All Merged

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Chapter
Introduction
Introduction
• Oil and natural gas are the important parts of everyday life. Their availability has
changed the whole world economy.
• Playing a vital role in industrialization and urbanization through supplying energy for
domestic, industrial, transport sectors
• and feed stocks for fertilizer, synthetic fiber, synthetic rubber, polymer, intermediate,
explosive, agrochemicals, dyes, paints, etc.
• Processing oil for producing fuel and other values added products has become very
important activity in modern petroleum refinery.
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• With expected population of 7.6 billion in 2020 [2], demand of products from
petroleum and petrochemical route is also expected to increase.
• The use of petroleum and its derivatives has been reported since pre-Christian
times. Petroleum and its derivatives such as asphalt, bitumen have been known and
used for almost 6000 years.
• First documented use of asphalt has been reported in 3800 BC. The Kerosene lamp
invented in 1854.
• Modern petroleum refining began in 1859 with discovery of petroleum in

Pennsylvania and further commercialization. The exploration of petroleum
originated in later part of nineteenth century.
• As a result of technological development and rise in demand of petroleum and

petrochemical products, today’s refinery is highly integrated and complex producing
fuel, lubricants and broad range of petrochemicals.
• A standalone refinery configuration in present context will have

(i) Flexibility to handle heavy and sour crude oils
(ii) Adequate capacity of secondary conversion and residue upgrading facilities to
ensure high overall yields of light and middle distillates
(iii) Appropriate upgrading facilities (hydro-desulfurization, CCR reforming,
isomerization, etc.)
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Chemistry of Crude Oil

• Petroleum/crude oil means rock oil.
• Natural organic material, composed principally of hydrocarbons in geological traps
• Its structure and composition varies according to its source
• Composed from hydrocarbon and/or sulphur, nitrogen and/or oxygen derivatives of

hydrocarbons with traces of wide range of metallic elements
• Accompanied by extraneous quantities of different substances (e.g. water, inorganic

matter and gas, etc.). The removal of such extraneous substances alone does not
change status of mixture as crude oil.
• C/H ratio = 6-8
• Wide range of physical and chemical properties (See table attached)
• Light crude oil: brown colour, pleasant (aromatic like) smell
• Heavy crude oil: black brownish colour, unpleasant (garlic like) odour due to sulphur
compounds
• Specific gravity = 0.73-1.02, mostly 0.80-0.95
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Table: Typical properties of crude oils
Composition of Crude Oil

• Elemental composition of crude oil (See table)
Element Amount (Wt%)
C 83.9-86.8
H 11-14
S 0.06-8.0
N 0.02-1.7
O 0.08-1.82
Metals 0.0-0.14
• Naphthenic acids, complex nitrogen compounds and mercaptans account for O, N

and S present in crude oil.
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• Resinous and asphaltic substances for O and S
• Dissolved H2S for inorganic sulphur
• Traces of metals in water impurities and some as complexes in hydrocarbon phase
• Water associated with crude, markedly saline, deficient in Mg and SO42+ as compared
to sea water
Transportation of crude oil & finished products

• Important characteristics for effective movement of crude oil: Density, temperature,
viscosity
• Marine transportation: As most of the countries are dependent on crude oil from
Middle East and Africa, crude is being supplied in cargo ships.
• Rail/Road transportation: Crude oil and different grades products (e.g. Gasoline,
LPG, etc.) are transported via this mode in pressurized or unpressurized tankers.
Most significant method of transportation of finished products.
• Pipeline transportation: Crude, natural gas, etc. use this mode. Most popular
method of crude transportation in India. Globally cross country pipelines are
recognized as safest, cost effective and environment friendly mode of transportation
of crude and products.
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Pipeline Transportation of Crude

• Most effective and economic mean for transportation of large quantities of crude
• Best protection for environment
• No handling of other traffic
• Not hindered by weather conditions
• Requires high investments
• Maintaining a constant flow rate without interruption, economical and efficient
operation
• Reasons for undesirable shutdowns,
• Inadequate stock of oil in terminal
• No delivery requirements by refineries
• Performing a pressure test to check leakage
• Maintenance shut down, automatic shutdown
• Shutdown longer than 3-4 days are not expected.
Problems in pipeline transportation of crude

• Crude contains a mixture of light and heavy hydrocarbons (typically paraffinic,
naphthenic and aromatic compounds, etc. as heavy as C60).
• If temperature of oil is decreased, the solubility of heavy hydrocarbons may be

sufficiently reduced to cause precipitation in form of solid waxy crystals.
• This changes flow behaviour to Non-Newtonian, increases energy consumption for

pumping, decreases the transportation capacity.
• Wax deposit in pipelines can lead to increase in pipeline roughness, reduction in

effective diameter, potential blockage and frequent shutdown.
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• Requires accurate prediction of wax formation and insulation requirements at early

stage
• Pigging of pipelines is useful for removing thin layers of wax only. The pipeline pigs
are introduced into line via a pig trap which includes a launcher and receiver. Without
interrupting the flow, pig sweeps the line by scrapping the sides of pipeline and
pushing debris ahead.
• Otherwise, use of expensive chemical injection, depress the pour point, improve flow
Methods for pipeline transportation of waxy crude oils

• Selects pumps to allow a parallel/series arrangement, which could transport at slower
rates and higher pressure when required.
• Use separate low flow, high head pumps for restarting
• Reverse pumping which prohibits static cool down
• Use of pour point depressants/ flow improvers

• Ashless polymeric materials
(e.g. Alkyl acrylate polymers and copolymers, SWAT-104)
• Added in oil at 300-600 ppm to reduce viscosity and pour point of oil
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• Should be added above or around its cloud point and also at a temperature of
around 20°C above pour point of additive
• More attractive, cheap and variability of dosage
• Adding of less waxy crude or light distillate if easily available for blending and does
not affect product specification after crude processing, but disadvantage of reducing
crude oil carrying capacity of pipeline
• Injection of water to form a layer between pipe wall and crude
• Conditioning of crude
• Used before pipelining to change the wax crystal structure and to reduce pour
point and viscosity
• Crude oil is first heated to temperature of 100°C in heat exchangers and tube
heaters to melt and dissolve the wax.
• Thereafter, subjected to dynamic cooling to 65°C with cold crude oil in heat
exchangers.
• Crude oil at 65°C is passed to static cooling vessels (conditioning vessels) with
batch time of 208 minutes, from 65°C to 18.5°C, with circulating water.
• Much improved physical properties of crude than original crude oil
• Subdivision of pipeline into smaller segments or reducing batch length of waxy crude
to increase maximum shear stress available
• Mixing water with crude to form an emulsion, with disadvantage of reducing crude
oil carrying capacity of pipeline
• Combination of any of above methods
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World Petroleum Resources

• Oil is more scattered in world as compared to coal.
• Self-sufficient in energy: Russia and Eastern Europe
• Major oil producers and exporters: Middle east and Africa
• Near and middle east countries reserve 70% of worlds petroleum stock and hold the
control in the energy export.
• Countries rich in oil production: Iran, Iraq, Russia, Venezuela, Saudi Arabia, USA,
Kuwait, etc.
• Present trade of oil is governed by OPEC (Organization of the Petroleum Exporting

Countries).
• Global oil reserves: 1900×109 bbls [3]
• Now a days, the activity of finding deposits of oil under deep oceans is more.
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Petroleum Industries in India

• Many planners believe that oil consumption is directly related to growth rate.
• In India, margins in refining is very high (4 $ per barrel) as compared to world’s

average [3].
• After liberalization the multi nationals have entered the oil fields and are giving good
competition to native companies.
• Major industries: IOC, HPCL, BPCL, IBP, Shell, ONGC, GAIL, RIL, etc.
• The growth in consumption of petroleum products, mainly in fuels, is surpassing 6%,

which is difficult to managed by Indian industries, thus foreign companies have
visited again after nationalization of oil companies.
• Indian situation is clear in having poor resources in oil and gas. Hence alternative
fuel and blending play a vital role.
• In this direction, the hope is in alcohol and vegetable oils. However, there is huge
shortage of edible oils and limited land for cultivation in India.
• Blending gasoline with alcohol is not only to reduce the consumption of hydrocarbon
but to reduce pollution is a necessity as it is available in plenty in India.
• Indian oil industry is second oldest industry next to sugar/gur/textile in India.
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• In march 1867, the first oil well in the Asian continent was dug in Makum Namdang
area of upper Assam.
• By end of 2020, India may have to import 120 MMTPA assuming a yearly 5.5%
growth in consumption of petroleum fuels [3].
• The gas accounting to 6% of commercial energy [2018] of country can go up to 7-8%

in two/three years.
• The sedimentary basins of India, on land and offshore total of 3.14 sq. km, of which
about 30% is unexplored.
• Crude intake during 2018 was 127.3 MMT which included imports of 98.5 MMT.
Figure: Prospective and existing hydrocarbon deposits and other petroleum activities
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Thanks
12
Petroleum Technology 12-03-2021
Chapter
Classification
and
Characterization
Classification of crude oil

• Required to provide a guide to quality of oil. Concept of base of crude oil has been
used to provide information of a crude oil.
Classified as
• Paraffinic base: Crude which on distillation yields residue containing paraffin
waxes.
• Asphaltic base: Crude which contains asphaltic materials in residue on atmospheric

distillation.
• Intermediate base: Crude which contains both paraffinic waxes and asphaltic
material in residue after atmospheric distillation.
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• Hybrid or Naphthenic base: Crude which contains asphaltic materials with small
amount of paraffinic wax in residue after atmospheric distillation.
Classification of crude oils according to the US Bureau of Mines

• Based on specific gravity of two key fractions. From distillation of crude at
atmospheric pressure, the fraction boiling between 250 and 275°C is collected as
key fraction 1.
• Continuing distillation at 40 mm Hg, the fraction boiling between 275 and 300°C is
collected as key fraction 2.
• As per specific gravity of both fractions, crude is classified in one of the nine
categories (e.g. Paraffinic, Paraffinic- intermediate, etc.).
• Other methods of classifications: IFP method, Characterization factor (KUOP),

Correlation index, Method of structural group analysis
Characterization of petroleum fractions

• Distillation of crude yields number of cuts of varying boiling ranges.
• In order of increasing boiling range, the main fractions from distillation of crude are
three as following:
• Light distillates (Gas, light-neptha, gasoline, kerosene): used for solvents, fuels,
motor spirits, illuminating oils, heating oil, etc.
• Middle distillates (Gas oils): Diesel fuels, cat-cracking oil, etc.
• Heavy distillates: Lubes, wax, fuel oils, etc.
• Residues: Asphalts, Bitumen, etc.
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Properties of Petroleum Products
Liquid Petroleum Gas (LPG)

