other ways to categorize distillation are by the

equipment type (trays, packing), process
configuration (distillation, absorption, stripping,
azeotropic, extractive, complex), or process type
(refining, petrochemical, chemical, gas treating).
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CRUDE OIL DISTILLATION PROCESSES
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1.ATMOSPHERIC
2.VACCUM

46
ATMOSPHERIC DISTILLATION PROCESS
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STOCK PRODUCT
Crude Desalting Separation Gases Atm. Distillation tower

Naphthas Reforming or treatment
Kerosene or Treating
distillates
Gas oil Catalytic cracking
Residual Vacuum tower or

visbreaker
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Atmospheric distillation of crude oil
Carried out at pressures slightly above atmospheric pressures to
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1.Raise the bpt of the light ends
2.Pressure the uncondensed gases to the meant processing step

3.Allow for column pressure drop.
Crude oil is heated to a temp range of 350-360 oC
Steam is introduced at the bottom section of the column at a rate of 12-24kg/meter 3of column
bottoms
SPECIAL FEATURES
1.The side stream products are steam stripped to remove the lighter components
2.Pump-arounds :-By providing reflux to the column below a pump-around zone gives a more
Uniform liquid loading ,there by reducing the net liquid loading .
3.Intermediate refluxes are withdrawn to recover maximum heat and to have uniform vapour
and liquid loads in the column.
4.About 80% of heat can be recovered by circulating reflux.
48
3/3/2018
Atmospheric distillation of crude oil 49
Petroleum gas - used for heating, cooking, making plastics
•small alkanes (1 to 4 carbon atoms)
•commonly known by the names methane, ethane, propane, butane
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•boiling range = less than 104 degrees Fahrenheit / 40 degrees Celsius
•often liquefied under pressure to create LPG (liquified petroleum gas)
•
Naphtha or Ligroin - intermediate that will be further processed to make gasoline

•mix of 5 to 9 carbon atom alkanes
•boiling range = 140 to 212 degrees Fahrenheit / 60 to 100 degrees Celsius
Gasoline - motor fuel

•liquid
•mix of alkanes and cycloalkanes (5 to 12 carbon atoms)
Kerosene - fuel for jet engines and tractors; starting material for making other products
•liquid
•mix of alkanes (10 to 18 carbons) and aromatics
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Gas oil or Diesel distillate - used for diesel fuel and heating oil; starting material for making other
products
•liquid
•alkanes containing 12 or more carbon atoms
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Lubricating oil - used for motor oil, grease, other lubricants
•liquid

•long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics
Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products
•liquid
•long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics
•
Residuals - coke, asphalt, tar, waxes; starting material for making other products
•solid
•multiple-ringed compounds with 70 or more carbon atoms
•boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius
51
52
The typical yields of various products from atmospheric distillation
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unit processing different crudes
Sl. North Bombay UMM

Product Ankaleshwar Basrah Kirkuk
No. Gujarat High Shaiff
l. Gas, LPG & Loss 5.0 3.0 2.0 2.3 2.0 3.0
2. Naphtha (C5 – 145oC) 22.0 8.0 15.0 15.8 17.5 14.4
3. Kerosine (145 – 250oC) 20.0 13.0 15.0 17.5 20.0 20.0

High Speed Diesel Oil (270–370oC)
4. 35.0 16.0 38.0 20.0 22.0 23.1
Reduced Crude Oil (370oC+)

5. 18.0 60.0 30.0 44.4 38.5 39.5
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VACUUM DISTILLATION PROCESS
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STOCK PRODUCT

Residuals Atm. tower Separation Gas oil Catalytic Cracker
Lubricants Hydrotreating or
solvent
Residual Deasphalter,
Visbreaker, or
coker
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VACCUM DISTILLATION OF REDUCED CRUDE OIL
•The atmospheric residue called reduced crude oil, contains a large volume of distillable oils.

