1.

COAL AND PETROLEUM

PROCESSING

OUTLINE
 Origin of coal and its ranking

 Carbonisation of coal

 Gasification of coal

 Hydrogenation of coal

 Petroleum – origin, Classification and mining

 Distillation of petroleum

 Rating of Petrol and Diesel

 Cracking, Alkylation, Hydro treating and

Reforming
2
 INTRODUCTION
Fuels are substances that produce heat on
composition.
It includes substances that combine with
oxygen to generate a large amount of heat
energy. Fuels have two major purposes:
1. Domestic like wood, low quality coal, natural
gas
2. Industrial purpose such as coal and petroleum
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 1.1 ORIGIN OF COAL AND ITS
RANKING

❑ Coal is a combustible, dark and compact stratified

mass of decayed plant.
❑ Coal is formed by thousands and millions of years of
decomposition of plants that got buried deep inside the
earth due to various natural phenomena like
earthquakes and volcanoes.
❑ Coal has formed over geological time from buried
biomass by the action of :
Bacteria
High temperature and
High pressure

4
 CONT’D…

Coal is a complex combination of materials, and the

combination can greatly differ from one
formation or deposit to another. These differences
result from:
1. The varying types of vegetation from which the
coal originated.
2. The depths of burial, and the temperatures and
pressures at those depths.
3. The length of time the coal has been forming in
the deposit

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 RANK OF COAL
The parameters significant to determine the quality of final coals. Thus
quality differences give rise to the concept of coal rank, which is used
to indicate the stage of alteration, or degree of coalification
These parameters are
 The chemical and physical properties,

 The nature and the quantity of inorganic matter (mineral content)

 Moisture present

The greater the alteration implies the higher the rank of the coal.
High-rank coals are high in carbon and heat value, but low in hydrogen
and oxygen.
Low-rank coals are low in carbon but high in hydrogen and oxygen
content. Anthracite is the highest carbon content, followed by
bituminous, sub-bituminous and lignite coal, which has the lowest
carbon content

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 PEAT

o It is mass of recently accumulated to partially carbonized plant

debris and it is organic sediment
o It has carbon content of less than 60%
o Coalification will transform it into coal

Its plant debris source is

Still easily recognizable

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 LIGNITE
o It is the lowest rank of coal and it has been
transformed into a rock and that rock is a
brown –black coal
o It has a carbon content of b/n 60-70% on dry
ash
 when it is bringing to the surface it became soft
and crumbled easily as soon as it exposed to air

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 SUB-BITUMINOUS COAL
❑ It is a lignite that has been subjected to an organic
metamorphism. This metamorphism has driven off
some of oxygen and hydrogen from the coal
❑ This loss produces coal with a higher carbon content
(71-77% on a dry ash)

BITUMINOUS COAL
▪ It is the most abundant rank of coal
▪ It is formed when a sub bituminous coal is to high level
of organic metamorphism
▪ It has carbon content b/n 77-87% on dry ash and
heating value is much higher than lignite and sub
bituminous 9
 Photo of bituminous coal

It is banded sedimentary
rock

It is used to heat homes, power steam engines, create

steel and generate electricity.

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 ANTHRACITE

➢ It is the highest rank of coal

➢ It has carbon content of over 87% on a dry ash
➢ It has the highest heating value
➢ The heat generation is intense enough

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 1.2. CARBONISATION OF COAL

The conversion of organic substance in to carbon or carbon

containing residue through pyrolysis or destructive
distillation.
Generally coal is the product of the decomposition of
vegetable matter under great pressure.
During carbonization the following rxn can take place
dehydrogenation ,isomerization ,condensation and
hydrogen transfer
During Carbonisation of coal, the carbon content increases
and the hydrogen and oxygen contents decrease. The
percentage of volatile matter decreases until at the stage
when the hardest coal, anthracite, is formed
Example: Destructive distillation of coal
On strongly heating coal in air, destructive distillation
occurs.
Coal breaks down in different components such as coal gas,
ammoniacal liquor, coal tar and coke. 12
.

Coal gas - hydrogen, methane and carbon monoxide mixture

Ammoniacal liquor-A solution of ammonia in water

Coal tar-mixture of hundreds of carbon compounds

Coke- Coke consists of carbon only 13

 1.3. GASIFICATION OF COAL

It is the process of producing synthesis gas i.e mixture of

CH4,CO,H2,CO2 and water vapor from coal, water and
air.
process of gasification & chemical reactions
➢ Coal is blown through with O2& steam while being
heated under pressure
➢ The reaction occurring inside gasifier

Reactions: 1. Coal(3C) + O2 + H2O H2 + 3 CO

2. CO + H2O CO2 +H2

3.