• Used as domestic fuel, a fuel for IC engines and a feed stock for manufacture of
various chemicals and olefins, also used for portable blow-lamps, soldering,
brazing, welding, etc.
• Mixtures of saturated and unsaturated light hydrocarbons in C3, C4
• Consist one or more of propane, propene, n-butane, iso-butane, butene and traces of
ethane, ethene, pentane & pentene
• Low S content (max volatile S in commercial LPG = 0.02 wt%), No free entrained
water
• High calorific value, high degree of purity, non-corrosive, colourless, slightly toxic,
slightly anaesthetic if inhaled in high concentration
• Heavier than air, collects at ground level in case of any leakage
• Although odourless, distinctive odours (e.g. Mercaptans) are added to detection of

leakage.
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Important characters and tests for LPG
• Copper strip corrosion

• Vapour pressure
• Volatility
• Total volatile sulphur
• Dryness and purity
• Odour
• Calorific value
Vapour Pressure
• Pressure exerted by vapours above the liquid surface at given temperature
• For volatile, non-viscous petroleum products, determined by Reid vapour pressure

apparatus
• Consist of fuel chamber connected to an air chamber of four times volume and fitted
with pressure gauge
• For LPG, determination should be done at 65°C.
• High vapour pressure involves loss of product in storage and transportation.
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• Test in important with respect to safety in transport, vapour lock in gasoline engine,
type of storage tank employed and starting characters of motor fuels
• Required max. vapour pressure at 65°C for LPG (Commercial butane-propane

mixture) = 2 kgf/cm2 (source: IS: 4576-1978)
Copper-strip Corrosion Test

• Sulphur compounds remaining in petroleum products after refining, can have some
corroding effect on various metals.
• This test serves as a measure of possible difficulties with copper, brass or bronze parts of
the fuel systems.
• A cleaned and smoothly polished copper-strip is immersed in the sample, which is then
maintained at specified temperature for specified length of time. This strip is removed
from sample, washed with aromatic and sulphur free petroleum spirit and examined for
evidence of etching, pitting, discolouration.
• It is then compared with ASTM copper-strip corrosion standard colour code. The
classification code indicates that the numbers 1, 2, 3 and 4 designate slight tarnish,
moderate tarnish, dark tarnish and corrosion, respectively.
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Naptha
• Complex mixture of C5-C13, contains paraffins, oleffins, naphthenes and aromatics,
etc.
• Uses: Commercial solvent, varnish and paint manufacturing, fertilizer feed stock,
feed stock for steam cracker in petrochemical industry producing hydrogen,
methane, ethane, propene, butane, benzene, etc. which are raw material for further
processing
• Light distillate of crude oil, generic name given to light hydrocarbons boiling in
gasoline range of 36-235°C
• Boiling range of various napthas: e.g. C5-85°C, 60-85°C, C5-200°C
• Classification: Light neptha (B.P. < 100°C), Intermediate neptha (100 < B.P. <
150°C) and heavy naptha (B.P. > 150°C)
• Catalytic reforming of neptha yields a C6-C8 reformate rich in aromatic

hydrocarbons (Benzene, toluene, xylene, etc.) with high octane number 93-94,
suitable for gasoline blending
• Fluid catalytic cracking of neptha is used to produce high octane value product (92-
94) for gasoline blending
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Important characters and tests for Naptha

• Acidity
• Specific gravity
• Sulphur content
• C/H ratio
• Boiling point range
Acidity
• New and used petroleum products may contain acidic constituents present as
additives or as degradation products, such as oxidation products.
• Total acidity is an indication of the corrosive properties of the product.
• Total acidity is measure of combined organic and inorganic acidity.
• Inorganic acid is a measure of mineral acids present. Organic acidity is obtained by

deducting the inorganic acidity from total acidity.
• The acids in sample are extracted in neutral alcohol and then titrated against
standard alcoholic potassium hydroxide under hot conditions.
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Density and Specific Gravity

• Measured over range of temperatures, usually for convenience at the temperature at
which the fuel is to be stored.
• Specific gravity is the ratio of the density of a fluid to that of water at same
temperature. The temperature usually specified is 15.56°C.
• In USA, specific gravity of an oil is often expressed as ˚API.

.
°API = . ° / . °
− 131.5
• The specific gravity is an indication of the type of the hydrocarbon present, being
highest for aromatic and lowest for paraffins. The API gravity reverses the
relationship.
• The most accurate method of determining the specific gravity of the oil is to weigh a
known volume in a specific gravity bottle at 15.56°C.
• Another method for determining specific gravity of the oil is by means of a set of
hydrometers. A hydrometer is placed in oil sample at 15.56˚C and allowed to come
to rest. The specific gravity is shown on the scale at the point coincident with the
surface of the oil.
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Gasoline (Motor Spirit)

• One of most widely used petroleum product and light distillate (B.P. = 30-180˚C)
• Prepared by mixing various components (≈ C5-C10) produced from refining process

(e.g. atmospheric distillation, polymerization, alkylation, etc.)
• Constituents: Normal and branched paraffins, cyclo-paraffins, aromatics, olefins
• Isoparffins, cyclo-paraffins, aromatics present in gasoline have good octane

numbers. Minimum octane number reuired for motor gasoline = 87
• Olefins: unstable for storage and having gum forming tendency, Oxidation stability
= 360 minutes
• Total maximum sulphur content = 0.25 wt%, Max lead content: 0.8 g/L
• Primary quality factors required in any spark-ignition engines: Combustion,

volatility and cleanliness
• Use of additives to inhibit knocking, gum formation and icing of carburettor
Volatility Characteristics
• Sufficient volatile fuel, easy starting, rapid warm-up and adequate vaporization for
proper distribution between cylinders
• Not highly volatile to prevent excessive vapour loss from fuel tank and vapour lock
in fuel line
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• Total maximum sulphur content = 0.25 wt%, Max lead content: 0.8 g/L
• Primary quality factors required in any spark-ignition engines: Combustion,

volatility and cleanliness
• Use of additives to inhibit knocking, gum formation and icing of carburettor
Volatility Characteristics
• Sufficient volatile fuel, easy starting, rapid warm-up and adequate vaporization for
proper distribution between cylinders
• Not highly volatile to prevent excessive vapour loss from fuel tank and vapour lock
in fuel line
• Can be met by using more volatile gasoline in winter than summer
Oxidation Stability
• Slow oxidation (with atmospheric air or auto oxidation) in prolonged storage,
forming gummy residue
• Chain reactions in auto oxidation, producing hydroperoxides (mainly), alcohols,
aldehydes, acids, etc.
• Darkening in colour, gum formation and insufficient performance are symbols of
storage instability of gasoline.
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Additives used in gasoline

• Anti-knocking compounds: required to enhance the octane number
(e.g. TEL, MEL, Iron carbonyl, etc.)
• Anti-oxidants: reacts peroxides to inhibit chain reactions

(e.g. Alkyl phenols, phenylene diamine)
• Metal deactivators: Used to prevent the action of trace amount of metals (e.g. Cu) in
gasoline which could catalyse the oxidation reactions and have a pronounced damage
on the storage quality
(e.g. Ethylene diamine and propylene diamine derivatives of disalicydene)
• Anti-icing compounds: at high humidity and low ambient temperature, moisture in

air freeze in carburettor. Icing upset air/fuel ratio and increases fuel consumption.
Cryoscopic additives (e.g. dipropylene glycol, ethylene glycol mono methyl ether)
lower freezing point. Surface active additives (e.g. amides, fatty amines, etc.) form
protective layer at carburettor.
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Important characters and tests for gasoline

• Sulfur content
• Lead content
• Gum content
• Colour
• ASTM distillation range (30-180˚C, C5-C10)
• Octane number
• Oxidation stability
• Reid vapour pressure, etc.
Total Sulphur Content

• Important for refiner and user also because S compounds pose dual problem.
• Cause environmental pollution from their combustion products
• But are also naturally corrosive and cause severe problems to engine parts
• Determined by lamp method for volatile products and by bomb method for heavier
products.
• Sulphur in sample in oxidized by combustion and estimated volumetrically using

titration method after absorption in H2O2or by gravimetric method after converting
(precipitating) S into barium sulphate.
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Lead in Gasoline
• The lead alkyl is converted to lead chloride and extracted from gasoline by refluxing
with concentrated hydrochloric acid. The acid extract is evaporated to dryness.
• Any organic material present is removed by oxidation with nitric acid and lead is
determined gravimetrically as lead chromate.
• The method covers total lead content of gasoline and other volatile distillates
blended with lead alkyls
• Max. lead content in gasoline (MG 91 BHARAT STAGE IV IS 2796 – 2017, 6th
Revision, Amendment No. 01, Sept.18) = 0.005 gm/L
Gum Content
• The amount of gums points to the presence of olefins which have very poor storage
stability.
• Gum may cause piston ring sticking and deposits in engines.
• The gum compounds which can be produced in fuel are classified into two types
(Existing gum and Potential gum).
• Existing gum may be already formed in the fuel and can be deposited from solution
as fuel evaporates. This is amount of non-volatile heptane insoluble residue left
when sample is evaporated in a jet of hot air at 160°C.
• Potential gum may be formed under extended storage conditions during which
unstable hydrocarbons are thereby polymerized and oxidized to form gums. It is
amount of gum formed after the sample is aged in an oxidation stability bath and
evaporated under specified conditions.
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ASTM distillation
• In this test, 100 ml of sample is distilled in a standard flask at a uniform rate of 5
cc/minute. The distilled is condensed in a brass tube condenser, surrounded by a
water bath kept at 0°C by ice water mixture.
• First drop from the condenser must be available in 5 to 10 minutes after heating
started, at which recorded temperature is mentioned as initial boiling point (IBP) of
sample.
• The vapour temperature is recorded in each successive 10 cc distillate collected in a

measuring cylinder. Test continues till 95% of fraction is condensed.
• A drawback of very low IBP is vapour locking of engine due to high evaporation.
Kerosene
• Distillate fraction of crude oil in boiling range of 150-250°C or C10-C14
• Constituents: Paraffin, naphthenic, aromatics, non-hydrocarbon compounds

containing S, N, O & metals
• Requirements of kerosene (IS 1459-1974): Flash point = 35°C, smoke point = min.
18 mm, total sulphur content = max. 0.25 wt%
• Cannot be burnt in liquid state, has to be in form of vapour and mixed with oxygen
in air in the correct ratio to form a combustible mixture
• Vaporize to some extent when exposed to atmosphere, more when hot
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• Tendency of smoke formation:

Aromatics > Naphthenic > Isoparffins > Paraffin,
Hence a good quality kerosene must contain sufficiently high proportion of
paraffins.
• Tendency of smoke formation of aromatics and naphthenic decrease with increase in

molecular weight but phenomena is reverse for paraffin in kerosene.
• Uses: cooking, lighting, manufacturing of insecticides, herbicides and fungicides
• Straight run kerosene cut is unsuitable for marketing due to high aromatic (smoky)
content.
Important characters and tests for kerosene

