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Arunava Agarwala
1
Fuels
Fuels are combustible substance, containing carbon as main
constituents, which on proper burning gives large amount of
heat, which can be used economically for domestic and
industrial purposes.
Alternately, Materials which possess chemical energy is known
as fuel.
For example Wood, Charcoal, coal, Kerosene, petrol diesel, oil
gas etc.
C (s) + O2(g)
PRODUCTS + HEAT
Lesser heat energy content
CO2(g) + H= -94.1Kcal/mole
Classification of Fuels
These can be classified on the basis of their occurrence and
physical state
On the basis of occurrence they are of two types:
Primary Fuels: Fuels which occur in nature as such are
called primary fuels. E.g., wood, peat, coal, petroleum, and
natural gas.
Secondary Fuels: The fuels which are derived from the primary
fuels by further chemical processing are called secondary fuels.
e,g., coke, charcoal, kerosene, coal gas, producer gas etc.
On the basis of physical state these may be classified as:
Solid Fuels: woods, Peat, Lignite etc.
Liquid Fuels: Crude oil, Tar, Diesel, Petrol, Kerosene.
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System
Solid/Liquid Gaseous
Fuels
Fuels
CGS
MKS
B.T.U
Calories/gm
k cal/kg
BTU/lb
Calories/cm3
k cal/m3
BTU/ft3
= 2.2 C.H.U.
Therefore,
LCV=HCV-weight of hydrogen x 9 x latent heat of
steam
= HCV-weight of hydrogen x 9 x 587
Determination of Calorific value
1. Determination of calorific value of solid and non
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Bomb Calorimeter
Calculations
Let weight of the fuel sample taken = m g
Weight of water in the calorimeter = W g
Water equivalent of the Calorimeter, stirrer, bomb, thermometer
=wg
Initial temperature of water = t1oC
Final temperature of water = t2oC
Specific heat of water = S
Higher or gross calorific value = C cal/g
Heat gained by water = W x t x S
= W (t2-t1) S
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S O SO
2
2
2SO O 2H O 2H SO
2 2
2
2 4
2 N 5O 2H O 4HNO
2
2
2
3
14
H= -144,000 cal
H= -57,160,000 cal
The corrections must be made for the heat liberated in the bomb by the
formation of H2SO4 and HNO3. The amount of H2SO4 and HNO3 is
analyzed by washings of the calorimeter.
For each ml of 0.1 N H2SO4 formed, 3.6 calories should be subtracted.
For each ml of 0.1 HNO3 formed, 1.429 calories must be subtracted.
(C) Cooling correction: As the temperature rises above the room
temperature, the loss of heat does occur due to radiation, and the
highest temperature recorded will be slightly less than that obtained. A
temperature correction is therefore necessary to get the correct rise in
temperature.
If the time taken for the water in the calorimeter to cool down from the
maximum temperature attained, to the room temperature is x minutes
and the rate of cooling is dt/min, then the cooling correction = x dt.
This should be added to the observed rise in temperature
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Mass of Fuel
Some problems
Q:1 0.72 gram of a fuel containing 80% carbon, when burnt in a bomb calorimeter,
Increased the temperature of water from 27.3C to 29.1C. If the calorimeter contains
250 grm of water and its water equivalent is 150 grms, calculate the HCV of the fuel.
Give your answer in Kj/Kg.
Some problems
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Some problems
Some problems
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Some problems
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PROCEDURE:
Install the equipment on a flat rigid platform near an uninterrupted
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When the steady condition are established, then the reading are taken
simultaneously of:
The volume of gaseous fuel burnt (V) at given temperature and pressure
in certain period of time (t).
The quantity of water (W Kg) passing through the annular space during
the same interval of time
The steady rise in temperature (T2-T1)
The mass of water (steam) condensed (in Kg) in the outlet water.
