Course: Chemical Technology (Organic) Module VI

Lecture 3
Crude Oil Distillation




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LECTURE 3
CRUDE OIL DISTILLATION

INTRODUCTION
Refining of crude oils or petroleum essentially consists of primary separation processes and
secondary conversion processes. The petroleum refining process is the separation of the different
hydrocarbons present in the crude oil into useful fractions and the conversion of some of the
hydrocarbons into products having higher quality performance. Atmospheric and vacuum
distillation of crude oils is the main primary separation processes producing various straight run
products, e.g., gasoline to lube oils/vacuum gas oils (VGO). These products, particularly the light
and middle distillates, i.e., gasoline, kerosene and diesel are more in demand than their direct
availability from crude oils, all over the world.

PRETREATMENT OF CRUDE OILS

Crude oil comes from the ground, which contains variety of substances like gases, water, dirt
(minerals) etc. Pretreatment of the crude oil is important if the crude oil is to be transported
effectively and to be processed without causing fouling and corrosion in the subsequent
operation starting from distillation, catalytic reforming and secondary conversion processes.
IMPURITIES
Impurities in the crude oil are either oleophobic or oleophilic.

OLEOPHOBIC IMPURITIES: Oleophobic impurities include salt, mainly chloride &
impurities of Na, K, Ca& Mg, sediments such as salt, sand, mud, iron oxide, iron sulphide etc.
and waterpresent as soluble emulsified and /or finely dispersed water.
OLEOPHILIC IMPURITIES: Oleophilic impurities are soluble and are sulphur compounds,
organometallic compounds, Ni, V, Fe and As etc, naphthenic acids and nitrogen compounds.
Pretreatment of the crude oil removes the oleophobic impurities.

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PRETREATMENT TAKES PLACE IN TWO WAYS:

Field separation
Crude desalting
Field separation is the first step to remove the gases, water and dirt that accompany crude oil
coming from the ground and is located in the field near the site of the oil wells.
The field separator is often no more than a large vessel, which gives a quieting zone to permit
gravity separation of three phases: gases, crude oil and water (with entrained dirt).

CRUDE DESALTING
It is a water washing operation performed at the refinery site to get additional crude oil clean up.
Crude Oil Desalting consists of
Purifying process
Remove salts, inorganic particles and residual water from crude oil
Reduces corrosion and fouling
Desalting process is used for removal of the salts, like chlorides of calcium, magnesium and
sodium and other impurities as these are corrosive in nature. The crude oil coming from field
separator will continue to have some water/brine and dirt entrained with it. Water washing
removes much of the water-soluble minerals and entrained solids (impurities). There are two
types of desalting: single & multistage desalting. Commercial crudes, salt contents 10-200 ppb,
earlier 10-20 ppb were considered satisfactorily low. However, many refiners now aim at 5 ppb
or less (1-2 ppb) which is not possible through single stage desalting, hence two stage desalting
is required.
Desalting process consists of three main stage: heating, mixing and settling.
Crude oil is heated upto 135-141
o
C in the train of heat exchanger operating in two parallel
section. The temperature in desalting is maintained by operating bypass valve of heat exchanger.
Single stage desalting with water recycle is usually justified if salt content in crude is less than
40 ppb. Two stage desalting involves dehydration followed by desalting. Double stage desalting
is better for residuum hydrotreating. Fuel oil quality is better.
Desalting process is two stage process: forming emulsion of crude and water and demulsification
in which emulsion is broken by means of electric field and demulsifying chemicals.Desalting is
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carried out by emulsifying the crude oil and then separating the salt dissolved in water. Two
phases water/oil is separated either by using chemicals to break down the emulsion or by passing
high potential electric current. By injecting water the salts dissolved in the water and solution are
separated from the crude by means of electrostatic separating in a large vessel.

Operating Variables in Desalter: Some of the variables in the desalter operation are crude
charge rate, temperature, pressure, mixing valve pressure drop and wash water rate, temperature,
and quality, desalting voltage. Crude oil temperature charged to the desalter is very important for
the efficient operation of desalter. Lower temperature reduce desalting efficiency because of
increased viscosity of oil while higher temperature reduce desalting efficiency due to greater
electrical conductivity of the crude. Pressure in the vessel must be maintained at a high value to
avoid vaporization of crude oil pressure which result in hazardous ondition, erratic operation and
a loss of desalting efficiency. Flow diagram for crude oil desalting is given Figutre MIV