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 1.4. HYDROGENATION OF COAL

 It is the process of liquefaction of coal to form

petrol and any oil products.
 It is a destructive hydrogenation process, in which
the coal at a temperature sufficiently high to
break down the large and complicated molecules
of the coal substance.
 The main function of high temperature is to effect the
cracking reaction which simplifies the molecular
structure of the coal and produces molecules of the
size required.
 The essential parts of the reaction are that coal is
subjected to the action of heat and high pressure
hydrogen in the presence of catalysts.
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  The main function of high pressure hydrogen is to
increase the yield of the desired product by
preventing coke formation. When coal is heated in
the absence of hydrogen, the large coal molecules
which contain relatively littely hydrogen are broken
down into smaller molecules, some of which are rich
in hydrogen than the original coal and some are
poorer form the yield.

 When the heating of coal is carried out in the

presence of high pressure hydrogen, coke
formation can be avoided, since unsaturated
molecules react with hydrogen so that
polymerization is prevented and the yield of light
oil products is increased. 16
1.5. Petroleum – origin, Classification and mining

❑ Crude oil or petroleum is a dark viscous liquid

which has a strong smell.
❑ It is a mixture of several compounds of carbon
& is found deep within the earth’s crust.
❑ The name petroleum is derived from Latin:
Petra means rock and oleum means oil.
❑ It is formed from decomposition of organic
material, which buried under the sea over
millions of years ago.
❑ Decomposition occurred through the action of
bacteria, effects of pressure , heat & absence
of air
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 CLASSIFICATION
➢ Petroleum is a mixture of a very large number of
different hydrocarbons.
➢ Hydrocarbons within petroleum define its physical
properties , chemical properties, color & viscosity.
➢ It is classified according to nature of hydrocarbon
content., it can be classified in to three
1. Paraffinic or Paraffin oil based: if the residue contains a
molecules of alkanes (Formula Cn +H(2n+2)) (linear or
branched) Ex: Methane, ethane, butane.

Some of paraffin that

exist in petroleum
18
 .

2 Asphaltic or Asphalt base oils: if the residue contains,

hydrocarbons of one or more rings(naphthenes)

3. Aromatics : Lower members of aromatic

compounds are present in small amounts in crude oils

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 MINING
 Petroleum occurs under earth crust at various depths
and is brought to surface by drilling wells and
pumping out the oil.

 It is extracted by drilling holes in the earth’s crust and

sinking pipes into it till the pipe reaches the oil deposit
which may be as deep as 1Km.

 Sometimes the oil gushes out of the pipe due to the

pressure of the natural gas present inside. As the
pressure of the gas inside decreases, the oil is
extracted by pumping with the help of lift pumps.

 From the oil fields the crude oil is taken to the

refineries through pipe line which are either laid on
the ground or buried a few meters inside.
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 1.6. DISTILLATION OF PETROLEUM

❑ Petroleum has many impurities like water, salt, sand and also

complex mixture of many hydrocarbon compounds. The process

whereby the petroleum is separated into its components along with

the separation of impurities is called refining of petroleum.

❑ The refining is done by fractional distillation.

❑ Each hydrocarbon component with its own boiling point separates

out neatly when the petroleum is heated

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FRACTIONAL DISTILLATION OF PETROLEUM DIAGRAMMATICALLY

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 CONT…

❑ The crude oil obtained from the oil wells is heated to 400C
❑ The volatile components start evaporating & pass through a
fractionalizing column.
❑ Different components condense and are then separated out by
collecting funnels

❑ The vapors with higher boiling points condense first.

❑ The vapors having lower boiling points are collected at higher levels
in the tower
❑ Gases do not liquefy at such high temperatures and are removed at
the top of the tower
❑ Petroleum is distilled into many fractions, and there may be five to
six fractions
❑ The residue from the petroleum is removed from the bottom of the
furnace
❑ Residue is subjected to further fractional distillation by raising the
temperature above 400C in another fractional distillation tower. 23
 CONT…..
❑ Fractions obtained from distillation of crude oil
are : fuel oil, diesel oil, gasoline or petrol,
petroleum gas.
❑ Other fractions obtained after fractional
distillation above 400C include lubricating oil,
paraffin wax & asphalt.
The various fractions and their uses
➢ Fuel oil- Have 15 to 18 carbon atoms

-Their Bpt are b/n 350C and 400C

-used in industries for furnaces & boilers
-It is better than coal, B/se it does not
have any residue
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➢ DIESEL OIL
 Hydrocarbons have 13 to 15 carbon atoms
 Their boiling points are b/n 250C & 350C
 Used to run buses, trucks, railways, ships, & electric
generators.
➢ Kerosene oil
✓ hydrocarbons have 10 to 12 carbon atoms
✓ Their boiling points are b/n 170C & 250C
✓ used in homes for cooking, lighting lamps.