• Aniline point
• Fire point
• Smoke point
• Flash Point
• Sulfur content
• Volatility
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Aniline Point
• Aniline is poor solvent for aliphatic hydrocarbons and excellent one for aromatics.
• Lowest temperature at which oil is completely miscible with equal amount of aniline
• High aniline point, fuel is highly paraffinic.
• Equal volumes of the sample and aniline (5 ml each) are heated and cooled with
stirring in a jacketed test tube and temperature of complete miscibility is noted.
Fire Point
• Lowest temperature at which oil ignites and continue to burn for 5 seconds.
• Indirect measure of volatility of the product
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Diesel Fuels
• High speed diesel (HSD): Consumed in automotive purposes,
Light diesel oil (LDO): Used in ships end electricity generation
• Suitable boiling point range:150-400˚C, has C12-C18
• Hydrocarbons present: paraffins, naphthenes, olefins and aromatics
• Primary quality factors of concerned: combustion, volatility, cleanliness
• Cetane number: measure of ignition quality, must be > 42,
• Volatility: determinant of tendency to produce explosive vapours, important to start

and warm up
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• Proper viscosity to flow in pipelines, injector nozzles, etc.
• Diesel should not cause deposits in fuel injector system. Cleanliness during use depends
on carbon residue, ash content, sulphur content in diesel.
• Minimum pollution, corrosion and wear & tear found by less S %. Max S = 0.5%
• Other requirement of diesel fuels (IS: 1460-1974): Max ash = 1 wt%, Min flash point
(Abel) = 38°C
• Combustion depends on: Cetane number, distillation range, gravity, etc.
• Handling and storage depends on: Flash point, viscosity, contamination, copper corrosion,
cloud and pour point, etc.
Important tests for diesel fuels

• Cetane number (Min. 42)
• ASTM Distillation range (180-360°C)
• Specific gravity
• Flash point (Abel, Min. 38°C)
• Viscosity
• Contamination (Water or sediments)
• Cloud point
• Pour point
• Ash content
• Sulfur content
• Aniline point
• Calorific value
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Cetane Number
• Related to ignition delay of a fuel in diesel engine
• Long chain, saturated, un-branched hydrocarbons have high cetane numbers.
• Cetane (Hexadecane, C16H34): Low ignition delay time and arbitrarily chosen high
quality reference compound for cetane scale with cetane number 100
• 2, 2, 4, 4, 6, 8, 8-heptamethyl nonane (C16H34): Long ignition delay time and has

been assigned a cetane number of 15
• Cetane number is determined in a single cylinder CFR (Cooperative Fuel Research)

engine by comparing the ignition delay of diesel sample with reference blends of
known cetane number.
• Cetane number = % n-cetane + 0.15 (% heptamethyl nonane)
• High cetane number is easy starting of compression ignition engines, faster warm
up, increased engine efficiency and power output, reduced exhaust smoke, odour
and combustion noise.
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Flash Point
• Measure of volatility of the product
• Measure of tendency of the fuel to form a flammable mixture with air under controlled
conditions.
• Lowest temperature at which application of test flame causes the vapors above the oil to
ignite.
• Used in assessing the overall flammability hazard of a material, low flash points are
potential to fire hazards.
• Abel apparatus is used for determining the closed cup flash point of petroleum product
between 19-49°C.
Additives used for diesel fuels

• Detergents: Used as cleaners to remove carbonaceous and gummy deposits from
fuel injectors and to prevent further formations, composed mainly of ash less amines
and amides.
• Stabilizers: Used to retard natural degradation during long term storage
• De-emulsifier: To improve anti-haze characteristics
• Sludge retardant: To limit deposit build up
• Dispersant: To break up fuel droplets (e.g. polyamides)
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• Rust corrosion inhibitor: To prevent pitting and erosion of metallic surface
• Metal deactivator: To inhibit deterioration by trace metals
• Anti-oxidant: To retard formation of gums and deposits
• Cold weather additives: In cold temperatures, paraffin crystallize into wax. This
tend to clump together and clog fuel filters. Pour point depressants, flow improvers
and cloud point reducers (e.g. Olefin-ester copolymer) are three basic types.
• De-icer agents: break any fuel/water mixture and prevent water from freezing in
cold. (e.g. glycol-ether)
• Lubricity additives: Generally, the new low sulphur diesel fuels contains less
aromatic because of severe hydro treating necessary to lower the total sulphur
content. These low-aromatic fuels negatively impact the fuel’s natural lubrication
tendency and increase the need for supplemental lubrication enhancement.
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Lubricating Oil
• Also termed as lube oil or lubricants, distillation fraction which has average volatility
less than gas oil
• Types: Mineral oil based lubricants, Synthetic lubricants
• Lubricants amount only to 2-4% of total crude processed. Most of naphthenic crudes
are better for lube oil extraction. Bottom residue from atmospheric distillation is
suitable as feedstock for it.
• Basic functions: To reduce friction and wear, remove heat, prevent corrosion
• Requirements: Proper viscosity and fluidity, good thermal and oxidation stability.
• Particulate matter, moisture, acidic combustion products enter in use of it.
• Blend of lubricating oil base stock and desired additives, ranging in heavy duty to
light duty (as per applications)
Types of lube oil base stocks

• Low viscosity index (LVI) lube oil: VI < 30, rich in aromatics, used where VI and
oxidation stability are not critical.
• Medium viscosity index (MVI) lube oil: 30 ≤ VI ≤ 85, rich in aromatics and
paraffins, used where LVI are at disadvantage.
• High viscosity index (HVI) lube oil: VI > 85, rich in paraffins, used where good
oxidation stability and high VI are needed.
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Important characters and tests for lube oils

• Viscosity
• Viscosity index
• Pour point
• Flash point
• Oxidation stability
• Carbon residue, etc.
Viscosity Index (VI)

• Most widely used way of characterizing the effect of change of temperature on
viscosity of an oil
• An oil whose viscosity changes rapidly with change in temperature has low VI.
• The VI of an oil can be calculated from equation:

VI = [(L−U)/(L−H)]*100
where, U: kinematic viscosity of oil at 40°C
L: kinematic viscosity of Texas coastal oils at 40°C
H: kinematic viscosity of Pennsylvanian (paraffinic) oils at 40°C
2
Carbon Residue
• Defined as amount of carbon residue left over evaporation and pyrolysis of an oil
and is intended to provide some indication of relative coke forming tendency
Conradson method
• Used to determine carbon residue of petroleum products
• A weighed quantity of sample is placed in crucible and subjected to destructive
distillation.
• The residue undergo cracking and cocking reactions during fixed period of severe
heating.
• At the end of specified heating period, the crucible containing the carbonaceous
residue is cooled in desiccator and weighed. The residue remaining is calculated as
conradson carbon residue.
Petroleum Waxes
• Consists of normal & iso-paraffins and alkylated naphthenes of C18-C70
• Classification: Paraffin wax, Microcrystalline wax and Petroleum
• Recovery of these waxes from a crude depends on presence of wax in crude, nature
of crude, quantity & distribution of wax content in crude.
• Indian crudes are mostly suitable for paraffin and microcrystalline waxes.
3
Paraffin Waxes
• Produced from waxy distillate of paraffin-base or mixed-base crudes of high pour
point
• Consist mainly normal and slightly branched paraffins, pronounced crystalline
structure
• Requirements: melting point = 45-75°C, max ash = 0.03 wt%
• Uses: foodstuff packaging industry and cosmetic preparation, candle manufacturing,
coating of paper for general packaging, polishes, water proofing formulations,
processing rubber goods, impregnation of match sticks, textile, pencil industries
Microcrystalline Wax
• Manufactured from distillation residue of paraffin-base or mixed-base crudes, waxy
sludge deposited in their storage tanks
• Consist considerable quantity of branched-chained hydrocarbons

• Requirements: melting point = 74-88°C, flash point = 274-288°C
• Uses: Lamination, sealing compounds, petroleum jellies, rust preventives,
cosmetics, polishes, carbon paper, printing ink, paper coating and electrical
insulation, etc.
Petroleum
• Popularly known Petroleum jelly (e.g. Vaseline)
• Consist certain types of microcrystalline wax and oil
• Can be produced from certain heavy distillate or residue
4
Important characters and tests for wax

• Melting point
• Ash
• Oil content (Max. 3.5 wt% in paraffin wax and about 4 wt% in micro-crystalline wax)
• Colour
• Odour
• Viscosity
• Flash point
Melting and setting point of wax

• Cooling curve method is used to determine setting point of waxes.
• Molten wax is allowed to cool in a specified apparatus and temperature is recorded

for frequent intervals.
• The point at which the temperature remains with in range of 0.1°C for one minute is
taken as setting point.
• These are considered to be suitable for checking the quality of wax output in
refineries.
• M.P. of Paraffin wax = 45-75°C, Microcrystalline wax = 74-88°C
5
Ash
• Ash can result from oil, water soluble metallic compounds, or extraneous solids, such
as dirt or rust.
• A known amount of sample is ignited and carbonaceous residue left is heated to

800°C in muffle furnace, cooled and weighed as ash.
• A knowledge of the amount of product's ash forming material can provide

information on weather the product is suitable for use in given application.
• Max wt% of ash in paraffin wax = 0.03 %
Gas chromatography of petroleum gases and liquids
• A measured volume of gas sample is introduced into a chromatographic column and

transported through the column.
• The sample is split into various components, either by adsorption or partition,

depending on column packing.
• The composition of the sample is determined from the chromatograms by measuring

area under the peaks.
6
Thanks
7
22-03-2021
Chapter
Crude Oil Distillation
Impurities in crude oil

• Classified as Oleophobic (insoluble in crude) and Oleophilic (soluble in crude)
Oleophobic impurities
• Includes salts - mainly chlorides and sulphates of Na, Ca, Mg
• Sediments - as silt, sand, drilling mud, iron oxide, iron sulphate, etc.
• Water - as soluble, emulsifies and finely dispersed water
• Caused corrosion in atmospheric distillation over head system caused by HCl
• Increased consumption of ammonia to neutralize liberated HCl
• Erosion of crude oil pumps, pipe line and valves by suspended matter
• Plugging of equipments and fouling of heat transfer surfaces
• Product degradation (e.g. High ash content in fuel oil)
• Trace metal in distillates works as catalyst poison
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22-03-2021
• Removal of oleophobic impurities result in longer on-stream time, reduced

maintenance cost
Oleophilic impurities
• Includes sulphur compounds and nitrogen compounds
• Organometallic compounds containing Ni, V, Fe, As, etc.
• Natphthenic acids, etc.
• Must be removed to remove problems in subsequent operations
Need for desalting of crude oil

• Every crude oil has salt water together with sediments. Even crude oil can be
contaminated during shipping in tankers.
• Salt content is normally measured as pounds of salt, measured as sodium chloride, per
thousand barrel of oil (PTB), Normal salt range in oil = 10-200 lbs PTB of oil
• Early method of separating impurities was primarily settling. Improvements were

made by heating the oil before settling. Sometimes, chemical addition further
improved settling process also.
• Electrical desalting is used by most refinery presently to reduce salt content.
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Electrical desalting of crude oil

