ICH 208 PETROLEUM AND PETROCHEMICAL

CHEMISTRY

PURIFICATION OF PETROLEUM PRODUCTS;

FUEL PROPERTIES: HEATING VALUE, OCTANE &
CETANE NUMBER, DENSITY, VISCOUSITY E.T.C

BY
SAMSUDEEN OLANREWAJU AZEEZ
B.Sc (UDUS), M.SC (Ilorin)
 Purification of petroleum products
• Sweetening process:
 Petroleum products are termed as sweet if it contains less than 0.5%
sulfur.
 Sour crude oil have greater than 0.5% sulfur and some of this will be
in the form of hydrogen sulfide. Sour crude also contains more CO2

 Sulphur compounds darken gasoline, give it an offensive odor and

increase toxic sulphur dioxide engine emissions.
– Removal of sulphur and its compounds like H2S, mercaptans etc
from petroleum products is necessary.
– The mercaptans present in oil first reacts with sodium plumbite to
form oil soluble lead mercaptides which on further reaction with
elemental sulphur to form sweet smelling disulphide and give a
black precipitate of lead sulphide.
– Hydrogen sulphides also give black precipitate with the plumbite
solution (sodium plumbite)and sulphur.
• Dewaxing:
– Removal of wax from petroleum product, mainly lubricating oil.
– Petroleum waxes are solid hydrocarbons which are soluble in
petroleum and its products and cannot be separated by distillation as
their boiling points (35 – 95oC) overlap with other petroleum
products.
– At low temperatures, waxes crystallize and precipitate out from diesel
and lubricating oil, hence to maintain their fluidity they must be
dewaxed.
• Deasphalting:
– Removal of asphalts from heavy stocks.
– Asphalts are high molecular weight compounds present in petroleum
and have high boiling point in range of lube oil and heavy gas oil.
– Asphalts are undesirable in catalytic cracking because they form coke.
– Asphalts are readily oxidize and form carbonaceous sludge and hence
must be removed.
– Deasphalting is done by distillation (atmospheric or vacuum), acid
 FUEL PROPERTIES
Heating value (energy value ) of a substance, usually a fuel, is the
amount of heat released during the combustion of a specified amount
of it (fuel).
It is measured in units of energy per unit of the substance, usually mass,
such as: KJ/Kg, KJ/mol, kcal/Kg, Btu/lb.
Heating value is commonly determined by the use of a Bomb
Calorimeter.
There are 2 types viz:
1. Higher Heating Value (HHV)
2. Lower Heating Value (LHV)

The higher heating value is the amount of heat released by a specified

quantity (initially at 25°C) once it is combusted and the products have
returned to a temperature of 25°C, which takes into account the latent
heat of vaporization of water in the combustion products.
It is useful in calculating heating values for fuels where condensation
of the reaction products is practical
The lower heating value (also known as net calorific value) of a fuel is
defined as the amount of heat released by combusting a specified
quantity (initially at 25°C) and returning the temperature of the
combustion products to 150°C, which assumes the latent heat of
vaporization of water in the fuel and reaction products is not recovered.
It is useful in comparing fuels where condensation of the combustion
products is impractical.
 Octane Number
Octane number of fuel is defined as the % by volume of iso-octane in a
mixture of n-heptane and iso-octane with the same knocking tendency
as fuel.
Thus if a gasoline mixture produces as much as knocking as a mixture
which comprises of 80 parts iso-octane and 20 parts n-heptane then the
octane number of that gasoline will be 80.

 Higher the octane number – better the fuel .

Octane number increases in the order n-paraffins – olefins – naphthenes
– iso-paraffins – aromatic.

Octane number is determined by burning the fuel in a standard engine

and knock produces is measured by knockmeter.
Tetra-ethyl lead (TEL) was used as an additive to gasoline to increase its
octane number which is now replaced by methyl tertiary butly ether
(MTBE).
Octane no is the property of spark ignition engine and expresses its
knocking characteristics.
 Cetane Number
Cetane no of diesel oil is the % by volume of cetane in a cetane - α-
methyl naphthalene mixture that has the same ignition delay period and
performance in a standard compression ignition engine as that of the
fuel.

It is a characteristic property of diesel and is used to indicate its quality

and performance in compression ignition engine.

Cetane number increases in the order aromatics — iso-paraffins —

naphthene — olefins — n-paraffins , where as the octane number
decreases in the same order.

Cetane (C16H34) has a very small ignition delay period hence it is given
a cetane no rating of 100 and α-methyl naphthalene has a very high
ignition delay period, hence it is given a rating of zero.

Oils for high speed (>1500 rpm), medium speed and low speed should
 SPECIFIC GRAVITY
• Knowledge of specific gravity predicts the quality of product. It is
used to determines the energy per unit weight or per unit volume.
• Higher the specific gravity – heavier the hydrocarbon – higher the
carbon to hydrogen ratio
• Lower the specific gravity – lighter the hydrocarbon – lower the
carbon to hydrogen ratio.
• Lighter hydrocarbon have high calorific value per unit weight than
heavier hydrocarbon.
• Lighter the crude oil, the lager is the content of lighter constituents
like gasoline and kerosene.
• Hydrometer is used for determination of specific gravity up to 0.001.
• For heavy liquid specific gravity bottles are used.

