University of Science and Technology of Southern Philippines

Cagayan de Oro City

1st Semester SY 2021 - 2022
TOPIC 7

FUELS

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Outline

VII. Fuels
•The Chemistry of Fuels
•Categories of Fuels
•Combustion process

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Learning Outcomes

•Deduce the concept by which organic compounds become fuel;

•Compare the categories of fuels; and

•Explain the process of combustion process.

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Fuels

• Fuel is a combustible substance, containing carbon as a main

constituent, which on proper burning gives large amount of
heat, which can be used economically for domestic and
industrial purpose.

• e.g. wood, charcoal, coal, kerosene, petrol, diesel, producer gas, oil gas

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Fuels

• Fossil fuels are non-renewable energy resources , which were stored millions
of years ago by photosynthesis.
• e.g. coal, crude oil and natural gas

• Fossil fuels are both energy dense and widespread, thus much of the world’s
industrial, utility, and transportation sectors rely on them as energy sources.

• Notwithstanding concerns with global warming, fossil fuels remain to be the

dominant energy source at present and in the foreseeable future:
• The development and deployment of technologies to harness and utilize
renewable energy sources are uneconomic at present, and;
• Concerns over storage and/or disposal of spent nuclear fuel and nuclear
proliferation.

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Classification of Fuels

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Solid Fuels

ADVANTAGES DISADVANTAGES

1. Handling and transportation of solid 1. During burning, solid fuels produce a

fuels are easy. large amount of ash and disposal of ash
2. Solid fuels are cheap and easily is a big problem.
available. 2. The calorific value of solid fuel is
3. They have a moderate ignition comparatively low.
temperature 3. Since a lot of air is required for
4. This type of fuel can be stored complete combustion, its thermal
conveniently without any risk. efficiency is not so high.
4. A large space is required for storage.
5. Combustion is a slow process and it
cannot be easily controlled.

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Liquid Fuels

ADVANTAGES DISADVANTAGES

1. Liquid fuels do not yield any ash 1. Liquid fuels are comparatively costlier
after burning. than the solid fuels.
2. They require comparatively less 2. They give unpleasant odor during
storage space. incomplete combustion.
3. Calorific value of liquid fuel is higher 3. Some amount of liquid fuels will escape
than that of solid fuels. due to evaporation during storage.
4. Their combustion is uniform and 4. Special type of burners are for effective
easily controllable. combustion.

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Gaseous Fuels

ADVANTAGES DISADVANTAGES

1. Gaseous fuels can be easily 1. They are highly inflammable and hence
transported through the pipes. the chances for fire hazards are high.
2. They do not produce any ash or 2. Since gases occupy a large volume, they
smoke during burning. require large storage tanks.
3. They have high calorific value than
the solid fuels.
4. They have high thermal efficiency.

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Requirements of a Good Fuel

• A good fuel should have the following characteristics:

• High calorific value.

• Moderate ignition temperature.
• Low contents of non-combustible matters.
• Low moisture content.
• Free from objectionable and harmful gases like CO, SOx, H2S.
• Moderate velocity of combustion.
• Combustion should be controllable.
• Easy to transport and readily available at low cost.

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Combustion

• Combustion is an exothermic chemical reaction, which is

accompanied by development of heat and light at a rapid rate,
temperature rises considerably.
• During the process of combustion, carbon, hydrogen, etc., combine with
oxygen with a liberation of heat.

FUEL + O2 PRODUCTS + HEAT

More heat energy content Lesser heat energy content

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Combustion

• For proper combustion, the substance must be brought to its kindling (or)
ignition temperature, which may be defined as:
• The minimum temperature at which the substance ignites and burns without
further addition of heat from outside.

• Factors affecting the rate of combustion:

• The concentration of the fuel and air.
• The nature of the combustible substance.
• The temperature.
• With increase in pressure or surface area of the fuel the rate of combustion can
be increased.
• It increases with increase in pressure of air.
• It Increases with preheating of fuel and air.

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Calorific Value
• Heating value or calorific value is the most important characteristic
property of any fuel.

• Calorific value may be defined as “the amount of heat liberated by the

complete combustion of a unit mass of a fuel” or “the heat produced at
constant volume by the complete combustion of a unit quantity of coal”.