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Calculation:
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 =
LCV =
27
m x 587
LV
Kcal/m3
Problem-1
The following were obtained in the Boys 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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Some problems
During the determination of calorific value of a gaseous fuel by Boys
Calorimeter. The following results are obtained
Vol. of gaseous fuel burnt at NTP = 0.093 m3
Weight of water used for cooling the combustion products = 30.5 kg
Weight of steam condensed = 0.031 kg
Temp. of inlet water = 26.1C
Temp. of outlet water = 36.5C
Determine the gross and net calorific value of the gaseous fuel per cubic
meter at NTP provided that the heat liberated in condensation of water
Vapor is 587cal/g
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problems
Calculate the gross calorific value and net calorific value of a
gaseous fuel, 0.012m3 of which when burnt raised the temperature
of 3.5kg of water by 8.2K. Specific heat of water is 4.2 kJ kg-1K-1.
Latent heat of steam is 2.45 kJ kg-1. The volume of water collected
is 6.5cm3 .
V = volume of the gas burnt
W = mass of water
t2- t1 = rise in temperature
s = specific heat of water
v = volume of water collected
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= 0.015 m3
= 3.5 kg
= 15.6 K
= 4.2kJ kg-1K-1
= 6.5 cm3
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Substrate
Calorific value
Carbon
8080
Hydrogen
34500
Sulphur
2240
32
=H-O/8
33
Calculate the gross and net calorific value of coal having the following
composition carbon = 85%, hydrogen = 8%, sulphur = 1%, nitrogen = 2%,
Ash = 4 %, latent heat of steam 587cal/g.
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Solid Fuels:
Wood: Wood has been used as a fuel from ancient times. Due
to large scale deforestation, wood is no longer used.
Freshly cut wood contains 25-50% moisture.
Air dried wood contains about 10-15% moisture content.
The calorific value of air dried wood is about 3500-4500
kcal/kg.
When wood burns, the ash content is low but the oxygen
content is very high. This makes even dry wood a fuel of low
calorific value.
Wood charcoal is obtained by destructive distillation of wood.
The major use of wood charcoal is for producing activated
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carbon.
Coal formation
At various times in the geologic past, the Earth had dense forests
in low-lying wetland areas. Due to natural processes such as
flooding, these forests were buried under the soil. As more and
more soil deposited over them, they were compressed. The
temperature also rose as they sank deeper and deeper. As the
process continued the plant matter was protected from
biodegradation and oxidation, usually by mud or acidic water.
This trapped the carbon in immense peat bogs that were
eventually covered and deeply buried by sediments. Under high
pressure and high temperature, dead vegetation was slowly
converted to coal. As coal contains mainly carbon, the
conversion of dead vegetation into coal is called carbonization
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_____
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Wood
Peat
Lignite
Bituminous coal
Anthracite
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Type of
coal
20-40 0-0.5
VM
%
calorific
moist value
ure
Wood
45-50 5-6
70-90
Peat
90-95 3-4
2-3
0.5-2
40004500
41255280
66007100
66008800
Selection of coal
Calorific value should be high
Moisture content should be low
Ash content should be low
Sulphur and phosphorus contents of coal should be low
Size of coal should be uniform
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Analysis of Coal
In order to assess the quality of coal, the following two types of
analysis are made:
1.
Proximate analysis
2.
Ultimate analysis
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Proximate Analysis
Proximate analysis of coal determines the moisture, ash, volatile matter and
fixed carbon of coal. It gives information about the practical utility of coal.
1.
Loss in weight
x 100
Percentage of moisture =
Wt. of coal taken
Importance of Proximate analysis:
Excess of moisture is undesirable in coal.
Moisture lowers the calorific value of coal because it takes away
appreciable amount of the liberated heat in the form of latent heat of
vaporization.
Excessive surface moisture may cause difficulty in handling the coal.
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Loss in weight
x 100
Wt. of coal taken
Significance
A high percent of volatile matter indicates that a large proportion of fuel is
burnt as a gas.
The high volatile content gives long flames, high smoke and relatively low
heating values.
For efficient use of fuel, the outgoing combustible gases has to be burnt by
volatile matter in a coal denotes the proportion of the coal which will be
converted into gas and tar products by heat.
