Sunteți pe pagina 1din 67

Module I

Classification and Properties of Fuels


Fuels – Types and characteristics of fuels – Determination of
properties of fuels -Fuel analysis - Proximate and ultimate
analysis - Calorific value (CV) – Gross and net calorific
values (GCV,NCV) – Bomb Calorimetry – empirical
equations for CV estimation.
Fuel is a combustible substance which produces
large amount of heat.
Heat may be produced by
Combustion (Fuel)
Nuclear fission and fusion (Nuclear Fuel)
Combustion is a chemical process in which a substance (fuel)
reacts rapidly with oxygen and gives off thermal energy - Heat
Classification of fuels
Fuels are classified mainly into four general classes
•Fossil fuels
Derived from fossil remains of plants and animal life, found
in the crust of earth.
Ex. Coal, petroleum, natural gas
•By product fuel
Co product of some regular manufacturing process
Ex. coke oven gas –process of coke
blast furnace gas – process of iron making
• Chemical Fuel
Exotic nature and normally not used in
conventional processes
Ex. Hydrazine, ammonium nitrate, fluorine

• Nuclear fuel
Ex. Uranium, plutonium (release heat by fission),
deuterium, tritium (release heat by fusion)
On the basis of physical state of occurrence, these
may be classified as:
 Solid Fuels
 Liquid Fuels
 Gaseous Fuels
Primary (or) Natural fuel
 Solid - wood, peat, lignite, coal
 Liquid - crude oil
 Gaseous - natural gas

Secondary (or) Derived fuel


 Solid - coke, charcoal
 Liquid - tar, kerosene, diesel, petrol, fuel oil, lube oil
 Gaseous - coal gas, water gas, oil gas, producer gas, bio
gas, coke oven gas
On the basis of occurrence they are of two types:
(i)Primary Fuels (or) Natural:
Fuels which occur in nature as such are called primary fuels.
 Solid - wood, peat, lignite, coal
 Liquid - crude oil
 Gaseous - natural gas
(ii)Secondary Fuels:

The fuels which are derived from the primary fuels by further
chemical processing are called secondary fuels.

 Solid - coke, charcoal, coke, coal


 Liquid - tar, kerosene, diesel, petrol, fuel oil, lube oil
 Gaseous - coal gas, water gas, oil gas, producer gas, bio
gas, coke oven gas
•Manufactured fuel – which are made for some specific
purpose/process
Ex: Coke (iron making)
Producer gas (industrial heating)
Gasoline (made for IC engine)

•By product fuel – which are co product/side product of regular


manufacturing process

•Ex: tar, refinery gas, bagasse


Characteristics of Good Fuel:
(i) Suitability: The fuel selected should be most suitable for the
process. E.g., coke made out of bituminous coal is most suitable
for blast furnace.
(ii) High Calorific value
(iii) Ignition Temperature: A good fuel should have moderate
ignition temperature.
(iv) Moisture content: Should be low
(v) Non combustible matter content
(vi) Velocity of combustion: It should be moderate
(vii) Nature of the products
(viii) Cost of fuel, (ix) Smoke, (x) Control of the process
Solid Fuels
Primary as well as secondary are widely used in domestic and
industrial purposes.
e.g., wood, coal, charcoal and coke.
Wood:
Wood has been used as a fuel from ancient times. Due to large
scale deforestation, wood is no longer used except in forest
areas where wood is available at a low cost.
 Wood when freshly cut contains 25-50% moisture.
 Normally it is used in air dried condition with 10-15 percent
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 carbon.
Coal:
coal is regarded as a fossil fuel produced from the vegetable
debris under conditions of high temperature and pressure over
million of years.
The transformation of the vegetable debris to coal takes place in
two stages:
(a) Biochemical or peat stage: During this stage, the plant materials
were attacked by various micro organisms.
(b) Chemical stage or metamorphism: In this stage, the peat deposit
buried under sedimentary deposits, lose moisture and volatile
components under the effect of high temperature and pressure.
The peat gets enriched in carbon whereas its oxygen content
decreases.
The spongy peat transforms into hard brittle coal gradually. The
time required for the formation of young brown coal is of the
order of 107 years.
Classification of Coal:
Coals are mainly classified on the basis of their degree of
coalification from the parent material, wood. When wood is
converted into coal, there is gradual increase in the
concentration of carbon and decrease in the percentage of
oxygen and nitrogen.
Coal is given a ranking depending upon the carbon content of
the coal from wood to anthracite.
Type of Percentage (dry, mineral matter free % calorifi
coal basis) moistur c value
e
C H O N VM

