UNIT-IV – FUELS AND COMBUSTION

PART – B
1. Explain proximate analysis of coal.
In proximate analysis percentage of moisture content, volatile matter, ash content and fixed carbon
in coal is determined.
I) Moisture content
About 1 gm of powdered air-dried coal sample is taken in a silica crucible, and it is heated at 105-
110ºc in an electric hot-air oven for 1 hour and then cooled in a dessicator. The loss in weight of the
sample is found out and the % of moisture is calculated as
loss in weight of the coal
% of moisture in coal = �100
Weight of air-dried coal
II) Volatile matter
After the analysis of moisture content, the silica crucible with residual coal sample is covered
with a lid, and it is heated at 950 ± 20ºC for 7 minutes in an electric muffle furnace. The loss in weight
of the sample is found out and the % of volatile matter is calculated as
loss in weight of the coal
% of volatile matter in coal = �100
Weight of moisture free coal
III) Ash content
After the analysis of volatile matter the crucible, with residual coal sample is heated without lid at
700 ± 50 ºC for 30 minutes in an electric muffle furnace then the crucible is taken out cooled and
weighed. This process is repeated again and again till a constant weight of ash content is observed .From
this value the % of ash content is calculated as
Weight of ash formed
% of ash in coal = �100
Weight of dried coal
IV) Fixed carbon
The carbon content can be determined by subtracting the sum total of moisture, volatile and ash
contents from 100.
% of fixed carbon in coal = 100 - % of (Moisture content+ Volatile matter+ Ash content)
Significance (or) importance of proximate analysis
a) Moisture
 High percentage of moisture content is undesirable because it reduces the calorific value of
coal.
 Moisture in coal consumes more heat in the form of latent heat of evaporation and hence more
heat is to be supplied to the coal.
 It increases the transport cost.
b) Volatile matter
 Volatile matters also lower the calorific value of fuel since a large proportion of volatile matter on
heating escapes out unburnt.
  Coal with high percentage of volatile matter burns with a long flame with high smoke.
 The coal containing high percentage of volatile matter do not coke well.
c) Ash content
 Ash is a useless component present in the coal, which considerably reduces the calorific value.
 Ash causes hindrance to heat flow as well as produces clinkers, which blocks the air supply
through the fuel.
 It increases the transporting, handling and storage costs.
d) Fixed carbon
 Fixed carbon content is a great asset for the fuel.
 Greater the percentage of carbon content, the fuel burns efficient with oxygen of air and greater
will be calorific value.
 The percentage of fixed carbon helps in designing the furnace and the shape of the fire-box.
2. How is ultimate analysis of coal carried out?
In ultimate analysis the percentage of carbon, hydrogen, nitrogen, sulphur and oxygen in coal is
determined.
I) Carbon and hydrogen contents:
A small amount of well powdered coal sample is placed in a crucible and weighed accurately. The
crucible is introduced inside a combustion tube of the apparatus and the coal is burnt thoroughly through
the supply of a current of O2. The carbon and hydrogen present in the coal sample are converted into CO 2
and H2O respectively according to the following equations.
C + O2 C O2
H2 + ½ O2 H2O
The liberated CO 2 and H2O vapours are absorbed respectively in KOH and anhydrous CaCl 2
tubes of known weights. Increase in weight of KOH tube is due to the formation of CO 2 while increase in
the weight of CaCl2 is due to the formation of H2O . From the weights of CO2 and H2O formed, the % of
carbon and hydrogen present in the coal can be calculated as follows
Calculations
2KOH + CO2 K2CO3 + H2O
CaCl2 + 7 H2O CaCl2. 7 H2O
Let
m=Weight of the coal sample taken.
x =increase in weight of KOH tube
y = increase in weight of CaCl2 tube
i) % of carbon
C + O2 CO2
12 16 44 (by molecular weight)
44 gms of CO2 contains 12 gms of carbon
 Increase in weight of KOH tube 12
% of carbon taken= × ×100
Weight of coal sample taken 44
ii) % of hydrogen
H2 + ½ O2 H2O
2 16 18 (by molecular weight)
18 gms of water contains 2 gms of hydrogen.
Increase in weight of CaCl 2 tube 2
% of hydrogen = × ×100
Weight of coal sample taken 18
(II) Nitrogen content:
The determination of nitrogen content is carried out by kjeldahl’s method. A small amount of
powdered coal sample is placed in a crucible and weighed accurately. Weighed sample is heated with
excess con.H2SO4 in presence of K2SO4 (catalyst) in a
long necked flask known as kjeldahl’s flask. After heating nitrogen present in the coal is converted into
ammonium sulphate and a clear solution is obtained.
2N + 3H2 + H2SO4 (NH4) 2SO4
The clear solution is then treated with excess of NaOH and the liberated ammonia is distilled over and it
is absorbed in a known volume of standard N/10 HCl.
(NH4) 2SO4 + 2NaOH 2 NH3 + Na2SO4 + 2 H2O
NH3 + HCl NH4Cl
The volume of unused N/10 HCl is then determined by titrating it against standard N/10 NaOH.
Thus the amount of acid neutralized by liberated ammonia from coal is determined. From this, the
percentage of nitrogen is calculated as follows.
Calculation
[ HCl+ NH 3 NH4Cl ]
1 mole 1 mole
14× (V1 -V2 ) ×N/10
% of N 2in coal = �100 (or)
1000×weight of coal sample
1.4×Volume of acid consumed×Normality
% of N 2in coal =
weight of coal sample
III) Sulphur content:
A known amount of coal sample is burnt completely in a bomb calorimeter. During this
process sulphur is converted into sulphate, which is extracted with water. The extract is then treated
with BaCl2 solution so that sulphates are precipitated as BaSO 4 .The precipitate is filtered, dried and
weighed. From the weight of BaSO4 obtained, the sulphur present in the coal is calculated as follows.
Let, the weight of coal sample = m gms
Weight of BaSO4 obtained = x gms
S + 2O2 SO42- + BaCl2 BaSO4
32 16 233 (by molecular weight)
 233 gms of BaSO4 contains 32 gms of sulphur

