MODULE six

PETROLEUM AND COAL CHEMISTRY

Petroleum is a dark brown or almost black viscous liquid also known as crude oil or fossil fuel. It
is formed from the dead remains of living organisms (fossils) buried in the absence of air under
the earth in great depths at high temperatures and high pressure.
The composition of petroleum varies widely with different source. This variation is influenced
by several factors which includes; source organic matter, geographic region, the proportion of
hydrocarbon, sulphur, nitrogen, oxygen and trace of other elements such as nickel, vanadium etc.
contained in the crude oil.
ORIGIN OF PETROLEUM
Petroleum is a dark brown or black viscous liquid also known as fossil fuel. It is a mixture of
natural gas, liquid and solid hydrocarbons. It is formed from bacterial decomposition of dead
remains of living organisms (fossils) buried in the absence of air, under the earth in great depths
at both high temperature and pressure. The viscous liquid then collects under the earth.
The composition of petroleum is used as a measure of its quality. It is composed mainly of
carbon (83-87%) and hydrogen (10-14%). It also contains smaller proportion of compounds
containing, nitrogen, oxygen and trace of elements such as copper, vanadium iron and helium.

Since petroleum is mainly composed of hydrocarbon, it is classified by the percentage of

hydrocarbons it contains. The percentages of these hydrocarbons vary widely amongst different
petroleum sources depending on the source organic material and the geographic regions. The
classification is categorised into four main groups namely;
1. Paraffin based petroleum: - This consists of mainly straight chain alkanes. It has 15-
60% hydrocarbon.
2. Napthenes based petroleum: - This consists of mainly of cycloalkanes (particularly
cyclohexanes and cyclopentane). This class has hydrocarbon percentage of between 30%-
60%.
3. Aromatics based petroleum: - This contain mainly large amount of benzene and
alkylbenzene with 3-30% hydrocarbons.
4. Asphaltics: - This makes up the remaining composition and it contains lesser amount of
hydrocarbons. It is sometimes grouped together with the aromatics.
REFINING OF PETROLEUM
Petroleum obtained directly from the oil wells is mixtures of various components and also
contains impurities such as compounds of sulphur, water, sand and brine. In this crude state,
petroleum is undesirable for technical purposes. Therefore, to meet up with its desired need, the
crude needs to be refined.

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Refining of petroleum is a process whereby crude oil is upgraded or improved or transformed
into useful fractions or product such as liquefied petroleum gas (LPG), kerosene, asphalt base, jet
fuel, gasoline, heating oil, fuel oils etc. After the crude is mechanically freed from sand and brine
it is set for the refining process.
FRACTIONAL DISTILLATION
Fractional distillation involves the separation of petroleum into the different useful fraction each
with definite boiling ranges. The separation of crude oil by distillation is a physical process
because different chemical compounds are separated based on their different boiling points, for
example pentane, C5H12, boils at 36 °C, while nonane, C9H20, boils at 128 °C. The separation is
based only on a physical process (boiling), no chemical bonds are broken during distillation and
no chemical reactions take place at this stage.
Prior to fractional distillation, earthy impurities, brine and water are mechanically removed. The
crude oil is then heated to a temperature of 4000C where nearly all the component of the crude is
vaporised. At this stage dissolved gases are removed and subsequently the vaporized crude fed in
through the bottom of a heated fractionating column. The petroleum of the fractionating column
ranges from about 400C at the top to about 4000C at the bottom.
As the vapour containing the mixture of substances ascends the column, it cools, condenses and
separate out into several fractions according to the volatility of the substances in the mixture.
That means substances with high boiling points separates out at the lower part while those with
lower boiling points separates out at the upper part of the column. After fractional distillation,
further separation/ refining is still necessary to give pure yield of the required products.
The fraction of crude oil, uses and the temperature at which they are liberated are given in the
Table 1 below.
Table 1: Crude oil Fraction, uses and the temperature at which they are liberated
Fraction Composition Boiling point Uses
range
Natural gas C1 – C4 < 400C Fuel for cooking and
heating
Petroleum ether C4 – C8 400C – 1000C Solvent used in laboratory
and dry cleaning
Petro gasoline C4 – C12 400C Fuel for car and
motorcycle
Kerosene C2 – C18 2000C – 2500C Fuel for cooking, jet
engine aeroplane and
solvent
Gas oil or diesel oil C12 – C25 250 – 3500C Fuel for diesel engine e.g.
tractor car, generator

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 lorries
Lubricating oil (mineral oil) 3500C – 5000C Lubricating moving parts
Bitumen Road construction and
house roofing

