Lecture 2:

Composition and Classification of

crude oil

Department of Chemical Engineering, National Institute of Technology, Calicut

 Crude Oil Components
On average, crude oils are made of the following elements
or compounds:

• Carbon - 84%

• Hydrogen - 14%

• Sulfur - 1 to 3% (hydrogen sulfide, sulfides, disulfides, elemental sulfur)

• Nitrogen - less than 1% (basic compounds with amine groups)

• Oxygen - less than 1% (found in organic compounds such as carbon dioxide,

phenols, ketones, carboxylic acids)

• Metals - less than 1% (nickel, iron, vanadium, copper, arsenic)

• Salts - less than 1% (sodium chloride, magnesium chloride, calcium chloride

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 Major classes of hydrocarbons in crude oils(cont):

• Paraffins :
 general formula: CnH2n+2 (n is a whole number, usually from 1 to 20).
 Straight or branched-chain molecules can be gasses or liquids at room
temperature depending upon the molecule
 Examples: methane, ethane, propane, butane, isobutane, pentane,
hexane.

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 Major classes of hydrocarbons in crude oils(cont):
• Aromatics :
 general formula: C6H5 - Y (Y is a longer, straight molecule that connects to the
benzene ring)
 ringed structures with one or more rings.
 rings contain six carbon atoms, with alternating double and single bonds between
the carbons.
 Typically liquids
 Examples: benzene, naphthalene.

Department of Chemical Engineering, National Institute of Technology, Calicut

Major classes of hydrocarbons in crude oils(cont):
Naphthenes or Cycloalkanes:
• general formula: CnH2n (n is a whole number usually from 1 to 20).
• ringed structures with one or more rings.
• rings contain only single bonds between the carbon atoms.
• Typically liquids at room temperature.
• Examples: cyclohexane, methyl cyclopentane.

Department of Chemical Engineering, National Institute of Technology, Calicut

Major classes of hydrocarbons in crude oils(cont):

• Alkenes :
general formula: CnH2n (n is a whole number, usually from 1
to 20).
linear or branched chain molecules containing one carbon-
carbon double-bond.
can be liquid or gas.
examples: ethylene, butene, isobutene

Department of Chemical Engineering, National Institute of Technology, Calicut

Major classes of hydrocarbons in crude oils(cont):

Dienes and Alkynes:

general formula: CnH2n-2 (n is a whole number, usually from
1 to 20)
linear or branched chain molecules.
containing two carbon-carbon double-bonds
can be liquid or gas examples: acetylene, butadienes
Classifications of crude oil based on Sulphur content

The American Petroleum Institute or the API provides a

basis to measure the density of the oil.

If the presence of sulfur is low in the crude oil, it is

termed as 'sweet‘.

If the oil has high sulfur content then it is termed as

'sour'.

Department of Chemical Engineering, National Institute of Technology, Calicut

Classifications of crude oil Based on Geographical
Locations(cont):

North Sea Crudes - Brent, Osberg, Forties, North

Sea basket.

• Brent Sweet Light crude is light but not as light as the

West Texas Intermediate (WTI).

• Brent crude is suitable for the production of gasoline.

• The sulfur level is 0.36% whereas the API gravity is

around 38.5 degrees .

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Classifications of crude oil Based on Geographical
Locations(cont):

United State Crudes – West Texas Intermediate

(WTI), West Texas Sour (WTS), Light Louisiana Sweet
(LLS).

• The sulfur content is 0.24% and the API gravity is

39.6 degrees.

• The WTI is ideal for the production of gasoline due

to its low sulfur content and it is lighter than Brent
crude.

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Classifications of crude oil Based on Geographical
Locations(cont):

OPEC Reference Basket or West African Crude

Bonny light, Escravos, Forcados

• The OPEC Basket, including a mix of light and heavy

crudes, is heavier than both Brent crude oil, and
West Texas Intermediate crude oil.

• API gravity around 35 degrees and sulfur level of

0.2%.