 Specific gravity is given by API, which is:

[(141.5/Sp.gr) – 131.5]
where specific gravity is measure at 60 oF or 15.5 oC.
Typical specific gravity of petroleum and its products are given
below:
 Viscosity
• This is the quantity that describes a fluid's resistance to flow.
• Viscosity is an important fuel property because:
– high viscosity fuel oil cannot be properly atomized resulting in loss
of fuel.
– highly viscous oil has to be preheated to reduce the viscosity to
minimize the pressure drop in pumping to different refineries
from the oil field.
– high viscosity lubricating oil reduces its fluidity besides causing
undue friction.
– It affects the amount of fuel that can be drawn through a wick to a
flame by capillary action.
• Viscosity is determined by three makers of commercial viscometers:
– The Redwood viscometer (used in commonwealth countries) –
time for 50 cc
– saybolt viscometer (used in U.S.A.) – time for 60 cc
– Engler viscometer (used in Europe) – time for 200 cc
• Redwood Viscometer I is used for low viscosity oils whereas
Redwood Viscometer II is used for highly viscous oil.

• Saybolt universal viscometer is used for low viscosity of oils where as

Saybolt viscometer Furol viscometer is used for high viscosity oils.

• A fixed volume of a liquid at fixed temp is allowed to flow through a

standard capillary tube & the time of flow is noted.

• The results are expressed in terms of time by taken oil to flow

through a particular instrument e.g. Viscosity=100 Redwood sec at
20°C.
 Viscosity index
• It is an empirical number indicating the rate of change of viscosity of
an oil from 100oF to 210oF.
• The change in viscosity with change in temperature is sometime
express in term of viscosity index.
• Viscosity of liquid decreases with increase in temperature.
• Low viscosity index means a large change in viscosity with change in
temperature while high viscosity index shows a relatively small
change in viscosity with temperature.
• Paraffins oils which have very high viscosity index taking equals 100
while naphthenic oil which have very low viscosity index taking
equals 0 as a standard.
• Viscosity index – V.I = (L-U)/(L-H) x 100
where U = viscosity of oil sample at 100 oF, L = viscosity of standard oil
of V.I = 0 at 210 oF and H = viscosity of standard oil of V.I = 100 at 210
o
F.
• Viscosity index can be improved by adding polybutene.
•
Flash Point & Fire Point
Flash Point is the minimum temperature at which an oil gives out sufficient
vapours to form an inflammable mixture with air and catches fire
momentarily when flame is applied.
• Crude oil = -10 to 0 oC, Gasoline= - 40 to 30oC
Kerosene = 28 – 55oC, Diesel = > 55oC
Lube oil = 130 – 300oC, Fuel oil = > 66oC
• Flash point less then 23oC is dangerous and highly inflammable. The safe
value is greater than 60oC.
• Flash point give the idea about the volatility of fuel and the explosion hazard.
• Pensky – Martin’s apparatus is used for flash point above 50 oC.
• Cleveland open cup tester used for volatile oils having flash point > 50 oC.

• Fire point is the lowest temperature at which vapours given off by oil,
ignite and continue to burn for at-least five seconds, when flame is applied.
• Fire point is 5 – 40 oC higher than flash point
• It is also measured in same apparatus used for determination of flash point.
 Cloud, Pour & Freezing Point
• Cloud Point of oil is the temperature at which the oil become hazy
or cloudy when it is cooled at a specified rate.
• The haziness can be due to the presence of wax or increase in
viscosity at low temperature.
• Pour Point is the temperature at which the oil just ceased to flow for
five second when it is kept horizontal .
• It is used to determine the temperature at which an oil cannot be
used as a lubricant.
• The temperature at which the oil freezes completely and cannot
flow at all is called Freezing Point.
• Important in aviation fuels because at high altitude the temperature
is low enough that the fuel can freeze and chock the pipeline.
• The apparatus used for determination of these values is called cloud
and pour point apparatus.
• The freezing mixture used is ice+CaCl2.
 Aniline Point
• This is the lowest temperature at which an oil is completely
miscible with equal volume of aniline .
• Since the aromatics dissolve aniline which itself is aromatic
compound more readily than paraffins or iso-paraffins therefore
, Aniline Point is the measure of aromatic content in oil and
hence the characteristic of diesel.
• Higher the aniline point – lower the aromatics – higher the
paraffin content – higher the cetane number – making oil
suitable for use in diesel engine.
• Aniline point of oil also gives an indication of the possible
deterioration of rubber sealing since aromatics have tendency
to dissolve natural and some types of synthetic rubber.
Therefore lubricants should have high aniline point.
• Aniline point of cetane is 95oC and for hexyl benzene is -12oC.
 Smoke point
• This is the maximum height of flame in mm without smoke
formation when kerosene is burned in a standard lamp under
closely controlled conditions.

• Smoking of kerosene is mainly due to presence of aromatic

hydrocarbons.

• Paraffins are desirable in kerosene as it has the highest smoke point

where as aromatics are undesirable as it has the lowest smoke
point.

• Standard smoke point of kerosene is 20-30 mm.

• Aromatic should be removed from kerosene to improve its smoke

point.