System Solid/Liquid Fuels Gaseous Fuels

CGS Calories/gm Calories/cm3

MKS kcal/kg k cal/m3
B.T.U BTU/lb BTU/ft3

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Calorific Value

• There are different expressions of calorific value:

• Gross or high calorific value (GCV or HCV) includes the latent heat of
vaporization of water in the combustion products, i.e. water is in the form of a
liquid.
• “The total heat generated when a unit quantity of fuel is completely burnt
and the products of combustion are cooled to room temperature. ”

• Otherwise, when the water is not condensed, i.e. is in the form of a vapor, it is
called the Net or Lower Calorific Value (NCV or LCV).
• “The net heat produced when a unit quantity of fuel is completely burnt
and the products of combustion are allowed to escape. ”

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Determination of Calorific Value of Solid and Liquid Fuels

• The calorific value of a solid or liquid fuel can be determined by

using bomb calorimeter .

• Principle: A known amount of the fuel is burnt in excess of oxygen

and heat liberated is transferred to a known amount of water.
The calorific value of the fuel is then determined by applying the
principle of calorimetry.
• i.e. Heat gained = Heat lost

Heat released by fuel +

Total heat absorbed by (Water
Heat released by fuse wire + = + Bomb + Calorimeter)
Heat released by cotton thread
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Bomb Calorimeter

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Calorific Value

Note: The water equivalent of calorimeter is determined by burning a fuel of known calorific value
and using above equation. The fuels used for this purpose is benzoic acid (HCV =6325kcal/kg) and
napthalene (HCV= 9688kcal/kg) .

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Corrections

• For accurate results the following corrections are also incorporated:

a) Fuse wire correction: As Mg wire is used for ignition, the heat generated
by burning of Mg wire is also included in the gross calorific value. Hence
this amount of heat has to be subtracted from the total value.
b) Acid Correction: During combustion, sulfur and nitrogen present in the
fuel are oxidized to their corresponding acids under high pressure and
temperature.
S + 2H + 2O2 → H2SO4 + Heat
2N + 2H + 3O2 → 2HNO3 + Heat
• Formation of these acids is an exothermic reaction. Hence, these heat
values must be subtracted from HCV.

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Corrections

• For accurate results the following corrections are also incorporated:

c) Cooling Correction: When the bomb calorimeter is allowed to cool from
maximum temperature to room temperature, some amount of heat is
radiated. From the rate of cooling and actual time for cooling, cooling
correction is made and it is added to the temperature difference.

Therefore, Gross Calorific Value:

Gross calorific =
Value (HCV)

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Dulong’s Formula for Calorific Value (Theoretical calculation)

Gross calorific Value (HCV)

1 O
= [8080C + 34,500( H − ) + 2,240 S ]kcal / kg
100 8
• where: C, H, O & S represent the % of the corresponding elements in the fuel.
Net Calorific value (LCV)
9H
= [ HCV −  587]kcal / kg
100
= [ HCV − 0.09 H  587]kcal / kg

• where: H = % of H2 in the fuel.

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Calorific Value

HCV LCV
Amount of heat evolved when a unit weight (or Amount of heat evolved when a unit weight (or
volume in the case of gaseous fuels) of the fuel is volume in the case of gaseous fuels) of the fuel is
completely burnt and the products of completely burnt and water vapor leaves with the
combustion cooled to the normal conditions combustion products without being condensed.
(with water vapor condensed as a result).

Also known as higher heating vale (HHV) or gross Also known as lower heating vale (LHV) or net
calorific value (GCV). calorific value (NCV).
Total energy released when products have Energy released when products are hot.
cooled down to the room temperature and
water has been condensed out.
By products are allowed to condense. By products are allowed to escape.
Some of the heat or energy in by products can Heat or energy in by-products escapes the system.
be recovered through condensation.
High value. Low value.

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Example Problem 1:

PROBLEM:

GIVEN:
C = 90%; O = 3%; S = 0.5%; N = 0.5%; Ash = 2.5%
LCV = 8490.5 kcal/kg

REQUIRED:
%H
HCV

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Example Problem 1:

SOLUTION:
LCV = [ HCV − 0.09 H  587]kcal / kg
8490.5 = [ HCV − 52.8 H ]kcal / kg
HCV = (8490.5 + 52.8 H )kcal / kg 1
1 O
HCV = [8080C + 34,500( H − ) + 2,240 S ]kcal / kg
100 8
1 3
HCV = [(8080 x90) + 34,500( H − ) + (2,240 x0.5)]kcal / kg
100 8
1
HCV = [727200 + 34,500 H − 12937.5 + 1120]kcal / kg
100
HCV = (7153.8 + 345 H )kcal / kg 2
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Example Problem 1:

