9/27/2024

Engineering Chemistry, CHY 24106

M
A
N
I Dr. D. K. Sharma
Asst. Professor Chemistry, MANIT Bhopal

T Postdoc: Tokyo Institute of Technology, Tokyo, Japan

Ph.D. IIT Bombay, Mumbai, India

BHOPAL ID: 000-0003-4843-

ID: 55435535700
3457

UNIT –III Fuels

1. Introduction, Classification, Calorific value, Characteristic of a Good Fuel,

Comparison between Solid, Liquid and Gaseous Fuels. Numerical Problems based on
M Calorific Value.
2. Bomb Calorimeter, Numerical Problems based on calorimeter.
A 3. Coal: Classification, Selection Criteria, Proximate Analysis, Numerical Problems
based on Proximate Analysis.
N 4. Ultimate Analysis of coal, Numerical Problems based on Ultimate Analysis.
5. Pulverized Coal. Petroleum: Classification and separation.
I 6. Types of Cracking.

T 7. Knocking, Octane and Cetane Number.

8. LPG, Natural Gas, Producer Gas, Water Gas, Bio Gas.
BHOPAL

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Introduction to Fuel

“Fuel is any material that has stored energy”,

M  Heat
 Chemical
A  Electrical
N  Nuclear

I
T
BHOPAL

https://qph.fs.quoracdn.net/main-qimg-ebe7d92c3fe864e0bc918762b2eb291c

Combustion of the Fuel

“Exothermic Oxidation”
O2 media
M + Heat
A
N
I In Air
T + Heat
BHOPAL

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Classification of Fuels

Occurrence
M Primary: wood, coal, crude oil

A Secondary: petrol, charcoal Physical State

N Solid: wood, coal
I Liquid: Crude oil
and Gasolines
T
BHOPAL
Gas: natural gas

Solid Fuels

Primary Secondary
Wood, coal, Dung Coke & Charcoal
M
A
Advantages Disadvantages
N  Low production  High Ash content
I cost  Cost of handling &
 Moderate ignition difficult control
T temperature  Large heat waste
BHOPAL  Easy storage,  Burn with clinker
transport formation

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Liquid Fuel

Primary Secondary
Crude oil, vegetable oil Tar, Kerosene,
M diesel, petrol
A Advantages Disadvantages
N  Higher calorific value  Relatively higher Cost
I  Burn without dust ash  High risk for
clinkers inflammable liquids
T  Transport through  Bad odor
BHOPAL pipes

Gaseous Fuel

Primary Secondary
M Natural Gas Coal- Gas, Water gas,
Biogas,
A Advantages Disadvantages
N  Clean in use  Require special and
 No special burner large storage tanks
I
required
T  No ash, relatively  Highly inflammable so
BHOPAL nominal impurities fire hazardous

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Compare Fuels
Property Solid Liquid Gaseous
Calorific value Least Higher Highest
M Combustion Slow Fast and Very rapid and
A rate process efficient efficient
Combustion Cannot be Can be Can be
N Control controlled controlled or controlled by
stopped when regulating the
I required supply of air
T Smoke Produce some aromatics Negligible smoke
smoke and high C fuel
BHOPAL
invariably produce smoke

Compare Fuels
Property Solid Liquid Gaseous
Ash Produced & No such No such
disposal is a problem problem problem
M Thermal Least Higher Highest
efficiency
A Use in internal Cannot be Can be used Can be used
N combustion used
engine
I Fire-risk Less More Very high
T Storage Easy Closed Airtight
BHOPAL container container
Cost Cheap Costlier Costly
than solids

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Compare Fuels

M
A Gaseous fuels has high efficiency and
good quality but they are expensive
N and has high risk
I
T
BHOPAL

Characteristics of a Good Fuel

 Ignite easily : moderate ignition
temperature
M  Specific heat: High
A  Calorific value: High
N  Low moisture content
I  Low smoke and combustible matter
 Inexpensive and readily available
T
BHOPAL  Easy to store and transport
 No offensive odor

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Specific Heat Capacity

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N
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BHOPAL

Calorific Value

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BHOPAL http://hospitalitynu.blogspot.com/2012/08/fuel.html

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Bomb-Calorimeter

Calorimetry : -
M measuring Heat
A For Solid or Non-volatile
liquids
N Oxygen bomb calorimeter
I is most common instrument
Quantitative
T measurements of heat
BHOPAL exchange.
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry

Bomb-Calorimeter

M
A
N
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T
BHOPAL

https://www.youtube.com/watch?v=wwJG2JVg6qM

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Calorimeter

M
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N
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T
BHOPAL

Working Principle of Bomb Calorimeter

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N
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BHOPAL

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Working Principle of Bomb Calorimeter

