CHAPTER FOUR

PETROLEUM
REFINING
4.1. Why the oil industry is important
The oil industry is important because it is the major source of the
world's energy and chemicals. The products of this industry range
from petrol and other fuels for transport and oil heating systems to
polymers and detergents. Millions of tons of oil are extracted each
year and processed in refineries and other chemical plants.
First, you should know the origin of oil. Essentially, it is the decay
products of countless tiny sea creatures that have been trapped
under layers of rock. Usually the oil is accompanied by methane,
otherwise known as natural gas.
Once the oil is taken from the wells, it is transported to the
refineries this is best done by pipelines; however the transport
generally involves the use of massive, oil tankers. Once the oil
arrives at the refineries, the interesting chemistry begins.
Crude oil can be split into a number of fractions ranging from tarry
substances of very high boiling points to gaseous molecules of low
boiling point. Some of the fractions could be used immediately but
most require further treatment. The demand for the different
fractions is not uniform.

4.2. Petroleum Refining

It is the process by which the petroleum fractions are separated
according to their boiling points which means according to their
molar masses. Summary formula and names for some fractions are
listed below.
CH4 Methane C2H6 Ethane
C3H8 Propane C4H10 Butane
C5H12 Pentane C6H14 Hexane
 C7H16 Heptane C8H18 Octane
C9H20 Nonane C10H22 Decane
C11H24 Undecane 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 350 0C

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. The various
fractions are continuously tapped off and in some cases processed
by further distillation, whereas the gasoline, kerosene and diesel
oil fractions can be distilled at near atmospheric pressure, the
lubricating oil fraction is distilled under vacuum to reduce its
boiling point.

4.3. Main Petroleum Fractions

4.3.1. Gasoline
Gasoline, also known as petrol, is the fuel used in the spark –
ignition engine. It contains fractions distilled in the range of 60-
150 oC, 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. 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.

4.3.2. 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 some components are used
in gasoline.
4.3.3. 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 turbine-driven aircraft, and this fraction
 is consequently now rated an important product of the petroleum
industry.
4.3.4 Diesel Oil
The diesel engine is 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.
4.3.5. Fuel oils
Fuels that is distilled between about 300 and 400oC. 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.
4.3.6. 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,
its very low ash content makes it a suitable source of electrode
carbon, and like coal, it may also be used as a solid smokeless fuel.