SOLUTION:
Use equations 1 and 2 to solve %H:
HCV = (8490.5 + 52.8 H )kcal / kg 1
HCV = (7153.8 + 345 H )kcal / kg 2
(8490.5 + 52.8 H )kcal / kg = (7153.8 + 345 H )kcal / kg
345 H − 52.8 H = 8490.5 − 7153.8
292.2 H = 1336.7
1336.7
H=
292.2
H = 4.575%
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Example Problem 1:

SOLUTION:
Use equation 1 to solve HCV:
HCV = (8490.5 + 52.8 H )kcal / kg 1

HCV = [8490.5 + (52.8)(4.575)]kcal / kg

HCV = [8490.5 + 241.56]kcal / kg

HCV = 8732.0kcal / kg

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Example Problem 2:

PROBLEM:

GIVEN:
W =3500g; w =385g; t1 =26.50C; t2 =29.20C; m =0.83g
H = 0.7%; L = 587cal/g

REQUIRED:
HCV
NCV(LCV)

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Example Problem 2:

SOLUTION:
 (W + w)(t 2 − t1) 
HCV =   Specificheatofwater
 m 
 (3500 + 385) g (29.2 − 26.5)C 
HCV =   (1.0cal / g − C )
 0.83 g 
10489.5 
HCV =   cal / g
 0.83 

HCV = 12638cal / g
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Example Problem 2:

SOLUTION:

LCV = [ HCV − 0.09 H  L]cal / g

LCV = [12638 − (0.09)(0.7)(587)]cal / g
LCV = [12638 − 37]cal / g

LCV = 12601cal / g

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Example Problem 3:

PROBLEM: On analysis, a coal sample has the following composition by weight;

C = 75 %, O2 = 04 %, S = 05 %, and ash = 3%. Net calorific value of the
fuel is 9797.71kcal / kg. Calculate the percentage of hydrogen and
gross calorific value of coal.
GIVEN:
C = 75%; O = 4%; S = 5%; Ash = 3%
NCV=LCV = 9797.71 kcal/kg

REQUIRED:
%H
GCV(HCV)
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Example Problem 3:

SOLUTION:
LCV = [ HCV − 0.09 H  587]kcal / kg
8490.5 = [ HCV − 52.8 H ]kcal / kg
HCV = (9797.71 + 52.8 H )kcal / kg 1
1 O
HCV = [8080C + 34,500( H − ) + 2,240 S ]kcal / kg
100 8
1 4
HCV = [(8080 x75) + 34,500( H − ) + (2,240 x5)]kcal / kg
100 8
1
HCV = [606000 + 34,500 H − 17250 + 1120]kcal / kg
100
HCV = (5999.5 + 345 H )kcal / kg 2
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Example Problem 3:

SOLUTION:
Use equations 1 and 2 to solve %H:
HCV = (9797.71 + 52.8 H )kcal / kg 1
HCV = (5999.5 + 345 H )kcal / kg 2
(5999.5 + 345 H )kcal / kg = (9797.71 + 52.8 H )kcal / kg
345 H − 52.8 H = 9797.71 − 5999.5
292.2 H = 3798.21
3798.21
H=
292.2
H = 13.0%
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Example Problem 3:

SOLUTION:
Use equation 1 to solve HCV:
HCV = (9797.71 + 52.8 H )kcal / kg 1

HCV = [9797.71 + (52.8)(13)]kcal / kg

HCV = [9797.71 + 686.79]kcal / kg

HCV = 10484.5kcal / kg

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Solid Fuel - Wood

• Wood is derived from trunks and branches of trees.

• Contains about 15% moisture after airdrying.
• Contains lignocellulose-wood pulp mainly α cellulose and a very
small amount of β cellulose.
• Composition of wood on moisture free basis:
• C= 55%, H = 6%, O = 43%, Ash = 1%
• Calorific value varies from 4000 to 6400 Btu/lb.

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Solid Fuel - Coal

• Coal is an important primary solid fuel that has been

formed as a result of alteration of vegetable matter under
some favorable conditions.

• Coal is the generic term applied to fossil fuels which range from
lignite (which is basically a matured or modified peat) to meta-
anthracite which is around 98% carbon)
• Coal is highly carbonaceous and composed of C, H, N and O,
and non-combustible inorganic matter.

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Solid Fuel - Coal

• Coal is classified on the basis of its rank.