•To remove remaining distillates ,reduced crude oil is further fractionated under vacuum.
•Vacuum column is normally operated at an absolute pressure of 80-110 mm Hg
IMPORTANT POINTS TO BE CONSIDERED
Flash zone temp
Flash zone pressure
Pressure drops for different equipments like; pre-condenser, overhead line etc
55
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residue from the vacuum
column may be used for
bitumen production
56
1. The overflash condenses on the wash section plates and
returns to the flash zone and bottom stripping section,
prevents coking in the wash section plates and also
carryover of coke to the bottom side-stream product.
2. Steam (30 %of the total steam) is
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introduced in the furnace coil to
decrease the residence time and
minimize coking

the maximum flash
zone temperature is
380-400oC
• Requirement depends on PP of hydrocarbon

• to reduce the partial pressure of
hydrocarbons in the flash zone
• Also help to strip off light ends in the bottom
product
If vacuum residue
is left to remain at
high temperature,
coke formation
may start due to
cracking.
57
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Vacuum distillation plant
The pressure loss can be calculated from the following recommended pressure
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drop values.
Item Pressure drop value. mm Hg

Precondenser 3
Overhead line 3
Demisters 1
Fractionating trays 2.5
59
Approximate Steam Consumption of Condensing Steam Jet
Ejectors Operating with 8 kgf/cm2 Steam
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Pressure, mm Hg System kg steam per kg of total mixture
Average Range
200 2-stage 4.3 2.5-11

100 2-stage 6.0 3-17
70 2-stage 7.0 4-23
50 2-stage 8.2 4.5-27
40 2-stage 9.4 5-30
30 2-sta£e 10.2 6-35
20 3-stage 12.3 7-40
10 3-stage 16.8 10-50
7 3-stage 20.0 12-58
5 3-stage 23.0 14-64
4 3-stage 25.5 16-70
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Various products from the vacuum distillation of
atmospheric residues along with their uses are given below
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Product Uses

Light vacuum gas oil (LVGO) (a) A blending component for LDO
(b) Feedstock for catalytic cracker /hydrocracker
Heavy vacuum gas oil (HVGO) (a) A feed component for visbreaker
(b) Feedstock for catalytic cracker/hydrocracker
Vacuum residue (VR) (a) Bitumen production
(b) A feed component for visbreaker
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OPERATION OF FRACTIONATING COLUMNS
1. TEMPERATURE
• The top temperature of the column is usually dew-point
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temperature of the overhead vapors at the operating pressure
• The top temperature of the column must be just high enough to
allow complete vaporization of overhead product

2. COLUMN PRESSURE
• not the op. variable.
• High pr. Operation reduces relative volatility of components
• Column dia. Low at high pr.
• Lowest possible pr. is normally recommended
3. FLOW RATES
• Determined by feed composition and degree of separation
4. REFLUX : high reflux ratio is recommended
• V-L contact
• Maintained temp. gradient 62
5. REBOILER/STRIPPING STEAM
• Max. amount of the steam should be used subject to the
• Condenser should be able to take up load
• Lowest side product does not become colored and
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• Column does not get flooded
6. STABILITY OF COLUMN OPERATION
i. Pulsation:- This occurs when the amount of vapour passing through a tray is so small that

the bubble caps pass vapour intermittently
ii. Dumping:-This results at relatively high liquid loads when some of the upstream bubble
caps do not pass vapour.
iii. Coning:- This takes place when the combination of weir height and the liquid crest over the
weir does not adequately seal the cap slots.
iv. Blowing:-This results when the amount of vapour passing through the bubble caps is so
large that it literally tears holes in the liquid on the tray.
v. Entrainment:-It is of two types:
(i) A relatively fine mist is carried to the tray above by superficial vapour velocity
(ii) Large droplets of liquid are jetted from one tray to the next
vi. Flooding:-This occurs when the level of the liquid-foam mixture in the downpipe builds up
and overflows to the tray above
63
Thank you
64

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