• Mostly, 95% of salt content is found as brine solution and water (BSW), extremely
small droplet dispersed through the crude.
• In desalting operation, salt content can be brought down to the extent of 95% removal.
• Two step process: Initially emulsification of crude & water and later de-emulsification
by means of electrical fields
• Crude oil is heated at 120-130°C to reduce viscosity and to permit efficient mixing.
• Diluting high salt contained water with fresh water (normally 3-8% by volume of
crude oil) to form low salt water.
• Process of demulsification is accomplished by coalescing the small particles of
emulsion together so that they form droplets of sufficient size to permit separation by
gravity settling.
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• In presence of electric field (20-24 kV), water becomes polarized, orient themselves
in a straight line in electric force field and by random collision from larger droplets
which settle.
• Desalted crude overflows while the water along with salt and crude sludge is
withdrawn from bottom of the desalter vessel.
• Additional stages can be used to get additional reduction in salt content of crude oil
before atmospheric distillation column.
Variables affecting desalting

• Process variables which favour/ do not favour emulsification/ demulsification. So, a
compromise is required.
• Pressure drop through mixing valve
• Chemical addition: Required when emulsion is tight, known as de-emulsifiers
• Water injection rate
• Conductivity: High conductivity, high current, low voltage drop and poor de-
emulsification
• Voltage
• De-salter temperature: low viscosity leads to better emulsion and better settling
• Desalter pressure: should be kept high only to prevent vaporization in desalter.
• pH value: Either at high or low pH, conductivity increases.
• Solids at water-oil interface
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22-03-2021
Table: Typical operating conditions in desalters of different Indian refineries
Figure: Block diagram of two stage distillation process
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22-03-2021
• Desalted crude flows to atmospheric and vacuum distillation through crude pre
flashing section.
• Heavier fraction of crude oil obtained from atmospheric column requires high
temperature. In order to avoid cracking at higher temperature, the heavier fractions
are fractionated under vaccum.
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25-03-2021
Figure: Block diagram of two stage distillation process
• Desalted crude flows to atmospheric and vacuum distillation through crude pre
flashing section.
• Heavier fraction of crude oil obtained from atmospheric column requires high
temperature. In order to avoid cracking at higher temperature, the heavier fractions
are fractionated under vaccum.
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Table: Various streams from atmospheric and vaccum distillation

column
Atmospheric distillation of crude Oil
Figure: Atmospheric distillation of crude oil
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25-03-2021
• Atmospheric distillation is carried out slightly above atmospheric pressure to raise

boiling point of light ends, to pressure uncondensed gases and to allow for column
pressure drop.
• Desalted crude oil is first preheated (350-360˚C) in heat exchangers and furnaces for
required percentage of vaporization in flash zone.
• Furnace effluent is flashed into flash zone of atmospheric column where vapour
liquid separate.
• The liquid leaving the flash zone is steam stripped to recover the side-stream
components.
• The flashed hydrocarbon vapors from flash section are fractionated into different
sections above flash zone.
• Four fractions are separated in atmospheric column.
• Overhead vapours are condensed. Overhead product is separated as hydrocarbon and

water, in reflux drum from which water is withdrawn and sent to sour water section.
• The unstabilized neptha containing fuel gas, LPG and neptha is partially refluxed and
sent to neptha stabilizer section.
• Three other products kerosene, light gas oil and heavy gas oil are also withdrawn
from different sections of the column.
• Gas oil is withdrawn as other side stream from atmospheric column which is used as
diesel blending stock.
• Prefractionation: It is known that crude contains high percentage of light ends, a flash
drum or a pre-fractionator with an overhead condensing system may be used to
recover most of the light ends and a part of light naptha.
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Table: Typical yields of various products from atmospheric distillation unit
Table: Typical operating parameters for atmospheric crude distillation column
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25-03-2021
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25-03-2021
Vacuum Distillation Process
• The atmospheric residue, commonly called reduced crude oil, contains a large volume of
distillable oils and is further distilled.
Figure: Vacuum distillation process
• This is carried out at sub-atmospheric pressure, i.e. vacuum.
• Reduced crude oil is first preheated by heat exchange with products from vacuum column
and in furnace to get required percentage of vaporization in flash zone (at temperature of
380-400˚C).
• Condensation of over flashing prevents cocking in wash section and also carry over of coke
to bottom side steam product.
• Steam (about 30% of total steam) is introduced in furnace oil to decrease the residence time
and minimum cocking.
• Depending on vacuum column is used for middle distillate production or lubricating oil
production, there may be one or more side streams.
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• Residue from vacuum may be used for bitumen production or it can be blended with lighter
streams to meet specifications of products like fertilizer feedstock.
• Steam is introduced at bottom section of column to reduce the partial pressure of

hydrocarbons in flash zone. This steam also helps to strip off light ends in the bottom
product. Steam requirements depends on partial pressure of hydrocarbons in flash zone.
• Flash zone pressure has a significant influence on economy of vacuum column design.
Since raising the flash zone pressure increases the requirement of stripping steam and
column cross-sectional area and lowering the system pressure increase steam requirement
for vacuum producing jets in ejectors. This requires optimum pressure in flash zone.
• The vapours and steam rise in the column and products are withdrawn at different sections.
Circulating refluxes are also introduced at different sections of the column to balance the
liquid and vapour loads in the column.
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26-03-2021
• The vapours and steam rise in the column and products are withdrawn at different
sections. Circulating refluxes are also introduced at different sections of the column to
balance the liquid and vapour loads in the column.
• Overhead vapours are condensed by pre- and after condensers of ejector system.
Products are cooled and sent to storage tanks.
• If vacuum residue is left to remain at high temperature, coke formation may start due
to cracking. The vacuum column bottom product is quenched by adding a part of cold
vacuum residue in column, to avoid cracking of vacuum residue at high temperature
at bottom of the column.
Table: Uses of different products from vacuum column
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Operating parameters of distillation columns

Temperature
• The maximum limit of furnace outlet temperature is fixed at which the crude starts
cracking.
• Top temperature of column is usually dew point temperature of over head vapours at
operating pressure.
• Bottom temperature of column is bubble point temperature of bottom liquid and

controls quality of the bottom products.
• Side draw-off temperature is the temperature at which desired product is in liquid

phase at operating conditions in the column.
• Top temperature of column must be just high enough to allow complete

vaporization of overhead product. Vaporization at lower temperature can
incorporate desired overhead product in first side-stream product. A higher
temperature causes the inclusion of high boiling point components in overhead
products.
Column Pressure
• Normally pressure is not an operating variable. Higher pressure means higher
temperature requirement for vaporization.
• For residue stock distillation, even atmospheric pressure may be high considering
the temperature requirement for distillation and thermal stability of stock. So,
vacuum distillation is done.
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• Since high pressure operation reduces relative volatility of components, more

reflux and more reboiled heat are required for achieving the same fractionation at
higher pressure.
• The column diameter can lower at higher pressure due to higher vapour density.
Flow rates
• Feed to distillation column is determined by production demand placed on the plant
and by capacity of distillation equipments.
• Flow rates of overhead and bottom products from a column are determined by feed
composition and degree of separation which is a function of reflux rates.
Reflux
• Firstly, it provides liquid in the rectifying section to cause vapour-liquid contact
resulting in fractionation.
• Secondly, it is provided to maintain temperature gradient in the column.
• Higher reflux ratio results in better separation between light and heavy fraction but
requires higher condenser and reboiler loads (loss of energy).
Reboiler / Stripping Steam

• To provide vapour in stripping section of column for vapour-liquid contact, either
re-boiler is used or steam is admitted directly into bottom of the column.
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• Supplying steam has additional advantage of lowering partial pressure of liquid

being distilled throughout column.
Stability of Column Operation

• Effectiveness of the column depends on intimate contact of vapour and liquid
streams on each tray to provide vaporization of light fraction and condensation of
heavy ones.
• When the liquid or vapour rate inside the column becomes too low or too high, the
contact is insufficient and poor separation results.
• Pulsation: When amount of vapour passing through a tray is so small that bubble
cap pass vapour intermittently.
• Dumping: This results at relatively high liquid loads when some of the upstream
bubble caps do not pass vapour.
• Coning: This takes place when the combination of weir height and liquid crest over
weir does not adequately seal the cap slots. If the slots are not sealed properly,
vapours can pass to the tray without contacting liquid on the tray.
• Blowing: This results when amount of vapours passing through bubble caps is so
large that it literally tears holes in liquid on the tray.
• Entrainment: A relatively fine mist is carried away to the tray above by superficial
vapour velocity. Otherwise large droplets of liquid are jetted from one tray to the
next.
•
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26-03-2021
• Flooding: This occurs when the level of liquid-foam mixture in the downpipe builds
up and over flows to the tray above.
Important Points for Improvements in Fractionating Column

• Degree of separation achieved is a function of number of trays and reflux ratio for a
specific pressure. The addition of trays results in higher initial investment but it can
allow lower reflux ratios and thus energy requirement can be reduced.
• For efficient operation, the feed to a column should be admitted at correct point
according to composition.
• The consumption of stripping steam is dependent on three parameters, viz. degree of

fractionation obtained in main column, stripper design and desired quality of product
(flash point). Excessive use of steam is a wastage of energy apart from increase in
column and condenser loads.
Thanks
5
01-04-2021
Chapter
Conversion Processes
Types of Conversion Processes

• Thermal conversion processes
• Thermal cracking,
• Vis-breaking,
• Coking processes
• Catalytic conversion processes

• Fluid catalytic cracking,
• Catalytic reforming,
• Hydrocracking,
• Catalytic alkylation,
• Catalytic isomerization,
• Catalytic polymerization
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01-04-2021
Thermal Cracking Reactions

• Cracking starts at 315-370°C
• Reaction initiation as heat is applied
CnH2n+2 → Cn−2H2n−3* + C2H5*
• Chain reactions to form more free radicals or decompose to form olefins

C2H5* + CnH2n+2 → C2H6 + CnH2n+1*
CnH2n+1* → Cn−1H2n−2 + CH3*
Cn−2H2n−3* → C(n−2)/2Hn−2 + C(n−2)/2Hn−1*
CnH2n+1* → CnH2n + H*
Cn−2H2n−3* + H* → Cn−2H2n−2
• Cracking reactivity
n-paraffins > iso paraffins > cycloparaffins
> aromatics > poly nuclear aromatics
• Olefins are cracked to smaller olefins and

di-olefins.
• Naphthenes and aromatics with side chains

undergo shortening of side chains.
• Aromatics and poly-nuclear aromatic

undergo condensation reaction with
formation of asphaltic compounds, as given
in the figure.
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01-04-2021
• High T and residence time, leads to more cracking.
• Severe thermal cracking favours to more coke formation.
Thermal Cracking
• Earlier method to refine crude
• Feed: Distillates to heaviest crudes
and residual oils
• Employed in preparation of highly

aromatic thermal tar for production
of needle coke
• By products: Gas, neptha, middle
distillates
• Cracking Temp: 450-500°C

• Two coil operation
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01-04-2021
Vis-breaking
• A mild liquid phase thermal conversion process to reduce the viscosity of
atmospheric and vacuum residue to produce fuel oil
• Vis-braker gas oil can be produced, if necessary.

