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The number of isomers increases geometrically with the carbon number. While there are two isomers for
butane and three for pentane, there are 75 isomers for decane (C10H22).
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Paraffins in crude oil

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 Olefins

Olefins, also known as alkenes, are unsaturated hydrocarbons containing carbon–

carbon double bonds. Compounds containing carbon–carbon triple bonds are known as

acetylenes, and are also known as biolefins or alkynes.

The general formulas of olefins and acetylenes are

and respectively.

Alkadienes or, more commonly, dienes?

trienes, tetraenes and polyenes ?

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 The lightest alkenes are ethylene (C2H4) and propylene (C3H6), which are important
feedstocks for the petrochemical industry.
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Some diolefins (containing two double bonds) are also formed during processing, but

they react very rapidly with olefins to form high-molecular-weight polymers consisting of

many simple unsaturated molecules joined together.

What is diolefins?
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 Naphthenes (cycloalkanes)

Naphthenes, also known as cycloalkanes, are saturated hydrocarbons that have at least

one ring of carbon atoms. They have the general formula CnH2n.

They are classified according to boiling range and their properties determined with the help

of correlation factors such as the KW factor or CI.

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Naphthenes in crude oil

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 Aromatics
Aromatics are unsaturated cyclic compounds composed of one or more benzene rings
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Crude oils from various origins contain different types of aromatic compounds in different
concentrations. Light petroleum fractions contain mono-aromatics, which have one
benzene ring with one or more of the hydrogen atoms substituted by another atom or
alkyl groups.
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Complex aromatic compounds consist of a number of ‘‘fused’’ benzene rings. These are
known as polynuclear aromatic compounds.
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Aromatic hydrocarbons in crude oil

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 Sulphur Compounds

The Sulphur content of crude oils varies from less than 0.05 to more than 10 wt% but
generally falls in the range 1–4 wt%.

Crude oil with less than 1 wt % sulphur is referred to as low sulphur or sweet, and that
with more than 1 wt% sulphur is referred to as high sulphur or sour.

Sulphur containing constituents of crude oils vary from simple mercaptans, also known
as thiols, to sulphides and polycyclic sulphides.
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Mercaptans are made of an alkyl chain with –SH group at the end (R–SH)
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In sulphides and disulphides, the sulphur atom replaces one or two carbon atoms in the
chain (R–S–R’ or R–S–S–R’ ).
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Thiophenes are polynuclear aromatic compounds in which the sulphur atom replaces
one or more carbon atoms in the aromatic ring.
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 Oxygen Compounds

The oxygen content of crude oil is usually less than 2 wt%. A phenomenally high oxygen
content indicates that the oil has suffered prolonged exposure to the atmosphere.

Alcohols have the general formula R–OH and are structurally similar to water but with
one of the hydrogen atoms replaced by an alkyl group.

In phenols, one of the hydrogen atoms in the aromatic ring is replaced with a hydroxyl
group (–OH). Ethers have two organic groups connected to a single oxygen atom (R–O–
R’)
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Carboxylic acids have a carboxyl group as their functional group (–COOH), and their
general formula can be written as
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Carboxylic acid anhydrides are formed by removing water from two carboxyl groups and
connecting the fragments.
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Ketones are compounds with two carbon atoms bounded to the carbon of a carbonyl
group
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 Nitrogen Compounds

Crude oils contain very low amounts of nitrogen compounds. In general, the more
asphaltic the oil, the higher its nitrogen content.

The nitrogen compounds in crude oils may be classified as basic or non-basic. Basic
nitrogen compounds consist of pyridines. The greater part of the nitrogen in crude oils is
the non-basic nitrogen compounds, which are generally of pyrrole types.
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 Metallic Compounds

Metallic compounds exist in all crude oil types in very small amounts. Their concentration
must be reduced to avoid operational problems and to prevent them from contaminating
the products.

Even minute amounts of metals (iron, nickel and vanadium) in the feedstock to the
catalytic cracker affect the activity of the catalyst and result in increased gas and coke
formation and reduced gasoline yields.
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 Asphaltenes and Resins

Asphaltenes are dark brown friable solids that have no definite melting point and usually
leave carbonaceous residue on heating. They are made up of condensed polynuclear
aromatic layers linked by saturated links.

These layers are folded, creating a solid structure known as a micelle.

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Resins are polar molecules in the molecular weight range of 500–1000, which are
insoluble in liquid propane but soluble in n-heptane.