• The rank of coal denotes its degree of maturity.
• Vegetable matter, under the action of pressure, heat and anaerobic
conditions, gets converted into different stages of coal:

Increase in carbon contents, Calorific value and hardness

Decrease in H, O, S, N, contents and volatile matter

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Possible Route of Coal Formation

INCREASING
PRESSURE &
TEMPERATURE

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Classification of Coal & its Calorific Values

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Analysis of Coal

• Ranking of coal is done on:

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Analysis of Coal

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Analysis of Coal

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Significance (or) Importance of Proximate Analysis
• Moisture
• High moisture content in coal is undesirable because it,
• Reduces Calorific Value of coal.
• Increases the consumption of coal for heating purpose .
• Lengthens the time of heating.
• Hence, lesser the moisture content, better is the quality of coal.

• Volatile Matter
• During burning of coal, certain gases like CO, CO2, CH4, H2, N2, O2, hydrocarbons
etc. that come out are called volatile matter of the coal.
• The coal with higher volatile content,
• Ignites easily (e.g.: it has lower ignition temperature).
• Burns with long yellow smoky flame.
• Has lower Calorific Value.
• Will give more quantity of coal gas when it is heated in absence of air.
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Significance (or) Importance of Proximate Analysis

• Ash
• Ash is the combustion product of mineral matters present in the coal.
• It consists mainly of SiO2, Al2O3 and Fe2O3 with varying amounts of other oxides
such as Na2O, CaO, MgO etc.
• Ash containing oxides of Na, Ca and Mg melt early. (Low melting ash).
• During coke manufacture, the low melting ash forms a fused lumpy - expanded
mass which block the interspaces of the ‘grate’ and thereby obstructing the supply
of air leading to irregular burning of coal and loss of fuel.
• High ash content in coal is undesirable because it (a) increases transporting,
handling, storage costs, (b) is harder and stronger, (c) has lower Calorific Value.

• Fixed Carbon
• It is the pure carbon present in coal.
• Higher the fixed carbon content of the coal, higher will be its Calorific Value.

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Analysis of Coal

(b) Ultimate Analysis

• It means finding out the weight percentage of carbon, hydrogen,

nitrogen, oxygen and sulfur of the pure coal free from moisture and
inorganic constituents.

• This analysis gives the elementary constituents of coal.

• It is useful to the designer of coal burning equipments and auxiliaries.

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Analysis of Coal

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Analysis of Coal

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Analysis of Coal

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Analysis of Coal

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Analysis of Coal

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Analysis of Coal

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Significance (or) Importance of Ultimate Analysis

• Carbon and Hydrogen

• Higher the % of carbon and hydrogen, better the quality of coal and higher is its
calorific value.
• The % of carbon is helpful in the classification of coal.
• Higher the % of carbon in coal reduces the size of combustion chamber
required.

• Nitrogen
• Nitrogen does not have any calorific value, and its presence in coal is
undesirable.
• Good quality coal should have very little nitrogen content.

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Significance (or) Importance of Ultimate Analysis

• Sulfur
• Though sulfur increases the calorific value, its presence in coal is undesirable
because :
• The combustion products of sulfur, i.e, SO2 and SO3 are harmful and have
corrosion effects on equipments.
• The coal containing sulfur is not suitable for the preparation of metallurgical
coke as it affects the properties of the metal.

• Oxygen
• Lower the % of oxygen higher is its calorific value.
• As the oxygen content increases its moisture holding capacity increases and the
calorific value of the fuel is required.

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Liquid Fuel – Petroleum

• Petroleum or crude oil is a naturally occurring brown to black

colored viscous oil formed under the crust of earth, on shore or off
shore. Chemically it is a mixture of various hydrocarbons with small
amounts of N, O, S compounds.
• The approximate composition of petroleum:
• C = 80 - 84%
• H = 10 - 14 %
• S = 0.1 - 0.5 %
• N+ O = Negligible

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Classification of Petroleum

1. Paraffinic-base type crude oil

• Contains saturated hydrocarbons from CH4 to C35H72 and a little amount of
naphthalenes and aromatics.
• (e.g. : Pennsylvanian and gulf coast oil)

2. Asphaltic-base type crude oil

• Contains mainly cycloparaffins or naphthalenes with smaller amounts of paraffins
and aromatic hydrocarbons.
• (e.g.: Californian oil)

3. Mixed-base type crude oil

• Contains both paraffinic and asphaltic hydrocarbons and are generally in the
form of semi-solid waxes.
• (e.g. : Mexican oil)

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Processing of Crude Petroleum

• Petroleum is found deep

below the earth crust.