M
A
N Temperature
equalization
I
T
BHOPAL

http://www2.latech.edu/~hhegab/pages/me354/Lab2/Lab2_bombcal_Sp97.htm

Bomb-Calorimeter
Combustion takes place in sealed container

M ∆U = qcal + w no work crossing the system

boundary, W = 0.
A qcal = Ccal ∆T

N Ccal = Chardware + Cwater

I qcal = Chardware ∆T + Cs, water ∆T
T
BHOPAL
∆U = ∆H - ∆ ng RT

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Bomb-Calorimeter

Sample problem.
In a bomb calorimeter, 0.16 g of CH4 was exposed to
M combustion at 27°C. The temperature of the system
(including water) raised by 0.5°C.
A If the thermal capacity of calorimeter system is 17.7 KJ K-1 & R =
N 8.314 JK-1mol-1, Calculate the heat of combustion CH4 at:
a) constant volume and (∆U )
I (b) constant pressure (∆H)
T
BHOPAL

Working Principle of Bomb Calorimeter

M
A
N
I For more accurate results, corrections are:
I. Acid correction ( )
T II. Fuse wire correction ( )
III.Cotton thread correction ( )
IV. Cooling correction ( )
BHOPAL
+ − + − + +
. . =

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Working Principle of Bomb Calorimeter

i) Fuse wire correction :
Heat liberated by the fuse wire is also included which actually has to be excluded from gross
calorific value.

M ii) Acid correction

Fuels containing S and N also get oxidized under high pressure and temperature to sulphuric and
nitric acids respectively.
A S + 2H + 2O2  H2 SO4 + Heat

N 2N + 2H + 3O2  2HNO3 + Heat

The correction for 1 mg of Sulphur is 2.25 Cal and if 1 ml of 0.1 N HNO3 is formed the heat
I produced is 1.43 Cal.

iii) Cooling Correction

T Time taken for cooling the calorimeter water to cool from maximum to RT is ‘x’ minutes and the
rate of cooling is dt 0/ min. then the colling correction:
BHOPAL
Cooling correction = dt 0/ min.  X

Problems based on calorific value

 Net calorific value is the quantity of heat produced when unit mass of the fuel is burnt
completely and the products are permitted to escape.
 Hence net calorific value is the gross calorific value excluding the latent heat of
M condensation of steam.

N.C.V = G.C.V – Latent heat of condensation of steam

A = G.C.V – Mass of hydrogen × 9 ×Latent heat of steam

1. One part of hydrogen produces 9 parts of water

N H2 +
2
O2
16
 H2 O
18

I 2. The latent heat of steam is 587 cal/gm.

T Let H is the % of H2in the fuel

BHOPAL . . = . −( . × × 587 / )

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Problems based on calorific value

Q.2 A sample of coal contains 92% C, 5% H , 3% ash. When this fuel sample is tested in the
bomb calorimeter for finding the calorific value, the following results are obtained. Calculate
the gross and net calorific values of the fuel.

Weight of coal burnt = 0.95 g

M Weight of water taken = 800 g
Water equivalent of calorimeter = 1800 g
Rise in temperature = 2.600C
A Cooling correction = 0.030C
Fuse wire correction = 12.00 Cals + − + − + +
Acid correction = 58.00 cals . . =
N
I . . =
( .
.
.
= 7367.39 Cal/g

T . . = . −( . × × 587 / )
BHOPAL

Problems based on calorific value

When 0.5 g of a fuel containing 7% of H2 on complete combustion increases
temperature of 1000 g water in a calorimeter from 40.0 to 42.1 0C. Calculate
gross and net calorific value of the fuel if the the water equivalent of the
M calorimeter is 120 g.

A + − )
. . =
N
I
T
BHOPAL

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Calculations based on minimum quantity of air

required for the complete combustion of the fuel
The main elements present in most of the fuels are
M C,H,O and S. On combustion of fuel these elements
are converted into gases like CO2, H2O and SO2 etc.

A For efficient combustion, sufficient quantity of air

must be brought into intimate contact with the fuel.

N
I Combustion of carbon :
https://www.wcrouse.com/10841-2/
C + O2 CO2 (g)
T (12) (32) (44)
BHOPAL For complete combustion, 12 kg of carbon requires = 32 kg
32
 For ‘C’ kg of carbon in the fuel oxygen required for complete combustion  C
12

Combustion of Hydrogen
2H2 + O2 2H2O ( l ) 1 : 8
2 2 32 36 4 kg of hydrogen requires O for complete combustion
2
1 : 8
= 32 kg
 For complete combustion, H kg of hydrogen in the fuel
M requires =
32
 H kg of oxygen …….. (1)
4
A Some of the hydrogen is present in the combined form with
oxygen as H2O. This combined oxygen does not take part
N in combustion reaction.