• Vis-broken vacuum residue is utilized as fuel for furnaces and boilers in refineries.
• The fuel consumption in vis-breaking operation varies in range of net 1-1.5 wt% on
feed which forms the major portion (80%) of operating cost, but the visbreaking
operation leads to cutterstock requirement in order of 20-30 wt% on feed.
• In addition some light distillates (LPG, neptha) are produced, so altogether a fuel oil
reduction of 25-30 wt% on the feed to vis-breaker
• Types: Conventional and Soaker visbraking
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01-04-2021
Conventional Vis-braking
• Produces maximum of fuel oil of
suitable viscosity & pour point and
minimum of neptha from
atmospheric residue, vaccum residue
and other heavy feed stock
• Simplified flow diagram is attached.
• Feed is preheated to a temperature of

about 340ºC by heat exchange with
products and heated to 470-490ºC in
furnace.
• Sufficient residence time is given in

furnace.
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14-04-2021
Conventional Vis-braking
• Produces maximum of fuel oil of
suitable viscosity & pour point and
minimum of neptha from atmospheric
residue, vaccum residue and other
heavy feed stock
• Simplified flow diagram is attached.
• Feed is preheated to a temperature of

about 340ºC by heat exchange with
products and heated to 470-490ºC in
furnace.
• Sufficient residence time is given in

furnace.
• Furnace effluent is quenched by

visbroken residue (VR) to arrest further
reactions.
• Gas, neptha and light gas oil are

recovered from top section of
fractionator. VR is taken out from the
bottom.
• Neptha is debutanized in stabilizer and

gases are sent to refinery fuel system.
• The gas oil stream is extremely blended

with VR to obtain suitable fuel oil that
meets viscosity specifications.
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• At constant feed rate, the extent of

cracking increases with increase in
furnace outlet temperature.
• Resulting in viscosity reduction of VR

along with increased production of gas,
neptha and gasoil. Coke lay down in
tubes is also increased.
• Circulating reflux and top reflux in

main fractionator have to be increased
to maintain product quality.
• A high pressure supresses vaporization

and tends to produce a liquid phase and
yield of gas oil is more.
• Severity of visbreaking operation

decreases with increase in the feed rate
for same furnace temperature.
• Furnace temperature can be decreased

with feed rate to maintain same
viscosity of VR.
• A type of feed stocks having colloidal

asphaltene particles which are non-
volatile and very difficult to crack
thermally.
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14-04-2021
• Another type of feed stock having volatile heavy hydrocarbons which are easily
cracked thermally and a portion of which acts as a peptizing agent to hold asphaltene
in colloidal suspension.
• During visbreaking, heavy hydrocarbons are thermally converted into low boiling
compounds. Thus, concentrating asphaltenes in unconverted residue. If the
visbreaking reaction proceeds too far, asphaltenes precipitate from oil to form deposit
in furnace and produce VR residue unsuitable for sale as fuel oil.
• Feedstock having higher asphaltenes content and higher viscosity require more severe
operation for obtaining same viscosity of finished fuel oil.
• Typical operating conditions: Furnace inlet pressure = 22 kgf/cm2, Furnace outlet

pressure = 15 kgf/cm2, Residence time = 10 min, Fractionator pressure = 5 kgf/cm2,
Fractionator temperature range = 138-360ºC
Typical yield pattern: Gas including losses = 3 wt%, Neptha = 4 wt% and Fuel oil
(Vis-broken residue) = 93 wt%
Decoking of furnace tubes

• Production of olefinic compounds
• Polymerize to form coke and deposition on tube
• Severity determined by temperature and residence time
• Shutdown the unit for decoking
• Skin temperature of tubes (> 600°C) in radiant section
• Pressure drop through furnace coil
• Spalling of furnace tubes by steam injection (80-90% coke removal)
• Burning of furnace tubes with help of steam and air
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14-04-2021
Conventional Soaker Vis-braking

• A soaker drum is added between
furnace and fractionator
• Soaker run length = 50-300 days
• Increase in residence time in order to
improve conversion at lower furnace
outlet temperature
• Smaller furnace, lower capital
investment (10-15%)
• Lower waste heat recovery equipment
• Lower fuel consumption (30-35%)
• Better or more selective yields
Coking Process
• More severe form of thermal cracking
• Feed stock is a residual which may resist cracking by other means.
• Sometimes, used as a less expensive way to get more light distillates from crude oil
• Recently, used for increasing production of diesel oils and to produce low sulphur Petroleum
coke
• Coke can be used in manufacturing of electrodes and aerospace compounds, if feed to coking
has low S and metal contents.
• Mechanisms for coke formation
1. De-alkylation of straight chain compounds and CH2 groups from high molecular weight
compounds (asphaltene and resin), to form highly disordered structured C
2. Dehydrogenation of heavy oils, forms some disorder crystalline coke of superior quality
• Different coking processes: Delayed coking, Fluid coking, Flexicoking, etc.
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14-04-2021
Delayed Coking
• Feed is preheated before enter to column.
• Feed contacts heated vapours in column and
light component are flashed off.
• Heating in furnace: 480-515°C
• All cracking occurs over extended period
(24 hours) in a coke drum.
• Resulting in high gas/ liquid yields and
coke formation
• Coke drum temperature: 415-460°C
• Two coke drums (chambers): Used for coke
accumulation and hydraulic decoking
• Typical size of coke drums: Diameter = 4.5-
8.5 m, height = 25-35 m
• Sufficient residence time in coke drum

• As coke level builds up in first drum flow
diverted to second drum.
• Two day cycle for filling and decoking
• Coke drum is depressurized and steamed out
to strip uncondensed vapours.
• Coke drum is finally cooled with water and
opened at top and bottom.
• Coke cutting with high pressure (135-275
kgf/cm2) water jets
• At lower coke drum temperature, soft coke
forms and vice verse.
• Trend is to produce coke with 6-8 wt%
volatile combustible material (VCM), harder
coke
• Higher drum pressure leads to decrease in
heavier liquid yields and increase in coke
and gas yields.
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14-04-2021
• Feed stock characteristics such as carbon residue, °API, asphaltene, resin and oil contents,
boiling range and contaminants (Such as sulphur, nitrogen, oxygen, ash and metal) affect coke
yield.
• Hydro treating of feed stocks significantly change coke yield.
• Fractionator temperatures range: 150-350°C
• Fractionator pressure: 1.4-3.4 bar
• Typical yield of coke in different untreated delayed coker: 21.6 - 44.3%
Catalytic Conversion Processes

• Catalytic processes which change the carbon number (e.g. Catalytic cracking,
hydrocracking and polymerization), change the C/H ratio (Hydrogenation and
dehydrogenation) or which do neither of above two (catalytic isomerization)
• In some cases, some other substances (promoters) are added to improve catalytic
processes.
• The name of catalyst depends on the process where it is to be used. (e.g. reforming
catalyst)
• Catalysts can participate in process industries in stationary (fixed bed) or moving

bed (circulating) state.
• They gradually loose their activity and selectivity owing to ageing.
• Catalysts can be regenerated by heating.
6
14-04-2021
Fluid Catalytic Cracking

• Used for conversion of heavy gas oils to LPG, gasoline,
olefin rich light hydrocarbons which may be further
processed to more valuable products and fuel oils
• Operated either of processing objectives
• Maximization of middle distillates
• Maximization of LPG and gasoline
• Low pressure, intermediate to high temperature process
• Reactor and regenerator, connected by U-tube
• Hydro treating of FCC feed reduces S, N, metal contents.
• Removal of N prevents deactivation of acidic sites.
• Reduction of metals (V, Ni) minimizes dehydrogenation
reactions and formation of coke.
FCC Process
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14-04-2021
• Catalyst used is fine powder made of alumina and silica. Catalyst is kept fluidized with
steam, vapour and air.
• Hot regenerated catalyst mixes with fresh feed at bottom of the riser. Vaporized feed enters
at temperature of 470-540°C.
• Hydrocarbons vapors begin to crack. Catalyst and vapours rises in reactor.
• Reactions proceed through formation of carbonium ions, either by removal of H− or by
addition of H+ in presence of acidic catalyst.
• Undergo a number of reactions which include isomerization, C-C bond scission, hydrogen
transfer and termination
• Reactivity order:
Substituted aromatics < Paraffins < Polymethyl aromatics < Nephthenes < Alkylbenzens <
Olefins
• Cracking reactions are accompanied by a heavy coke lay down on catalyst.
• After steam stripping, spent catalyst is passed to regenerator. A steam stripping zone is
provided to prevent entrainment of valuable hydrocarbons from reactor to regenerator.
Cyclone separators are also used to remove vapour from catalyst.
• Regeneration of catalyst by burning of coke. Flue gas from regenerator is removed by

cyclone separators. Decoked catalyst flows back from regenerator to reactor and
cycle restart again.
• FCC units are called heat balanced when the heat generated in regenerator is equal to
heat required in reactor. This avoids need to install cooler in regenerator and feed
preheater before reactor.
• In the reactor, severity of cracking can be maintained by catalyst bed level and feed
rate. A required level of catalyst is also maintained in regenerator.
• Clarified oil is bottom product from fractionator contains catalyst fines also.
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14-04-2021
Effects of different parameters in FCC operation

• Increase in reactor temperature (at constant conversion) will increase lighter products
yields, olefins in liquid products.
• Reactor temperature can be varied by feed temperature and catalyst recirculation

rate.
• Increase in catalyst level will increase conversion, decrease in gasoline yield,

increase in coke yield, increase in regenerator temperature, etc.
• Effect of reactor pressure is small. Increase in reactor pressure will increase

temperature and conversion.
• Sometimes it is desired to recycle part of product (mainly cycle oils) in order to

increase the gasoline yields. This is determined by combined to fresh feed ratio.
• Increasing the recycle temperature is also one of the method of increasing

temperature of combined feed.
• An increase in catalyst circulation rate has an adverse effect on regeneration.
• An increase in °API gravity of feed will crack more easily.
• An increase in average boiling point of the feed will crack more so that either
conversion will increase or a decrease in reactor temperature will be possible.
• An increase in carbon residue of feedstock will generally result in an increase in

regenerator temperature.
• Metallic poisoning in feed results in increase in quantity of hydrogen and olefin in

total products. The most valuable measure of extent of metallic poisoning is ratio of
hydrogen/methane in total products.
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• S is undesirable in FCC feed stock as it causes corrosion of processing equipment.
• Water content in feedstock should be below 0.2 vol % to prevent shocks and
vibrations in feed lines resulting from flash vaporization of water drops.
Catalytic Reforming
• Employed to reform low octane naphtha into premium quality motor fuels
• To produce high yield of aromatics, high quality aviation gasoline and LPG
• Feed to reformer: normal and branched paraffin, nepthenes and aromatics but no
olefins of C5 to C12
• Several competing reactions during reforming:
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• Reactivity decreases with decreasing C number for each hydrocarbon.
• Dehydrogenation of cyclohexane homologs (Reaction 1) is very rapid.
• De-hydro-cyclization of paraffin (Reaction 2) is slowest of aromatic forming reactions.
• De-alkylation and trans-alkylation, which occur to a minor extent, determine the final
distribution of aromatic products.
• Increase in temperature increases both aromatization and hydrocracking reactions but

hydrocracking to a greater extent.
• An upper limit of 520°C is set to avoid excessive hydrocracking or coke formation over
catalyst.
• Pressure increases hydrocracking and decrease aromatization reaction.
11
14-04-2021
Figure: Process flow diagram of catalytic reforming process

