Cracking, Isomerisation and Reforming

The straight-run gasoline from the primary distillation makes poor petrol. Whilst some of this
is used in petrol most of it has to be treated further. The long-chain alkanes in this fraction
have to be converted into shorter-chain and branched alkanes that are more useful in petrol,
as well as to other types of hydrocarbons (cycloalkanes and arenes) also used in petrol.

A problem with long-chain alkanes is that they have a low octane rating (octane number).
This means that, when the fuel is mixed with air in the internal combustion engine, the fuel
has a higher tendency to ignite on being compressed before the spark is applied. This auto-
ignition, or premature ignition, results in two explosions on compression and when the
spark occurs. This produces a knocking or pinking sound in the engine.

Increasing the octane number of the fuel (by modifying the blend of hydrocarbons and
adding other substances such as oxygenates) reduces this problem.

Though crude oil contains both straight-chain and branched alkanes, there are not enough
of the branched isomers to give it a naturally high octane number. The job of the refinery is
to convert some of the less useful components into more useful ones. The processes
involved are: cracking, isomerisation, and reforming.

Also, the blend of petrol is adjusted to suit the temperatures during the summer and winter
months, and to the climate in different countries of the world.

Cracking

Catalytic cracking involves heating long-chain alkanes (typically 30-40 carbon atoms in
heavy oils such as gas oil) in the presence of zeolite catalysts. Many different hydrocarbon
products are obtained comprising shorter chain alkanes, branched alkanes, and alkenes, for
example.
Isomerisation

The straight-chain alkanes are heated in the presence of a catalyst so that the chains break
apart and joined back together as branched chains. An equilibrium mixture is formed
between the straight-chained and branched alkanes that are separated by passing them
over a form of zeolite that acts as a molecular sieve (see Chemical Storylines, Figure 15).

Reforming

This converts straight-chain alkanes (6 -10 carbon atoms in Naphtha) into ring structures.
The alkanes are heated to 500 C and passed over a finely divided platinum catalyst (called
platforming). Cycloalkanes form first, then aromatic hydrocarbons.
Oxygenates

Adding oxygenates to petrol is another way of raising the octane number. Oxygenates are
fuels containing oxygen in their molecules, such as alcohols and ethers.

MTBE (methyl tertiary butyl ether old name; 2-methoxy-2-methylpropane systematic

name) is a commonly used oxygenate. Oxygenates also help the petrol to burn more
cleanly, producing less carbon monoxide, though some states in the USA have banned the
use of MTBE in petrol because it is soluble in water and spillages can pollute water supplies.

Petrol blenders want to produce the best quality fuel they can at the minimum cost. Blending
is done in batches of around 20 000 000 litres at a time. Thorough mixing is important to give
a homogeneous liquid.

Diesel engines
Diesel engines work differently from petrol engines. The diesel fuel-air mixture must auto-ignite on compression.
A diesel fuel is given a cetane number. A high cetane number means there is a high tendency to ignite. A typical
cetane number is 50, though there is very little cetane in most diesel fuels.
This is how the cetane number of a fuel is derived
Cetane is hexadecane, C16H34, which ignites very easily under compression, and is given a cetane number of
100. An aromatic compound called methylnaphthalene has a very low tendency to ignite and is given a cetane
number of 0. The cetane number of a fuel is the percentage of cetane in a mixture of cetane and
methylnaphthalene that ignites at the same compression as the fuel.
Other important features of diesel fuel are:
Lubricity
Provided by additives. Previously sulphur compounds, now removed, provided this.
Flash point
Higher for diesel than for petrol since it is not required to burn when sparked.
Cloud point
Diesel consists of longer chain hydrocarbons and solidifies when the weather gets cold, making it look cloudy.
Winter diesel as a lower cloud point than summer diesel.