Figure M-VI 2.1 Crude oil Desalting

CRUDE OIL DISTILLATION
Desalted crude flows to atmospheric and vacuum distillation through crude pre flashing section.
Atmospheric distillation column (ADU) and Vacuum distillation column (VDU) are the main
primary separation processes producing various straight run products, e.g., gasoline to lube
oils/vacuum gas oils (VGO). These products, particularly the light and middle distillates, i.e.,
gasoline, kerosene and diesel are more in demand than their direct availability from crude oils,
all over the world.
Two stage Desalter
Desalted
Crude Oil
Effluent
Water
Process
Water
Unrefined
Crude Oil
Demulsifier
Preheat heat
exchanger
Mixing
Unit
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Crude oil distillation consists of atmospheric and vacuum distillation. The heavier fraction of
crude oil obtained from atmospheric column requires high temperature. In order to avoid
cracking at higher temperature the heavier fraction are fractionated under vacuum. Typical flow
diagram of crude oil distillation is given in Figure M-VI 2.2. Various Streams From
Atmospheric And Vacuum Distillation Column is given in Table M-VI 2.2



Figure M-VI 2.2: Atmospheric and Vacuum Crude oil distillation





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Table M-VI 2.2: Various Streams From Atmospheric And Vacuum
Distillation Column

Column Fraction Temperature Carbon
range
Uses
Atmospheric
column
Fuel Gases >40 C
1
-C
2
Fuel
LPG C
3
-C
4
Domestic fuel
Straight run
gasoline/
20-90 C6-C10 Gasoline pool
Naphtha
(Medium and
heavy)
130-180 C6-C10 Catalytic reforming
and aromatic plant
feed stock
Steam cracker,
synthesis gas
manufacture
Kerosene 150-270

C11-12 Aviation turbine fuel,
Domestic fuel, LAB
feed stock (paraffin
source)
Light gas oil 230-320 C13-C17 High speed diesel
component
Heavy gas oil 320-380 C18-C25 High speed diesel
component
Vacuum
column
Light vacuum
gas oil
370-425 C18-C25 Feed to FCC /HCU
Heavy vacuum
gas oil
425-550 C26-C38 Feed to FCC /HCU
Vacuum slop 550-560 RFCCU feed
Vacuum Residue >560 >C38 Bitumen/ Visbreaker
feed

ATMOSPHERIC COLUMN: Various steps in atmospheric crude oil distillation are
Preheating of Desalted crude
Preflash
Distillation
Stabilization of Naphtha
The desalted crude oil from the second stage desalting process is heated in two parallel heat
exchanger. The preheated crude having temperature of about 180
o
C is goes to pre flash drum where
about 3-4percent of light ends are removed. The preheated crude from the preheater section is further
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heated and partially vaporized in the furnace containing tubular heater. The furnace has two zones:
radiant section and convection section. The radiant zone forms the combustion zone and contains the
burners. In convection zone the crude is further heated (inside the tube) by the hot flue gases from the
radiant section.
Heated and partially vaporized crude from the fired heaters enters the flash zone of the column and
fractionated in the atmospheric column. The distillation section consist of overhead section, heavy
naphtha section, kerosene section, light gas oil section, heavy gas oil section and reduced crude section
each section contains circulating reflux system.
Naphtha stabilizer, caustic wash and naphtha splitting section: The unstablished naphtha from the
atmospheric distillation column is pumped to the naphtha stabilizer section for separation of stabilized
overhead vapours which is condensed to recover LPG which is treated in caustic and amine treating
unit. The stabilized naphtha is further separated into light, medium and heavy naphtha.
PRODUCTS of ADU: Major product from atmospheric column are light gases and LPG, light
naphtha,medium naphtha,heavy naphtha,kerosene,gas Oil(diesel),atmospheric residue.
Unstabilized Naphtha consists of LPG, naphtha and light gases (C-5 115
o
C)
Intermediate Naphtha (Bombay High) (135
o
C) Solvent Naphtha
Heavy Naphtha (130-150
o
C) routed to diesel or naphtha.
Kero/ATF (140-270/250
o
C)
Light Gas Oil (250/270-320
o
C)
Heavy Gas Oil (320-380
o
C)
Reduced Crude Oil
Major products separated in atmospheric column:
Operating Variables in ADU unit are
Furnace coil outlet temperature
Crude distillation Column top pressure and top temperature
Stripping Steam flow
Product withdrawal Temperatures
VACUUM DISTILLATION COLUMN (VDU)
The bottom product also called reduced crude oil, from the atmospheric column is fractionated in the
vacuum column. Reduced crude oil is very heavy compared to crude oil distilling under pressure
requires high temperature. Distillation under vacuum permits fractionation at lower temperature which
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avoid cracking of the reduced crude oil and coking of the furnace tube. Vacuum is maintained using
three stage steam ejector. The reduced crude oil from atmospheric column at about 360
o
C is heated
and partially vaporized in the furnace. The temperature in the flash zone of the tower is controlled by
the furnace coil outlet temperature. The preheated and partially vapourised reduced crude enters the
flash zone of vacuum column where it is fractionated into various streams.
PRODUCTS FROM VDU: Various products from VDU areLight gasoil, Heavy gas oil, light
lube distillate, medium lube distillate, heavy lube distillate and vacuum column residue
OPERATING PRESSURE OF VACUUM COLUMN:
About 90-95 mm Hg at the top and
About 135-140 mm Hg at the bottom