OCTANE NUMBER/RATING
Octane rating or octane number (ON) is a measure of the quality or performance of petrol. It
measures the combustion performance of the petrol. The petrol fraction obtained directly from
the fractional distillation has manly straight chain alkanes. It burns unevenly in the internal
combustion engine with series of rattling metallic sound causing the engine to knock.
Meanwhile, petrol composed of manly branched alkanes, cycloalkanes and aromatic
hydrocarbons burns smoothly in the internal combustion engine resisting the knocking of the
engine (i.e. have anti knocking quality). Engine knock increases the quantity of fuel consumed
per distance travelled as compared to a smoothly running engine. It is also subjects the engine to
increased wear and physical damage. Straight-chain paraffins have a much higher tendency to
knock than do branched-chain paraffins

The octane rating or octane number (ON) evaluates the performance of petrol on a scale that
rates 2, 2, 4-trimethylpentane (iso-octane) as 100, while n-heptane with the potential to make
engine knock easily is rated 0. The ON is the percentage of iso-octane in a gasoline blend. That
is, the proportion of 2, 2, 4-trimethylpentane that is mixed with n-heptane in a fuel. For example,
if gasoline has ON=80, it means that the gasoline is a blend of 80% iso-octane and 20% n-
heptane. The higher the octane number, the less likely it is for the gasoline cause engine knock.

The three options available for improving the octane number include;
1. Converting straight-chain paraffins to branched chain compounds
2. Blending ring-containing aromatic compounds into the gasoline, because aromatic
compounds have very high octane numbers.
3. Addition of special antiknock compounds into the gasoline

Blending aromatic compounds in gasoline is on the decline because it leads to more smoke and
soot formation as compared to paraffins. Thus an increased concern about air pollution demands
that future gasoline formulations should contain fewer aromatics. Furthermore, long-term
exposure to benzene has been implicated to cause leukemia in humans. Also, before now, the
most widely used antiknock additive was tetraethyllead. The use of tetraethyllead in gasoline is

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now completely stopped because of environmental concerns. Lead oxides produced when
tetraethyllead burns in the engine get into the environment, accumulates in plants, humans and
other animals until it reaches toxic level. Most lead compounds are poisonous to humans and
other animals. Thus the best strategy for improving the octane number of gasoline is to convert
straight chain paraffins into branched-chains.
Therefore, converting straight-chain paraffins into branched chain compounds (cracking) is the
best option. Cracking operation is done in the presence of solid materials containing silicon and
aluminum oxides as catalysts which helps to converts large paraffin molecules into smaller ones
and also changed straight chained carbon to branched structures.

OTHER REFINING METHODS

Gasoline also called petrol is the major product of petroleum and of the highest demand. And the
quantity of petrol obtained from fractional distillation cannot satisfy the very large demand for
the product. Fractional distillation can only converted about 20% of high-quality crude oil into
gasoline. Also, the octane number of the gasoline obtained is low (about 50-60), thus having the
potential to cause knocking in engines. To solve these problems further refining is necessary to
improve the quality and quantity of the fractions. To this end, modern refinery technology are
now used to convert almost 50% of crude oil to gasoline with octane number that can be higher
than 90. The modern refinery technologies that can be used are;

1. Cracking
2. Reforming
3. Desulphurization
1. Cracking
Cracking is the most important method used to improve the quality and quantity of petrol. After
fractional distillation the petrol fraction obtained is mainly high molecular mass hydrocarbon
with poor fuel anti-knocking properties. The breaking down of the high molecular mass
hydrocarbon to lower molecular hydrocarbon with suitable properties as fuel is called cracking.
Several types of cracking processes are available but the three main types are discussed;
a. Thermal Cracking: - This involves the use of both high temperature (over 500 0C) and
pressure to break down less volatile, long chain hydrocarbon into short chained more
volatile hydrocarbon with superior fuel properties. The disadvantage of this process is
that it converts a lot of the petrol hydrocarbon into tar and coke instead of converting all
the petrol to high-value gasoline. Thus giving low yield and high cost.

b. Catalytic Cracking: - Catalytic cracking employs the use of catalyst at low temperatures
and pressures to break down long hydrocarbon into short chained. In most cases,
aluminium oxide, silicon (IV) oxide and thorium oxide are used as the catalyst. The
quality and quantity of fuel obtained from catalytic cracking is usually higher than that of
thermal cracking. In catalytic cracking, the octane number is usually higher than 70, with
more branched chain and ring compounds.