8 parts of oxygen combines with 1 part of hydrogen

I  The amount of hydrogen available for combustion
O
T = H –
8
BHOPAL  Oxygen required for combustion of hydrogen
32  O
=  H   ……. (2)
4  8

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Combustion of sulphur
S + O2 SO2 (g)
32 32 64

M 32 kg of sulphur required oxygen for complete combustion

= 32 kg
A The given sulphur (S) required oxygen for complete
32
N combustion =
32
S …….. (3)

I
T
BHOPAL

O2/ Air requirement for Combustion

On combining the above three combustion equations, we
get the equation for the theoretical oxygen requirement for
the combustion of C, H and S
M =
32  O
 C  8 H    S
12  8
A Air contains 21% by volume of oxygen & 23% by weight of oxygen

 Minimum weight of air required for combustion

N
100  32 O 
I = 
23 12

 C  8 H    S 
 8 
T  Minimum volume of air required for combustion
BHOPAL 100  32  O 
=   C  8 H    S 
21 12  8 

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What is the molecular weight of Air

Air contains 21% by volume of oxygen & 23% by weight of oxygen ?

Nitrogen: (78.084 / 100) x 28.0134 = 21.8739 g/mol

M Oxygen: (20.947 / 100) x 31.9988 = 6.7025 g/mol
Argon: (0.934 / 100) x 39.948 = 0.373 g/mol
A Carbon dioxide: (0.035 / 100) x 44.01 = 0.013203 g/mol

N
If we add these up we get:
I 21.8739 + 6.7025 + 0.373 + 0.013203

T https://www.pinterest.jp/pin/389983648968183715/

= 28.96 g / mol.
BHOPAL

O2/ Air requirement for Combustion

On combining the above three combustion equations, we
get the equation for the theoretical oxygen requirement for
the combustion of C, H and S
M =
32  O
 C  8 H    S
12  8
A Air contains 21% by volume of oxygen & 23% by weight of oxygen

 Minimum weight of air required for combustion

N
100  32 O 
I 
23 12

 C  8 H    S 

=
8 
T  Minimum volume of air required for combustion
BHOPAL 100  32  O 
=   C  8 H    S 
21 12  8 

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Combustion
Excess air supply
It is necessary to supply excess air for complete combustion of the fuel.
The amount of air required if excess air is supplied
M
Theoretical amount of air
A 
100
 [100  % Excess air]

N Important points on combustion reactions

(1) We know that air contains 21% oxygen by volume and 23% of oxygen by weight.
I (2) From the amount of oxygen required for the combustion by the fuel, the amount
T (weight) of air can be calculated.

BHOPAL (3) From the combustion reaction equations, we can calculate the quantity of oxygen by
weight or volume.

Summary
Step 1 : Write combustion reaction equation.
Step 2 : Calculate the amount of oxygen required by the elements or compounds present in
the fuel.
M Step 3 : If oxygen is mentioned in the problem , subtract the weight or volume of oxygen
already present in the fuel from total oxygen required by the other elements or
compounds.
A Step 4 : Since, N2 , CO2 and H2O do not burn , they do not require any oxygen (air) .
Therefore, their values is mentioned in the problem can be ignored.
N Step 5 : Finally calculate the amount of air required by the fuel by multiplying 100/21 ( if
volume %) with total amount of oxygen required and 100/23 ( if weight % ) with total
I amount of oxygen required.
Step 6 : Excess air for combustion : More than the theoretical amount of air is necessary
in practice to achieve complete combustion. This excess air is expressed in percentage of
T the theoretical air
BHOPAL
Theoretica l amount of air
  [100  % Excess air]
100

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Air requirement for Combustion

Fuel oil has the following analysis C = 90%; H = 6% S = 2.5%, O= 1%,
ash = 0.5%. Calculate the quantity of air required for complete
combustion of 1 kg of the fuel if 30% excess air is used.
M Solution 100  32 O 

C = 0.9 kg Weight of air required   C  8 H    S 
A H = 0.06 kg

23  12  8 
S = 0.025 kg
N O = 0.01 kg = 12.586 kg of air

I  The amount of air required if 30% excess of air is used

(100  30)
T = 12.586 
100
BHOPAL = 12.586  1.3
= 16.362 kg of air

Air requirement for Combustion: Numerical

The percentage composition of a sample of coal is C = 88%; H2 = 5% O2 = 4% N2 = 2% S = 1%
i) Calculate the minimum weight of air required for combustion
ii) Calculate the percentage composition of dry products by weight.

(i) C = 0.88 kg O2 = 0.04 kg H2 = 0.05 kg S = 0.01 kg

M ℎ =
100 32
× 0.88 + 8 0.05 −
0.04
+ 0.01
23 12 8
A
44 64
N CO2 F ormed 
12
 0.88  3.23 kg SO2  Formed   0.01  0.02kg
32
I Products Weight %
= ℎ + ℎ
CO2 3.23 kg x%
T =
78
100
× 11.81 + . ≈ 9.22 kg
SO2 0.02 kg y %
BHOPAL N2 9.22 kg z %
Total = 12.351 %

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Air requirement for Combustion: Numerical

Q. 4 Kg coke (C only) sample burnt in 10% excess of air. Calculate the amount of theoretical
air required by weight and volume for complete combustion.