(Typical yields: Reformate = 93%, Gas + loss = 7%)
Parameters affecting reforming

• Aromatization reactions are most desirable in process of catalytic reforming.
• Space velocity: A low space velocity results in severe hydrocracking and fast coking.
A higher space velocity results incomplete desired reactions. A change in flow rate
has a much small effect on aromatization but a larger effect on hydrocracking.
• Hydrogen recycle: It prevents coke formation on the catalyst. Higher hydrogen

recycle to feed ratio is not harmful but result in wastefulness of equipment and
higher pressure drop.
• Higher reactor inlet temperature, lower reactor charge rate, lower reactor pressure
will increase severity of reforming.
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• Hydrocracking is not desirable reaction but if the feedstock is heavy and more of
paraffinic nature, then mild hydrocracking could be allowed to attain desired
severity.
• Sulphur, nitrogen, oxygen compounds if present in reformer feed act as catalyst

poisons.
Hydro-Processsing
Types
• Hydrogenation
(The chemical reaction of hydrogen with another substance, especially with an
unsaturated organic compound and usually under the influence of temperature,
pressure and catalysts)
• Hydro-cracking
(The production of high octane petroleum fuel and kerosene by hydrogenating large or
complex hydrocarbons and then cracking them)
• Hydro-treating
(A chemical engineering process in which reaction with hydrogen is used to remove
impurities, especially as part of oil refining.)
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Hydro-cracking
• Feedstock: Any fraction from naphtha to asphalt
• Products: Lighter than feedstock
• Complete saturation of olefins and removal of S, N, O from feed stock
• The hydrocracking of vacuum gas oils to high quality lubricating oil base stocks is an
important application of the hydrocracking.
• Carbon to carbon bonds in paraffins are broken and the fragments are hydrogenated
to form two or more lower molecular weight paraffins.
• The polycyclic aromatics are partially saturated and ring opening in one or more
places follows at least one ring is usually retained.
• Stable products from hydrocracking as compared to catalytic cracking
• Higher operating cost than that of a catalytic cracker and more difficult from
maintenance point of view
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14-04-2021
• Selection of the catalyst is governed by type of feed used, product desired, operating
conditions of the process and contacting pattern of the reactant.
• Catalysts are made of alumina, silica in different proportions and with acid function.
The hydrogenation function is provided by tungsten oxide or nickel oxide.
• Can be single stage or multi stage (See figure given)
• Operating pressure: 3.5-20.8 MPa, temperature: 260-427°C
Figure: Process flow diagram of hydro-cracking process
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Catalytic Alkylation
• Catalytic process used to upgrade light olefins (from catalytic cracker, cocker and
vis-braker) into highly branched paraffin (Alkylate)
• Alkylate: Blending component for making gasoline
• Reaction of iso-butane with light olefin in presence of an acid catalyst
• Some impurities in feed (e.g. mercaptans, butadiene, etc.) form acid soluble
compounds and increase acid make-up requirements.
16
16-04-2021
Catalytic Alkylation
• Catalytic process used to upgrade light olefins (from catalytic cracker, cocker and
vis-braker) into highly branched paraffin (Alkylate)
• Alkylate: Blending component for making gasoline
• Reaction of iso-butane with light olefin in presence of an acid catalyst
• Some impurities in feed (e.g. mercaptans, butadiene, etc.) form acid soluble
compounds and increase acid make-up requirements.
• Reaction scheme
1
16-04-2021
• Similar reactions can be see with other olefins.
• Undesirable reactions
H2SO4 Alkylation Process-Time Tank Process

• Chillers used for removal heat of
reactions
• Average hydrocarbon residence

time = 20-30 Min.
• Caustic and water wash: to remove

acid and ester in hydrocarbon phase
• Circulation time: 1-2 Min.
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16-04-2021
Catalytic Isomerization Process

• Used to convert n-butane to i-butane, which may be further alkylate to liquid
hydrocarbons in range of gasoline
• Also used to convert relatively low octane parffins (mostly C5 and C6) into more
desirable isoparaffins which have higher octane number
• Mild exothermic reactions
• Reaction in hydrogen environment to prevent coke formation over catalyst
UOP Butamer Isomerization Process
• One type of catalytic

isomerization process
• Feed: Mixed butane
• Pt catalyst reactor
• Dissolved gases and

break down products
separation in stabilizer
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Catalytic Polymerization
• Process in which two or more molecules combine to produce single larger molecule
• Used to convert light olefins (e.g. propene and butene) into high octane number
gasoline component (Polymer gasoline)
• Can also be used for alkylation of aromatics with olefins to form cumene, ethyl
benzene, etc.
• Most often carried out in presence of solid phosphoric acid supported on kieselguhr
• Impurities such as sulphur compounds and ammonia present in feed, are to be

removed out by washing with alkanol-amines
• Exothermic reaction
• Scheme for dimerization (Polymerization) of propene
4
16-04-2021
• Water injection at feed to

maintain hydration of
phosphoric acid catalyst
• Increase of reactor
temperature above 200°C
promote formation of di-
olefins and deactivation
of catalyst
• Injection of cold propane

as quench in reactor
Figure: UOP catalytic polymerization process
Thanks
5
19-04-2021
Chapter
Finishing Processes
Introduction
• Different contaminants found in most refinery products before their finishing (See
table)
Table: Major contaminants of distillates and their effects
• Finishing processes: Secondary refining processes which are necessary to make the
petroleum products suitable for use with respect to performance, corrosivity,
suitability on storage, odour, etc.
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19-04-2021
• Some of these effects can also be eliminated by proper use of additives (e.g.
antioxidants, metal deactivators, etc.)
• Types of finishing processes

• Sulphur conversion processes
• Sweetening process
• Solvent extraction processes
• Hydro treating processes, etc.
Sulphur Conversion Processes

• Processes used for conversion of sulphur impurities into their useful forms (e.g. elemental S)
Classified in three different categories as:

1. Dry oxidation of H2S to sulphur and water: Claus process is one of the basic type of dry
oxidation process to convert H2S to elemental sulphur. This is most widely used in
refineries.
2. Wet oxidation to sulphur and water: Primarily used for H2S removal in sulphur recovery
and tail gas treating applications when both concentration of H2S in gas stream and sulphur
production tonnage are low.
3. Thermal cracking of H2S to sulphur and hydrogen
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19-04-2021
Claus Process • Consisting thermal stage

followed by two or three
reactor stages
• Thermal stage: Includes

reaction furnace, waste heat
re-boiler and condenser
• Reaction involved
3H2S + 3/2 O2 →
2H2S + SO2 + H2O
Exothermic reaction and
temperature reach up to
Figure: Process flow diagram for Claus process 1200ºC in the stage.
• Catalytic stage: Consisting

feed heater, catalyst bed and
condenser
• In this stage gases reheated

to 200-260ºC before
passing to reactor
containing bed of bauxite
catalyst.
• Reaction involved
2H2S + SO2 →
3/n Sn + H2O
Figure: Process flow diagram for Claus process
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19-04-2021
• For maximum sulphur

recovery, H2S to SO2 mole
ratio of 2:1
• Sulphur recovery efficiency

for three catalytic reactor
stages with rich acid-gas
feed is about 96-97%.
Figure: Process flow diagram for Claus process
Thermal Cracking of H2S

• Can be integrated with existing Claus sulphur plants
• A portion of H2S acid-gas stream (As much as 25% of total H2S) is fed to cracker to
form H2 and S.
• Energy required for cracker is supplied by sending remaining portion of feed H2S to
conventional Claus furnace and recovered energy from that.
• H2 is separated and can be reused in hydrodesulphurization.
• Separated S and uncracked H2S are recycled to Claus process.
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19-04-2021
Sweetening Processes
• Organic S contaminants mostly found in petroleum products: Alkyl and aromatic
mercaptans (R-SH)
• Cause foul odour, corrosion to metals, oxidative deterioration of various additives

(e.g. TEL)
• Sweetening processes are used to reduce S contents (mostly mercaptans) from

different naphtha products (e.g. gasoline).
Types of sweetening processes

1. Process which removes mercaptans but do not affect materially other sulphur
compounds (e.g. Caustic scrubbing, merox extraction, solutizer process and unisol
process, etc.).
2. Processes which convert mercaptans to disulphides (e.g. Doctor sweetening, PbS

sweetening, merox sweetening and copper chloride sweetening, etc.).
3. Processes which remove some or all of different types of S compounds (e.g. Acid
treating, clay treating, catalytic processes and sodafining, etc.).
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Caustic Treatment
• Caustic treating of petroleum products is as old as the industry itself.
• This uses non-regenerative caustic wash.
• Used for removal of hydrogen sulphide in low concentration, naphthenic acids, aryl
mercaptans, alkyl phenol from C4, C5 and naphtha feed
• Calcium, ammonium and sodium hydroxides (being by far the most widely) are used.
• Has no competition in C4, C5 treating but not too satisfactory on heavier stocks
Merox Processes
• Efficient and economical catalytic process to remove mercaptans (Merox extraction)
or to convert them into di-suphides (Merox sweetening)
• Used for liquid phase treating of LPG, Natural gas liquids, naphtha, kerosene, jet
fuels and heating oils
• Extraction and sweetening can be used singly or in combination depending upon the
type and content of mercaptans in the feed and finished product specification.
• Based on ability of a catalyst to catalyse the oxidation of mercaptans to disulphides in

alkaline medium at ambient temperature using air
• Merox catalyst: Sulphonated derivate of Cobalt phthalocynine complex
6
19-04-2021
• Mild caustic wash of feed before Merox processes, to remove H2S, lower mercaptans
and acidic catalyst toxins
• Overall reaction
2RSH + ½ O2 → RSSR + H2O
Merox Extraction
• Used to extract lower mercaptans from
gases, LPG and light naphtha fractions
• Low molecular weight mercaptans are

soluble in caustic solution.
• Mercaptans are extracted by

countercurrent caustic stream.
RSH + NaOH ↔ RSNa + H2O
Figure: Process flow diagram
7
19-04-2021
• Forward reaction is favoured by low

temperature, low molecular weight of
mercaptans and high caustic
concentration.
• Treated product passes overhead.
• Regeneration of caustic
RSNa + ¼ O2 + ½ H2O →
NaOH + ½ RSSR
Figure: Process flow diagram
8
26-04-2021
Doctor Treating Process

