UNIT-II: ENERGY – SOURCES, CONVERSION AND STORAGE

Syllabus
Unit-2
Energy : Sources, Conversion and Storage 08 hours
Chemical fuels - Introduction, Calorific value - definition, gross and net calorific values;
Determination of calorific value of a solid / liquid fuel using Bomb calorimeter and numerical
on calorific value; Petroleum cracking - fluidized bed catalytic cracking; Octane number-
Reformation of petrol.
Sustainable energy sources: Hydrogen as a fuel - advantages, production and storage.
Biofuels- Production of Biodiesel. Solar cells - Construction and working of Si based PV cell,
advantages. Quantum Dot Sensitized Solar Cells (QDSSC’s)- Principle, Properties and
Applications.
Electrochemical Energy Systems: Introduction to batteries, Classification of batteries -
primary and secondary batteries; Battery characteristics; construction, working and
applications of Lithium ion batteries.

Self-study: Fuel cells and Zinc-Air, Na-Ion batteries.

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Chemical Fuels
Definition: Chemical fuel is a combustible substance, containing carbon as main
constituent, which on proper burning gives large amount of heat, which can be used
economically for domestic and industrial purposes.
Example: Wood, charcoal, kerosene, petrol, diesel etc.
Combustion reaction of a fuel can be represented as follows:

 As most of the fuels contain carbon or carbon and hydrogen, the combustion
involves the oxidation of carbon to carbon dioxide and hydrogen to water.
 Sulphur, if present, is oxidized to sulphur dioxide while the mineral matter
forms the ash.

Classification of fuels:
 Chemical fuels are classified as primary and secondary fuels.
A. Natural or primary fuels: They are found in nature as such. Eg: wood, peat,
coal, petroleum
B. Artificial or secondary fuels: They are prepared from the primary fuels Eg:
charcoal, coke, kerosene oil, petrol etc.
 Chemical fuels are further classified as
A. Liquid fuels
B. Gaseous fuels
Physical state Primary fuels Secondary fuels
Solid Wood, coal Charcoal, coke
Liquid Petroleum Petrol, diesel, kerosene
Gas Natural gas LPG

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Importance of hydrocarbons as fuels:

 Petroleum, coal and natural gas are excellent hydrocarbons.

 These fuels are important sources of energy in daily life.
 Hydrocarbons are used as energy sources in cooking, lighting, automobiles,
production of electricity in thermal power plants etc.
 These hydrocarbon fuels meet 80% of the world’s energy demand. Thus,
hydrocarbons are important sources of energy.

Characteristics of a good/ ideal fuel:

1. It should possess high calorific value.
2. It should have moderate ignition temperature. The ignition temperature of the fuel
should neither be too low nor too high.
3. It should not produce poisonous products during combustion. In other words, it
should not cause pollution on combustion.
4. It should have moderate rate of combustion.
5. Combustion should be easily controllable i.e., combustion of fuel should be easy to
start or stop as and when required.
6. It should not leave behind much ash on combustion.
7. It should be easily available in plenty.
8. It should have low moisture content.
9. It should be cheap.
10. It should be easy to handle and transport.

Calorific value:
Definition: It is defined as the total amount of heat liberated when a unit mass or
volume of fuel is burnt completely in air or oxygen.

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Gross (High) calorific value (GCV or HCV)
Definition: The total amount of heat liberated when a unit quantity of fuel is burnt
completely in air and the products of combustion are cooled to room temperature. It is
also called as higher calorific value (HCV).

Net (low) Calorific value (NCV or LCV)

Definition: It is the amount of liberated when a unit quantity of a fuel is burnt
completely in air or oxygen and the products of combustion are allowed to escape.

Why GCV value is higher than NCV?

 In case of GCV, on cooling the combustion products, steam gets condensed to
water and liberates its latent heat.
 The measured GCV includes the latent heat of steam. Therefore, it is always
higher than the net calorific value.
 Whereas in case of NCV, the products of combustion are let off in to the
atmosphere, the calorific value does not include the latent heat of steam.
 Therefore, NCV is always lower than GCV.
Two main reactions that occur during combustion are:
 Carbon and hydrogen present in the fuel are converted in to carbon dioxide and
steam respectively, on combustion.