C = 4 kg O2 = 0 kg H2 = 0 kg S = 0 kg
M
Solution
A C + O2 CO2
12 32
N weight of oxygen required for combustion of 4 kg of coke
= = 10.666 kg
Amount of air required for the complete combustion of 4 kg of coke = × 4 = 46.38 kg
I Amount of air required for the complete combustion of 4 kg of coke in 10% excess of air
T = ×4 × =51.02 Kg

BHOPAL

Air requirement for Combustion: Numerical

Q. Calculate the volume of air needed for complete combustion of 1 m3 of producer gas having
the following composition by volume.
Hydrogen = 25%; CO = 15% , CH4 = 5% ; Nitrogen 52%

M Solution
The combustion equations are:
A H2 + ½ O2 H2 O Volume of O2 needed for complete combustion of
1 vol 0.5 vol 1 vol
N CO + ½ O2 CO2
1m3 of gas
= 0.250.5 + 0.15 0.5 + 0.05  2
1 vol 0.5 vol 1 vol = 0.3 m3
I CH4 + 2O2 CO2 + 2H2O
Volume of air needed for complete combustion =
100
× 0.3= 1.428 m3
1vol 2 vol 1 vol 2vol 21
T
BHOPAL

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Bomb Calorimeter: Numerical

Q. A coal sample contains 84% C, 8% H, 3% N2, 2% S, 1% P, 2% ash. When this fuel sample
is tested in the Bomb calorimeter following results are obtained.
Weight of coal burnt = 0.84 g
Weight of water taken = 800 g
M Water equivalent of calorimeter = 1800 g
Rise in temperature = 2.60 C
Cooling correction = 0.030C
A Fuse wire correction = 12.00 Cals
Acid correction = 58.00 cals’
Calculate the gross and net calorific values of the fuel.
N + − + − + +
. . =
I ( . .
. . = = 8057.14 Cal/g
.
T
BHOPAL . . = . −( . × × 587 / )

Energy Consumption in India

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BHOPAL

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Energy Consumption in India

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BHOPAL

World Coal Consumption

https://www.eia.gov/

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BHOPAL

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Coal & its formation

Brown/Black Fossil Fuel, layers of partially decayed plant
material in the earths crust, altered by heat and pressure
M In Situ Theory:
i) Substances accumulated at the point of
origin.
A ii) Under coal seam large amount of fossil
fuels
N iii) Composition don’t vary significantly
iv) Low in ash content

I Drift Theory: Flood/ Tsunami (~600 mpH)

i) Percentage of inclined trunks of fossil is
much more in horizontal
T ii) For 1 m of coal seam100 m of peat seam
BHOPAL is required, which is found no where https://www.zmescience.com/science/geology/how-coal-is-formed/
iii) Layered structure, not the mixed one
iv) High in ash content

Coal formation
Plant Debris Anthracite

Peat Semi Anthracite

M
A Lignite
Bituminous

N Brown Coal Sub-Bituminous

I
T
BHOPAL

https://www.examrace.com/

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Coal seam & Metamorphism of Coal

Dark brown or black banded deposit of coal that is
visible within layers of rock.

M
A
N https://www.nps.gov/neri/learn/nature/images/neri_geology_2.jpg
-” Alteration of the composition or structure of a

I rock by heat, pressure, or other natural agency.”

-Coal is polydispersed polymeric colloidal system.
T -Degree of polymerization is enhanced by continued
earth pressures.
BHOPAL
-The compaction of the coal-gel leads to dehydration,

http://www.eu-geology.com/?page_id=173

Coal Ranks

M
A
N
I
T
BHOPAL
https://www.apsense.com/article/coal-biomass-coal-
ranks-coal-gasification-encyclopedia.html

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Coal Analysis

M
Proximate Ultimate
A Physical Components Chemical-components

N  Fixed C, Moisture  Carbon, Hydrogen

 Ash, Volatile content etc.  Nitrogen, Oxygen
I  Useful to find out GCV  Sulphur etc.
T  Easy, quick analysis  Useful for furnace design

BHOPAL  Fare idea about quality of  Laboratory analysis

coal  Essential for heat balancing

Compare different types of Coal

Coal Type Peat Lignite Bituminous Anthracite

Proximate Analysis
M Moisture 20 10-30 3.5-8 2
Volatile matter 50 40-45 16-36 4.99
A Fixed Carbon 25 30-35 49-72 79.69
Ash 5 3.5-7.5 7-8.5 15.32
N Calorific Value (K
Cal/ Kg)
5400 6500 8000 8600

I C 55
Ultimate Analysis
70-73 68.5-79.5 86

T H
O
6
33
4.6-5.5
22-26
4.5-5.5
4.5-16.5
1.34
11.85
BHOPAL
N 3 0.6-1. 0 1-1.4 0.56
S 1 0.6-1. 5 0.1-1 0.21

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Proximate Analysis Methods

Moisture, Volatile Matter, Fixed C, Ash content by wt %
 Moisture content: -105-110 0C for 1 hr.
M  Ash: 750 ±50 0C for 1/2 hr. (without lid- in air)

