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Definition:
- Asubstance that releases the energy as heat energy on combustion in air or oxygen
This heat can be converted into mechanical energy via heat engines.

Principal elements present in chemical fuels are carbon and hydrogen.

On combustion the carbon and hydrogen converted into carbon dioxide and water.

The heat content of combustion products is lower than that of the reactants and hence
chemical fuels release the heat during the combustion process.
Eg. Wood, coal, crude oil, natural gas etc..

HEAT PRODUCED ON
COMBUSTION OF FUELS
Fuels can be classified as two types based on their
physical state
Classification:

Chemical fuel cells primarily used as heat and power as well as reducing agents in metallurgical applications
Calorific Value
“The amount of heat released when unit quantity of a fuel is burnt completely in air or oxygen”

Its an important parameter to know about the heating efficiency. The performance of fuel
can be find out by using the calorific value.
Units: solids/liquids: Calori/gram (cal/g) or Kcal/kg or Joul/kg
gas: J/m? or Cal/m? [1 cal: 4.185 J= 4.185x107 erg]

Gross (Higher) calorific value:

Amount of heat released when unit quantity of fuel is burnt in air and the combustion
products are cooled to room temeperature.
On cooling, the combustion products liberates latent heat.
Hence it is gross calorific value
Net (lower) calorific value:

Amount of heat released when a unit quantity of fuel is burnt completely in air and the
combustion products are let off into the atmosphere.
Products are not cooled to room temperature.
Net calorific value < Gross calorific value

Net calorific value = Gross calorific value - Latent heat of steam

587
— GCV = 9 x 0%H x _—_
nr

Because 1g of hydrogen gives 9g of water and the latent heat of steam is 587 cal/g.
Bomb Calorimeter
“Process of measuring heat is Calorimeter”

Principle: Beckmann's
thermometer

Electrically
cover operated shrrer

Electrodes
to which a fing” "ej
iS attached

. Copper
Alorne'er

Construction: Stainless st
Resistance wire
bornd

Weighed pallet
of given fuel sample
Working:

¢ Put the known amount of sample in crucible

« Stainless-steel Crucible with fuel place in the bomb stirer ignition §3 magnifying
wires Gee eyepiece
_—— /

« Steel bomb place in the large well insulated ra

calorimeter.

* Calorimeter has a accurate quantity of water :

¢ Initial temperature of water is measured carefully insulating— ff “)
jacket
* Combustion of fuel is initiated by allowing the oxygen
and by passing electric current through the coil air space —~

¢ The liberated heat will be absorbed by the water

« Note the maximum temperature

¢ Water equivalent of the calorimeter is determined by
burning a fuel of known cv.
Calculations

Heat can be calculated using the following process;

Weight of the fuel =mg

Weight of the water taken in the calorimeter = W1 g
Water equivalent of calorimeter =W2g
change in temperature (initial-final); (t,-t;) = At°C

Heat lost by 'm’g of fuel = heat gained by the water + heat gained by the calorimeter
= (W,+W))

Higher calorific value of the fuel = (W,+W-,) (to-t,)/m cal/g

eleva — y Cer ike

KO eed
Net calorific value:

If the fuel contain 'H’ % of hydrogen

2H a VD) O, ~~ H,O

From this reaction; 2g of hydrogen produces 18g of water

 If the fuel contain 'H’ % of hydrogen
2H + % Oo------ me)

From this reaction; 2g of hydrogen produces 18g of water

Water formed by 1g of fuel = = x a = 0.09Hg

Latent heat of steam = 587 cal/g

Latent heat of water formed = 0.09H x 587 cal/g
Lower calorific value = GCV-0.09H x 587 cal/g
Boy’s Calorimeter
* CAV. of gaseous and volatile liquid fuels

Principle:
Water
CN. is determined by burning a known volume of gas %
inlet

sample. S
S
|
The released heat is quantitatively absorbed by cooling ~+ Insulated
A