Department of Chemical Engineering, National Institute of Technology, Calicut

Department of Chemical Engineering, National Institute of Technology, Calicut
Classifications of crude oil Based on Geographical
Locations(cont):

Persian Gulf Crudes – Dubai, Arab and Qatar

• API gravity around 37 degrees and 1.08% of sulfur
level are the measures.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Classification Based on Chemical Composition

Type of Composition of 250–350°C Fraction % Wax % Asphalt

Crude
% Paraffinic % Naphthenic % Aromatic

Paraffinic 46–61 22–32 12–25 1.5–10 0–6

Paraffinic- 42–45 38–39 16–20 1–6 0–6
naphthenic

Naphthenic 15–26 61–76 8–13 Trace 0–6

Paraffinic- 27–35 36–47 26–33 0.5–1 0–10

naphthanic-
aromatic

Aromatic 0–8 57–78 20–25 0–0.5 0–20

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By Compound type:
 Paraffin Base: This classification was based on the fact
that some petroleum oils separated paraffin wax on
cooling leading to the conclusion, that these consisted
mainly of paraffins (e.g. methane, ethane, propane etc.
with generic formula CnH2n+2).

 Asphaltic Base: These were the petroleum oils which

gave no separation of paraffin wax on cooling again
leading to the conclusion that these predominantly
contained cyclic (or napthenic) hydrocarbons.

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Mix Base: These petroleum oils leave a mixture of paraffin
wax & asphaltic bitumen when subjected to nondestructive
distillation & hence the name.

a simple triangular diagram

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Classification Based on C/H and H/C Ratio in Petroleum

Type of Species C/H Ratio H/C Ratio

Simple aromatics (eg, 1.00 1.00
benzene)

Condensed aromatics 1.25 0.80

(eg, naphthalene)

Polycondensed >1.40 <0.75

aromatics
General aliphatic Ca 0.50 Ca 2.00
hydrocarbons

Paraffins Ca 0.50 Ca 2.00

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 Classification of Petroleum-Based Products

Natural Materials Derived Manufactured

Materials Materials

Natural gas Saturates Synthetic crude

Petroleum Aromatics oil
Heavy oil Resins Distillates
Bitumen Asphaltenes Lubricating oil
Asphatite Wax
Coal Residuum
Asphalt
Coke
Tar
Pitch

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 Classification of Crude oil

 Mallison Classified the crude on the basis of residuum, a material left after
distillation
 Residue containing more than 5% paraffins is paraffinic crude
 Residue containing less than 2% paraffins is napthatheenic crude
 Residue containing 2-5% paraffin's is considered as mixed base
 US Bureau of Mines classification
key fraction no.1 : has a boiling range of 250 -275 C ( kerosene)
Key fraction no.2 : boiling range of 275-300C (Lube)
According to API gravity,
Key fraction 1 has =>40 API gravity – Paraffinic
< 33 API gravity - Naphthenic
33-40 API gravity- mixed base
Key fraction 2 has =>30 API gravity – Paraffinic
< 20 API gravity - Naphthenic
20-30 API gravity- mixed base
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 Important characteristics of crude oil

Numerous important feed and product characterization properties

in refinery engineering include
• API gravity
• Watson Characterization factor
• Viscosity
• Sulfur content
• True boiling point (TBP) curve
• Pour point
• Flash and fire point
• ASTM distillation curve
• Octane number
• Cetane number
• Aniline point
•

Department of Chemical Engineering, National Institute of Technology, Calicut

 API Gravity
• API gravity of petroleum fractions is a measure of density of the stream.
Usually measured at 60°F, the API gravity is expressed as
°API = 141.5/specific gravity – 131.5
where specific gravity is measured at 60 °F.

• According to the above expression,10°API gravity indicates a specific

gravity of 1 (equivalent to water specific gravity).

• In other words, higher values of API gravity indicate lower specific gravity
and therefore lighter crude oils or refinery products and vice-versa.

• As far as crude oil is concerned, lighter API gravity value is desired as

more amount of gas fraction, naphtha and gas oils can be produced from
the lighter crude oil than with the heavier crude oil.

• Therefore, crude oil with high values of API gravity are expensive to
procure due to their quality.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Watson characterization factor

• The Watson characterization factor is usually expressed as

K = (TB)1/3/specific gravity
Where TB is the average boiling point in degrees R taken from five
temperatures corresponding to 10, 30, 50, 70 and 90 volume %
vaporized.

• Typically Watson characterization factor varies between 10.5 and 13 for

various crude streams.

• A highly paraffinic crude typically possesses a K factor of 13.

• On the other hand, a highly naphthenic crude possesses a K factor of

10.5.

• Therefore, Watson characterization factor can be used to judge upon the

quality of the crude oil in terms of the dominance of the paraffinic or
naphthenic components.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Sulpuhr content
• Usually, crude oil has both organic and inorganic sulphur in which the inorganic
sulphur dominates the composition.