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 c. Hydrocracking: - This method is used to produce high grade petrol consisting of manly of
branched chained alkanes. Unsaturated hydrocarbons are not produced. It involves
passing the fraction through excess dry hydrogen gas at moderate temperature in the
presence of sodium silicate and platinum catalyst.
2. Reforming
For example, straight chain and unbranched hydrocarbon can be converted into cyclic and
aromatic compounds. Reformation results to the production of fuel with high octane rating.
N-hexane and n-heptane can be converted into benzene and toluene respectively.
Several reforming methods are available which includes;
a. Dehydrogenation
b. Isomerization
c. Cyclization
d. Alkylation

a. Dehydrogenation: - This involves the loss of hydrogen from cycloalkanes converting

them to aromatics.

b. Isomerization: - This involves rearrangement straight chained alkanes to branched

alkanes. The conversion occurs by the use of moderate temperatures in the presence of
platinum or aluminium as catalyst.

c. Cyclization:- Here, straight chained hydrocarbons are converted into cyclic

hydrocarbons. The hydrocarbons formed can further be dehydrogenated to form
aromatics

d. Alkylation: - This is involves the coupling two smaller hydrocarbons such as an alkane
and an alkene to produce fraction with very high octane number and thus used component
for high quality gasoline.

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3. Desulphurization
This is the process of removing traces of sulphur from petroleum

COAL
Coal is a black solid matter formed as a result of anaerobic decomposition of vegetable matter
under high pressure. Coal contains mainly carbon and hydrogen with other inorganic elements
such as nitrogen, sulphur and metal salt. Coal is classified into three groups based on the
formation stage
Lignite coal: This has the lowest carbon content (35 – 55%). Its low carbon content makes it
look brownish and as such known as brown coal.
Bituminous coal: This coal is harder and contains more carbon content than lignite. Bituminous
carbon content is about 50 – 75%.
Anthracite coal: This coal is the hardest and contains the highest carbon content (exceeding
80%)
CARBONIZATION OF COAL
This is the destructive distillation of coal at high temperatures (1100 – 13000C) in an oxygen free
environments to produce a number of products; further filtered into Coal Gas, Coal Tar, and
Coke.

Coal gas: Coal gas is product from the destructive distillation of soft coal. It is a mixture of
gasses without a fixed composition, consisting mainly of hydrogen and methane, together with
small quantity of ethane ethyne carbondioxide, hydrogencynide carbon monoxide carbon
dioxide, and nitrogen etc. Coal gas is a flammable gas used as industrial fuel.

Ammoniacal liquor: It a product of the destructive distillation of bituminous coal consisting of

a concentrated solution of ammonia and ammonium compounds. Other constituent of
ammoniacal liquor includes amines, pyridine, hydrogen sulphide, other sulfur compounds etc.
Ammonical liquor is used mainly for the production of ammonia fertilizers because it is rich in
ammonia.

Coal tar: This is the viscous liquid fraction of the carbonization of coal and it contains mainly
aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene and their
homologues. After distilling coal tar, it is further filtered at different temperatures into the
desired aromatic compounds.

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 Table 1: Fraction from coal tar
Fraction Boiling Constituents
range
Light oil < 2000C Benzene, toluene
Middle oil 200 - 2500C Naphthalene, phenol
Heavy oil 250 - 3000C Cresol, Pyridin, naphthalene,
phenol and xylols
Anthracene 300 - 3500C Anthracene phenanthrene etc
Pitch >3000C Used as asphalt

Coke
Coke is the grey, hard solid residue of carbonization of coal containing mainly carbon and a few
inorganic impurities. It is widely used as a reducing agent in extraction of metal (e.g iron) and in
the preparation of ethyne by converting carbide into ethyne.

Hydrogenation of coal: This is the process by which coal is converted to a viscous liquid;
distillation of this viscous liquid gives fractions that can be used as fuel. The process is called
Bergius process.

REVIEW QUESTIONS
1. Indicate whether the following statements are true or false:
(a) A gasoline that has an octane number of 54 contains 54% iso-octane and 46% heptane.
(b) In recent years domestic oil production has exceeded domestic consumption.
(c) Distillation of crude oil is a physical process.
(d) Reforming of crude oil changes the number of carbon atoms in the molecule chain.
(e) Cracking of crude oil does not change the number of carbon atoms in the molecule
Chain
2. How many mols of carbon dioxide are produced by burning a mole of gasoline fuel? Assume
that gasoline can be represented as octane

3. Briefly explain the following;

a. Cracking
b. Octane number
c. Reforming

4. Explain why cars now use unleaded gasoline.