APPLIED CHEMISTRY

LECTURE 7
LIQUID FUEL
Liquid fuels are those combustible or energy
generating molecules that can be harnessed to
create mechanical energy, usually producing kinetic
energy.
They also must take the shape of their container.
PROPERTIES OF LIQUID FUELS
 Viscosity is a measure of a fluid's resistance to The viscosity of liquids decreases rapidly with
flow. It describes the internal friction of a moving an increase in temperature, and the viscosity
fluid. A fluid with large viscosity resists motion of gases increases with an increase in
because its molecular makeup gives it a lot of temperature. Thus, upon heating, liquids flow
internal friction more easily, whereas gases flow more
sluggishly In liquids Increasing
Viscosity temperature results in a
decrease in viscosity
because a larger
temperature means
• Measure of fuel’s internal resistance to flow particles have greater
• Most important characteristic for storage and use thermal energy and are
more easily able to
• Decreases as temperature increases overcome the attractive
forces binding them
Calorific value is the amount of energy together.
released or produced when 1 kg of fuel Increasing gas temperature
Calorific value burns or any other substance is burnt in causes the gas molecules to
the presence of oxygen and the products collide more often. This
of combustion are cooled to STP. Its SI increases the gas viscosity
• Heat or energy produced unit is kJ/kg. because the transfer of
momentum between
• Gross calorific value (GCV): highest heat value stationary and moving

• Net calorific value (NCV): lowest heat value

molecules is what causes
gas viscosity.

The total amount The heat produced by combustion of unit quantity of

of heat released a solid or liquid fuel when burned, at a constant
when a fuel is pressure of 1 atm (0.1 MPa), under conditions such
burned is called that all the water in the products remains in the form
GCV. of vapor is known as NCV.
Sulphur content

• Depends on source of crude oil and less on the

refining process
• Furnace oil: 2-4 % sulphur
• Sulphuric acid causes corrosion
The inorganic components present in the fuel
remain in oxidized form after combustion of fuel and
Ash content are referred to as ash.

• Inorganic material in fuel

• Typically 0.03 - 0.07%
• More carbon content more will be the ash.
Carbon residue

• Tendency of oil to deposit a carbonaceous solid

residue on a hot surface

Water content

• Normally low in furnace oil supplied (<1% at

refinery)
• Free or emulsified form
• Can damage furnace surface and impact flame
Crude oil is a mixture of different hydrocarbons. They
can be separated by fractional distillation according
to their boiling point which change according to
their size (carbon atoms).

The most volatile fraction, i.e. with the lowest boiling

point evaporates off first and goes to the top of the
column.
The remaining, longer chain hydrocarbons also
separate out according to their boiling points.
SEPARATING HYDROCARBONS

Fractional distillation of crude oil, a mixture of

hydrocarbons is able to separate different ‘fractions’
based on their boiling points.
The longest the chain, the higher the boiling point.
Methane, ethane and propane, all short chained
hydrocarbons have very low boiling points, whereas
hydrocarbons containing a hundred of more carbon
atoms have relatively high boiling points.
Hydrocarbons in crude oil

Crude oil contains two families of hydrocarbon compounds: The alkanes and
alkenes.

The alkanes have a general formula of CnH2n + 2 and are used mainly as
fuels for combustion.

They include methane (natural gas), the simplest alkane with the formula
CH4.

Alkanes can have up to 200 carbon atoms in a long carbon chain, but their
general formula does not change.

Longer chains are used for diesel engines, lubricating oils and domestic fuels.

Alkanes with more than 100 carbon atoms are found in bitumen or tar.
Useful alkanes include natural gas, petrol and diesel.

When we combust these fuels with oxygen, energy in

the form of heat is released.

The products of complete combustion are water and

carbon dioxide.
SUPPLY AND DEMAND OF CRUDE OIL FRACTIONS

There is a greater demand by those who use fossil fuels

for the low carbon, more volatile hydrocarbons which
are used for fuel in cars, other vehicles and lorries.

However, there is a greater supply of the high carbon,

less volatile hydrocarbons.

By breaking up the surplus large fractions to form small

volatile fractions, companies like Shell and BP can
balance supply and demand.
This is called cracking.
Cracking, in petroleum refining, the process by which heavy
hydrocarbon molecules are broken up into lighter molecules
by means of heat and usually pressure and sometimes
catalysts. Cracking is the most important process for the
commercial production of gasoline and diesel fuel.
Crude oil contains far too many long chained
hydrocarbons with more than 15 carbon atoms in
them.

Cracking is also used to form ethene, the starting product

for most plastics and other polymers.