Wood 45-50 5-6 20-40 0-0.5 - 70-90 4000-


4500
Peat 45-60 3.5-6.5 20-45 0.75-3 45-75 70-90 4125-
5280
Brown Coal 60-75 4.5-5.5 17-35 0.75-2 45-60 30-50 6600-
7100
6600-
Bituminous 75-90 4.0-5.5 20-30 0.75-2 11-50 10-20 8800
coal

8470-
Anthracite 90-95 3-4 2-3 0.5-2 3.8-10 1.5-3.5 8800
Analysis of Coal
Coal is analyzed in two ways:
1. Proximate analysis
2. Ultimate analysis
The results of analysis are generally reported in the
following ways:
 As received basis
 Air dried basis
 Moisture free basis (oven dried)
 Moisture and ash free basis
Proximate Analysis
The data varies with the procedure adopted and hence it
is called proximate analysis.
It gives information about the practical utility of coal.
Proximate analysis of coal determines the moisture, ash,
volatile matter and fixed carbon of coal.
1. Moisture Content: Air dried moisture is determined by
heating a known amount of coal to 105-110 oC in an
electric hot air oven for about one hour. After one hour,
it is taken out from the oven and cooled in a desiccator
and weighed.
Percentage of moisture= Loss in weight X 100
Weight of coal taken
•Excess of moisture is undesirable in coal.
•Moisture lowers the heating value of coal and 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.
•Presence of excessive moisture quenches fire in the
furnace.
2. Volatile Matter: consists of a complex mixture of
gaseous and liquid products resulting from the thermal
decomposition of the coal.
It is determined by heating a known weight of moisture free
coal sample in a covered platinum crucible at 950  20oC
for 7 minutes.
Percentage of volatile matter =
Loss of weight due to volatile matter 100
Weight of coal sample 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.
High volatile matter content is desirable in coal gas
manufacture because volatile matter in a coal denotes the
proportion of the coal which will be converted into gas
and tar products by heat.
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 ½ an hour
without covering
Weight of the residue left
100
Percentage of ash =
Weight of the coal

Ash can be classified as intrinsic ash and extrinsic ash.