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(3) Ash: Coal contains inorganic mineral substances which are converted
into ash by chemical reactions during the combustion of coal. Ash usually
consists of silica, alumina, iron oxide and small quantities of lime,
magnesia etc.
Ash content is determined by heating the residue left after the removal of
volatile matter at 700 50oC for an hour without covering. The crucible
is taken out, cooled first in air, then inside a desiccator and weighed. The
residue is reported as ash on percentage basis.
Significance
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C + O2
CO2
H2 +1/2 O2
H2O
12
44
18
2KOH CO K CO H O
2
2 3
2
CaCl 7 H O CaCl .7 H O
2
2
2
2
Nitrogen H SO Heat
( NH ) SO
2 4
42 4
The contents are then transferred to a round bottomed flask and solution is
heated with excess of NaOH.
The ammonia gas thus liberated is absorbed in a known volume of a
standard solution of acid used.
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( NH ) SO 2 NaOH
Na SO 2 NH 2 H O
42 4
2 4
3
2
NH H SO ( NH ) SO
3
2 4
42 4
The unused acid is then determined by titrating with NaOH. From the
volume of acid used by NH3 liberated, the percentage of nitrogen can be
calculated.
(3) Sulfur is determined conveniently from the bomb washing from combustion
of a known mass of coal in bomb calorimeter experiment. The washing contain
Sulfur in the form of sulfate which it is precipitate as BaSO4
%S =
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Liquid Fuels: The importance of liquid fuels is the fact that almost all
combustion engines run on them.
Benefits of Liquid fuel:
They are easy to handle, store and transport.
After burning they do not leave any applicable amount of ash
Liquid can easily kindled. The combustion can be started or stopped at once
The rate of combustion can easily controlled as desired
Less excess air is needed in case of liquid fuels as compare to solid fuel
The furnace space is required is lesser than solid fuel
Operation is cleaner
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Petroleum: The term petroleum means rock oil. It is also called mineral oil.
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Refining of Petroleum
Crude oil reaching the surface, generally consists of a mixture of solid, liquid
and gaseous hydrocarbons containing sand and water. After the removal of
dirt, water and much of the associated natural gas, the crude oil is
separated into a number of useful fractions by fractional distillation and
finally converted into desired specific products. The process of refining
involves the following steps
Step 1: Separation of water (Demulsification): The crude oil coming out
from the well, is in the form of stable emulsion of oil and salt water, which is
yellow to dark brown in color. The demulsification is achieved by Cottrells
process, in which the water is removed from the oil by electrical process.
The crude oil is subjected to an electrical field, when droplets of colloidal
water coalesce to form large drops which separate out from the oil.
Step 2: Removal of harmful impurities: Excessive salt content such as
NaCl and MgCl2 can corrode the refining equipment. These are removed by
washing with water. The objectionable sulphur compound are removed by
treating the oil with copper oxide. The copper sulphide (solid) so formed is
separated by filtration
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Below 30C
30-70C
40-120C
120-180C
180-250C
250-320C
320-400C
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Cracking
Gasoline (petrol, C4-C12)) is the most important fraction of crude
petroleum. The yield of this fraction is only 20% of the crude oil. The yield of
heavier petroleum fraction is quite high. Therefore, heavier fractions are
converted into more useful fraction, gasoline. This is achieved by a
technique called cracking.
Cracking is the process by which heavier fractions are converted into
lighter fractions by the application of heat, with or without catalyst.
Cracking involves the rupture of C-C and C-H bonds in the chains of
high molecular weight hydrocarbons.
C H Cracking
C H
C H
5 12 5 10
10 22
Decane
n -pentane pentene
B.Pt 174C
B.Pt 36C
C H Cracking
C H
C H
5 12 3 6
8 18
alkanes.
Unsaturated hydrocarbons are obtained from saturated hydrocarbons.
Cyclization may takes place.
Cracking can also be used for the production of olefins from naphtha's, oil
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new reactions which considerably modify the yield and the nature of the products.
The yield of the gasoline is higher.
The process can be better controlled so desired products can be obtained.
The product contains a very little amount of undesirable sulphur because a major
takes
place.