We can separate long chain molecules into short

chained molecules.
Cracking these hydrocarbons requires heat, a catalyst
and an oxygen free atmosphere

cracking need
oxygen free
atmosphere.
 PETROLEUM
Petroleum is a naturally occurring liquid found
beneath the earth's surface that can be refined
into fuel. Petroleum is a fossil fuel, meaning that
it has been created by the decomposition of
organic matter over millions of years.
• Latin word Petra – rock, oleum – oil
• Natural occurring brown to black
• Mainly comprising of hydrocarbon
• Found under the crust of earth (on shore / off shore)

Petroleum is formed when large quantities of dead organisms–primarily zooplankton

and algae–underneath sedimentary rock are subjected to intense heat and pressure.
MODERN THEORY:

Petroleum is of animal as well as plant origin.

Petroleum is believed to be formed by the decay and
decomposition of marine animals as well as plants of
prehistoric forest.
It is thought that due to some upheavals or earthquakes,
these pre-historic forest and marine animals got buried
under the crust of earth.
Then due high pressure and temperature under the earth
crust for long period of time these biological matters
decomposed into petroleum. The modern theory explains
the presence of:
• Brine and coal in the vicinity of petroleum.
• It also explains the presence of nitrogen and sulphur
compounds.
•Chlorophyll and optically active compounds are still not
explained
COMPOSITION OF PETROLEUM
 The principal component of petroleum are hydrocarbons,
small amount of sulphur, nitrogen and oxygen compound as
impurities.
 Hydrocarbon found in petroleum are paraffins, naphthenes,
aromatics, olefins etc.
 Sulphur compound found in petroleum are hydrogen
sulphide, thiophene, mercaptons etc.
 Oxygen occur in combined form in phenols and alcohols etc
 Nitrogen compounds includes pyridines, quinolines etc.
 Typical composition by weight percent of petroleum is given
bellow:
– Carbon: 84 – 87%
– Hydrogen: 11 – 15%
– Sulphur: 0.1 – 3%
– Nitrogen: 0.1 – 1.5%
– Oxygen: 0.3 – 1.8%
PRODUCTION OF PETROLEUM

 Petroleum always occurs along with natural gas.

 After drilling in the crust of earth both natural gas and oil
flow up through pipes initially.
 When the oil pressure decreases, then the residual
either sucked by creating vacuum or pressure is
created by injecting compressed gas.
 When the oil well contain oil and gas it is called wet
well and if it contain only gas then it is called dry well.
 For digging an oil well rotary drilling system is used.
 The main boring is of 20 – 30cm in diameter and its
depth may varies from 1.5 to 4.5 km.
 The entire well is provided with a steel casing to
prevent boring wall to collapse.
Pre-treatment of crude oil

• Oil and gas when they come out of oil field are separated
(Phase separator).
• The natural gas is compressed to liquid (LPG) which is used
for heating domestic and industrial ovens.

• Crude oil is made free from:

– water (up to25%), requires extra heat for distillation.
– salts (MgCl2, CaCl2, NaCl etc.) scaling
–sediments ,(1 – 1.5%) cause erosion and scaling.

Scaling is a common term in the oil industry used to describe solid

deposits that grow over time, blocking and hindering fluid flow through
pipelines, valves, pumps etc. with significant reduction in production rates
and equipment damages
 Crude oil stabilisation (or stabilization) is a
partial distillation process that renders
crude oil suitable for storage in
atmospheric tanks, or of a quality suitable
for sales or pipeline transportation

• It is then made free of some dissolved gases into it by the

process called stabilization.

• Crude oil is subjected to centrifuging, filtration and settling

after heating it to 120 to 160 degree C at 6 – 8 atm to
remove these impurities and dissolved gases.

Phase separation is the creation of two distinct phases from a

single homogeneous mixture. The most common type of phase
separation is between two immiscible liquids such as oil and
water.
CLASSIFICATION OF PETROLEUM

 Depending upon nature of hydrocarbon present in petroleum is

classified into:

Paraffinic:
Saturated hydrocarbons with general formula CnH2n+2 where n =
1 to 35. When n = 1 to 5 then it is gases (methane, ethane, butane
etc)
when n = 5 to 15 then it is liquid (gasoline) and when n = 16 and
above then it is semi-solid (paraffin wax)

 Naphthenic:
Saturated ring hydrocarbon having general formula CnH2n
(cyclohexane).
 Asphaltic:
Aromatic hydrocarbon contains 6 hydrocarbon in form of
hexagon ring and are unsaturated compound having
general formula C6H2n-6 where n = 1 to 6.