The mineral matter originally present in vegetable matter
from which the coal was formed is called intrinsic ash. It
consists of oxides of Na, K, Mg, Ca and Si.
The mineral matter like clay, gypsum, dirt which gets mixed
up during mining and handling of coal constitute the
extrinsic ash which remains as a residue after the
combustion. E.g., CaSO4, CaCO3, Fe2O3 etc.
The high percentage of ash is undesirable. It reduces the
calorific value of coal.
In furnace grate, the ash may restrict the passage of air
and lower the rate of combustion.
High ash leads to large heat losses and leads to formation
of ash lumps.
The composition of ash and fusion range also influences
the efficiency of coal.
When coal is used in boiler, the fusion temperature of ash
is very significant. Ash having fusion temperature below
1200oC is called fusible ash and above 1430oC is called
refractory ash.
Apart from loss of efficiency of coal, clinker formation also
leads to loss of fuel because some coal particles also get
embedded in the clinkers.
Fixed Carbon: Fixed carbon content increases from lignite
to anthracite. Higher the percentage of fixed carbon greater
is its calorific value and better is the quality of coal.
The percentage of fixed carbon is given by:
Percentage of fixed carbon=100-[% of moisture+volatile
matter+ash]
Significance: Higher the percentage of fixed carbon,
greater its calorific value
•The percentage of fixed carbon helps in designing the
furnace and shape of the fire-box because it is the fixed
carbon that burns in the solid state.
Ultimate analysis:
It is carried out to ascertain the composition of coal.
Ultimate analysis includes the estimation of carbon,
hydrogen, sulphur, nitrogen and oxygen.
1. Carbon and Hydrogen: A known amount of coal is
taken in a combustion tube and is burnt in excess of pure
oxygen.
C  O  CO
2 2
H  1O  H O
2 2 2 2
Estimation of carbon and hydrogen
2KOH  CO  K CO  H O
2 2 3 2
CaCl  7 H O  CaCl .7 H O
2 2 2 2
44 g of CO2 contain = 12 g of carbon
Y g of CO2 contain = 12  y
44
Percentage of carbon  12  y 100
44 weight of coal taken
18 g of water contain = 2 g of hydrogen
Z g of water contain  2  zg of hydrogen
18
Percentage of hydrogen  2  z100
18 weight of coal taken

Significance:
Calorific value of a fuel is directly related to its carbon
content.
A higher percentage of carbon reduces the size of the
combustion chamber
High percentage of hydrogen also increases the calorific
value of coal. The content of hydrogen in coals varies
between 4.5 to 6.5 percent from peat to bituminous stage.
2. Nitrogen: Nitrogen present in coal sample can be
estimated by Kjeldahl’s method.
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.
Fig 4. Estimation of nitrogen by Kjeldahl’s method

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.
   Na SO  2 NH  2H O
( NH ) SO 2NaOH
42 4 2 4 3 2

NH  H SO  ( NH ) SO
3 2 4 42 4

% of Nitrogen = (Volume of acid consumed x Normality x


1.4)/weight of coal sample
Determination of sulphur:
Bomb calorimeter is used to determine the sulphur. A known mass of
coal sample is taken in calorimeter. If sulphur is burnt with oxygen,
sulphur is converted to sulphate.

The washing are treated with barrrium chloride solution.

When barrium sulphate is precipitated the precipitate is filtered,


washed and heated to constant weight.

% sulphur = ( weight of BaSO4 obtained x 32 x 100)/(weight of


coal x233)
Determination of Oxygen:

Oxygen is determined by difference

% oxygen = 100 - % (C + H +S + N)
Problem1:
A sample of coal was analyzed as follows. Exactly 2.5 g was
weighed into a silica crucible. After heating for 1 hr at 110oC, the
residue weighed 2.415 g. the crucible next was covered with a
vented lid and strongly heated for exactly 9 min at 950±20oC. The
residue weighed 1.525 g. The crucible was then heated without the
cover, until a constant weight was obtained. The last residue was
found to weight 0.245 g. Calculate the % results of the above
analysis.

Ans:
% moisture = 3.40
% V.M = 35.48
% ash = 9.80
% F.C = 51.32
Problem 2:
A sample of finely ground coal of mass 0.9945 g was placed in a
crucible of 8.5506 g in an oven, maintained at 105oC for 1 hr. The
sample was then removed, cooled in a desiccator and reweighted, the
procedure being repeated until a constant total mass of 9.5340 g was
attained. A second sample of mass 1.0120 g in a crucible of mass
8.5685 g was heated with a lid in a furnace at 920oC for 420 sec on
cooling and reweighing, the total mass was 9.1921 g. This sample was
then heated without a lid in the same furnace maintained at 725oC
until a constant mass of 8.6255 g was attained. Calculate the
proximate analysis of the sample and express the results on “as
sampled” and “dry ash free” basis.
Ans:
Proximate analysis as ‘received basis’
Moisture= 1.11 %
Ash= 5.63%
FC = 55.99%
Proximate analysis on dry, ash free ‘basis’