CLL
container
water, circulated through the copper coils surrounded ‘
S
\
the combustion chamber. sy‘
A
The mass of the cooling water, rise in temperature and '
Ny
the mass of water produced by condensation of steam NY
recorded. ( ‘
S
WM
TAKEDA.

fd
The calorific value of the gas sample is then calculated
from these data.
Construction:
* Gas burner
* Combustion chamber with copper tube coil
en Aelia mnie)
¢ Insulated chamber
* Two thermometer
Calculations

The volume of gas burnt at a given temperature and pressure during a certain time t=V
The amount of water passed through the coil during the same time interval, t=w
Temperature of incoming water = t, °C
Temperature of outgoing water = t, °C
The amount of water condensed during the experiment = m

Calculations:
Total heat liberated = V. gq
Total heat absorbed = wi(t,-t,)
Now heat liberated = heat absorbed (Assuming no heat loss in the steady state cnditions)
i.e. V.q = w(to-t,)

w(t,—t,)
Therefore GCV ; g = v
the amount of water condensed by 1m? of gas - m/v
The latent heat of steam - 587 kcal

Therefore NCV = q —m x =
Numerical:
Calculate the gross and net calorific value of a sample from the following data obtained from the bomb
calorimeter experiment.
Weight of coal (m)=0.73g
Weight of water taken in calorimeter (w)=1500g
Water equivalent of calorimeter (w,)= 470g
Initial temperature (t;)} =25°C
Final temperature (tp) = 27.3 °C
% ofH in coal sample Vnewo
Latent heat of steam 587 cal/g

Solution:

- Aa ee eee Aaa
High calorific value (GCV) = > aor J/k a cal/g

_ (1500+470)(27.3-25)
0.73
= 6206.8 cal/g
ols 25969.3x 103 J/kg (1 cal = 4.187 J)

Net calorific value (NCV) = GCV-heat released by the condensation of steam

SL ae ee a Ye eae PLL RRB Ce
Chemistry of Fuels

Lecture-2
 Coal & Its Analysis
* Coal is a highly carbon containing matter formed from vegetable
matter (i.e. plants) buried from the soil under the effect of pressure,
heat, action of aerobic and anaerobic bacteria for a long time.

¢ The primary elements are C, H, N, O and some non-combustible

inorganic matter.

¢ Considerable amounts of free and hygroscopic moisture and traces of

S, As, P etc.
 Analysis
¢ To decide the quality of fuel it must be analyzed.
¢ The analysis also required to know the amount of oxygen required for
the efficient production of energy.
¢ To determine the percentage of various constituents present in coal
which directly effect the calorific value.
¢ This C. V. decides the price of the coal

there are two types of analysis

1. Proximate analysis: % moisture, % volatile matter, % of ash and %
fixed carbon
2. Ultimate analysis: %C, %H, %S, %O, %ash and %N
 Proximate Analysis
Moisture:
* Known amount sample should be taken
¢ Heated in oven at 105-110 °C for 1 hour
¢ Cooled in desiccator and measured the weight
¢ The difference gives the % of moisture
¢ This heating, cooling and weighing should be repeated until get the constant values

m—m
% of moisture = difference in the weight of the coal x 100 = x 100
m

weignt of the coal taken

¢ The difference is the loss in weight

Volatile matter:
¢ Moisture free is covered with a vented lid. Must use moisture free.
¢ Heated in a muffle furnace at 920-950 deg C for 7 min
¢ It is cooled in desiccator and then weight in loss is determined

% of volatile matter= loss in weight of the coal x 100

weight of the coal taken

¢ If not moisture free sample

Then % of volatile matter= loss in weight of the coal x 100 - moisture %
weight of the coal taken
%volatile + %moisture = loss in weight due to volatile + moisture
weight of the coal taken
% Ash:
¢ Ash is non-combustible inorganic matter in coal
* coal which is free from moisture and volatile will be heated at 750 deg C for 30
min in muffle furnace.
¢ It is cooled in desiccator and then weighed.
¢ Heating, cooling, weighing of crucible is repeated till constant weight is obtained.