32 ×Weight of BaSO 4 obtained

% of sulphur in coal = �100
233 �Weight of coal sample
IV) Ash:
Determination of ash content is carried out as in proximate analysis
V) Oxygen:
The percentage of oxygen is calculated as follows
% of oxygen in coal = 100 -% of (C+ H+ N+ S+ ash)
Significance (or) importance of ultimate analysis
I) Carbon and Hydrogen
 Higher the % of C and H, higher is its calorific value and the quality of coal is better.
 % of carbon is helpful in classification of coal.
II) Nitrogen
 Nitrogen does not have any calorific value, and its presence in coal is undesirable.
 Good quality coal should have very little nitrogen content.
III) Sulphur
 Sulphur increases the calorific value, but its presence in coal is undesirable because the
combustion products of sulphur, i.e., SO2 and SO3 are harmful and have corrosion effects on
equipments.
 The coal containing sulphur is not suitable for the preparation of metallurgical coke as it affects
the properties of the metal.
IV) Oxygen
 Lower the % of oxygen higher is its calorific value.
 As the oxygen content increases, its moisture holding capacity increases, and the calorific value
of the fuel is reduced.
3. Describe the Otto-Hoffman method of coke manufacture and the recovery of various by product.
The oven consists of a number of silica chambers. Each chamber is provided with a charging hole
at the top.
Coal is introduced into the silica chamber and the chambers are closed. The chambers are heated
to 1200°C by burning the preheated air and the producer gas mixture in the interspaces between the
chambers.
 The air and gas are preheated by sending them through 2 nd and 3rd hot regenerators. Hot flue gases
produced during combustion are allowed to pass through 1 st and 4th regenerators until the temperature has
been raised to 1000°C. While 1st and 4th regenerators are heated by hot flue gases, the 2 nd and 3rd
regenerators are heated by incoming air and gas mixture.
For economical heating, the direction of inlet gases and flue gases are changed frequently. The
above system of recycling the flue gases to produce heat energy is known as “the regenerative system of
heat economy”. When the process is complete, the coke is removed and quenched with water.
Time taken for complete carbonization is about 12-20 hours. The yield of coke is about 70%.
The valuable by products like coal gas, tar, ammonia, H 2S and benzol, etc., can be recovered from
flue gas.
Recovery of by-products
1. Tar
The coal gases are first passed through a tower, in which liquor ammonia is sprayed. Tar and dust
get dissolved and collected in a tank below.
2. Ammonia
The gases are passed through another tower, in which water is sprayed. Here ammonia gets
converted to NH4OH.
3. Naphthalene
The gases are passed through another tower, in which cooled water is sprayed. Here naphthalene
gets condensed.
4. Benzene
The gases are passed through another tower, in which petroleum is sprayed. Here benzene gets
condensed.
5. Hydrogen sulphide
The remaining gases are then passed through another tower, in which Fe 2O3 is sprayed. Here H2S
is retained.
The final gas left out is called pure coal gas which is used as a gaseous fuel.
4. What is synthetic petrol? How is it manufactured by Bergius process?
 The conversion of solid coal into liquid fuel by heating it with hydrogen to high temperature
under high pressure is called synthetic petrol.
Bergius process
Finely powdered coal + heavy oil+ catalyst powder (tin or nickel oleate)