• Typically, crude oils with high sulphur content are termed as sour crude (0.5 – 5 wt
% ). On the other hand, crude oils with low sulphur content are termed as sweet
crude ( < 0.5 wt %).

• The sulphur content in the crude oil is responsible for numerous hydrotreating
operations in the refinery process.

• Presently, India is heading towards the generation of diesel with Euro III standards
that indicates that the maximum sulphur content is about 500 ppm in the product.
This indicates that large quantities of inorganic sulphur needs to be removed from
the fuel. Typically, inorganic sulphur from various intermediate product streams is
removed using hydrogen as hydrogen sulphide.

• A typical refinery consists of good number of hydrotreaters to achieve the desired

separation.

Department of Chemical Engineering, National Institute of Technology, Calicut

 TBP/ASTM distillation curves

• The most important characterization properties of the

crude/intermediate/product streams are the TBP/ASTM distillation curves.

• Both these distillation curves are measured at 1 atm pressure. In both

these cases, the boiling points of various volume fractions are being
measured.

• However, the basic difference between two curves is that while TBP curve
is measured using batch distillation apparatus consisting of not less than
100 trays and very high reflux ratio, the ASTM distillation is measured in a
single stage apparatus without any reflux.

• Therefore, the ASTM does not indicate a good separation of various

components and indicates the operation of the laboratory setup far away
from the equilibrium.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Viscosity content
• Viscosity is a measure of the flow properties of the refinery stream.
Typically in the refining industry, viscosity is measured in terms of
centistokes (termed as cst) or saybolt seconds or redwood seconds.

• Usually, the viscosity measurements are carried out at 100 °F and 210 °F.
Viscosity is a very important property for the heavy products obtained
from the crude oil.

• The viscosity acts as an important characterization property in the

blending units associated to heavy products such as bunker fuel.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Flash, fire, Cloud and Pour point

• Flash and fire point are important properties that are relevant to the safety
and transmission of refinery products.

• Flash point is the temperature above which the product flashes forming a
mixture capable of inducing ignition with air.

• Fire point is the temperature well above the flash point where the product
could catch fire.

• These two important properties are always taken care in the day to day
operation of a refinery.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Flash, fire, Cloud and Pour point

• When a petroleum product is cooled, first a cloudy appearance of the

product occurs at a certain temperature. This temperature is termed as
the cloud point.

• Upon further cooling, the product will ceases to flow at a temperature.

This temperature is termed as the pour point.

• Both pour and cloud points are important properties of the product
streams as far as heavier products are concerned.

• For heavier products, they are specified in a desired range and this is
achieved by blending appropriate amounts of lighter intermediate
products.

Department of Chemical Engineering, National Institute of Technology, Calicut

 Octane number
• An octane number is a measure of the knocking tendency of gasoline fuels in
spark ignition engines.

• The ability of a fuel to resist auto-ignition during compression and prior to the spark
ignition gives it a high octane number.

• The knocking tendency of the gasoline is defined in terms of the maximum

compression ratio of the engine at which the knock occurs.

• The octane number of a fuel is determined by measuring its knocking value

compared to the knocking of a mixture of n-heptane and isooctane (2,2,4-trimethyl
pentane). Pure n-heptane is assigned a value of zero octane while isooctane is
assigned 100 octane. Hence, an 80 vol% isooctane mixture has an octane number
of 80.

• Two octane tests can be performed for gasoline.

• The motor octane number (MON) indicates engine performance at highway

conditions with high speeds (900 rpm). On the other hand, the research octane
number is indicative of low-speed city driving (600 rpm).
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 Cetane number

• 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).

• 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(750F) and lower cetane numbers (CN = 30).

Department of Chemical Engineering, National Institute of Technology, Calicut

 Smoke and Aniline point
Smoke point
• The smoke point is a test measures the burning qualities of kerosene and jet fuel.

• It is defined as the maximum height in mm, of a smokeless flame of fuel.

• One of the standard tests is ASTM D1322.

Aniline point
• The lowest temperature at which an equal volume mixture of the petroleum oil and
aniline are miscible.

• A petroleum fractions with high aromatic content will be miscible in aniline at

ambient conditions.

• But if the oil has more paraffin's, it will require a higher temperature and thus
higher aniline point in order to be miscible in aniline.

• This property is important for the specifications of diesel fuels. It is measured by

ASTM D611.

Department of Chemical Engineering, National Institute of Technology, Calicut