➢ Gasoline or petrol
▪ Hydrocarbons have 5 to 10 carbon atoms
▪ Their boiling points are b/n 40C & 170C
▪ used in cars and other vehicles as fuels & as solvent
in industries.
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➢PETROLEUM GAS
 Hydrocarbons have 1 to 4 carbon atoms
 Their boiling point is below 40C
➢ Lubricating oil
▪ Hydrocarbons have 10 to 20 carbon atoms
▪ Their boiling point is more than 400C
▪ The oil is not used as a fuel rather used for lubricating
various machine parts
➢ Paraffin wax
▪ Hydrocarbons have 20 to 30 carbon atoms
▪ Their boiling point is above 400C
▪ Used to make candles, wax paper, ointments, grease and
many toiletry goods.
➢ Asphalt
▪ Hydrocarbons have 30 to 50 carbon atoms
▪ It is used for making road surfaces 26
 1.7. RATING OF PETROL(GASOLINE)
 Gasoline is a complex mixture of over 500 hydrocarbons.
 It contain smaller amount of alkanes & aromatic cpds

 almost no alkene & alkyne

➢ The octane number :

❑ Fuel octane requirements for gasoline engines vary with the
compression ratio of the engine
❑ Engine compression ratio is the relative volume of a cylinder
from the bottom to the top most position of the piston's stroke
❑ The higher an engine's compression ratio, the greater the
amount of heat generated in the cylinder during the
compression stroke.
❑ If fuel octane is too low for a given compression ratio, the fuel
ignites too early and the fuel charge explodes, loss in power, 27
possible engine damage, and an audible "knock
 CONT’D…
 The octane number of gasoline is a measure of its
resistance to knock.
 It is determined by comparing the characteristics of a
gasoline to isooctane (2, 2, 4-trimethylpentane) and
heptane.
 Isooctane is assigned an octane number of 100

 It is highly branched compound that burns smoothly

with little knock.
 Heptane, a straight chain, un branched molecule

 It has octane rating of zero because of its bad knocking

properties
 Gasoline (directly from the refinery distillation column)
has an octane number of 70. 28
 CONT’D…
 Cracking, isomerization, and other refining processes
used to increase the octane rating of gasoline to about 90
 Anti-knock agents may be added to further increase the
octane rating
 Octane rating versus type of compound:
✓ Octane ratings decrease with increasing carbon chain length.
✓ Octane ratings increase with carbon chain branching.
✓ Octane ratings increase in aromatics with same number of
carbons.
❖ Generally for most automobiles, use the lowest grade of
87 octanes, unless specifically use a higher octane
gasoline
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 1.8. CRACKING, ALKYLATION, HYDRO TREATING AND
REFORMING

➢ Cracking
From the fractional distillation of petroleum, there is a
great demand for the gasoline, thus higher boiling
fractions such as heavy oil are converted to gasoline by
the cracking process.

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 CONT’D…
 Cracking processes break down heavier hydrocarbon
molecules (high boiling point oils) into lighter products such
as petrol and diesel
 The processes include catalytic cracking, thermal cracking
and hydro cracking.
1. Catalytic cracking
▪ Used to convert heavy hydrocarbon fractions by vacuum
distillation into a mixture of useful products like petrol &
light fuel oil
▪ The feedstock undergoes a chemical breakdown, under
controlled heat (450 - 500oC) , pressure &catalyst
▪ silica - alumina or silica - magnesia are most effective
catalysts
▪ (petrol, LPG, unsaturated olefin compounds), a liquid
residue called cycle oil, light gases and a solid coke residue
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 2. THERMAL CRACKING
 Uses heat to break down the residue from vacuum
distillation
 By alkylation or polymerization cracked gases are
converted to petrol
3. Hydrocracking
▪ It is catalytic cracking in the presence of hydrogen.

▪ Used to produce light distillates & increase the yield of

petrol
▪ It does not produce residue

▪ It results in desulphurization, (removal of sulphur),

denitrification (removal of nitrogen compounds) and
conversion of olefins to paraffins
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 ALKYLATION
 Alkylation refers to the chemical bonding of propylene
and butylene light molecules with isobutane to form
larger branched-chain molecules (isoparaffins) that make
high octane petrol in the presence of an acid catalyst,
usually sulphuric acid or hydrofluoric acid
C4H10 + C4H8 C8H18
Reforming
❑ It rearranges hydrocarbon molecules naphthas into high
octane petrol and petrochemical feedstock
❑ naphthas are hydrocarbon mixtures containing many
paraffins and naphthenes
❑ Through Reforming paraffins and naphthenes converts to
isoparaffins and aromatics.
❑ isoparaffins and aromatics used to blend higher octane
petrol 33