A  Volatile content : 925 ±20 0C for 7 min (with lid)

N  Fixed Carbon : by difference

Reporting : As received, Moisture free, Dry or Dry Ash free basis

I
T
BHOPAL

Proximate Analysis Question Samples

A coal sample of 0.9945 g was placed in a crucible of 8.5506 g in an oven, maintained at 1050C for 67
min. The sample was then removed, cooled in a desiccator and reweighed; the procedure being
repeated until a constant total mass of 9.5340g was attained.
M mass of moisture
% Moisture = ×
A
Another sample, of mass 1.0120 g in a crucible of mass 8.5506 g was heated with a lid in a furnace at
N 920 0c for 420 s and the weight of crucible observed as 9.1921 g. This sample was then heated
without a lid in the same furnace maintained at 7250C until a constant total mass of 8.6255 g was
attained.
I Heating up to 920 0c in absence of air removes volatile
T matters. Subsequent heating up to 725 0c in presence of
air burns all fixed carbon of the sample leaving ash in the
BHOPAL
crucible !

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Proximate Analysis Question Samples

Volatile matter (VM) : Initial wt. of sample+ Crucible
=1.0120 + 8.5685 =9.580 g
Final wt. after heating up to 920 0C (without air) =9.1921 g
M
A Mass of volatile matter + Moisture = 9.5805-9.1921 g
= 0.3884 g
N % Moisture + Volatiles = 0.3884 ×
100
.
= 38.38 %

I % Volatile matter = 38.38-1.11 =37.26 %

T
BHOPAL Fixed Carbon = 100- % VM- % Ash- % Moisture

Importance of Proximate Analysis

Moisture: Greater % low C.V, quenching fire, But up to

10% uniform fuel-bed & less fly ash
M
A Volatile matter: High long flame, high smoke, low C.V.

N Ash: Useless, non-combustible matter, forms clinker,

obstruction in air supply, wear on furnace
I
T Fixed C: Greater is better
BHOPAL

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Coal: Ultimate Analysis

Measure C, H, S, O, N
Used in combustion calculations to determine:
M
Fuel rates, heat release rates
A
SO2 and CO2 emissions
N
Boiler performance: Hg big problem in NTPC
I Used to quantify: Chemicals and reagents or sorbents
T like lime stone used in reducing sulfur emissions
BHOPAL

https://www.slideshare.net/djk239/ch-20102-coal

Determination of C & H
Known amount of C and
H is burnt in dry O2

M (C CO2 & H H2O)

Products of
A https://www.learncbse.in/ combustion is passed
N × ×
over a weighted tubes,
% H= increase in the weight
I ×
of CaCl2 tube  H2O &
KOH CO2
T
× ×
BHOPAL
% C=
×

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Determination of N
Heat in presence of K2SO4 Heat, Alkali

N+ H2SO4  (NH4)2SO4  2NH3 ----

Acid Solution
M (NH4)2SO4 + NaOH 2NH3+ 2H2O

A % N=
× × .
N https://www.quora.com/

I  1g of powdered coal is heated in conc.H2SO4 & CuSO4

 It is treated with excess of KOH/NaOH
T  Liberated NH3 is distilled, cooled and absorbed in a known volume
BHOPAL of standard H2SO4 acid solution.
 Unused acid is determined by back titration with standard NaOH

Determination of N
Heat in presence of K2SO4 Heat, Alkali

N+ H2SO4  (NH4)2SO4  2NH3 ----

Acid Solution
M (NH4)2SO4 + NaOH Na2SO4 + 2NH3+ 2H2O

A Volume of Acid used = Blank titration-main

titration (After NH3)
N https://www.quora.com/

I × × ×
% N=
×
T
BHOPAL × × .
% N=

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Determination of S
Sulphur
. × ×
 S is converted into Sulphate % S=
×

M  Washings are then treated with BaCl

 BaSO4 is precipitated, filtered and heated to constant weight
A
Oxygen  % O= 100- % (C+ H+ S+ N+ Ash)
N
I
T
BHOPAL

Coal: Ultimate analysis

Fuel % C % H % O % N % S % Ash
M Peat 23 10 59 1.5 0.5 6
Lignite 42 7 43 1 1 6
A
Bituminous 77 5 5 1.5 0.5 11
N Sub- 59 6 29.5 1 0.5 4
I Bituminous
Semi- 80 3.5 4.5 1.5 0.5 10
T Anthracite
BHOPAL
Anthracite 86.5 3.5 4.5 1.5 0.5 10

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Importance of Ultimate analysis