% of Ash = weight of ash x 100

weight of the coal taken
% Fixed carbon:
¢ Higher the carbon higher calorific value
Fixed carbon%= 100-(%moisture+% volatile+%ash)
Significance:
1. Higher the moisture increases the ignition point of coal, calorific value
decreases, difficult to handle.
2. Higher volatile also decreases the calorific value. It burns with long smoky and
pollutes the atmosphere.
3. Ash will form the clinkers and creates hindrance to the air supply to coal.
disposal is an issue, decreases calorific value.
Carbon increases calorific value increases.
5. A good quality coal should contain low content of moisture, low content of
volatile matter, low content of ash and high content of fixed carbon.
 Ultimate Analysis
It is also known as elemental analysis.
It is used tot determine the C, H, N, S, ash and O percentage in the coal.
1. Carbon and hydrogen:
A known amount of coal is burnt in the presence of oxygen.
Then C + 0, > CO,
1

Sample in
platinum container

Combustion tube

Furnace

Pure dry
oxygen
Anhydrous CaCl, KOH Solution

Water absorbed by CaCl, and CO, absorbed by KOH

° 2KOH + CO, > K,CO3+ H,O0
44 g of CO, has 12 g of carbon
X g of CO, has x x g

% of carbon =
q
12
44.
=
weight of coaltaken
x 100

* CaCci, + 7H,0 — CaCl,.7H,O0

18g of H,O contain 2 g of hydrogen
y g of H,O contains = XVVg

% of hydrogen = - 8 x »
weight of coal taken
x 100
2. Sulphur (Eschka method)
A known amount of sulphur containing coal is burnt ina bomb pot in oxygen.
Then S + 0, — SO, > SO;

SO, +H,0 > H,SO,

H,SO, + BaCl, > BaSO,

Washing, drying and weighing the BaSO,.

233g of BaSO, contains 32g of sulphur
_ 32
z g of BaSO, contains 533 29

32 Z
% of sulphur = x x 100
233 weight of the coal taken
2. Nitrogen (Kjeldahl’s method)
A known amount of nitrogen containing coal is taken to Kjeldahl’s flask and heat
in concentration H2SO4.

N nS0y [Rey u)s50q

)504 AKI
AlKall? A, joy
bso Coo) Catalyst 2

(NH,),SO,+2Na0H > Na,SO,+2NH, + 2H,0

7 :
NH, + NaOH = (NH,),SO,

% of nitrogen can be calculated from + Gus, 1

. gompeuns oJ

the amount of acid consumed. Riekdahs

digestion (heating tn Kjeldahl's flask)

Amount of acid consumedz= blank titration reading — main/back titration reading

volume of acid consumed X normality of NaOH x 14

% of N= : x 100
weight of the coaltaken x 1000

volume of acid consumed X normality of NaOH x 1.4

0 =
% of N weight of the coal taken

To know the oxygen percent first we should calculate the % of ash.

% of Ash : coal burnt at 750 deg C for 30 min. repeat for same readings
weigh the ash amount after completion of combustion.

weight of ash
0 =
/o of ash weight of the coal taken x 100
% of oxygen = 100-(%C + %H + %N + %S +% ash)
Significance:
1. Good quality coal should contain high percentage of carbon.
2. Lowcontent of moisture, nitrogen, Sulphur, ash and oxygen.
Lecture 3
Chemistry of Fuels
 Liquid Fuels
Coal, Petroleum and natural gas are the natural sources of
energy and formed several millions of years ago

Petroleum/Crude oil:
* Dark colored viscous oily liquid.
* Composed of aliphatic hydrocarbons
* Crude oil can found under earth crust
* Not usable without processing
* artificial fuels obtained by distillation of crude oils.
examples: Petrol/gasoline
Kerosine
Diesel etc..
Petrol/gasoline:
Distillation at 65-220 deg C gives petrol
Petrol is lightest and more volatile gasoline
Used for light petrol engines

Kerosine: ;
Found by the distillation at 220-345 deg c Diesel: .
Heavy and less volatile than petrol Heavier than petrol and kerosine
Can bring out by the stellation at 345-470 degC
Can be used for diesel engine.
Advantages:

* They are better economical and more useful than solid fuels

* Petrol, diesel fuels use for the transportation in small and big vehicles as well as for aircrafts.