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Cooler
Dissolved gas
Gasoline
Heavy
oil charge
Pre Heater
(425-450C)
Catalyst chamber
(425-450C)
Fractionating
column
Heavy
oil Gasoline +
Dissolved gas
Stabilizer
The heavy oil are heated in a pre heater to cracking temperature (425-450C) and then
forced through the catalytic chamber (containing artificial clay and mixed with zirconium
Oxide) maintained at 425-450C and 1.5 Kg/cm2 pressure. During their passage through
the tower about 40% heavy oil converted into gasoline and about 2-4% carbon formed.
The vapour produced then passes through fractionating column, where heavy oil fraction
condensed. The vapour are then led through a cooler, where some of the gas are condense
along with the gasoline and uncondensed gas move on. The gasoline containing gas is
then sent to stabilizer, where the dissolved gas are removed and pur gasoline are obtained
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Procedure:
(1) The solid catalyst is very finely powered, so that it behave almost as a fluid,
which can be circulated in a gas stream.
(2) The vapours of cracking stocks mixed with fluidized catalyst is forced up into a
large reactor in which heavier molecules are cracked into lighter molecules. Near the
top of he reactor, there is a centrifugal separator (called cyclone), which allow only
the cracked oil vapours to pass on to fractionating column, but retain all the catalyst
powder in the reactor itself
(3) The catalyst powder gradually becomes heavier, due to coating with carbon and
settles to the bottom from where it is forced by an air blast to regenerator (maintained
600C)
(4) In regenerator, carbon is burnt and the regenerated catalyst then flow through a
stand pipe for mixing with fresh batch of incoming cracking oil.
(5) At the top of regenerator, there is an separator, which permits only gases (CO2
etc.) to
pass out, but holds back catalyst.
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Zeolites
Zeolites are microporous, aluminosilicate minerals commonly
used as commercial adsorbents
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Reforming
Reforming is a process of bringing about the structural modification in
components of straight run gasoline (prepared by the fractional distillation
of the crude oil), with primary object of improving the octane number.
Reforming can be accomplished by increasing in volatility (reduction of
molecular size) or by the conversion on n-paraffins to isoparafins, olefins,
Aromatics and naphthens to aromatics.
500-600C and a pressure of 85atm. The fed stock is straight run gasoline. To avoid
the formation of gas (at the expanse of gasoline), the condition are controlled by
quenching (rapid cooling) the products by spread of cold oil.
(2) Catalytic reforming: To get better grade and yield of gasoline, catalyst reformin
[Pt (0.75%) supported on alumina] is carried out by using either fixed bed or fluid
bed methods at 460-530C and 35-50 atm. The following are the main reaction during
75catalyst reforming:
Isomerization:
CH3-(CH2)4-CH3
CH3-CH-CH2-CH2-CH3
CH3
n-Hexane
2-methyl pentane
Dehydrogenation:
-3H2
Cyclohexane
CH3
Benzene
CH3
-3H2
Methyl-cyclohexane
Toluene
Dehydrocyclization:
CH3
CH2
H2C
H2C
CH3
C
H2
CH3
CH3
-H2
-3H2
CH2
Hydrocracking:
CH3-(CH2)8-CH3 + H2
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n-Decane
[Pt]
CH3-(CH2)5-CH3
n-Pentane
Knocking
In an internal combustion engine, a mixture of gasoline vapours and air is used as fuel.
After the initiation of the combustion reaction by spark in the cylinder, the flame should
be spread rapidly and smoothly through the gaseous mixture, thereby the expanding gas
drive the piston down the cylinder.
The power output and efficiency of an IC engine depends on the Compression ratio
which is the ratio of the volume of the cylinder at the end of the suction stroke to the
volume of the cylinder at the end of the compression stroke.
Volume of cylinder at end of suction stroke
Compression ratio =
Volume of cylinder at end of compression stroke
The efficiency of IC engine increase with increase in compression ratio, which is
dependent upon the nature of constituents present in gasoline.