• The oil is found floating

over salt water or brine.

• Generally, accumulation
of natural gas occurs
above the oil.

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Refining of Petroleum

• The process of removing impurities and separating out the oil

into various fractions having different boiling points is known as
refining of petroleum.

• Refining plants are called oil refineries.

• The process of refining involves 3 steps:

• Separation of water
• Removal of impurities
• Fractional distillation.

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Refining Step 1: Separation of Water

• The crude oil from the well is an extremely stable emulsion

of oil and salt water. The crude oil is allowed to flow
between 2 highly charged electrodes, where colloidal water
droplets coalesce to form large drops, which is then
separated out from the oil.

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Refining Step 2: Removal of Impurities

• The presence of NaCl and MgCl2 in the crude oil can corrode
the refining equipment, hence these salts are removed by
electrical desalting and dehydration methods.

• The sulfur compounds present in the crude oil is removed by

treating the oil with copper(II) oxide, which results in the
formation of copper sulfide, which is then removed by
filtration.

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Refining Step 3: Fractional Distillation

• The crude oil is heated to about 400°C, whereby all volatile

substances are evaporated. The hot vapors are then passed up a
fractionating column, which is a tall cylindrical tower containing
a number of horizontal stainless steel trays at short distances.

• When the vapors of the oil go up the fractionating column, they

gradually cool and condense at different heights of the column.
The fractions having higher boiling point condense at lower trays
whereas the fractions having lower boiling points condense at
higher trays.

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Refining Step 3: Fractional Distillation

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Refining Step 3: Fractional Distillation

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Common Fractions from Crude

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Heavy Oils on Refraction Gives:

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Some Important Fractions of Petroleum:

1. Petrol or Gasoline (C5-C9)

• It is a low boiling fraction of petroleum obtained between 40 – 120oC.
• It is a mixture of hydrocarbons pentane to nonane (in terms of carbon
atoms C5 - C9).
• Its calorific value is about 11,250 kcals/kg.
• It is used as fuel in ICE of automobiles and aero planes.
• Its antiknock value can be improved by the addition of Tetra Ethyl Lead
(TEL).
• It is used as a fuel in IC engine and also used in dry cleaning and as a
solvent.

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Some Important Fractions of Petroleum:

2. Naphtha (C9-C10)

• It is a colorless, light fraction obtained between 1200C to 1800C during

fractional distillation of petroleum. It is a mixture of hydrocarbons such
as nonane and decane.

• Naphtha is also called as white spirit, which is generally used in dry

cleaning and as thinner for varnish, floor and furniture polishes etc. The
lightest portion of the distillate is used as solvent for fats and rubbers,
whereas the heaviest portion of the same is used as a fuel.

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Some Important Fractions of Petroleum:

3. Kerosene( C10-C16)

• It is relatively a high boiling fraction obtained between 180-250oC

during fractional distillation of petroleum. It is a mixture of
hydrocarbons such as decane to hexadecane approximate composition
is C = 84%, H = 16%, > 0.1% S. Its calorific value is about 11,100 kcal/kg.

• It is mainly used as a domestic fuel in stoves and lamps.

• It is also used as jet engine fuel and for making oil gas.

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Some Important Fractions of Petroleum:

4. Diesel (C15-C18)

• It is also a high boiling fraction obtained between 250-320oC during

fractional distillation of petroleum. It is a mixture of hydrocarbons such
as C15H32 to C18H38. Its calorific value is about 11,000 kcal/kg.

• It is used as a very good diesel engine fuel.

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Some Important Fractions of Petroleum:

5. Heavy oil or Residual fuel oil (C17 – C30)

• The left over portion of petroleum after distilling off all the lighter
fractions are called Fuel Oil.
• The approximate composition of fuel oil is C = 86%, H = 12%, S =
1%, H2O = 0.6%; sediments = 0.4%.
• Its calorific value is about 9200 kcal/kg.
• The following fractions are obtained on further vacuum distillation of
the fuel oil.
i) Light fuel oil = 350 -420oC
ii) Heavy neutral oil = 420-500oC
• It is used as fuel for ships and also used in metallurgical furnaces.
• Gasoline is also obtained from oil by cracking process.
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Some Important Fractions of Petroleum:

6. Asphalt

• Asphalts are obtained by:

i) The oxidation of residual heavy oil in presence of air at higher
temperature.
ii) The deep vacuum distillation of residual heavy oil.