¢ LPG use for cooking, heating and for other domestic purposes

* High demand due to the high calorific value

* Low biproduct formation

* Used as coating bodies of boats, walls of temples, for embalming and for other puposes

Disadvantages:

* High risk of fire

* Requirement of special container for storage and transportation etc.
Cracking:

Breaking of high molecular weight hydrocarbons into low molecular weight hydrocarbons
or
Conversion of high boiling fractions into low boiling fractions

Involve breaking/rupturing of C-C and C-H bonds to low boiling alkanes/alkenes and small amounts of hydrogen

Fixed bed
catalytic cracking
Catalytic cracking
Moving bed
Cracking catalytic cracking

In the absence of air

oo & Catalyst at high
temp. & Pressure
Advantages of Catalytic Cracking:

Yield of petrol is higher

* |so-paraffins occurs and thereby better petrol is produced

* A much lower pressure is needed

* Easily controlled to have desired products

¢ Product contains less amount of undesirable S because a major portion of it escapes out as H,S gas

* Only Selective catalysts helps in cracking the high-boiling hydrocarbons

Moving (Fluidized) bed catalytic cracking

ree Flue Gases | Cracked Vapour

es IMA d emacs loti al 4 Cooler

c+0,>CO,% ‘—
Gases
Catalyst Regenerator
Gases
Regenerated
Catalyst
|
)
Feed Oil
—_—_—_—_—

* Gasoline + Gas

Reactor Fractionating
pent Catalyst Column
Stabilizer
“% e —_™~ Heavy Oil |
Catalyst + Oil » a
Pre-heater %,
‘Cuasuae { Sar
a
(425-450°C)
 20 *C
C, to C, gases liquefied petroleum gas

fractions °
decreasing in 70 Cc
density and
boiling point C, to C, naphta
chemicals

120 °C
C,toC,,petrol petrol for vehicles
(gasoline)

wore SS
C,, to C,, jet fuel, parrafin for
iarions kerosine lighting and heating
increasing in (paraffin oil)
density and °
boiling point 270 C

Cy to c. diesel fuels
crude oil diesel oils
ie oll

fie
305-405 °C

C,, to C., lubricating oils,

lubricating oil waxes, polishes

C,, toc fuels for ships, factories

= a and central heating
fuel oil

> C,, residue DS a

bitumen for roads
and roofing
Lecture 4
Chemistry of Fuels
 Synthetic Petrol
¢ Liquid hydrocarbons/synthetic fuels can be derived from natural gas,
coal and biomass, other solids like plastics/ rubber waste.

biomass

natural gas
Production methods:

* Polymerization : smaller molecules of hydrocarbons will be combined

to form heavier molecule resembling gasoline.

¢ Fischer-Tropsch method: Petrol can be synthesized from water gas

derived from coal

¢ Bergius method: Directly from coal into liquids by Hydrogenation

process at high temperature and hydrogen pressure conditions.
 Fischer-Tropsch Process
¢ Conversion of water gas which is a mixture of carbon monoxide and
hydrog gen (CO + H,) with hydrogen into liquid hydrocarbons in the presence
catalysts like Fé and Co at 180-250 degC

¢ It’s a gas-liquid conversion technology

Process: C+H,O >~CO+H,

Water gas

Water gas is freed from dust, H,S and Sulphur compounds.

Water gas + H,----> synthetic gas

* This process is received well attention due to the low sulfur diesel fuel and
to address the supply or cost of petroleum derived hydrocarbons
Bi iomass
= die —$ light product
Electricity

Heat
:
— (“trigeneration”)
——

‘Green’ Diesel

nCO + 2nH, — C,H,, + 2H,0 + heat

nCO + (2n +1) H, > C,H,, 2+ 2H,0 + heat

The water gas with hydrogen is purified by transitory from side to side Iron oxide
and then from a mixture of Fe,0, + Na,CO3.

