Solid Fuels

Solid Fuels which occur naturally are primary fuels. For example: wood and different types
of coal constitute the important primary solid fuels.

The fuels which are derived from the natural varieties are secondary fuels. For example
charcoal and coke.

Wood: it has been used as a fuel from ancient times. However, due to deforestation, wood
is no longer used except in forest areas where wood is available at a very low cost. The
calorific value of air-dried wood is about 3,500 to 4,500 kcal/kg. It burns with a long and non
smoky flame, leaving a small amount of ash. Although ash content is low, the oxygen content
is very high. This makes, even dry wood a fuel of low calorific value. Wood is largely used as
a domestic fuel.

Coal: it is regarded as a fossil fuel produced from the vegetable debris under conditions of
high temperature and pressure over a million of years.

• The transformation of the vegetable debris to coal takes place in two stages:
1. Biochemical or Peat Stage: In this step, the plant materials come under the presence
of microorganisms. The end product of this stage is peat.
2. Chemical Stage or Metamorphism: In this stage, the peat deposit loses moisture and
volatile Components. The peat deposit buried under sedimentary deposits loses
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.

Coal can be analysed in two ways:

1. Proximate analysis
2. Ultimate analysis
 1. Proximate Analysis: It is an important analysis. The data varies with the procedure
adopted hence it is called proximate analysis. In this analysis we determine moisture,
ash, volatile matter and fixed carbon.

i. Moisture: The original coal is always associated with moisture. When a wet coal is
exposed to the atmosphere, the external moisture evaporates but the apparently dry
coal still contains some moisture. This moisture is referred to as air dried moisture.
Air dried moisture is determined by heating a known amount of coal to 105 to 110oC.
In an electric oven for about an hour. After one hour, it is taken out from the oven
and cooled in the desiccator and Weighed.

Loss in weight of coal is reported as moisture content on percentage basis.

% Moisture = Loss in weight/weight of coal taken x100

Significance
• Excess of moisture is undesirable in coal.
• Moisture lowers the heating value of coal and the heat is wasted in the form of latent
heat of vaporisation.
• Hence, lower the moisture content better is the quality of coal as a fuel.

ii. Volatile Matter: The volatile matter comprises of complex mixture of gaseous and
liquid products resulting from the thermal decomposition of the coal. It consists
mainly of combustible gases such as H2, CO, and CH4 and other hydrocarbons.

It is determined by heating a known weight of moisture free coal sample in a covered

platinum crucible at 950o C for 7 minutes. The crucible is cooled, first in air, then inside a
desiccator and weighed. Loss in weight is reported as volatile matter on percentage basis.

% Volatile Matter = (Loss of weight due to removal of volatile matter/

Weight of coal sample taken) x 100

Significance
 • A high percentage of volatile matter in fuel indicates that a large portion of the fuel
is burnt as gas or vapours or even may escape unburnt.
• The high volatile matter content gives long flames, high smoke.
• However, 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.( It is discussed later in carbonisation)

iii. 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
approximately 700oC for half an hour without covering. The cooled mass is weighed
.From the weight of the residue, the % of ash is calculated

% Ash = Weight of the residue left/Weight of the coal x 100

Significance
• The high percentage of ash is undesirable.
• Ash may restrict the passage of air and lower the rate of combustion.
• High ash leads to large heat losses and cause problems of clinkering (forming of ash
lumps).It has been estimated that one percent rise in coal ash is equivalent to 0.3 to
4% decrease in boiler efficiency.

iv. Fixed Carbon: Fixed carbon content increases from low ranking coals such as lignite
to high ranking coals such as 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:

% of fixed carbon= 100-[% of moisture + volatile matter + ash]

Significance: Higher the percentage of fixed carbon, greater is the calorific value.
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 .The carbon and hydrogen present in the fuel are converted
to CO2 and H2O respectively.
C + O2 → CO2
H2 + ½ O2 → H2O

The gaseous products of combustion are passed through two bulbs, one containing
weighed amount of anhydrous CaCl2 which absorbs water, and the other containing
weighed amount of KOH which absorbs carbon dioxide. The percentage of carbon and
hydrogen are calculated from the increase in weight of the respective absorption tubes.

2 KOH + CO2 → K2CO3 + H2O

CaCl2 + 7 H2O → CaCl2.7H2O

Let, weight of coal sample taken = x g

Increase in weight of CaCl2 tube = z g
Increase in weight of KOH tube= y g
44g of CO2 contain = 12g of carbon
Y g of CO2 contain = 12/44 X y g of carbon
% of carbon = (12/44 x y)/weight of coal taken x 100

18 g of water contain= 2 g of hydrogen

z g of water contain = 2/18 x z g of hydrogen
% Hydrogen = ((2/18 x z) / weight of coal taken) X 100
Significance : Higher the percentage of carbon and hydrogen in the fuel, higher is the
calorific value.