• Asphalts are available in the market in liquid, semi-solid and solid

forms.

• It is used for road making and making water-proofing roofs.

• It is also used for the manufacture of water proofing concrete and
water proofing paints.

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Properties of Liquid Fuels

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Properties of Liquid Fuels

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Standard Ignition Temperature and Flash Point

• Standard Ignition Temperature (SIT)

• It is the lowest temperature that a fuel will ignite without the help of
any external flame or ignition source.

• Flash Point
• It is the lowest temperature at which a fuel can be heated so that the
vapor gives off flashes when an open flame is passed over it.

• This gives an indication of the flammability of the fuel.

• Its significance is in the safety aspects of storing and handling the

fuel.
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Fire Point and Smoke Point

• Fire Point
• It is the temperature to which the oil must be heated so that the
vapor pressure is sufficient to maintain the flame after the flame
source is removed.

• Smoke Point
• It is an arbitrary scale related to the height of the flame of the fuel
burning in a standard lamp without smoking.

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Cracking

• Cracking is defined as the decomposition of high boiling

hydrocarbons of high molecular weight into smaller, low boiling
hydrocarbons of low molecular weight.

• The crude oil on fractional distillation yields only about 15 - 20 %

gasoline. This is known as Straight Run Gasoline.

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Cracking

During cracking:

• Straight chain alkanes are converted into branched chain

hydrocarbons.
• Saturated hydrocarbons are converted into mixture of
Saturated and Unsaturated hydrocarbons.
• Aliphatic alkanes are converted into cyclic alkanes.
• All hydrocarbons obtained by cracking have lower boiling point
than the parent hydrocarbons.

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TypesTwo
of Cracking
Types ofinCracking
Use in Use:
1. Thermal Cracking

• In this process, the heavy oil is subjected in high temperature and

pressure, when the bigger hydrocarbon molecules break down to
give smaller molecules of the paraffins, olefins, and hydrogen.
• The cracked products are then separated by fractional distillation.

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Types of Cracking in Use

2. Catalytic Cracking
• In this process, cracking is carried out in the presence of a
catalyst at a lower temperatures and pressures. The catalysts
like aluminum silicate, Al2SiO3, or alumina Al2O3, used in
cracking gives higher yield and better quality of gasoline

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Fixed Bed Catalytic Cracking

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Moving Bed Catalytic Cracking

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Knocking

• The rate of ignition of the fuel gradually increases and the final
portion of the fuel-air mixture gets ignited instantaneously
producing an explosive sound known as knocking.

• Knocking property of the fuel reduces the efficiency of engine.

So a good gasoline should resist knocking.

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Octane Number or Octane Rating

• It is introduced to express the knocking characteristics of petrol.

It has been found that n-heptane knocks very badly and hence,
its anti-knock value has been given zero (0). On the other hand,
iso-octane gives very little knocking and so, its anti-knock value
has been given 100.

• Octane number is defined as the percentage of iso-octane

present in a mixture of iso-octane and n-heptane.

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Cetane Number or Cetane Rating

• It is introduced to express the knocking characteristics of diesel. Cetane has a

very short ignition lag and hence its cetane number is taken as 100. On the
other hand, 2-methyl naphthalene has a long ignition lag and its cetane
number is taken as zero (0).
• Cetane number is defined as the percentage of hexadecane (n-cetane) present
in a mixture of hexadecane and 2-methyl naphthalene, which has the same
ignition lag as the fuel under test.
• The cetane number decreases in the following order:
• n-alkanes > cycloalkanes > alkenes > branched alkanes > aromatics
• The cetane number of a diesel oil can be increased by adding additives called
dopes. Some important dopes include ethyl nitrate and iso-amyl nitrate.

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Chemical Structure and Knocking

• The knocking tendency of fuel hydrocarbons mainly

depends on their chemical structures. The knocking
tendency decreases in the following order:

• straight-chain paraffins > branched-chain paraffins >

cycloparaffins > olefins > aromatics

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Improvement of Antiknock Characteristics

• The octane number of fuel can be improved by:

1. Blending petrol of high octane number with petrol

of low octane number, so that the octane number
of the latter can be improved

2. The addition of anti-knock agents

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Leaded Petrol

• Anti-knock properties of a gasoline can be improved by the

addition of suitable additives. Tetraethyl lead or (C2H5)4Pb is an
important additive added to petrol. Thus, petrol containing
tetraethyl lead is called leaded petrol.