The clean gas is compressed to 5-25 atm pressure and forced to catalytic reactor

The converter in catalytic chamber provided with a catalyst bed consisting of a

mixture of 100 parts cobalt, 5 parts thoria, 8 parts magnesia and 200 parts
kieselguhr earth

Reaction takes place at 200-250 deg C to form saturated and unsaturated

hydrocarbons.

The crude liquid oil obtained from the condenser and this mixture forced to
fractionating column to yield gasoline

Heavy oil collected from the bottom which will be cracked further to get gasoline.
 Power Alcohol
* Power alcohol is a mixture of petrol and alcohol in the
ratio of 4:1.
¢ When ethyl alcohol is mixed in petrol (5-25%) to use as
fuel in internal combustion engine, is called power
alcohol
¢« Also contains Benzene and ether
Manufacture of power Alcohol:
Saccharine materials (such as molasses, sugar cane, etc..)
and starchy materials (such as starch, potatoes, cereal
grains, etc.), cellulose materials (such as Sulphite liquor
from paper mills) and hydrocarbon gases are the raw
materials for alcohol manufacturing.
Ethyl alcohol from molasses
Molasses is a dark colored viscous liquid left after the
crystallization of cane sugar from cane juice.
¢ Molasses is converted into ethyl alcohol in
the presence of yeast.
¢ Yeast contains enzymes invertase and
zymase which are responsible for
fermentation

(CoH, 905) +nH,0 > (C42H22011)n ES Ss ; ie

Starch Maltose
Invertase

Ci9H9201;, > CeHy206

+ CeH,20¢
Glucose Fructose

Zymase
CHO. = 20,H.0H +200;
¢ Ternary mixture boils at 65 deg C and pure alcohol boils at 78.5 degC.

¢ The vapor of ternary mixture go out at 65 degC and taking away all the water and

leaves the absolute alcohol behind.

Power alcohol as a fuel:

¢ Power alcohol used as a motor spirit in internal combustion engines by blending

with petrol

¢ Blends contains upto 25% of alcohol

¢ Industrial alcohol contains 95% alcohol and 5% water can also be blended by

using some blending agent such as benzene, ether etc..

Advantages:

1. Good anti-knocking agent

2. Alcohol has good octane number 90 while petrol has 60-70.

Due to higher octane number, alcohol-blended petrol can be used in engines with higher
compression ratio. This compensates for the lower heating value of alcohol in the blend.

No starting difficulties

Ability to burn completely

Ability to absorb moisture

Cheaper than petrol

Lubrication of blended fuel is same as that of pure petrol

Less air is required for complete combustion

Disadvantages:

1. Lowers the calorific value due to low calorific value of alcohol.

2 Special arrangements are needed to use

3 Air entering the cylinder needs to be regulated by modifying the air inlet

4. Easily get oxidized to acids, then It may cause corrosion to engine

5 Alcohol obtained from fermentation process cannot be mixed directly

with petrol

Alcohol absorbs moisture and as a result separation of alcohol and

petrol layers takes place especially at low temperature. Blending agent

should be added.
 Lecture 5
Chemistry of Fuels
 BIO DIESEL
¢ It is a vegetable oil or animal fat based diesel fuel consisting of long
chain alky esters (methyl, ethyl or propyl). Also known as
triglycerides.
* Commonly produced by the transesterification of the vegetable oil or
animal fat.
¢ Trans-esterification process involves combining any natural oil
(vegetable or animal) with virtually any alcohol and a catalyst

Catalyst
Vegetable oil or animal fat + alcohol — biodiesel
Commonly used vegetable oil - rapeseed oil, soyabean oil, sunflower oil, palm oil,
coconut oil, mustard oil, jathropha oil or any waste vegetable oil