Paste

Pumped into the converter

Heated 400-450ċ
200-250atm

Saturated higher hydrocarbons formed

Decomposition

Mixture of lower hydrocarbons

Condenser

Crude oil is obtained

Fractionated

(i) Gasoline (ii) Middle oil (iii) Heavy oil

H2 Hydrogenated Fresh coal dust

Gasoline
Recycled for making paste
 The middle oil is further hydrogenated in vapour phase to yield more gasoline. The heavy oil is
recycled for making paste with fresh coal sample. The yield of gasoline is about 60% of the coal used.
5. Explain the refining of petroleum or crude oil in detail. What are the properties and applications
of its various fractions?
The crude oil obtained from the earth is a mixture of oil, water and unwanted impurities.
The process of removing impurities and separating the crude oil into various fractions
having different boiling points is called refining of petroleum or crude oil.
STEP-I Separation of Water (Cottrell’s process)
The crude oil is always mixing with brine solution forming stable emulsions. The emulsion is
allowed to flow between highly charged electrodes, where colloidal water droplets combine to form large
drops, which can be removed out from the oil.
STEP-II Removal of Harmful Sulphur Compounds
After removal of water, the crude oil is treated with copper oxide to remove sulphur. The copper
Sulphide formed is separated out by filtration.
STEP-III Fractional Distillation
The purified crude oil is then heated to bout 400C in an iron retort, where the volatile constituent
of oil gets vapourised except the residue.
The hot vapours are then passed into the bottom of the “fractionating column”. The fractionating
column is a tall cylindrical tower containing a number of horizontal stainless steel trays at short distance.
Each tray is provided with a small chimney covered with a loose cap.
When vapours of the oil go up in the fractionating column, they become gradually cooler and get
condensed at different trays. The fractions having higher boiling points condense at lower trays whereas
the fractions having lower boiling points condense at higher trays.
Various fractions, compositions and their uses:

S.No Name of the Fraction Boiling Range Composition Uses

As a fuel under the name of

1 Uncondensed gases Below 30C C1-C4
LPG

2 Petroleum ether 30-70C C5-C7 As a solvent

Fuel for internal combustion

3 Gasoline or Petrol 40-120 C C5-C9
of engines.

As a solvent in paints and in

4 Naphtha or solvent sprit 120-180 C C9-C10
dry cleaning

Fuel for stoves and jet

5 Kerosene oil 180-250 C C10-C16
engines.

6 Diesel oil or fuel oil 250-320 C C15-C18 Diesel engine fuel

Fuel for ship and production

7 Heavy oil 320-400 C C17-C30
of gasoline by cracking

Heavy Oil on fractionation gives:

S.No Name of the Fraction Uses

 1 Lubricating Oil As lubricants.

2 Petroleum jelly (or) Vaseline Used in medicines and cosmetics.

3 Greases Used as lubricants.

4 Paraffin Wax Used in candles, boot polishes etc.,

Used for making roads, water proof

5 Pitch at about 400 C
roofing etc.,

6. How is producer gas manufactured? State its composition and uses.

Producer gas
 It is a mixture of CO, N2 & H2 with small amount of CH4 & CO2.
 Its calorific value is about 1300 Kcal/m3.
Composition of producer gas