• Knocking follows a free radical mechanism, leading to a chain

growth which results in an explosion. If the chains are
terminated before their growth, knocking will cease. Lead
decomposes thermally to form ethyl free radicals which combine
with the growing free radicals of knocking process and thus the
chain growth is stopped.
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Gaseous Fuels

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Gaseous Fuel – Natural Gas

• Natural gas is always found above the oil in the oil wells.
• It is also called Marsh gas.
• It consists of methane and other saturated hydrocarbons.
• The average composition of natural gas is as follows :
• Methane = 88.5 %
• Ethane = 5.5 %
• Propane = 4 %
• Butane = 1.5%
• Pentane = 0.5%
• Its calorific value varies from 12,000 to 14,000 kcal/m3.
• If natural gas contains lower hydrocarbons like methane and ethane it is
called lean or dry gas. In the natural gas contains higher hydrocarbons
like propane, butane along with methane it is called rich or wet gas.
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Gaseous Fuel – Water or Blue Gas

• Water gas essentially a mixture

of combustible gases like CO, H2
with a little non combustible
gases like CO2 and N2.
• Its Calorific Value is 2800
kcals/m3.
• The average composition is as
follows :
• H2 = 48 %
• CO = 44 %
• CO2, N2 and CH4 = 8 %

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Gaseous Fuel – Producer Gas

• It is prepared by passing air mixed

with a little steam over a red hot
coal (or) a coke bed maintained at
above 1100° C in a special reactor
called ‘‘ Gas Producer’’.
• Its Calorific Value is 1800 kcals/m3.
• The average composition is as
follows:
• N2 = 50 %
• CO = 30 %
• H2 = 10 %
• CO2, and CH4 = 10 %

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Gaseous Fuel – Liquified Petroleum Gas (LPG)

• It is a mixture of propane and butane.

• It is obtained as one of the top fractions in the fractional distillation of
petroleum.
• It is easily liquified and so can be economically stored and transported
in cylinders.
• Its Calorific Value is 27000 kcals/m3.
• The approximate composition is as follows:
• N-Butane = 70 %
• Isobutane = 17 %
• N-Propane = 11 %
• Butylene and Ethane = 2 %

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Boys or Junkers Gas Calorimeter

AIM :To determine calorific

value of gaseous fuel by
Junkers gas calorimeter

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Boys or Junkers Gas Calorimeter

92
Calculation: 93
Volume of gas burn at STP in certain time (t)= V
Mass of the cooling water used in time t = W
Temperature of inlet water = T1
Temperature of outlet water = T2
Mass of steam condensed in time t in graduated cylinder = m
Higher calorific value of fuel = L
Specific heat of water = S
Heat absorbed by circulating water = W(T2-T1)×Specific heat of water (s)
Heat produced by combustion of fuel = VL
Thus
VL = W(T2-T1)×S

HCV (L) = W(T2-T1)×S/V

LCV = L - amount of water collected x latent heat

V

LCV =

1 cm3 of water = 1 g of water 93

 94
Example Problem 4:

PROBLEM:

94
 95
Example Problem 4:

SOLUTION: Basis: 1m3 of gaseous fuel.

95
 96
Example Problem 4:

SOLUTION:

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 97
Example Problem 5:

PROBLEM: The following were obtained in the Boy’s gas calorimeter experiments

Volume of gas used = 0.1 m3 at NTP

Weight of water heated = 25 Kg
Temp. of inlet water = 20 ˚C
Temp. of outlet water = 33 ˚C
Weight of steam condensed = 0.025 kg
Calculate the gross and net calorific value per m3 at NTP. Take the heat
liberated in condensing water is 580 Kcal/Kg

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Biofuels

• Biogas: from animal manure, other organic wastes, energy crops

• Bioethanol/Ethanol: from sugar/starch

• Biodiesel: from vegetable oils, animal fats

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Biogas

• These gases generally produced by the fermentation of bio wastes, sewage

wastes, other organic wastes and energy crops by anaerobic bacteria.
• The chief constituent of biogas is methane, so the process is also called
biomethanation.
• Its Calorific Value is 5400 kcals/m3.
• The composition is as follows:

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Biogas

Gobar gas plant

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Power Alcohol

• When ethyl alcohol is used as fuel in an internal

combustion engine, it is called power alcohol. Generally,
ethyl alcohol is used as a 5-25% mixture with petrol.

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Advantages of Power Alcohol

• Ethyl alcohol has good anti-knocking property. The addition od

ethyl alcohol increases the octane number of petrol.