• Found to be suitable for treating light
and heavy naphtha at all mercaptan
contents and for treatment of sour
gasoline
• Mixing of feed and doctor solution

(Mixture of sodium plumbite
(Na2PbO2) and caustic soda) in mixer-1
• Formation of lead mercaptide in

Mixer-1:
2RSH + Na2PbO2 → Pb(SR)2 + 2NaOH
• A stream of naphtha containing

dissolved S is then mixed.
Pb(SR)2 + S → PbS + R2S2
• Regeneration: PbS + NaOH (excess)

+ (1/2)O2 → Na2PbO2 + S + H2O
• Controlled addition of S to avoid

polysulphide formation and not to
increase S amount in end product
• Very versatile process but disadvantage

of controlling polysulphide formation
1
26-04-2021
• Depressant effect of polysulphides on

octane nurnter, TEL susceptibility, gum
content and colour stability
Copper Chloride Sweetening

• Used to sweeten gasoline/ kerosene
• Direct oxidation of mercaptans to

di-sulphides using CuCl2
• Moisture removal by dehydrated

salts like CaCl2
• Feed heated to 40-60°C
• Reactions involved:
2RSH + CuCl2 → (RS)2Cu + 2HCl
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26-04-2021
(RS)2Cu + CuCl2 →
RSSR + Cu2Cl2
Cu2Cl2 + 2HCl → Cu2Cl2.2HCl
Cu2Cl2.2HCl + ½ O2
→ 2CuCl2 + H2O
• Water washing in settler 3
• Advantage: Absence of formation

of higher alkyl polysulphides
• Disadvantage: Corrosive nature of

CuCl2
Merox Sweetening
• Liquid-liquid sweetening
• Applicable for straight run and

cracked naptha feed
• Reaction involved:
2RSH + 2NaOH → 2RSNa + 2H2O
2RSNa + ½O2 + H2O →
2NaOH + RSSR
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26-04-2021
• Higher boiling products require

more mixing
• Fixed bed sweetening used for

heavier feeds
Catalyst Desulfurization
• All fraction lighter than diesels can be feed.
• Conducted at higher temperature (≤ 400°C)
• Vapour phase reaction
• Catalyst-Natural bauxite
• Provide 90-95% S removal
4
26-04-2021
Solvent Extraction Processes

Edeleanu Process
• Kerosene requires desulphurization as well as removing of aromatics (Smoke
causing).
• Maximum to 20% aromatics in kerosene
• Removal of aromatics from kerosene by liquid SO2 extraction (Edeleanu) process,
leading to enhanced burning properties
• This method is also applied to selected naphtas.
• Normal boiling point of SO2 = −10°C
• Aromatic and unsaturated hydrocarbons are completely miscible in SO2.
Edeleanu Process
• Feed is passed through rock salt
bed at 40-45°C to remove traces
of water.
• Then, deaerated in vaccum

column
• Cooling to 10°C in coolers and

drying in CaCl2 driers
• Further chilled to -15°C and sent

to extractor
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26-04-2021
• Chilled SO2 feed at −26°C
• Water and caustic wash to

remove and neutralize traces of
SO2 in final extract and raffinate
• Further water wash for caustic

removal
Different Solvent Extraction Processes

Udex Process
• Used for removal of benzene, toluene, ethyl benzene, xylenes and heavy aromatics
from straight-run naphthas or from reformed naphthas rich in aromatics
• Uses concentrated aqueous solution of di or tri ethylene glycol as the extraction
solvent
Sulfolane Process
• Used for production of high purity toluene, xylenes, high-octane aromatic
concentrates, jet fuel components and specialty solvents of closely controlled
aromatic contents by extraction of suitable feedstocks
• Also applicabie for de-aromatization of naphthas for producing food-grade hexane
solvent
6
26-04-2021
• Uses sulfolane as the extraction solvent

• Favourable selectivity, excellent solvent power, high specific gravity, low heat
capacity, relatively high boiling point and good stability
Hydro-treating Process
Applications
• Reduction of sulphur in the feed to the catalytic reformer (Low octane naphtha)
• Desulphurization of naphtha, kerosine, gas oils and fuel oils
• Improvement of colour, odour, oxidation stability of lubricating oil base stocks and
waxes
• Mild hydrogenation of aromatics into naphthenes in streams like high aromatics
kerosines and gas oils to improve smoke point and cetane number, respectively
• Hydrogenation of olefinic streams produced from thermal cracking process
7
26-04-2021
Hydro-treating reactions:
• De-sulphurization
RSH + H2 → RH + H2S
R1SR2 + 2H2 → R1H + R2H + H2S
R1SSR2 + 3H2 → R1H + R2H + 2H2S
• De-nitrogenation
• De-oxygenation
• Olefin saturation
CH3CH2CH2CH2CH2CH=CH2 + H2 → CH3CH2CH2CH2CH2CH2−CH3
8
26-04-2021
Hydro-treating process for distillate desulphurization
• Feed mixed with recycled H2 gas

• Fixed-bed Reactor
• Higher partial pressure of H2 in the
reactor
• Reactor temperature: 175-450˚C
• Catalyst used: Co-Mo, Ni-Mo, Ni-Co-
Mo over alumina/zeolite support
• Liquid product from high pressure
separator to low pressure separator
• Light gases are stripped off in low P
separator
Thanks
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06-05-2021
Petroleum and Petrochemicals
Chapter
Lube Oil Manufacturing Processes
Introduction to lube oil manufacturing

• Manufactured by mixing of the
selected lube oil base stock and
additives
• Lube oil base stocks are produced

from heavy waxy distillate fractions
obtained from vacuum distillation
of atmospheric residue.
• Straight run vacuum distillate

fractions require further treatment
up to desired specifications.
• Schematic diagram (See figure)
1
06-05-2021
• Solvent deasphalting unit: To

remove asphalt
• Solvent extraction unit: To

remove undesirable naphthenic and
aromatic hydrocarbons to improve
viscosity index of lube oil
• Solvent de-waxing unit: To

remove wax content to improve
pour point
• Hydro-finishing unit: To improve

colour, oxidation stability
Solvent Extraction from Lube Oil Base Stocks

• Method of removing aromatics and other undesirable constituents from lube oil
fraction
• To improve viscosity index, thermal stability, oxidation stability, inhibition response
of lube oil base stock
• Most common commercial solvents used: Furfural, Phenol and N-methyl-2-
pyrrolidone (NMP)
Selection criterions of a good extraction solvent

• Selectivity for undesirable component
• Good solvent power (low solvent to feed ratio)
• Easy to recover
• Stable to avoid chemical and thermal degradation
2
06-05-2021
• Non-corrosive
• Non-toxic (Environmentally safe)
• Reasonable cost, etc.
• Comparison of extraction solvents
• Furfural: Best choice solvent, low toxicity, low cost, availability, history of
commercial experience, adaptability to extraction of gas oils, etc.
• Phenol: Suitable for paraffinic base lube stocks which require high extraction
temperatures
3
06-05-2021
Furfural Extraction Process

• Used to remove aromatics and
other undesirable constituents
from lube oil fraction
• Rotating disc contactor
• Removal of furfural from

raffinate phase by flashing and
steam stripping under vacuum
• Extract phase recovery contains a

double effect evaporator system.
• Wet and dry furfural layer
• Furfural fractionator
• Azeotrope of furfural and water

as overhead product of
distillation column
• Decanter
• Furfural stripper
• Azeotrope of furfural and water

as overhead product of water
removal column
4
06-05-2021
Hydro-finishing Process
• Stabilizes the undesirable oil

components (S, O, N, etc.) by
catalytic hydrogenation
• If not removed, would effect
corrosion, de-emulsification number,
colour, oxidation stability, etc.
• Catalyst: Co-Mo, Ni-Mo, Ni-Co Mo
over alumina
• Reactor temp.: 280-340°C
• High pressure separator (H removal)
• Low pressure separator (H2S
removal)
• Steam stripper
Manufacture of Petroleum Wax
• Manufactured from deoiling of petroleum wax concentrate (slack wax) which is a by product
in de-waxing of lube stock
• Slack wax: having less than 30% oil, soft wax and hard wax
• Methods of de-oiling of slack wax: Wax sweating, solvent de-oiling
• Wax sweating: Process of drainage, fractional fusion and solution, Complicated batch process
• Solvent deoiling is in current trends and economical for large scale units. Ketone deoiling
continues to be the most widely used process today.
• In recent years, MIBK (Methyl iso-butyl ketone) is widely practiced as deoiling solvent.
5
06-05-2021
Solvent Deoiling Process
• Feed: Slack wax along with

recycle filterate
• Solvent to fresh feed ratio:2
• Solvent dissolves the oil
and soft wax.
• Primary and Secondary
filters, filteration rate
important parameter
• Filteration temperature:
10°C, marked effect on
plant economics
• Crystallization and
repulping
• Steam stripper
Finishing of wax
• Low oil content waxes from deoiling are generally yellow in colour with strong smelland
darken rapidly from light.
• Particularly, food packaging and preservation uses waxes, subjected to a finishing operation
to improve colour, oxidation stability, odour, FDA purity, etc.
• Finishing eliminates S, N, O and impurities of intermediate nature
• Conventional finishing process: Clay or bauxite treatment or a combination of acid and clay
treatment
• Hydro-finishing process: Treatment with H2 gas in fixed bed catalytic reactors
6
06-05-2021
Thanks
7
23-06-2021
Chapter
Petrochemicals
Introduction to Petrochemicals Industry

