Energy Conversion Systems

(ME341)
Date: 18th March 2024

Lecture-5
Fossil Fuels: Refining, Properties and
Combustion Analysis

IIT (BHU), Varanasi

Dr. Akhilendra Pratap Singh

Department of Mechanical Engineering
IIT (BHU), Varanasi, India
Email: akhilendra.mec@itbhu.ac.in
 Fossil fuels
Formation– Dead marine animals and plant matter
accumulated over millions of years, transformed into oil in
sedimentary rocks due to heat and pressure.
Deposits found beneath the crust, have a liquid body below
and pressurized natural gas above.
Thick and dense rock layer seals of the deposit, ensuring no
leakage.

Conventional
 Drilling through the rock layer causes pressure release,
Petroleum Drilling
pushing oil and gas to surface.
Advanced Petroleum
 When pressure is attenuated, oil can be pumped up. Drilling

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 Liquid Fuels - Composition
 Oil is a mixture of hydrocarbons, which may also contain small fraction of N2, O2, S.
 Major portion of hydrocarbons are paraffin like methane, ethane, propane, butane
(in gas form) and pentane, hexane and octane (in liquid form). The proportion
of hydrocarbons varies with deposit location, deposit composition, etc.
 Irrespective of crude oil source, the proportion of basic elements C (75 to 80%), H
(11 to 16 %), O + N (0 to 7% ) and S (0 to 4%) is fairly constant within limits.
 It may also contain cyclo-paraffin, iso-paraffin and aromatic compounds.
 Additionally, it may contain some moisture and sediment.

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 Fossil Fuels - Gases
Natural gas is formed with petroleum in the subterranean deposits.
Oil wells are drilled to extract the gas as well and transported through
pipelines.
In some cases, gases are used as fuel for power generation in drilling
stations, however, mostly flared off or burned in some cases due to
lack of transport facility.
Composition – Mixture of methane to pentane
Properties - Cleanest of the fuels, undergoes complete combustion while
mixing well with air with no smoke.
Heat of combustion – 33.5 to 40 MJ/m3; Specific Gravity – 0.63 relative to
air.
Storage – Major component is Methane, cryogenic temperature is required
to store the gas as a liquid at moderate pressures.

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 Fossil Fuels - Gases
Liquefied Natural gas (LNG): Transported by tankers and stored in
spherical vessels for emergency use during peak loads.
Liquefied Petroleum Gas (LPG): Consists of hydrocarbons like
propane, propylene, butane, butylene etc., used for domestic purposes.
Compressed Natural Gas (CNG): Used as alternative in automobiles.

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 Petroleum Refining

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Processing Chart for Fossil Fuels

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 Petroleum Refining Processes
Cracking
Breaking down large, complex hydrocarbons into simpler ones.
Thermal cracking – high temperature and pressure cause large molecules to
breakdown into smaller ones with lower boiling points.
Catalytic cracking – use of catalyst allows breakdown at lower temperatures
and pressures.
Catalytic cracking imparts better antiknock characteristics than
thermal cracking.

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 Petroleum Refining Processes
Isomerization
 Isomerization converts n-butane, n-pentane and n-hexane into their
respective isoparaffins of substantially higher octane number.
 The straight-chain paraffins are converted to their branched-chain
counterparts whose component atoms are the same but are arranged in a
different geometric structure.
Reforming
 Reforming is a petroleum refinery process in which low octane distillation
products known as naphthas are chemically converted into high octane
reformates.
 Reforming process involves restructuring hydrocarbon molecules in the
naphthas in such a way that they form more complex chemical structures
with higher octane ratings.

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 Fuels Properties
(1) Calorific Value
Solids and Liquids -Defined as the heat liberated in kJ by complete
combustion of 1 kg of fuel.
For Gases – Expressed in kJ/m3 of gas at S.T.P.
(a) Higher Calorific Value (HCV)
All fuels containing hydrogen in the available form will react with oxygen
during combustion to generate steam. The steam may condense when the
products of combustion are cooled to initial temperature.
This results is maximum heat being extracted. This heat value is called
Higher or Gross Calorific Value (HCV).