• It has the property of absorbing any traces of water if present in

petrol.

• It contains oxygen atoms, which help for the complete combustion

of power alcohol and largely reduces the polluting emissions of CO,
hydrocarbons, and particulates.

• It is cheaper than petrol.

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Disadvantages of Power Alcohol

• Ethyl alcohol has a lower calorific value than petrol. Use of power
alcohol significantly reduces the power output.

• Ethyl alcohol has high surface tension and its atomization, especially at
lower temperature, is difficult causing starting trouble.

• It may undergo oxidation reduction to form acetic acid, which corrodes

engine parts.

• As it contains O atoms, the amount of air required to complete

combustion of power alcohol is less and therefore requires the
modification of the carburetor and engine.

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Production of Ethanol

• The basic steps for large-scale production of ethanol are: microbial

(yeast), fermentation of sugars, distillation, dehydration, and
denaturing.

• Prior to fermentation, some crops require saccharification or

hydrolysis of carbohydrates such as cellulose and starch into
sugars. Saccharification of cellulose is called cellulolysis. Enzymes
are used to convert starch into sugar.

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Production of Ethanol: Fermentation

• Ethanol is produced by microbial fermentation of the sugar. Two

major components of plants, starch and cellulose, are both made
up of sugars, and can, in principle be converted to sugars for
fermentation.

• Currently, only the sugar (e.g. sugar cane) and starch (e.g. corn)
portions can be economically converted. There is much activity in
the area of cellulosic ethanol, where the cellulose part of the plant
is broken down to sugars and subsequently converted to ethanol.

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Production of Ethanol: Distillation

• For ethanol to be usable as fuel, the majority of the water must be

removed. Most of the water is removed by distillation, but the
purity is limited to 95-96% due to the formation of a low boiling
water-ethanol azeotrope with maximum 96.5% v/v ethanol and
3.5% v/v water.

• This mixture is called hydrous ethanol and can be used as a fuel

alone, but unlike anhydrous ethanol, hydrous ethanol is immiscible
in all ratios with gasoline, so the water fraction is typically removed
in further treatment in order to burn in combination with gasoline.

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Production of Ethanol: Dehydration

• There are three basic dehydration processes to remove water from

an azeotropic ethanol-water mixture:

• Azeotropic distillation – adding benzene or cyclohexane to the

mixture.
• Extractive distillation – adding a ternary component which will
increase ethanol’s relative volatility.
• Molecular sieves – ethanol vapor under pressure passes through a
bed of molecular sieve beads, which absorbs water.

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Biodiesel

• A fuel derived from organic oils, such as vegetable oil, rather than
petroleum. The use and production of biodiesel are increasing. It is
typically used for aircraft, vehicles, and as heating oil.

• Grease or cooking oil can be converted to biodiesel and is more

sustainable.

• It has challenges on its scalability and concerns on competition

with food sources.
 109
Biodiesel

• A fuel derived from organic oils, such as vegetable oil, rather than
petroleum. The use and production of biodiesel are increasing. It is
typically used for aircraft, vehicles, and as heating oil.

• Grease or cooking oil can be converted to biodiesel and is more

sustainable.

• It has challenges on its scalability and concerns on competition

with food sources.
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Bioethanol vs Biodiesel

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Philippines: Biofuels Act of 2006

• Develop and utilize indigenous renewable and sustainably-sourced

clean energy to reduce dependence on imported oil.
• Mitigate toxic and greenhouse gas emissions.
• Increase rural employment and income.
• Ensure the availability of alternative and renewable clean energy
without any detriment to the natural ecosystem, biodiversity and
food reserves of the country.

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Philippines: Biofuels Act of 2006

• At present, 5% ethanol and 2.5% biodiesel.

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REFERENCES
REFERENCES

R. Mukhopadhyay & S. Datta. Engineering Chemistry.

Syed Shabudeen P.S. Fuels and Combustion. Retrieved from https://www.researchgate.net/publication/265602602
K. Sesha Maheswaramma. Engineering Chemistry.
J. A. Moulijn, M. Makkee, A.E. Van Diepen. Chemical Process Technology.
H. Schobert. Chemistry of Fossil Fuels and Biofuels.
Wiley Critical Content. Petroleum Technology. Volume 1-2 .
J.G. Speight. The Chemistry and Technology of Petroleum.

C.S. Hsu & P.R. Robinson. Springer Handbook of Petroleum Technology.

L.J. Gonzaga. Lectures 5-9 Fuels. [Powerpoint Slides].

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