• Petrochemicals are an indispensible part of our life and are providing key feedstock
to chemical industry for making thousands of different chemicals (Rubber,
polyethene, etc.) which people usually encounter as end products.
• An increasing demand of growing population and limited resources like coal, cotton,
jute, wood, natural rubber, molasses, and alcohol based chemicals, etc. has resulted in
higher production of synthetic chemicals, derived from petroleum, as a substitute of
natural resources.
• Petrochemical linked industries: Packaging, agriculture, telecommunication,

construction, home appliances, health care, personal care, textile, tyre,
pharmaceuticals, explosives, etc.
• List of chemical feed stocks are given in figure 1.
1
23-06-2021
Figure 1: Chemical feedstock sources
Table 1: Petrochemical social linkage
• Increase in demand of plastic and rubber after world war II, led to rapid growth of
petrochemicals.
• Around 95% of organic chemicals are based on petrochemicals.
• Petrochemical industry is highly technological and capital-intensive.
2
23-06-2021
Figure 2: Structure of petrochemical complex
Figure 3: Petroleum and petrochemical interface
3
23-06-2021
Figure 4: Overall view of petrochemical complex
Olefins Production
• Important olefins produced: Ethylene, Propylene, Butadiene, etc.
• Major building blocks for petrochemicals due to their reactivity and versatility
• Applications areas: In manufacture of polymers, chemical intermediate, synthetic

rubber, etc.
• Major technologies for olefin productions: Steam cracking, Fluid catalytic

cracking, Oxidative coupling of methane, Catalytic dehydrogenation, Deep catalytic
cracking, methanol to olefin technology, etc.
4
23-06-2021
Steam Cracking for Production of Olefins
• Steam cracker in petrochemical complex produces large number of products other

than light olefins, as butane, isoprene, pyrolysis gasoline, etc.
• Various feed stocks used in steam cracker: Naphtha, natural gas liquid, gas oil,
ethane, propane and ethane-propane mixture
• Cracking reaction temperature: 700-900°C (Depending on type of feed stock)

• Choice of feedstock depends on its availability and range of downstream production.
• Olefins plants are complex as well as costly and both increase with increase in
heaviness of feed.
• Still, heavier feedstock is gaining importance because of more production output
from it.
Naphtha/NGL Cracker Unit
5
23-06-2021
Hot Section of Cracker

• Feed is preheated by quench water and steam before entering to furnace.
• Further, preheated and mixed with super heated steam (as diluent) in furnace.
• Steam minimizes the side reactions responsible for formation of coke, improves the
selectivity to produce desired olefins by lowering partial pressure.
• Lighter feedstock required less steam as compared to heavy one.
• Temperature of radiant section of furnace = 650°C
• Residence time = 0.15-1.2 S
• Indirect and direct quenching to control the reaction
6
23-06-2021
Cracked gas compression and dehydration

• Top effluent from primary fractionator to multi-stage compressor
• Gas before final compression stage is de-suphurized and CO2 removal through
caustic scrubber.
• This removal also avoids corrosion and formation of CO2 ice in cold section at later
stage.
• Cracked gases are dried in dehydrator before entering cold section.
Cold section
• Dried cracked gas is cooled to −165°C in cascade refrigeration system.
• Cold section contains demethanizer, deethanizer, acetylene hydragenation unit,
ethylene separation, depropanizer, C3 hydrogenation and debutanizer.
7
23-06-2021
• Feed temperature to deethanizer = −10°C

• Acetylene hydrogenation unit: Pd Catalyst, 40°C temperature
• Ethylene separator: Distillation column at −35°C
• Debutanizer: Pyrolysis gasoline is important source of gasoline.
Aromatic Production
• Important (aromatic) petrochemicals generally produced: Benzene, toluene and
xylene (BTX), ethyl benzene, etc.
• Products which use above basic aromatics as one of the raw materials: Synthetic
fibres, elastomers, explosives, pesticides, dyes, detergents, resins, etc.
• Major sources of benzene: Catalytic reformer, pyrolysis gasoline from steam cracker,
toluene disproportionation and coal
• Major sources of xylene: Catalytic reformer, pyrolysis gasoline from steam cracker,
toluene disproportionation
8
23-06-2021
• Catalytic reforming: Converts low octane naphtha (BP in range of 60-180°C) to high
octane gasoline and aromatics rich in BTX
• Steam cracking of naphtha: Produce liquid product (pyrolysis gasoline) rich in

aromatics containing about 65% aromatics about 50% of which is benzene.
• Toluene disproportionation: Conversion of toluene in benzene and xylene
• Coal carbonization (Coke oven plant): Heating of coal in absence of air, light oil is
obtained as by product which contains 2-8 kg benzene, 0.5-2 kg toluene and 0.1-0.5
kg xylene per tonne of coal
9
23-06-2021
Derived Polymers
• Polymers: Material of choice due to their versatility, their physical and chemical
strengths, lightness in weight, chemical and corrosion resistance, economic viability,
easy processability, attractiveness and durability in all weather conditions
• Uses:
• Elastomers
• Plastics
• Fibres
• Surface coatings
• Adhesives, etc.
10
23-06-2021
• Polymers are produced by intermolecular reaction of molecules having a

functionality of two or more.
• Thermoplastic market: 10% of global chemical industry (Olabisi, 1997)
• Poly-olefins: Largest group of thermoplastic polymers (e.g. LDPE, LLDPE, HDPE,

Polypropylene)
• Major success factors of poly-olefins: Easy accessibility, reasonable raw materials,

low production cost, non-polluting processes, resource saving products,
environmentally safe products, energetically exploitable after usage, broad product
portfolio, etc.
Polyethylene (PE)
• Largest volume thermoplastic resin in the world with growth rate of 3-5%
• Second largest commodity player used in India, after PVC
• Applications: Packaging, foam, insulation, containers, toys, car parts, etc.
• Major types of PE: LDPE, LLDPE, HDPE, metallocene polyethylene
• LDPE (Low density polyethylene): Prepared by high pressure using tubular or
stirred autoclave reactors
• LLDPE (Linear low density polyethylene), HDPE (High density polyethylene):
Prepared at low pressure in fluidized beds in presence of suitable catalyst
• LLDPE offers improved tensile strength, puncture resistance, higher elongation,
exceptional draw down, improved stress crack resistance, low temperature
brittleness.
11
23-06-2021
Union Carbide (HDPE and LLDPE) Process
• Gas phase using fluidized bed reactor

• Bed consists of catalyst plus newly
formed and growing PE
• H2 to control molecular weight
• High gas recycle rate with conversion to
PE of about 2% per pass only
• Single stage compressor
• Granular product flows intermittently into
discharge tank where unreacted gas
separates and return to reactor.
• Hydrocarbon remaining with product are
removed by purging with N2.
BTX Derivatives
• Benzene, toluene and xylene (BTX) and Ethyl benzene: Major feedstock for large
number of intermediate which are used in production of synthetic fibres, resins,
synthetic rubber, explosives, pesticides, detergents, dyes, intermediates, etc.
• Major application of Benzene: A source of styrene, alkyl benzene, cumene, large
number of aromatic intermediate and pesticides, etc.
• Major application of Toluene: A major solvent, manufacture of benzoic acid, chloro
derivatives, nitro toluene, toluene sulphonic acid, benzaldyhyde, etc.
• Major application of p-Xylene: Feed stock for DMT/TPA,
• Major application of o-Xylene: Manufacture of Phthalic anhydride
• Styrene: Versatile monomer exclusively used for manufacture of plastic including
polystyrene (PS), expandable polystyrene (EPS), acrylonitrile butadiene styrene
copolymer (ABS), Styrene acrylonitrile resin (SAN), Styrene butadiene rubber
(SBR)
• Above derivatives account for 75-80% of total styrene consumption.
12
23-06-2021
Manufacture of Polystyrene
• Important thermoplastic having
wide application: In consumer
durable goods, electronics,
packaging, toys, structural foams,
wall tiles, shoe soles, lenses,
bottle caps, wire and cable
sheathing, automobile interior
parts, etc.
• Properties: Inexpensive, hard,
rigid and transparent, easily
coloured, moulded and fabricated,
good electrical and moisture
resistance, low moulding
temperature
• Suspension polymerization
process
• Agitation catalyst and

chain transfer agents are
also added in reactor.
• Polymerization reaction is
controlled by temperature
and chain transfer agents.
13
23-06-2021
Thanks
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12-03-2021

• Modern petroleum refining began in 1859 with discovery of petroleum in

• As a result of technological development and rise in demand of petroleum and

• A standalone refinery configuration in present context will have

Chemistry of Crude Oil

• Natural organic material, composed principally of hydrocarbons in geological traps

• Its structure and composition varies according to its source

• Composed from hydrocarbon and/or sulphur, nitrogen and/or oxygen derivatives of

• Accompanied by extraneous quantities of different substances (e.g. water, inorganic

• C/H ratio = 6-8

• Wide range of physical and chemical properties (See table attached)

• Light crude oil: brown colour, pleasant (aromatic like) smell

• Specific gravity = 0.73-1.02, mostly 0.80-0.95

Table: Typical properties of crude oils

Composition of Crude Oil

• Naphthenic acids, complex nitrogen compounds and mercaptans account for O, N

• Resinous and asphaltic substances for O and S

• Dissolved H2S for inorganic sulphur

• Traces of metals in water impurities and some as complexes in hydrocarbon phase

Transportation of crude oil & finished products

Pipeline Transportation of Crude

Problems in pipeline transportation of crude

• If temperature of oil is decreased, the solubility of heavy hydrocarbons may be

• This changes flow behaviour to Non-Newtonian, increases energy consumption for

• Wax deposit in pipelines can lead to increase in pipeline roughness, reduction in

• Requires accurate prediction of wax formation and insulation requirements at early

Methods for pipeline transportation of waxy crude oils

• Use separate low flow, high head pumps for restarting

• Reverse pumping which prohibits static cool down

• Use of pour point depressants/ flow improvers

• Injection of water to form a layer between pipe wall and crude

• Combination of any of above methods

World Petroleum Resources

• Self-sufficient in energy: Russia and Eastern Europe

• Major oil producers and exporters: Middle east and Africa

• Present trade of oil is governed by OPEC (Organization of the Petroleum Exporting

• Global oil reserves: 1900×109 bbls [3]

Petroleum Industries in India

• In India, margins in refining is very high (4 $ per barrel) as compared to world’s

• The growth in consumption of petroleum products, mainly in fuels, is surpassing 6%,

• Indian oil industry is second oldest industry next to sugar/gur/textile in India.

• The gas accounting to 6% of commercial energy [2018] of country can go up to 7-8%

Classification of crude oil

• Asphaltic base: Crude which contains asphaltic materials in residue on atmospheric

Classification of crude oils according to the US Bureau of Mines

• Other methods of classifications: IFP method, Characterization factor (KUOP),

Characterization of petroleum fractions

Properties of Petroleum Products

Liquid Petroleum Gas (LPG)

• Mixtures of saturated and unsaturated light hydrocarbons in C3, C4

• Heavier than air, collects at ground level in case of any leakage

• Although odourless, distinctive odours (e.g. Mercaptans) are added to detection of

Important characters and tests for LPG

• Copper strip corrosion

• For volatile, non-viscous petroleum products, determined by Reid vapour pressure

• For LPG, determination should be done at 65°C.

• High vapour pressure involves loss of product in storage and transportation.

• Required max. vapour pressure at 65°C for LPG (Commercial butane-propane

Copper-strip Corrosion Test

• Boiling range of various napthas: e.g. C5-85°C, 60-85°C, C5-200°C

• Catalytic reforming of neptha yields a C6-C8 reformate rich in aromatic

Important characters and tests for Naptha

• Boiling point range