GCV is total heat liberated by fuel including heat of condensation of water and NCV is
heat liberated by combustion of fuel excluding heat of condensation of water. Both are
related by,
NCV = GCV – heat associated with steam

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Calculation of Heat associated with steam
NCV = GCV – heat associated with steam
Heat associated with steam = Mass of H2O formed in combustion x Latent heat of H2O
Mass of H2O formed in combustion = 9 x Mass of H2 present
(1 part by mass of hydrogen produces 9 parts by mass of water)
% of Hydrogen present in fuel
Mass of H2 present= 100
= 0.01 x % of hydrogen present in fuel

∴ Mass of H2O formed in combustion = 9 x 0.01 x % of hydrogen present in fuel

= 0.09 x % of hydrogen present in fuel
Heat associated with steam = 0.09 x % of hydrogen present in fuel x Latent heat of H2O
Latent heat of steam = 587 cal/g
∴NCV= [GCV- 0.09 x % of H2 X 587] cal/g
OR 1 Cal = 4.186 J

NCV= [GCV- 0.09 x % of H2 X 2454] KJ/Kg

Note: The unit of latent heat of water and unit of GCV, NCV should be same.

S. I. unit of calorific value: For solids, calorific value is expressed in KJ kg-1 (KiloJoules
per kg). For gaseous fuels it is expressed in J m-3 (Joules / m3).

Specific heat: Specific heat of water is the amount of heat energy required to increase the
temperature of one kg of water by one degree C.

Units: J/kg/oC.
Latent heat of steam: Latent heat of steam is the amount of heat energy required to convert 1
Kg of liquid to vapor or steam
Units:K J/kg.

Determination of Calorific Value of a fuel using Bomb Calorimeter

The calorific value of solid and non-volatile liquid fuels is determined by bomb
calorimeter.
Principle: A known mass of a solid/liquid fuel is burnt in excess oxygen. The
surrounding water in the calorimeter absorbs the heat liberated. Thus, the heat liberated

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by the fuel is equal to the heat absorbed by the water in the calorimeter. By recording
the rise in temperature of water and knowing specific heat of water, calorific value is
calculated.
Construction & working: The bomb calorimeter consists of a stainless-steel vessel with
an airtight lid. This vessel is called bomb. The bomb has an inlet valve for providing
oxygen atmosphere inside the bomb and an electrical ignition coil for starting of
combustion of fuel. The bomb is placed in an insulated copper calorimeter. The
calorimeter has a mechanical stirrer for dissipation of heat and a thermometer for
reading the temperature.
A known mass of the solid fuel is placed in a crucible. The crucible is placed inside the
bomb. The lid is closed tightly. The bomb is placed inside a copper calorimeter. A
known mass of water is taken in the calorimeter. The bomb is filled with oxygen at a
pressure of 25-30 atm. The temperature t 1 in the thermometer is noted.
On passing an electric current through the ignition coil, the fuel gets ignited. The fuel
burns liberating heat. The water is continuously stirred using the stirrer. The maximum
temperature attained by the water, t 2 , is noted.

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 Figure 1: SCHEMATIC REPRESENTATION OF BOMB CALORIMETER

Observations and calculations:

(W1 + W2) × S × (t2 − t1)
GCV = KJ/Kg
m
Where,
W1 = mass of water in the calorimeter, in kg
W2= water equivalent of the calorimeter, in kg
s = specific heat of water, in J kg -1 oC-1
t = t2-t1 = rise in temperature, in oC
m = mass of the fuel, in kg
and NCV can be calculated by
NCV = GCV – 0.09 x %H x Latent Heat of steam (J/Kg)

NCV = GCV – (0.09 × %H × 587 × 4.186) kJ/kg

NCV = GCV – (0.09 × %H × 2457) kJ/kg

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Supporting Info:
Water equivalent is nothing but the amount of water that would absorb the same
amount of heat as the calorimeter per degree temperature increase.
[Numerical problems based on GCV and NCV: Refer your class notes]

Chemical processing of crude petroleum

Processing of crude oil into desired products involve three main steps:
1. Fractional distillation
2. Cracking of petroleum
3. Reforming of petrol

CRACKING OF PETROLEUM
Definition: The decomposition of bigger hydrocarbons into simpler, low boiling
hydrocarbons of low molecular weight.

What is the need for cracking?

Cracking is very important in the petroleum industry for following reasons:
1. To produce extra petrol: Heavy fractions in less demand can be cracked to
produce extra petrol.
2. To improve the quality of ‘straight-run’ gasoline. It has to be properly blended. It
is important to note that the characteristics of gasoline obtained by cracking are
far more superior to the straight run gasoline.
3. To produce alkenes: Cracking always produces alkenes that van be used to many
useful organic chemicals.
4. There is surplus of heavier petroleum fractions.

