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Petroleum Refining

Crude Oil

ASTM D-288

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The OPEC Reference Basket of Crudes (ORB) is made up of the following:

Saharan Blend (Algeria), Girassol (Angola), Oriente (Ecuador), Rabi Light
(Gabon), Iran Heavy (Islamic Republic of Iran), Basra Light (Iraq), Kuwait
Export (Kuwait), Es Sider (Libya), Bonny Light (Nigeria), Qatar Marine
(Qatar), Arab Light (Saudi Arabia), Murban (UAE) and Merey (Venezuela).

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Major oil refining

companies of the
world

1 bbl = 159 L

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Classes of crude oils

The higher the API

gravity, the lighter the
crude

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Brent is the reference for about two-thirds of the oil traded world
wide, with WTI the dominant benchmark within the U.S. and
Dubai/Oman influential within the Asian market.

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Brent blend is a light crude oil (LCO) containing approximately 0.37% of

sulphur, classifying it as sweet crude. Brent is suitable for production of petrol
and middle distillates. It is typically refined in Northwest Europe.
Brent Crude has an API gravity of approximately 38.06 which is equivalent to
a specific gravity of 0.835

Indian Crude Basket

 The Indian Crude Basket is a weighted average of the prices of

Oman and Dubai sour crude price benchmark; and the Brent
sweet crude price benchmark.
 The weightage for Oman and Dubai sour grade is 68.2 per cent
(with a roughly equal distribution i.e. 34.1 per cent, between
themselves) while the rest – i.e. 31.8 per cent is for Brent
(dated) sweet crude price benchmark. The Oman and Dubai is a
slightly lower grade than WTI or Brent.
 The price of Indian Basket is updated on the site of Petroleum
Planning and Analysis Cell.
 The Indian Crude basket is used as an indicator of the price
of crude imports in India. Similarly, it is one of the elements
watched by the Indian government when examining domestic
price issues.

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PONA

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In the reforming reaction, naphthenes

are targeted to generate aromatics which
have higher octane numbers

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REFINERY PROCESSES
Desalting of Crude Oils

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REFINERY PROCESSES

Refining of crude oils: primary separation processes and

secondary conversion processes.

Separation processes
Atmospheric and vacuum distillation of crude oils is the
main primary separation processes producing various
straight run products, e.g., gasoline to lube oils/vacuum
gas oils (VGO). These products, particularly the light and
middle distillates, i.e., gasoline, kerosene and diesel are
more in demand all over the world.

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VDU operates at 25-40 mm Hg

Residual Fluidized Catalytic Cracking (RFCC)

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VDU

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ADU

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VDU

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naphtha
 Light naphtha is the fraction boiling
between 30 °C and 90 °C and consists of
molecules with 5–6 carbon atoms.

 Heavy naphtha boils between 90 °C and

200 °C and consists of molecules with 6–
12 carbons.

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CONVERSION PROCESSES

 Upgrade lower-value materials such as heavy residues

to more valuable products such as naphtha and LPG.
Naphtha is mainly used to supplement the gasoline
pool, while LPG is used as a fuel.

 Improve the characteristics of a fuel. For example, a

lower octane naphtha fraction is reformed to a higher
octane reformate product. The reformate is mainly
blended with naphtha for gasoline formulation or
extracted for obtaining aromatics needed for
petrochemicals production.

Octane Number

 % volume of Iso-octane (2,2,4-tri-methyl

pentane) in a mixture of Iso-octane and n-
heptane that gives same knocking (untimely
burning of fuel in SI engine) characteristic as
the fuel under consideration.

 Iso-paraffins and aromatics have high

octane number while n-paraffins/cycloparaffins
have very low value, unsaturates do have high
octane values but not preferred due to gum
contribution.

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 Reduce harmful impurities in petroleum fractions and

residues to control pollution and to avoid poisoning
certain processing catalysts.

For example, hydrotreatment of naphtha feeds to catalytic

reformers is essential because sulfur and nitrogen
impurities poison the catalyst.

THERMAL CONVERSION PROCESSES

 Steam cracking

 Coking

 Vis-breaking

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STEAM CRACKING OF HYDROCARBONS

(Production of Olefins)
 Producing light olefins, especially ethylene.

 The feedstocks for steam cracking units

range from light paraffinic hydrocarbon
gases to various petroleum fractions and
residues.

Coking
 Coking is a severe thermal cracking process
designed to handle heavy residues with high
asphaltene and metal contents, which if fed to
catalytic cracker may poison the catalysts.

 Products are hydrocarbon gases, cracked naphtha,

middle distillates, and coke.

 Hydrotreatment is usually required to saturate

olefinic compounds and to desulfurize products from
coking units.

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Viscosity Breaking (Vis-breaking)

 Viscosity breaking aims to thermally crack long-
chain feed molecules to shorter ones, thus reducing
the viscosity and the pour point of the product.
 Feed is usually a high viscosity, high pour point fuel
oil that cannot be used or transported, especially in
cold climates, due to the presence of waxy
materials.
 Vis-breaking is a mild cracking process that
operates at approximately 450°C using short
residence times.

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Cracking

Chemistry of cracking

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Process steps:
 Gas oil feed is dispersed into the bottom of
the riser using steam
 Thermal cracking occurs on the surface of
the catalyst
 Disengaging drum separates spent catalyst
from product vapors
 Steam strips residue hydrocarbons from
spent catalyst
 Air burns away the carbon film from the
catalyst in either a “partial-burn” or “full-
burn” mode of operation
 Regenerated catalyst enters bottom of riser-
reactor

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UOP side by side FCCU - CPCL

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Reforming

 To improve the octane number of a naphtha

feedstock by changing its chemical composition.

 Catalytic reforming is considered the key process for

obtaining benzene, toluene, and xylenes (BTX).

• Feedstock: Hydrotreated Heavy Naphtha

• Catalyst: Pt/porous alumina or Pt/silica-alumina
• H2 is obtained as a byproduct

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Dehydrocyclization

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Isomerization
 Converting straight chain alkanes to side
chain paraffins, which have high octane
number.

 n-pentane = 61.7
iso-pentane = 92.3

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 isomerisation of butane (from LPG) to 2-

methylpropane (isobutane):

 Butane vapour is passed over a solid catalyst,

aluminium chloride, on an inert solid at ca 300 K. The
two alkanes are then separated either by distillation or
by passing them through a molecular sieve, an
aluminosilicate. The branched chain alkane is trapped
and the straight chain passes through and is
recirculated into the reactor. The 2-methylpropane is
subsequently released and used to make a branched
alkane, 2,2,4-trimethylpentane (iso-octane), for
petrol.

110-170 oC and 14-20 atm

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Alkylation
 The reaction of olefins with paraffins to form higher iso-
paraffins.

 Produces larger hydrocarbon molecules in the gasoline

range from smaller molecules. The products are saturated
branched hydrocarbons having high octane ratings. (butane
alkylate = ON 92-97)

 Acid catalyzed reaction between isobutane and various light

olefins, and the product is known as the alkylate.

 concentrated sulfuric acid or anhydrous hydrofluoric acid is

used as a catalyst

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50 oC and 30 bar

Polymerization
 Combining of two or more olefinic
molecules to yield larger molecules.
 Typical feedstocks for polymerization
process are C3 and C4 olefins that are
obtained from catalytic cracking.
 The end product from polymerization
reactor is a dimer or a trimer of the
olefins.
 Sulphuric acid, phosphoric acid, copper
pyrophosphate as catalysts.

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150-220 oC and 10-80 atm

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