It is believed that the resins are responsible for dissolving and stabilizing the solid
asphaltene molecules in petroleum.
Individual Assignment (2 marks)

Write down the 10 each Chemical Structures of Paraffin's, Olefins, Naphthenes

(cycloalkanes), Aromatics, Sulphur Compounds, Oxygen Compounds and Nitrogen
Compounds.
PRODUCT ANALYSIS

 Products Composition

Over 2000 individual refinery products.

Intermediate feed stocks can be routed to various units to produce different blend
products depending on market demand
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Principal petroleum products with carbon numbers and boiling ranges

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 LPG

Liquified petroleum gas is a group of hydrocarbon-based gases derived from crude oil

refining or natural gas fractionation. They include ethane, ethylene, propane, propylene,

normal butane, butylene, isobutane and isobutylene.

 Lube Oil

Lubricants are based on the viscosity index. Paraffinic and naphthenic lubricants have a

finished viscosity index of more than 75.

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 Asphalt
Asphalt is an important product in the construction industry and comprises upto 20% of
products. It can be produced only from crude containing asphaltenic material.

 Petroleum Coke

Carbon compounds formed from thermal conversion of petroleum containing resins and

asphaltenes are called petroleum cokes. Fuel grade coke contains about 85% carbon

and 4% hydrogen.
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 Residual Fuel Oil

It is mainly composed of vacuum residue. Critical specifications are viscosity and sulphur
content. Low sulphur residues are in more demand in the market.

 Gasoline
Gasoline is classified by octane ratings (conventional, oxygenated and reformulated) into
three grades: Regular, Midgrade and Premium.
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 Kerosene
Kerosene is a light petroleum distillate that is used in space heaters, cook stoves and
water heaters and which is suitable for use as a light source.

Kerosene has a maximum distillation temperature of 204 C (400 F) at the 10% recovery
point, a final boiling point of 300 C (572 F), and a minimum flash point of 37.8 C (100F)
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 Jet Fuel
This category comprises both gasoline and kerosene and meets specifications for use in
aviation turbine power units.
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 Fuel Oil
The fuel oils are mainly used in space heating and thus the market is quite high specially
in cold climates.

No. 1 fuel oil is similar to kerosene and No. 2 fuel oil is very similar to No. 2 diesel fuel.

Heavier grades of No. 3 and 4 are also available.

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 Diesel Fuel

The quality of diesel fuels can be expressed as cetane number or cetane index.

The cetane number (CN) is expressed in terms of the volume percent of cetane
(C16H34) which has high ignition (CN = 100) in a mixture with alpha-methyl-naphthalene
(C11H10) which has low ignition quality (CN = 0).
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Diesel fuel includes No.1 diesel (Super-diesel) which has cetane number of 45 and it is
used in high speed engines, trucks and buses.

No. 2 diesel has 40 cetane number. Railroad diesel fuels are similar to the heavier
automotive diesel fuels, but have higher boiling ranges upto 400 C (750 F) and lower
cetane numbers (CN = 30).
SARA Analysis (ASTM D4124)

The SARA analysis determines the content of saturate aromatics, resins and
asphaltenes in crude oils, heavy cuts and residues.
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The separation of these four classes of compounds is done in different stages.

First, asphaltenes is precipitated by n-heptane. The deasphalted oil called maltenes is

subjected to liquid chromatography.

Liquid chromatography is similar in principles to gas chromatography in that the

compounds are eluted from a packed column by a carrier, in this case a liquid instead of
a gas.
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The saturated hydrocarbons are eluted by n-heptane, the aromatics by a 2:1 volume
mixture of n-heptane and toluene and the resins by an equal volume mixture of
dichloromethane, toluene and methanol.
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A method for characterization of heavy oils based on fractionation, whereby a heavy

oil sample is separated into smaller quantities or fractions, with each fraction having a
different composition. Fractionation is based onthe solubility of hydrocarbon components
in various solvents used in this test. Each fraction consists of a solubility class
containing a range of different molecular-weight species.
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Schematic diagram of SARA analysis

What is SR Naphtha?

Straight run naphtha is a basic constituent of refined petroteum products. It consists

mainly of aliphatic hydrocarbons along with small amounts of naphthenic and aromatic
hydrocarbons.

Continuous catalytic reforming of naphtha can produce aromatic compounds in amounts

up to 70% of the reformat.