Carbon: Greater % Better Quality and C.V

M
Hydrogen: in form of moisture and volatile
A
N Nitrogen: Doesn't burn, no C.V. negligible N% is
good for coal
I
Sulphur: It increases C.V. but also SOx
T
BHOPAL
Oxygen: Mostly in form of moisture not good

Classification of Coal by Rank

M
A
N
I
T
https://www.uky.edu/KGS/coal/images/5a_bituminous%20rank%20parameters.jpg
BHOPAL

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Pulverized Coal
Raw coal powdered, size consist coal
Pulverization
M 1. Crushing / Grinding
2. Iron Separation
A 3. Drying till moisture <2%
4. Ball milling for fine particles
N 5. Air mixing
I
T
BHOPAL

https://www.thinkymixer.com/en-us/library/glossary/pulverization-1-definition-and-purpose/
https://www.coalhandlingplants.com/boiler-in-thermal-power-plant/

Pulverized Coal

Advantage Disadvantages
M Low grade coal can be burnt Additional equipment is
Low % of air is required in required
A firing Fly ash removal required:
N Rate of combustion can be 40% of the ash passes up
controlled easily through the chimney and
I Combustion of pulverized spread itself upon the
coal can readily be adopted surrounding.
T to automatic control. Chances of explosion
BHOPAL
Pulverizing instrument is enhanced: Burns like gas
located out side the furnace

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Some unusual solid fuels

Cannels: Rare, High H2 Burn with smoke and

bright flame, doesn’t fall in any category
M
Torbanites: fine grained coal, named after https://www.britannica.com/science/cannel-coal

A Torbane hill of Scotland, rich in paraffin oil

N Methane Clathrate:
I 1 mole of methane in 5.75 mole of H2O
Available in deep sea: Antarctica
T 15000 Gt= 21×1015 m3
BHOPAL

Petroleum
Lt. Petra- “rock” & Oleum - “oil”
A thick, flammable, yellow-to-black mixture of solid, liquid, and gaseous
M hydrocarbons that occur naturally beneath the Earth's surface.

A
Crude Oil Natural Gases
N  After Processing:
After refining: the Transportation,
I chief source of manufacturing,
transportation fuels fertilizers etc.
T  Still very limited
BHOPAL

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Petroleum
Lt. Petra- “rock” & Oleum - “oil”
A thick, flammable, yellow-to-black mixture of solid, liquid, and gaseous
M hydrocarbons that occur naturally beneath the Earth's surface.

A
Crude Oil Natural Gases
N  After Processing:
After refining: the Transportation,
I chief source of manufacturing,
transportation fuels fertilizers etc.
T  Still very limited
BHOPAL

Origin of Petroleum
Carbide Theory

M
A
Dmitri Mendeleev
N
Problems
I Under high temperature and Pressure
No field evidence
(i) Ca +2  CaC2
T In presence of water Presence of S, Chl., N,
BHOPAL haemen, porphyrines and
(ii) CaC2+2H2O + Ca(OH) 2 +CH4
optically active C compounds etc.

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Organic Origin of Petroleum

Most acceptable theory: Biological origin of petroleum
Phytoplankton Petroleum
M Zooplankton

A
N
I
T
BHOPAL

Oil in the earth crust

M
A
N
I
T
BHOPAL

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Oil in the earth crust

M
A
N
I
T  1.5 trillion barrel still available (34 billion barrel/year)
BHOPAL
 Availability is more but extraction is not sure

India Crude oil Production

Commonly employed
M methods for oil exploration:
A 1.Geological

N 2.Geophysical
I 3.Geochemical
T
BHOPAL

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Oil exploration

M
A
N
I
T
BHOPAL

Oil exploration: Geochemical methods

M • Ground water
• Surface water
A • Stream sediments
N • Soils
• Biological
I • Ore samples
T • Track etch (identify radioactivity)
BHOPAL

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Petroleum Mining
If the petroleum is trapped
and under pressure, it will
M rise naturally; no pumping
needed.
A
Gas released during
N extraction is valuable but
must be trapped and
I processed;

T
BHOPAL As the pressure drops, flow slows and operators must use “secondary
recovery” techniques for to recover petroleum. The most common
technique: injection of water or gas

Petroleum Refining
Process of converting crude oil into
useful products.
M
Process is divided in three basic
A steps
N 1. Separation

I 2. Conversion
3. Treatment
T
BHOPAL

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Petroleum Refineries in India

M
A
N
I
T
BHOPAL

Fractional Distillation

M
A
N
I
T
BHOPAL

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Contents of Crud oil Fractional Distillation

M
A
N
I
T
BHOPAL

Composition

M
A
N
I
T
BHOPAL

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CRACKING

Cracking is the breaking up large

hydrocarbon molecules into smaller
M and more useful bits.

A Source of large hydrocarbon

molecules is often naphtha fractions
N or the gas oil fraction distillation of
crude oil.
I
T Fractions obtained from the
distillation process as liquids but are
BHOPAL
re-evaporated before cracking.