CHEMICAL INJECTION SYSTEM:
Chemical injection system consist of caustic injection and ammonia injection and use of
corrosion inhibitor, use of demulsifier, addition of trisodium phosphate in boiler feed water..
Corrosion in the atmospheric tower overhead system is a common phenomenon and the problem
is increasing with increasing use of the heavier crude oil. Corrosion is primarily due to hydrogen
chloride, which is produced by hydrolysis of the chloride salts remaining after desalting. Other
sours of corrosion are naphthenic acid and hydrogen sulphide. High caustic injection is to
avoided as high caustic injection system may lead to fouling in vacuum and visbreaker furnaces.
ammonia injection is done to maintain the pH. Corrosion inhibitor in kerosene and naphtha is
required to combat the corrosion. De-emulsifier is used to demulsify the water and crude
emulsion. Trisodium phosphate is used to maintain pH and prevent corrosion in the boiler drums
EFFECT OF CRUDE CHARACTERISTICS:
Crude oil characteristics plays important role in the product distribution, processing scheme and
quality of product. Effect of Crude Characteristics on Performance of crude distillation. Effect of
Crude Characteristics on Performance of crude distillation is given in Table M-VI 2.3


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Table M-VI 2.3. Effect of Crude Characteristics on Performance of crude

distillation
Characteristics Effect
API API A Measure of heaviness or lightness
API =(141.5 / density) - 131.5
API >30 Light Crude
API <28 Heavy Crude
Viscosity: A measure of resistance to flow and is important parameter for
effective desalting and highly dependant on temperature. High
viscosity crudes need high temperatures for effective desalting.
There is a limit for temperature in desalters.
UOP
K(Characterisation
factor)
It is measure of parafinity vis--vis aromaticity of Crude
High UOP K is desired for high conversion in FCC
High UOP K is desired for high conversion in FCC
Aromatic molecules can not be cracked in FCC. They will simply
take ride through the plant.
Total acid
number(TAN)
Total Acid Number: A measure of Naphthenic Acid contents in
Crude leads to corrosion in various sections of the unit Over 1,500
known NA species are present in crude.
All Nap. Acids are not corrosive. Latest research indicates that
TAN is not a complete Corrosion Index
TAN with 2.5 may corrode at higher rate than TAN with say 6 !
Detailed metallurgical reviews & monitoring mechanism must be
put in place.
BS&W
Bottom
Sediments &
Water

BS&W Bottom Sediments & Water is a measure of water, water
dissolved ,substances, mud, sand & sludge. Lower the BS&W - the
higher the reliability of the Unit. BS&W is one of the major pointer
for corrosive materials in crude.
Sulfur Sulfur is a measure of sourness & sweetness of crude
passed onto products as much as regulations or market accepts
. It is removed in hydrotreaters by reacting with H
2
and recovered
as elemental Sulfur in sulphur recovery unit
S >2.5 Sour Crude, S <2 Sweet Crude
Total salts Total salts A Measure of contaminant in Crude that will cause
overhead corrosion or foul-up exchangers by settling &
scaling. It is removed in desalters by washing & settling
VGO metals VGO metals is a measure of metals content in VGO
fraction Ni & V are known poisons of VGO hydrotreter catalyst.
Metals in VGO are controlled by controlling wash rate in Slop
Wax section of vacuum column



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References
1. Mall, I.D., Petrochemical process technology First edi., New Delhi, Macmillan India 2007
2. Mandal, K.K. Improve desalter control, Hydrocarbon processing, April, 2005,p.77
3. Watkins, R.N. Petroleum refinery distillation, Second edition,1979, Gulf Publishing
Company, Houston