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 Fuels Properties
(b) Lower Calorific Value (LCV)
The heat absorbed by water during its conversion to vapor reduces the heat
released by fuel, which is known as lower calorific value (LCV).
The latent heat of vaporization is considered equal to 2466 kJ/kg. Hence,
L.C.V. = (H.C.V. – x . 2466) kJ/kg
Here , ‘x’ – fraction of water vapor present in the products of combustion for
1 kg of fuel.

With Steam= LCV

Without Steam= HCV

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 Fuels: Performance Properties
(2) Flash point
 Lowest temperature at which a volatile substance can vaporize to form a
ignitable mixture with air.
 Different from Auto-ignition temperature which does not require an
ignition source or Fire point viz. temperature above which the fuel
continues to burn after being ignited.

(3) Pour point

 Lowest temperature at which the liquid becomes semisolid and loses its
flow characteristics.

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 Fuels: Performance Properties
(4) Volatility
 Depends on fractional composition
of the fuel in terms of hydrocarbon
components.
 Standard process of measuring the
volatility of the fuel is by distillation
at atmospheric pressure, in
presence of its vapor.
 The fraction that boils off at a
particular temperature is measured.
 Characteristic points – 10, 40, 50 &
90 % of fuel evaporation and the
temperature at which boiling
ceases. Distillation curves for Petrol

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 Fuels: Performance Properties
(5) Octane Number
Rating of SI engine fuels is based on its antiknock property.
The property is compared with that of a mixture of iso-octane (C8H18) and
normal heptane (C7H16). (Iso-octane – rating 100, heptane- rating 0).
Octane number is the percentage by volume of, iso-octane in a mixture of iso-
octane and normal heptane, which exactly matched the knocking intensity in
a standard engine under standard conditions.

(6) Cetane Number

Cetane number is the percentage by volume of normal cetane in mixture of
reference fuels that gives same knocking intensity as of the fuel under
standard conditions.
Reference fuels are normal cetane (rating 100) and alpha methyl naphthalene
(rating 0).
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 Fuels: Performance Properties

(7) Antiknock Quality

Abnormal burning causes unwanted temperature and pressure surges in
the cylinders, affects the efficiency.
Antiknock quality resists the tendency for detonation during
combustion.
It depends on self ignition characteristics of the fuel.
Better SI engine fuel –> less knocking –> higher compression ratios
–> better efficiency -> more power output.

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 Thermo-Chemistry of Fuel-air Mixture
Thermo-chemistry is the combination of thermodynamics with chemistry to
predict the amount of heat, which will be released from a chemical reaction.
The chemical process in which a fuel, for example methane, is burned in presence of
air.

 The reactions are carried out in air, which can be approximated as 21% O2 and 79%
N2 . This composition is referred to as theoretical air.
Gas ppm by volume Molecular
weight
O2 209500 31.998
N2 780900 28.012
Ar 9300 38.948
CO2 300 40.009
Air 1000000 28.962

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Combustion of Fuels
 O2 is the reactive component in the air. For 1 mole O2 there is 3.773 mole of N2.

 Nitrogen is not part of the combustion process, it leaves the combustion chamber at
the same temperature as the other products.
 At very high temperatures, reaction may occur between the nitrogen and oxygen,
which gives rise to oxides of nitrogen.
Basic equation of combustion can be given as:
C  O 2  CO 2 ; 2H 2  O 2  2H 2 O; S  O 2  SO 2
In case of insufficient O2 , combustion will be incomplete and forms CO as given,
2C+O2=CO
Combustion is governed by a four letter word “MATT”-
M- Sufficient Mixture Turbulence,
A- Proper Air-Fuel Ratio,
T- Temperature,
T- Enough Time for Combustion
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 Stoichiometric Combustion of Fuels
Complete combustion of fuel cannot be achieved without applying excess
air than stoichiometric.
Percentage of excess air can be given as:

maa  mat
 100
maa
Where maa is the actual air supplied for complete combustion of 1kg of fuel.
For large utility boiler, percentage of excess air varies from 15 to 30%.

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 Numerical Approach

Consider the of propane gas with stoichiometric air.

 With 80% theoretical air, above equation becomes with addition of

formation of carbon monoxide due to incomplete combustion.

 Carbon balance gives: 3=a + b; Oxygen balance gives: 8=a + 2b + 4

 By solving: a=2, b=1 ,combustion equation is-

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Energy Conversion Systems (ME341)