Commonly used animal fats are — tallow, lard, chicken fat, fish oil

The most commonly used alcohol is methanol as it is cheapest

Ethyl alcohol also can be used to produce biodiesel

Bio diesel can be used alone or can be blended with petro diesel. It is green fuel,
does not contribute to the carbon dioxide and produces drastically reduced
engine emissions

Biodiesel has combustion properties similar to those of the petroleum diesel and
can replace it in most current uses
Chemical reaction involved as follows:

ed
catalyst ! i
CH,OH
co

° 3CH,COOR, 4 es
CHCOOR + 3CH,OH
| ui CH,OH
CH,COOR
Biodiesel Glycerin
Vegetable oil

Triglyceride oil

Catalyst : NaOH, 60 deg C. here R is the long alkyl chain group.

 Schematic of Biodiesel Production Path

Vegetable Oil/
imal Fat/Waste

|
Methanol
plus Catalyst oo
Crude Gycorm

Y
Advantages:
¢ Biodiesel is derived from the renewable energy sources such as
vegetable oil- a sustainable resource that will not run out
¢ Unlike petroleum diesel, It is biodegradable and non-toxic
¢ It can be produced from the waste vegetable oil also and simple to
make
¢ Biodiesel use does not lead to any overall change in the amount of
CO, in the atmosphere.
e Less noxious — biodiesel lacks the unpleasant odour of petroleum
diesel. One can expect the 100% reduction in SO2, 40-60% reduction
in soot and particulates, 10-15% reduction in CO and a reduction in all
poly aromatic hydrocarbons
¢ Non-hazardous. Flash point is very high. So safe to store and transport

¢ Burns more efficiently then petroleum diesel

¢ High lubricity than petrol diesel. Hence can reduce engine wear and

prolong engine life

¢ |t creates self-emplyoment and encourages the farming activities

Hydrogen as a source of energy:
¢ Hydrogen is a simplest and most abundant element on the earth. But it does not

exist by it self in nature. It should be produced from the compounds that contain

it.

¢ Hydrogen can be produced from diverse, domestic resources, currently, most

hydrogen is produced from fossil fuels, specifically natural gas.

¢ Currently, electricity-from the grid or from renewable sources such as biomass,

geothermal, solar or wind also used to produce hydrogen

¢ In long term- solar energy and bio mass also can be used more directly to

generate the hydrogen

Common ways to produce hydrogen:
¢ There are many ways to produce hydrogen using sunlight.
Such as photobiological, photoelectrochemical, photovoltaic-
driven electrolysis and solar thermochemical processes.
Hydrogen Fuel Cell
Water Out
¢ Steam methane reforming- a high temperature process where
steam reacts with a hydrocarbon fuel to produce hydrogen

¢ Water splitting into oxygen and_ hydrogen-electrolysis

(electrolyser produces hydrogen from water).

¢ Hydrogen gas can produce by biological processes also using

microbes such as bacteria and microalgae. Microbes produce
hydrogen gas by consuming the plant material.
Applications:
Its a clean fuel. Hydrogen can be used in fuel cells to generate electricity, power and heat
Petroleum refining and fertilizer production
Due to High efficiency and zero-emissions operation, hydrogen and fuel cells have potential to
reduce greenhouse gas emission in many applications
Hydrogen gas usage is there in all sectors such as transportation, commercial, industrial,
residential and portable utilities
Currently, hydrogen is mainly used as a fuel in the NASA space program. Liquid hydrogen is
used to propel space shuttle and other rockets, while hydrogen fuel cells power the electrical
systems of the shuttle. The hydrogen fuel cell is also used to produce pure water for the
shuttle crew.
Hydrogen is also used in agriculture to create fertilizers, and to make cyclohexane and
methanol, substances used in the production of plastics and pharmaceuticals. Oil-refining
processes also make use of hydrogen gas
The greatest challenge for hydrogen production from renewable sources is providing
hydrogen at lower cost
For transportation fuel cells, hydrogen must be cost competitive with conventional fuels and
technologies