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There are two methods for cracking:
1. Thermal cracking: The heavy oils are subjected to high temperature and
pressure; when the bigger hydrocarbon molecules break down to give smaller
molecules.
2. Catalytic cracking: the cracking procedure involves a suitable catalyst like
aluminium silicate, Al2(SiO3)3 or alumina, Al2O3

Fluidized-bed catalytic cracking (Moving-bed catalytic cracking):

Reaction conditions
Feed stock: Heavy oil
Catalyst used: y-type zeolite activated with a rare-earth oxide (12.5% Al2O3 + 87.5%
SiO2)
Temperature: 450-550 0C
Pressure: 1 atm
Yield: 70-80%
 The solid catalyst is very finely powdered, so that it behaves almost as a fluid,
which is circulated in gas stream.
 The vapors of heavy oil mixed with fluidized catalyst are forced up in to large
reactor bed in which cracking of the heavier into lighter molecules occurs.
 Near the top of the reactor, there is a centrifugal separator called cyclone, which
allows only the cracked oil vapors to pass on to the fractionating column, retains
the catalyst in the reactor itself.
 Spent catalyst from the cracking chamber is continuously transported into the
regeneration chamber through an air stream.
 The carbon deposited on catalyst particles is burnt off in regeneration chamber.
The regenerated catalyst is transported back in to the cracking chamber together
with feed stock.

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 Figure 2: Fluidized-bed catalytic cracking

Advantages of fluidized-bed catalytic cracking:

1. The yield of petrol is higher.
2. The quality of petrol produced is better.
3. Fuel after cracking has higher percentage of branched chain.
4. Fuel after cracking has higher percentage of aromatics.
5. Highly controlled process.
6. No wastage of catalyst.

Disadvantages of fluidized-bed catalytic cracking:

1. Rapid mixing of fuel and catalyst may lead to non uniform residence time.
2. Agglomeration of fine particles.
3. Fine particles of catalyst may be carried away during pressurized flow.
4. Erosion of pipes.

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OCTANE NUMBER
Octane number of a fuel is defined as the percentage of isooctane in a mixture of
isooctane and n-heptane, which has the same knocking characteristics as that of the fuel
under examination, under same set of conditions.

 It is observed that n-heptane knocks very badly; hence, it was arbitrarily

assigned an antiknock value of zero.
 On the other hand, isooctane (2,2,4-trimethylpentane) has a high resistance to
knocking and hence was arbitrarily assigned a value of 100.
 The octane number changes with the change in the structure of the hydrocarbons
as follows

Straight chain alkanes < branched chain alkanes < alkenes < cycloalkanes < aromatics

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REFORMATION OF PETROL
Definition of reformation of petrol: Conversion of straight chain hydrocarbons in
petrol into branched chain, cyclic and aromatic hydrocarbons, resulting in up gradation
of quality of the petrol is known as reformation.

How reformation improves the quality of petrol?

The octane number for straight chain hydrocarbons is low. For branched chain, cyclic
and aromatic hydrocarbons, the octane number is high. Thus reformation converts the
low octane number petrol into high octane number petrol.

Reformation reaction conditions:

The reaction conditions
Feed stocks: pre-processed gasoline
Catalyst: Platinum supported on alumino-silica.
Temperature: 460-530 0C
Pressure: 35-50 atm.

Reformation reactions:
The main reformation reactions are:
1. Isomerization
2. Cyclization
3. Aromatization
4. Dehydro aromatization

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 1. Isomerisation : Conversion of linear hydrocarbons into branched isomer.

CH3-CH2- CH2- CH2- CH2-CH 3

(n-hexane) (2-methyl pentane)

2. Cyclization: conversion of linear hydrocarbons into cyclic compounds

CH3-CH2- CH2- CH2- CH2-CH 3

(n-hexane)
Cyclohexane

3. Aromatization: Dehydrogenation of cyclic hydrocarbons to aromatic hydrocarbons.

4. Dehydro aromatization: Cyclization of linear alkanes followed by dehydrogenation.

Disadvantages of non-renewable energy

1. Once a non renewable energy source is used up it cannot be replaced again.
2. Non renewable energy source are highly polluting sources and increase the
greenhouse gases.
3. The exposure to non renewable energy sources has increased the level of
pollution.
4. The rise in temperature due to greenhouse gas accumulation.

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