2. Nitrogen: Nitrogen present in the coal sample can be estimated by Kjeldahl’s method.
A known weight of the given coal sample along with K2SO4 + HgSO4 which acts as a catalyst
is heated with conc.H2SO4.Nitrogen present in coal gets converted to (NH4)2SO4. The
contents are then transferred to a round bottom flask and the solution is heated with
excess of NaOH. The NH3 gas thus liberated is absorbed in a known volume of a standard
solution of acid. 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.

Nitrogen + H2SO4 → (NH4)2SO4

(NH4)2SO4 + NaOH → Na2SO4 + 2NH3 + 2H2O
NH3 + H2SO4 → (NH4)2SO4

Let the weight of coal taken = W g

Volume of the acid used up = V1 mL
Normality of the acid = N1
V1 mL of N1 acid = V2 mL of N2 NH3
V2 mL of 1N NH3 = V1 X N1 mL of acid
But 1000ml of 1N NH3 solution = 17g of NH3 = 14g of Nitrogen
V2 mL of 1 N NH3 solution = [14/1000] X N1 X V1 g of Nitrogen (because V2 = N1V1ml)

Percentage nitrogen = [14/1000] x [N1 x V1X1000/W]

= 1.4 x N1x V1/ W

3. Sulphur: Sulphur present in the coal is oxidised by fuming nitric acid into sulphuric acid.
The sulphuric acid is precipitated as BaSO4 by the addition of BaCl2,quantitatively. The
precipitate of BaSO4 so obtained from the above method is filtered and heated to a
constant weight. From the weight of BaSO4 obtained, the sulphur present in the coal is
calculated.
Let the weight of coal sample= W g
The mass of the precipitate = W1 g
233 g of BaSO4 = 32 g of sulphur
W1 g of BaSO4 = 32/233 W1 g
% of sulphur = [32/233] X [W1/W] X 100

Significance: Sulphur is a undesirable constituent as it emits corrosive SO2, SO3 during

combustion and highly objectionable H2S during carbonization of coal. These gases cause
atmospheric pollution. Sulphur containing coal is not suitable for the preparation of
metallurgical coke as it adversely affects the properties of metal.

4.Ash: calculated same as in proximate analysis.

5. Oxygen: The oxygen is usually determined by the method of difference.

% of Oxygen = (% of carbon + hydrogen+ Nitrogen + sulphur)

Significance: Lesser the oxygen content better is the coal. This is because oxygen content
of coal is associated with moisture, low calorific value and low coking power (discussed
later).

Carbonization of Coal
The process of converting coal into coke is called carbonization. Heating the coal in absence
of air, to a sufficiently high temperature, so that coal undergoes decomposition to yield a
residue. The residue is richer in carbon content than the original fuel.

Process of Carbonization
• Moisture and occluded gases are driven off.
• ~2600-2700C, Carbon, water & H2S, some low molecular alkenes and alkanes are
evolved.
 • ~3500C decomposition of coal is accompanied by evolution of gases and elimination
of tarry vapors.
• Around 4000C, caking coals become soft & plastic.
• At about 7000C, hydrogen is evolved.
• At about 8000C, main gaseous products are evolved.
• Gases evolved form plastic mass, expand to give foam like appearance
• further high temperature, this foam like mass solidifies to form solid mass with
porous structure called coke.

Caking coals: the coals that have a tendency to soften and swell at higher temperature form
a solid coherent mass with porous structure. The residue thus formed is called coke.

Coking coals: If the coke is hard, porous and strong than the coal from which it is formed is
called coking coal. This property is found only in bituminous type of coal.

All Coking Coals Are Caking Coals But All Caking Coals Are Not Coking Coals.

Types of Carbonization

Depending upon the temperature upto which coal is heated in absence of air, the
carbonization is of two types:

1. Low temperature carbonization (LTC)

2. High temperature carbonization (HTC)

L.T.C. H.T.C.

