CHAPTER FOUR

PETROLEUM
REFINING
 Oil Industry
 It is the major source of the world's
energy and chemicals.
 Petroleum [Oil of Rock] comes from
Latin words Petra = Rock and Oleum =
Oil.
 The products: a- petrol and other fuels for
transport b- oil heating systems c- polymers
and detergents.
 Origin of oil: it is the decay products of
countless tiny sea creatures trapped under
rock.
 Oil is accompanied by methane (natural
gas).
 Oil is transported via pipelines to the
refineries where the interesting chemistry
begins.

 Crude oil can be split into: tarry

substances (very high boiling points) to
gaseous molecules (low boiling points).
 Most of fractions require further
treatment.
 Petroleum Refining
 It is the process by which the petroleum
fractions are separated according to their
molar masses (i.e., boiling points)
Some Alkanes are:
CH4 Methane
C2H6 Ethane
C3H8 Propane
C4H10 Butane
C5 H12 Pentane
C6 H14 Hexane
C7 H16 Heptane
C8 H18 Octane

up to C12H26 (Dodecane)
 C1 – C4 Gas boiling point less than 30 oC

Gasoline ( Petrol)boiling range 60-150 oC

C5 – C9 Fuel for cars

C6 – C11 Naphtha boiling range 70-200 oC

Solvents and Gasoline

Kerosene (Paraffin),
LOWER BOILING POINT

C11 – C14
LOWER MOLAR MASS

Boiling Range 200-250

Vapor feed
Fuel for aircraft
350oC
Diesel oil (Solar or Mozot), Boiling
C14 – C18 range 250-300 oC
Lorries and Trains.
C18 – C23 Fuel Oil, Boiling Range 300-400 oC
Fuel for ships and heating

C21 – C27 Lubricating oil, Boiling

o
Range 350-
450 C
Lubricants for engines and
machines
Steam

Residue: pitch, tar

PETROLEUM FRACTIONATION

In the refining process the petroleum is

first heated to about 3500C at which
temperature it is almost completely
vaporized. The vapor is then fed into the
fractionating column where the pressure
is maintained at a level slightly above
atmospheric. All the liquid fractions are
collected above special trays. The more
volatile materials condense in the upper
plates of the column whilst the less
volatile fractions are collected in the
lower plates.
Main Petroleum Fractions
1. Gasoline
Gasoline, also known as petrol, is the fuel
used in the spark – ignition engine. It
contains fractions distilled in the range of
o
60-150 C, the most important fraction in
Gasoline is the Octane C8H18. Primary
distillation of crude petroleum will never
yield more than about 30% gasoline
(“straight-run gasoline”), and usually less
than this. Market demands are now so
severe that straight-run gasoline supplies
have to be heavily supplemented by
cracking higher boiling fractions.

Thermal and catalytic cracking: thermal

cracking of some suitable petroleum
fractions was first used to increase
gasoline yields, however cracking in the
presence of a catalyst is now favored. It is
important to note that the milder
conditions which can be used in catalytic
cracking give higher yields of better
quality gasoline and less elemental
carbon.
Octane numbers: n-heptane, C7H16, CH3-
CH2-CH2-CH2-CH2-CH2-CH3 which has
very poor resistance to knocking, is given
an octane number of zero; iso-octane:
(2, 2, 4-trimethylpentane), C8H18, CH3-C
[CH3]2-CH2-CH [CH3]-CH3,
which has a high resistance to knocking, is
given an octane number of 100. The

octane number of a gasoline type is

the percentage of iso-octane in a
mixture of iso-octane and n-
heptane having the same knock
resistance as this gasoline type.
The Knock resistance is measured
by a special machine which gives
the knock percent.
In case of using improper gasoline of low
octane number, the combustion may
produce shock waves of much greater
velocity than normal. These waves produce
a characteristic sound which is a pre-
ignition phenomenon called knocking or
pinking. Engine knock results in a drop in
efficiency, and can also cause mechanical
damage.
2. Naphtha
This fraction has some solvents with
boiling point range from 70-200oC. and
Carbon atom number from C6-C11. The
main applications of naphtha are to
produce solvents and gasoline.
3. Kerosene
Kerosene or "paraffin ", is a petroleum
fuel consists of fractions have boiling
point between 200-250oC, it has an
illuminating flame and used in aviation
jet engine. Kerosene, or kerosene blended
with gasoline, is used as fuel for aircraft,
and this fraction is consequently now
rated an important product of the
petroleum industry.
4. Diesel Oil
The diesel oil is used in lorries, in a
compression- ignition engine which uses
petroleum fuels that is distilled between
about 250 and 300oC. The process of
injecting oil into a combustion chamber
needs an efficient atomization (make the
fuel in the form of very small droplets)
which is necessary in a compression –
ignition engine if combustion is to be
complete. For diesel fuels, viscosity is an
important factor in determining ease of
atomization.
5. Fuel oils
Fuels that is distilled between about 300
o
and 400 C. While the light petroleum
fractions we have been considering are
generally used as sources of heat and
power, the term "fuel oil" is reserved for
viscous oils which are used in furnace
combustion as alternatives to coal or
gaseous fuels. Liquid fuels have a higher
thermal storage capacity than the solid
fuel, (fuel oils have a gross calorific value
of about 19,000 Btu per pound where as a
good quality coal about 15,000 Btu per
pound.
6. Other petroleum products
From the heavy residues of crude
petroleum a number of valuable products
are extracted. Some of these products
include:
(1) Lubricating oils which are a valuable
range of petroleum waxes and greases
obtained by extensive refining.
(2) Bitumen which is used chiefly as a
road-making material, but has many
other applications.
(3) Petroleum coke, the ultimate solid
residue of petroleum distillation, it has
very low ash content which makes it a
suitable source of electrode carbon, and
like coal, it may also be used as a solid
smokeless fuel.