Thermal CRACKING

High Temperature (500-700 0C) &

Pressure (~70 atm.) are used to break
M the large HCs
A Gives mixture of products containing
N high proportions of HCs with double
bonds- alkenes.
I
Free radical mechanism: carbon-carbon
T bonds break with equal distribution of
BHOPAL bonding electrons

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Catalytic Cracking
In presence of catalyst, cracking can
be carried out low temperatures (150-
370… 0C) & Pressures (~1-3 atm.).
M
A Rate of undesired reactions like over
cracking & polymerization can be
N minimized to enhance the yield of
desired product.
I
Fluidized bed catalytic
T cracking (FCC) and
BHOPAL moving bed catalytic
cracking are used.

Catalytic cracking: Zeolites

• Zeolites are the aluminosillicates and
are large lattices of Al, Si and O atoms
carrying a negative charge associated
M with +ve ions Na+.
• Zeolites used in catalytic cracking are
A chosen to give high percentages of HCs
of C5-C10 atoms
N • It produces high proportions of
branched alkanes and aromatic HCs like
I benzene.
• Zeolites has sites which can be remove
T a Hydrogen from alkane together with
BHOPAL the two e-s which bound it to the
carbon. That leaves the C with a +ve
charge, i.e. carbonium ion
DOI: 10.1002/adma.201701139

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Heavy Fuel Oils

M
A
N
I
T https://direns.mines-paristech.fr/Sites/Thopt/en/co/petrole.html
BHOPAL
Source: Dr. Semih Eser
https://en.wikipedia.org/wiki/Heavy_fuel_oil#/media//

Hydro-treating
Hydrotreating is the reaction of organic compounds in the presence of high pressure
hydrogen to remove oxygen (deoxygenation) along with other heteroatoms (nitrogen,
sulfur, and chlorine).

M The purpose of a hydrotreater unit is primarily to remove sulfur and other contaminants
from intermediate streams before blending into a finished refined product or before
A being fed into another refinery process unit.
Hydrotreaters also saturate aromatics and olefins if operated at high pressure, which is
N great for diesel quality (raises cetane) but bad for gasoline (reduces octane).

I
T
BHOPAL

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Petroleum: Knocking
Sharp metallic sound produced in the internal combustion engine

Compression Air + Fuel enters and

M then compressed
Power  Fuel ignites and
A remaining's exhaust

N
I
T
BHOPAL

Petroleum: Knocking
https://animagraffs.com/how-a-car-engine-works/

M
A
N
I
T
BHOPAL

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Knocking
Knocking is a mild explosion occurring in an internal combustion engine
common to both petrol and diesel engine.
Petrol engine Due to the highly branched or
M aromatic hydrocarbon
Diesel engine Due to delayed Ignition
A
Symptoms: Audible knocking or pining
N sound under acceleration

I Effect:
• Noise and Vibrations
T • Mechanical Damage to piston & Cylinder
• Increase of heat loss
"rattle rattle",
"cancan cancan"
BHOPAL • Reduces the efficiency of engine
or "kinkin-kinkin".

Knocking measure : Octane number

Chemist “Russell marker” : Quality of petrol fuel can be
determined by octane number.
Isooctane : octane number 100 (no tendency to knock)
M n-heptane : octane number 0 (causes great knocking)

A
N
I
T
BHOPAL

LPG have octane rating > 110 & Triptane ~125

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Different types of “Octane” number

Different octane number depending on test protocol:

 RON – Research Octane Number (used in

M Europe) & India – 87 (regular )"Speed 93-97"

 MON – Motor Octane Number

A
 PON – Pump Octane number
N PON = (RON+MON)/2  (US, CAN)
I
T
BHOPAL

Knocking measure : Cetane number

 Used to determine the quality of diesel fuel.
 n-hexadecene : cetane number 100
M  alpha-methyl napthalene : cetane number 0

A
N
I
T ASTM D976 &  Regular diesel: 48
ASTM 4737  Premium diesel: 55
BHOPAL
fuel density and  Biodiesel (B100): 55
boiling/evaporation  Biodiesel blend (B20): 50

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Anti-Knocking compounds
Compounds which are added to fuel to increase the octane number of
petrol or gasoline by reducing its knocking characteristics.

M Eg: tetraethyl lead (TEL)

Methyl tertiary butyl ether (MTBE)
A Disadvantages of TEL – cause environmental pollution
by throwing lead bromide.
N Cetane boosters
I Added to the fuels to prevent the knocking of diesel engines.
Eg. 1-nitro-2-hexene, 1-nitro-2-octane
T 1-methyl-1-nitro-2-pentene
BHOPAL 1-methyl-1-nitro-2-hexane Look for commercially
available Cetane
boosters

Octane vs. Cetane

Octane Cetane
Measure of the performance Measure of the delay of
of a fuel the ignition of a fuel
Important for predicting Important for
M knocking of an engine predicting the ignition
of an engine

A Given for Gasoline

Octane rating is done
Given for diesel
Cetane rating is done
considering the octane no of considering the ignition
N https://petroleumservicecompany.com/blog/the-difference-between-cetane-and-
isooctane (8C) as 100 of Cetane (16C)
octane/ N-heptane is given min. number α-methylnaphthalene is
I ‘0’ given a minimum Cetane
number ‘0’
Octane numbers are generally Used for relatively light
T used between 0-100. But it can distillate diesel oils, for
be higher than 100 also, for eg. heavy (residual) fuel oil
BHOPAL LPG. The fuels having better two other scales are
anti-knocking property than used CCAI and CII
isooctane are rated in other
scales like octane performance.