Constituents Percentage (%)

CO 30
N2 51-56
H2 10-15
CO2 + CH4 Rest

Manufacture
The reactor used for the manufacture of producer gas is known as gas producer. It consists of a
tall steel vessel inside of which is lined with refractory bricks. It is provided with cup and cone feeder at
the top and a side opening for producer gas exit. At the bottom, it is provided with a inlet pipe for passing
air and steam
When a mixture of air and steam is passed over a red hot coke maintained at about 1100°C in a
reactor, the following reaction take place at different zones.
 The reactions of producer gas production can be divided into four zones as follows.
i) Ash Zone
This is the bottom most part of the layer consists of mainly ash. The incoming air and steam
mixture is preheated in this zone. This Zone protects the heat supplied to the coke which is above it.
(ii)Combustion or Oxidation Zone
This is the zone next to ash zone. Here coke burns with air mixture (oxygen) the carbon is
oxidized to CO and CO2. Both the reactions are exothermic. Hence, the temperature of the bed reaches
around 1100°C.
C+1/2 O2 CO + 29.5 Kcal ; Exothermic
C+ O2 CO2 + 97 Kcal ; Exothermic
(iii)Reduction Zone
This is the middle zone. Here both CO2 and steam are reduced.
C + CO2 2CO - 36 Kcal ; Endothermic
C + H2O CO+H2 – 29 Kcal ; Endothermic
C + 2H2O CO+2H2 – 19 Kcal ; Endothermic
The above reactions are endothermic. Hence the temperature of the coke bed falls to 1000°C.
iv) Distillation or Drying Zone
This is the top most layer of the coke bed maintaining a temperature range of 400-1000°C by the
outgoing gases.
Uses:
 It is used as a reducing agent in metallurgical operations.
 It is also used for heating muffle furnaces. Open – hearth furnaces etc.
7. How the flue gas analysis is carried out by ORSAT METHOD? Explain with neat diagram.
Flue gas:
The mixture of gases (like CO2, O2, CO) coming out from the combustion chamber is called flue
gases. The analysis of a flue gas would give an idea about the complete or incomplete combustion
process.
Orsat's apparatus:
 It consists of a horizontal tube.
 At one end has U-tube containing fused CaCl2.
 In other end has graduated burette with water reservoir.
 Middle of the horizontal tube is connected with 3 bulbs (A, B and C) for absorbing flue gases.

BULB REAGENTS ABSORPTION OF GASES

A Potassium Hydroxide (KOH) CO2
B Alkaline Pyrogallol O2
C Ammonical Cuprous Chloride CO
Working of orsat apparatus:
 The three way (3 ways) stop cock is opened.
 Water and air is excluded from the burette.
 3 way stop cock is connected to flue gas supply.
 Flue gas is taken in the burette and volume of flue gas is adjusted by raising and lowering the
reservoir. 3 way stop cock is now closed.
Absorption of gases in bulbs:
i) Absorption of CO2
 Flue gas is enters into bulb ‘A’.
 CO2 present in flue gas is absorbed by KOH.
 The decrease in volume of flue gas in burette indicates the volume of CO 2 .Now the bulb ‘A' is
closed.

ii) Absorption of O2
 Flue gas is enters into bulb 'B'.
 O2 present in the flue gas is absorbed by alkaline pyrogallol.
 The decrease in volume of flue gas in burette indicates the volume of O 2.
 Now the stopper is closed.
iii) Absorption of CO
 Flue gas is enters into bulb 'C'.
 CO present in the flue gas is absorbed by ammoniacal cuprous chloride.
 The decrease in volume of flue gas in burette indicates the volume of CO.
 The remaining gas in the burette after the absorption of CO2, O2 and CO is taken as nitrogen.
Significance:
 It gives an idea about the complete or incomplete combustion process.
 Flue gas with more CO shows incomplete combustion and demand of oxygen.
 Flue gas with more O2 shows complete combustion and excess of oxygen.
Precautions:
 All the air from the reservoir bottle should be expelled.
 It is essential that CO2, O2 and CO is absorbed in that order only.