 Mixed:
Crude containing all paraffinic, naphthenic and asphaltic
constituents.
DIFFERENCES BETWEEN COAL AND PETROLEUM
OIL SHALES
Kerogen is solid, insoluble organic matter in sedimentary
rocks. It is the most abundant source of organic
compounds on earth, exceeding the total organic content
of living matter 10,000-fold

Oil shales contain a

solid combustible
mixture of
hydrocarbons called
kerogen.
HEAVY OILS FROM OIL SHALE

Heavy and tarlike oils from oil shale could supplement

conventional oil, but there are environmental
problems.
High sulfur content.
Extracting and processing produces:
 Toxic sludge
 Uses and contaminates larges volumes of water
Sludge is a semi-solid slurry that
can be produced from a range of
industrial processes, from water
treatment, wastewater treatment or
on-site sanitation systems.
 Gasoline is a clear petroleum-
derivative, flammable liquid, that is

GASOLINE OR PETROL AND ITS CHARACTERISTICS

used primarily as a fuel in most
spark-ignited internal combustion
engines

Gasoline is the most widely used liquid fuel.

Production of gasoline is achieved by distillation
of crude oil.

The desirable liquid is separated from the crude oil in refineries. It

contains some unsaturated straight chain hydrocarbons and
sulphur compounds. It has boiling range of 40-120 C.

Liquid gasoline itself is not actually burned, but its

fumes ignite, causing the remaining liquid to
evaporate and then burn. Gasoline is extremely
volatile and easily combusts, making any leakage
potentially extremely dangerous.
CHARACTERISTICS OF IDEAL GASOLINE

It must be cheap and readily available.

It must burn clean and produce no corrosion.
It must be knock resistant.
It should be pre-ignite easily.
It must have a high calorific value
KEROSENE OIL

Kerosene oil is obtained between 180-250 C during

fractional distillation of crude petroleum.
When kerosene is used in domestic appliances, it is
always vaporized before combustion.
By using a fair excess of air it burns with a smokeless
blue flame.

USES
Illuminant
Jet engine fuel
Tractor fuel
Additives
DIESEL FUEL AND ITS CHARACTERISTICS

Conventional diesel is similar to gasoline in that it is a

mixture of aliphatic hydrocarbons extracted from
petroleum.
The diesel fuel is obtained between 250-320oC during the
fractional distillation of crude petroleum.

Diesel generally contains 85% C and 12% H.

Diesel fuels consist of longer hydrocarbons and have low

values of ash, sediment, water and sulphate contents.

Calorific value is about 11,000 kcal/kg.

Diesel easily ignite below compression temperature.

It is used in diesel engine.
HEAVY OIL AND ITS CHARACTERISTICS

It is a fraction obtained between 320-400oC during

fractional distillation of crude petroleum.

This oil on re-fractionation gives :

Lubricating oils which are used as lubricants.

Petroleum-jelly (Vaseline) which is used as lubricants in
medicines and in cosmetics.
Greases which are used as lubricants.
Paraffin wax which is used in candles, boot polishes,
wax paper and for electrical insulation purpose
 The Fischer–Tropsch process is a collection
of chemical reactions that converts a mixture of
carbon monoxide and hydrogen into liquid
hydrocarbons. These reactions occur in the

SYNTHETIC
presence of metal catalysts, typically at
LIQUID FUEL temperatures of 150–300 °C (302–572 °F) and
pressures of one to several tens of
atmospheres

Liquid fuel from coal and/or natural gas.

When petroleum is not easily available, chemical

processes such as the Fischer-Tropsch process can
be used to produce liquid fuels.

These are known as non-petroleum fossil fuels.

BIODIESEL
Biodiesel is an alternative fuel similar to conventional
or ‘fossil’ diesel.

Biodiesel can be produced from straight vegetable oil,

animal oil/fats, tallow and waste cooking oil.

The process used to convert these oils to Biodiesel is

called trans esterification.

The Trans esterification process is the reaction of a

triglyceride (fat/oil) with an alcohol to form esters and
glycerol
ALCOHOL FUEL
Methanol
Methanol is the lightest and simplest alcohol, produced from the
natural gas component methane and by distillation of wood.
Its application is limited primarily due to its toxicity.
Used in some race cars and model airplanes.

Ethanol
Used as a fuel, most often in combination with gasoline.
There is increasing interest in the use of a blend of 85% fuel ethanol
blended with 15% gasoline. This fuel blend called E85.

Butanol
It is formed by fermentation of biomass by bacterium Clostridium
acetobutylicum. It has high energy content about 10% lower than
gasoline. Major disadvantages of butanol fuel are high flash point,
toxicity and foul odour.
Advantages

 Possesses higher calorific value.

 Combustion without the formation of dust, clinker or ash.

 Firing easier & easily extinguishable.

 Less excess furnace space.