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Synthetic Petrol
History : During first world war in 1926 this process was
successfully utilized.

M
A
N
I
T
BHOPAL Carried out by means of hydrogenation in high temperature,
using ferric oxide as a catalyst

Methods of producing Synthetic Petrol

1. Polymerization
2. Fisher –Tropsh method
M 3. Bergius process

A 1. Polymerization: Smaller HCs heavier HCs

(a)Thermal polymerization
N (b)Catalytic polymerization
I
T
BHOPAL

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Methods of producing Synthetic Petrol

1. Thermal Polymerization: Carried out at high temperature

(500-600 OC) & pressure (70-350 kg/Cm2)
M
A 2. Catalytic Polymerization:
N Carried out at low temperatures in presence of
catalysts like H3PO4
I Rate of reactions are faster
T
BHOPAL
Obtained gasoline is of improved quality & possess
high antiknock properties than the gasoline
obtained from thermal process

2. Fisher-Tropsch process
1. Water gas is varied with Hydrogen and the combination is purified by
transitory from side to side Fe2O3 and then into a mixture of Fe2O3 +
Na2CO3.
2. The cleanse gas is dense to 5-25 atm. and then led from side to side a
M converter which is preserved at a temperature of 200-300 0C.
3. The converter is provided with a caralyst bed considering of a mixture
A if 100 parts cobalt, 5 parts thoria (ThO2), 8 parts magnesia (Mg(OH)2) and
200 parts keiselghur earth (SiO2)
N
I
T
BHOPAL

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Liquefied Petroleum Gas

Mixture of hydrocarbons
• Commercial propane
• Commercial butane
M • High energy fuel
• Very light in weight
• Non-corrosive
A • Combustion
Stored under pressure as liquid
Large Vapor to liquid ratio.
N C. V. : 10900 kcal / kg.
Flame temp with air - 2000 deg.
I Cent.With oxygen - 2800 deg. Cent.

T • Ignition temp.
BHOPAL – Auto ignition temp. - 410 - 580 deg.
Cent.

Natural Gas
Natural Gas - What is it ?
Naturally occurring complex Hydrocarbon Gas mixture
LIQUID
M GASEOUS

A
N
SOLID
I
Crude oil wells: associated gas, can be separate or in mixed form
T
Dry gas wells: non-associated gas/ plant condensate
BHOPAL
Condensate wells: Wet gas/ associated gas

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Natural Gas Characteristics

M
A
N
I  Compressibility
 Non-toxic
T  Narrow Flammability limits
BHOPAL
 High Ignition temperature
 Specific Gravity

Compare CNG & LPG

CNG LPG
Constituents Methane Propane and Butane
M Source Natural gas-and-
condensate wells, oil wells,
From gas fields , and by-product of
cracking process during crude-oil
A coal bed methane wells. refining.
Main Uses Substitute for gasoline Heating /cooking, refrigeration,
N industrial, agricultural, catering
Environment Releases lesser greenhouse Releases CO2 which is a greenhouse
I al effects gas. gas but is cleaner
Properties lighter than air and Highly inflammable, heavier than air
T disperses quickly in the and on leakage will settle to ground
event of spillage. and accumulate in low lying areas.
BHOPAL
Safety Easily disperses, hence risk Since it is difficult to disperse risk
of ignition is minimized. of fire is more.

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Producer Gas & Water gas

Producer gas is the mixture of combustible
and non-combustible gases.
Combustible gases
M • 18-22 % Carbon monoxide (CO)
• 8-12 % H2
• 2-4 % Methane (CH4)
A
Non-combustible gases
N o 8-12 % CO2
o 45-50 % N2
I
Water gas: mixture of flammable gases while producer gas is
T a mixture of both flammable and non-flammable gases.
We can produce water gas from syngas by enriching the
BHOPAL syngas with hydrogen while reducing the carbon dioxide level.
In addition, we can produce the producer gas via combustion
of carbonaceous materials.

Bio-Gas

M
A
variety of sources of biomass:
N • plant materials
• certain types of crops
I • recycled or waste vegetable oils

T  Can replace conventional diesel/petrol entirely

respectively
BHOPAL  Can be blended for different proportions:

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Compare Gaseous Fuels

M
A
N
I
T
BHOPAL

52