Moisture + ash = 6.74%


F C = 60.04%
V M = 39.95%
Problem 3:
0.5 g of sample of coal used in a bomb calorimeter for the
determination of calorific value. The calorific value of the coal
was found to be 8600 cal/g. The ash formed in the bomb
calorimeter was extracted with acid and the acid extract was
heated with barium nitrate and a precipitate of barium sulphate
was obtained. The precipitate was filtered, dried and weighted.
The weight of precipitate was found to be 0.05 g. Calculate the
percentage of sulphur in the coal sample.

Ans:
Percentage of sulphur = 1.3734 %
Problem 4:
1 g of a sample of coal was used for nitrogen estimation by Kjeldahl’s
method. The evolved ammonia was collected in 25 ml 1/10N H2SO4.
To neutralize excess acid, 15 ml of 0.1 N NaOH was required.
Determine the percentage of nitrogen in the given sample of coal.

Ans:
Percentage of nitrogen = 1.4%
Calorific value:
It is defined as the total quantity of heat liberated when a unit mass
of a fuel is burnt completely.
Units of Calorific value:
System Solid/Liquid Gaseous Fuels
Fuels
CGS Calories/gm Calories/cm3
MKS k cal/kg k cal/m3
B.T.U BTU/lb BTU/ft3
The quantity of heat can be measured in the following units:
(i) Calorie: It is defined as the amount of heat required to raise the
temperature of 1gm of water by 1oC
1 calorie = 4.184 Joules
(ii) Kilo Calorie: 1 k cal = 1000 cal
(iii) British thermal unit: (B. T. U.) It is defined as the amount of
heat required to raise the temperature of 1 pound of water through
1oF.
1 B.T.U. = 252 Cal = 0.252 k cal
(IV) Centigrade heat unit (C.H.U): It is defined as the amount of
heat required to raise the temperature of 1 pound of water through
1oC.
1k cal = 3.968 B.T.U.
= 2.2 C.H.U.
Gross and Net calorific Value
Gross Calorific Value:
It is the total amount of heat generated when a unit quantity of fuel
is completely burnt in oxygen and the products of combustion are
cooled down to the room temperature.
As the products of combustion are cooled down to room
temperature, the steam gets condensed into water and latent heat is
evolved. Thus in the determination of gross calorific value, the
latent heat also gets included in the measured heat. Therefore, gross
calorific value is also called the higher calorific value.
The calorific value which is determined by Bomb calorimeter gives
the higher calorific value (HCV)
Net Calorific Value:
It is defined as the net heat produced when a unit quantity of fuel is
completely burnt and the products of combustion are allowed to
escape.
The water vapor do not condense and escape with hot combustion
gases. Hence, lesser amount than gross calorific value is available. It
is also known as lower calorific value (LCV).
LCV=HCV-Latent heat of water vapors formed
Since 1 part by weight of hydrogen gives nine parts by weight of
water i.e.