 No wear & tear on furnace parts like solid fuels.

 Low sulphur content.

 For equal heat output lesser space & weight then solid.
DISADVANTAGES

 Costlier than solid fuels.

 Requires costly storage tanks.

 High risk of fire hazards especially of volatile liquids.

 Requirement of especially designed burners for

efficient burning.

 They give bad odour.

 The composition of LPG is
Hydrogen and Carbon, also
known as Hydrocarbons.
Specifically, LPG consists of a

USES OF PETROLEUM PRODUCTS combination of Propane (C3H8 ),

and Butane ( C4H10)

• Liquefied petroleum gas (LPG) – Domestic and industrial fuel. Also

called refinery gas. Mixture of propane and butane.

• Gasoline (Petrol) – Fuel for spark ignition internal combustion engine.

• Naphtha – Used as a solvent, paint thinner, most important use is in
the production of H2 by its steam reforming.

• Jet fuel – Fuel for jet planes and turbine engines.

• Kerosene – Used for domestic illuminant.

• Diesel – Fuel for compression ignition internal combustion engine.

• Gas oil – It is gasified for fuel gas production.

• Lubricating oil – Used for lubrication in machines and
engines. Petrolatum, or petroleum jelly, derived from petroleum, is
often used in personal care products as a moisturizing
agent.

• Petrolatum – base material for grease which is semi-solid

lubricant.

• Light fuel oil – Used as a fuel in industrial furnaces.

• Heavy fuel oil – After blending it with light fuel oil or

naphtha, it is used as a furnace fuel

• Bitumen or tar – Used as a binder and moisture proof

coating for roads.

• Wax – Used for making candles and other wax stuffs.

Pitch, in the chemical-process industries, the black or dark brown residue obtained by
distilling coal tar, wood tar, fats, fatty acids, or fatty oils.

• Residue Pitch – Used for making roads and electrodes.

POLLUTION USING CRUDE OIL
The oil industry, including companies like Shell and Exxon have a
responsibility to make sure that their company and staff do not
pollute the environment.
Occasionally, either during extraction, transport or supply of
crude oil, these companies can pollute the environment with
devastating consequences.
An oil tanker spilling its load at sea or near to populated
coastlines can destroy the local ecosystems and peoples’
livelihoods. These effects can sometimes last for many decades.
GREENHOUSE EFFECT

Over the last century, our use of fossil fuels has released huge
amounts of carbon dioxide into our atmosphere.
This has disrupted the balance between carbon in the form of
carbon dioxide and carbon found tied up under rock in crude oil,
natural gas and coal.
Currently we are adding an extra 3 billion tonnes of carbon each
year into the atmosphere.
Slowly our planet is warming because of the rising carbon dioxide
levels.
EFFECTS OF GLOBAL WARMING

Scientists have many theories as to what may happen over the

next century because of rising carbon dioxide levels in the
atmosphere, as a result of combusting fossil fossils and the
subsequent rising global temperatures.

There is now increasing agreement amongst scientists

that atmospheric carbon dioxide levels need to be controlled.

Many countries have signed ‘The Kyoto Agreement’ which aims

to reduce carbon emissions over the next 20 years. This will
perhaps stop global warming. Only one country, America has
not signed up, she is the biggest carbon polluter
EFFECTS OF GLOBAL WARMING
The greenhouse effect is a natural process where the 750 billions
tones of carbon dioxide in the atmosphere maintains the Earth’s
atmosphere at hospitable temperatures, which are supportive of
life, here on Earth.

Combusting fossil fuels is adding to this ‘warming effect’ causing

average global temperature to rise over the last fifty years.

Global warming will continue, whilst we continue to combust

fossil fuels like coal and oil.

The World’s weather, habitats and temperature are set to change

over the next century.
ACID RAIN AND FOSSIL FUELS

Carbon dioxide is not the only pollutant that is released into the
environment during the combustion of fossil fuels.
Sulphur and nitrogen, in small quantities are also present in crude
oil.
During combustion, both sulphur and nitrogen combine with
oxygen to form sulphur dioxide and nitrogen oxides.
These gases form weak acids when they react with water present
in the atmosphere.
Acid rain can damage forest and plant life. It can also acidify
lakes and ponds disrupting natures balance.
RENEWABLE ENERGY SOURCES

Renewable alternatives to using crude oil for generating

electricity are now being developed. These reduce our
dependence on crude oil, as well as reducing carbon
dioxide emissions.
Many sources of electricity that we currently use every
day are now renewable. This means that unlike coal,
natural gas and crude oil they are not used up.
Many scientists are working to develop the technology
to use these renewable sources of energy
to generate electricity
THANKYOU