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+ 7/2 O2
2 CO2
+ 3H2O
+ O2
Thus, olefines of the same carbon chain length possess better anti-knocking
Properties than the corresponding paraffins and so one
Effects of knocking:
Decreases life of engine
PbBr2 + H2C
CH2
These convert the lead into lead halides, which are volatile and escape with
exhaust gases. But, elease of lead compounds pollutes the atmosphere.
Catalytic converters (rhodium catalyst) are used in IC engines to convert
CO in the exhaust to CO2. Lead tetraethyl used as anti knocking agent
poisons the catalyst and hence leaded petrol is not advisable in such IC
engines.
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CH3
H
14
The cetane rating of a fuel depend upon the nature and composition of
hydrocarbon. The straight chain hydrocarbons ignite quite readily
while aromatics do not ignite easily. Ignition quality order among the
constituents of diesel engine fuels in order of decreasing cetane no, is
as follows:
Synthetic Petrol
Synthetic petrol can be produced from coal by the following methods
(1) Fisher-Tropsch Process:
In this process, coke is heated and steam is passed over it, thereby, water
gas (CO + H2) is formed
C + H2O
(CO + H2)
Water gas is purified by passing through the Fe2O3 (to remove H2S) and
then into Fe2O3 . Na2O3 (to remove organic sulfur compounds).
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n CO + (2n+1) H2
CnH2n + n H2O
CnH2n+2 + n H2O
The issuing gas are led to condenser, where a liquid resembling crude oil
is obtained, which fractionated to get (a) gasoline (b) middle oil (c) heavy
Oil.
The heavy oil is used again for making paste with fresh coal
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Producer gas
Coal at 1100C
The producer gas production reactions can be divided into four zone as follows
(a) Ash zone: It is lowest zone consisting mainly of ash. The ash protects the grate
from the intense heat of combustion. Moreover the temperature of supplied air
and steam is increased as they pass through this zone.
(b) Combustion zone: It is the zone next to the ash zone. It is also known as a
oxidation zone. Here carbon burn and forms CO and CO 2. the temperature of this
zone is about 1100C.
C + O2
C + 1/2 O2
CO2 + 97 Kcal
CO + 29.5 Kcal
(c) Reduction zone: In this zone, CO2 and steam combines with red-hot coke and
liberated free hydrogen and CO.
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-36 Kcal
CO2 + C
2CO
C + H2 O
CO + H2
C + 2 H2 O
CO2 + 2H2
-29 Kcal
-19 Kcal
(d) Distillation Zone: In this zone (400-800C), the down coming coal is heated by
the out going gases, since the gases give their sensible heat to the coal. The heat give
by the gases and heat radiated from reduction zone helps to distill the fuel.
Compositions:
CO = 22-30%
H2 = 8-12%
N2 = 52-55%
CO2 = 3%
Calorific values = 1300 Kcal/m3
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Coal at 1000C
Steam supply
Air supply
Reactions:
(1) Supplied steam reacts with red hot coal at 900-1000C to form carbon
monoxide and hydrogen. The reaction is endothermic , so the
temperature of bed falls.
C + H2O
CO + H2
-29 Kcal
(2) In order to rise the coal bed at about 1000C, the steam supply is
temporarily blown in, when the following exothermic reaction occurs.
C + O2
2 C + O2
CO2
+ 97 Kcal
2 CO + 59 Kcal
The temperature again rise bed to about 1000C. the cycles of steam run
and air blow are thus repeated alternatively to maintain proper temperatur
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Natural gas
Natural gas is obtained from wells dug in the oil bearing regions. When
natural gas occurs along with petroleum in oil wells is called wet gas.
The wet gas is treated to remove propane, propene, butane and butene,
which are used as LPG. When the gas is associated with the crude oil,
It is called dry gas.
The approximate composition of natural gas
CH4= 70-90%
C2H6= 5-10%
H2= 3%
CO+CO2= rest
Calorific value= 12000 to 14000 kcal/m3
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Coal gas
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Oil Gas
98
99
100
O2(g)
32
O2(g)
32
2H2O (g)
2X18=36
SO2 (g)
64
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