H  1O  H O
2 2 2 2
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
volatile liquid fuels: It is determined by bomb
calorimeter.
Principle: A known amount of the fuel is burnt in excess of
oxygen and heat liberated is transferred to a known
amount of water. The calorific value of the fuel is then
determined by applying the principle of calorimetery i.e.
Heat gained = Heat lost
Calculations
Let weight of the fuel sample taken = x kg
Weight of water in the calorimeter = y kg
Weight of apparatus (Calorimeter, stirrer, bomb,
thermometer )= z kg
Initial temperature of water = t1oC
Final temperature of water = t2oC
Higher or gross calorific value = C kcal/kg
Heat gained by water = y (t2-t1)
Heat gained by Calorimeter = z (t2-t1) kcal
Heat liberated by the fuel = x C kcal
Heat liberated by the fuel = Heat gained by water and
calorimeter
x C = (y+z) (t2-t1) kcal
C = (y+z)(t2-t1) kcal/kg
x
Net Calorific value:
Let percentage of hydrogen in the fuel = H
Weight of water produced from 1 gm of the fuel = 9H/100
gm
Heat liberated during condensation of steam
= 0.09H  587 cal
Net (Lower calorific value) = GCV-Latent heat of water
formed
= C-0.09H  587 cal/gm
Corrections: For accurate results the following corrections
are also incorporated:
(a) Fuse wire correction: As Mg wire is used for ignition,
the heat generated by burning of Mg wire is also
included in the gross calorific value. Hence this amount
of heat has to be subtracted from the total value.
(b)Acid Correction: During combustion, sulphur and
nitrogen present in the fuel are oxidized to their
corresponding acids under high pressure and
temperature.
S  O  SO
2 2
2SO  O  2H O  2H SO
2 2 2 2 4 DH = -144,000 Cal
2 N  5O  2H O  4HNO
2 2 2 3 DH = -57,160 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 0.01 HNO3 formed, 1.43 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.
Therefore, Gross calorific value
C=[(y+z)(t2-t1+Cooling correction)-(Acid+ fuse corrections)] /
Mass of the fuel.
Problem
A sample of coal contains C = 93%, H =6% and ash = 1%. The
following data were obtained when the above coal was tested in
Bomb calorimeter.
Weight of coal burnt = 0.92 g
Weight of water taken = 550 g
Water equivalent of Bomb calorimeter = 2200 g
Raise in temperature = 2.42oC
Calculate the GCV, NCV of coal.
Latent heat of steam as 580 kcal/kg.

Ans:
GCV = 7168.5 cal/g
NCV = 6855.3 cal/g
Problem:
Calculate the NCV at 298 K of a sample fuel oil having
C/H ratio 9.33 (by weight)and containing sulphur to the
extent of 1.3 % by weight.
Data:
GCV of the fuel oil at 298 K and 25oC = 41785 kJ/kg
Latent heat of water vapour at 298 K = 2442.5 kJ/kg

Ans:
NCV = 39635.2 kJ/kg fuel oil
Problem:
Crude oil found to contain 87 % carbon, 12.5 %
hydrogen and 0.5 % sulphur. Calculate the NCV of
crude oil at 298 K.

Data:
GCV of crude oil at 298 K = 45071 kJ/kg oil
Latent heat of water vapor at 298 K = 2442.5 kJ/kg

Ans:
NCV = 42323.2 kJ/kg oil
Problem:
On burning 0.83 g of solid fuel in a Bomb calorimeter,
temperature of 3500 g of water increased from 26.5oC to
29.2oC. Water equivalent of calorimeter and latent heat of
steam are 385 g and 587 cal/g respectively. If the fuel
contains 0.7 % hydrogen, calculate it GCV and NCV.

Ans:
GCV = 12638 cal/g
NCV = 12601 cal/g
Problem:
Theoretical calculation of Calorific value of a Fuel: The
calorific value of a fuel can be calculated if the percentages
of the constituent elements are known.

Substrate Calorific value

Carbon 8080

Hydrogen 34500

Sulphur 2240
If oxygen is also present, it combines with hydrogen to
form H2O. Thus the hydrogen in the combined form is not
available for combustion and is called fixed hydrogen.
Amount of hydrogen available for combustion = Total mass
of hydrogen-hydrogen combined with oxygen.
1
H 2  O2  H 2O
2
1g 8g 9g
Fixed Hydrogen = Mass of oxygen in the fuel
Therefore, mass of hydrogen available for combustion =
Total mass of hydrogen-1/8 mass of oxygen in fuel
=H-O/8
Dulong’s formula for calculating the calorific value is
given as:
Gross calorific Value (HCV)
1 O
 [8080C  34,500( H  )  2,240S ]kcal / kg
100 8

Net Calorific value (LCV)


9H
 [ HCV   587]kcal / kg
100
 [ HCV  0.09 H  587]kcal / kg
Assumptions in Dulong formula:

• GCV od C, H and S are 8080, 34500 and 2220


kcal/kg
• O2 is combined with H2 so that surplus H2 available
for combustion(H-O/8)
• N2 in the coal has been neglected. If accounted, then
replace (H-O/8) by (O+N-1)/8
• C.V of fuel is sum of C.V of its constituent
elements.
Coutal formula:
GCV = 82 F + a. V
Where F is fixed carbon %, V is volatile matter %

Central Fuel Research Institute (CFRI)


For low moisture coals ( M< 2%)
GCV = 91.7 F + 75.6 (V-0.1A) – 60 M

For high moisture coals ( M> 2%)


GCV = 85.6 [100-(1.1 A + M)] – 60 M

Where
M = Moisture %, V = Volatile matter %
A = Ash %, F = Fixed carbon %
Problem
Calculate the GCV and NCV of coal having the
following composition. Carbon 85%, hydrogen 8%,
sulphur 1%, nitrogen 2%, ash 4%. Latent heat of steam
587 kcal/kg.

Ans:
GCV = 9650.4 kcal/kg
NCV = 9227.8 kcal/kg
Problem:
Coal has the following composition by weight C = 90
%, O = 0.3 %, S = 0.5 %, N = 0.5 % , ash = 2%. NCV
of a coal was found to be 8490.5 kcal/kg. calculate the
% of hydrogen and GCV of coal.

Ans:
H = 4.576%
GCV = 8731.8 kcal/kg
Problem:
The composition of a refinery gas by volume H2=74%, CH4 =
13.5%, C2H6 = 7.4%, C3H8 = 3.6%, nC4H10 = 1.2% and nC5H12 =
0.3%
Data:
Component GCV, kJ/mol NCV, kJ/mol
CH4 890.65 802.62
C2H6 1560.17 1428.64
C3H8 2219.17 2043.11
nC4H10 2877.40 2657.32
nC5H12 3535.77 3271.67

ΔHf of H2O (g) = -241.82 kJ/mole at 298 K


ΔHf of H2O (l) = -285.83 kJ/mole at 298 K
Specific volume at 298 K at 101.3 kpa = 24.465 m3/kmol
Calculate GCV and NCV in kJ/mol, kJ/kg and kJ/m3
Ans:
GCV = 572.27 kJ/mol
NCV = 508.275 kJ/mol

GCV = 68486.12 kJ/kg


NCV = 60827.55 kJ/kg

GCV = 23391.4 kJ/m3


NCV = 20775.6 kJ/m3
Boy’s gas calorimeter
Junker’s gas Calorimeter
Calculation of GCV

Volume of gas burnt in time T =V


Weight of water passed through coil in time T =W
Temperature of incoming water = t1
Temperature of outgoing water = t2
Weight of condensed water (steam) = W’
Higher (gross) calorific value =C
Heat absorbed by circulating water = W(t2-t1)
Heat produced by the combustion of fuel =VxC
Heat produced = Heat absorbed
VxC = W(t2-t1)
C = W(t2-t1)/V
Calculation of NCV
Weight of water condensed from 1 m3 of gas = W’/V
Latent heat of steam/m3 of gas = (W’x 587)/V
Lower calorific value = C- [(W’x 587)/V]
Problem:
The following data were obtained in a Boy’s calorimeter
experiment.
Volume of gas used = 0.1 m3
Weight of water heated = 25 kg
Temperature of outlet water = 33oC
Temperature of inlet water = 20oC
Weight of steam condensed = 0.025 kg
Calculate HCV, LCV per m3 assuming that the heat liberated in
condensing water vapour and cooling the condensate is 580
kcal/kg.

Ans:
HCV = 3250 kcal/m3
LCV = 3105 kcal/m3
Orsat Flue gas analysis Apparatus