Temp. range: 500-700oC Temp. range: 900-1200oC

Produce semi coke, called soft coke, not strong Pure, hard, strong ; mechanically strong

Yield is about 75-80 % 65-75%

5 to 15 % volatile matter 1-3 % volatile matter
 Used as domestic fuel Industrial + domestic fuel

Low rank coals, produce smoke Less smoke

Higher calorific value of gas about 6500-9500 Lower calorific value of gas about 5000-
kcal/m3 6000 kcal/m3

Higher % Hydrocarbons Lower % hydrocarbons

Lower % aromatics Higher % aromatics

Metallurgical Coke
The properties of coke depend on porosity, reactivity and the amount of volatile matter
retained by coke during carbonization. Coke is mainly used as a heat source and reducing
agent in metallurgy. A good coke in metallurgical process should possess the following
characteristics:

1. Purity: The metallurgical coke should contain lower percentage of moisture, ash,
sulphur and phosphorous.
2. Porosity: The coke should be porous so as to provide contact between carbon and
oxygen.
3. Strength: The coke used in metallurgical process should have high strength so as to
withstand the weight of the ore, flux etc. in the furnace.
4. Size: Metallurgical coke should be of medium size.
5. Combustibility: Coke should burn easily. The combustibility of coke depends on the
nature of the coal, carbonization temperature and reaction temperature.
6. Calorific value: It should be high.
7. Cost: Coke should be cheap and easily available near the site of the metallurgical
plant.
8. Reactivity: Reactivity of coke is its ability to react with CO2 , steam, air and oxygen.
The reactivity should not be too high. The reactivity toward CO2 represent the
reduction of CO2 according to equation
CO2 (g) +C (s) ⇔ 2CO (g)
Otto-Hoffmann’s Oven (Byproduct Oven)
1. The beehive ovens have been replaced by chamber ovens which work on Regenerative
Principle of Heat Economy.
2. All the valuable byproducts are recovered from the outgoing flue gases.

Construction: It consists of no. of narrow rectangular chambers made of silica bricks. The
usual dimensions are 12-14 m length, 4-5 m height and 0.5 m width. The chambers are
tightly closed so that no air can enter. At the top of each chamber there are three holes for
charging the coal. One single oven is capable of holding 16 to 24 tons of coal.

Working: Coal is charged into the chamber and the chambers are closed tightly at both the
ends. Ovens are heated 1200oC by burning gaseous fuels. Process of carbonization takes
place layer by layer in the coal charge starting from the two side walls of the oven. As the
coal adjacent to the oven walls gets heated, a plastic zone is formed which moves away from
the walls towards the central zone? As the coal is converted into coke, there is decrease in
volume because of removal of volatile matter in the form of tar and gas at about 500oC. At
further high temperature, the plastic mass solidifies into hard and porous mass called coke.
Carbonization of a charge of coal takes about 11-18 hours. After the process is complete,
red hot coke is pushed outside by means of a ram which is electrically driven. The coke falls
into a quenching car. The yield is 75 % of the coal. Regenerators work on the principle of
alternate heating and cooling cycles. This is achieved by periodically changing the direction
of flow of gases through the vertical flues every 30 min or so.

1. Dry quenching: the inert gases like nitrogen present in the atmosphere are able to
come in contact with the hot coke and cool it naturally over a period of time.
 2. Wet quenching: Water is sprayed over the red hot coke for cooling it down. As a
result of this, some gases escape from the hot surface of the coke in form of steam
and cause pollution.
• Dry quenching is preferred over wet quenching;

Recovery of Byproducts: The gases evolved on carbonization in coke ovens are not allowed
to mix with the combustion and are collected separately. The coke oven gas is treated
separately for the recovery of the valuable byproducts

1. Recovery of Tar: The gas from the coke ovens is passed through a tower in which
liquor ammonia is sprayed. Tar and dust get collected in a tank. The tank is provided
with heating coils to recover back ammonia.
2. Recovery of ammonia: The gases are then passed through a tower where water is
sprayed to recover ammonia. The ammonia can also be recovered by dissolving it in
H2SO4 to form (NH4)2SO4, which is then used as a fertilizer.
3. Recovery of Naphthalene: The gases are passed through a cooling tower, where
water at a low temperature is sprayed. The gas is scrubbed with water until its temp.
Reduces.
4. Recovery of Benzole: The gases are then introduced into a light oil or benzol
scrubber, where benzene along with its homologue is removed and is collected at the
bottom.
5. Recovery of H2S and other S compounds: H2S and other S compounds are removed
from the coke oven gas after the light oil has been separated out.
Fe2O3 + 3H2S → Fe2S3 + 3H2O
2Fe2S3 + 4O2 → 2FeO +3SO2
4FeO + O2 → 2Fe2O3
• The SO2 obtained can be used for the manufacturing of sulphuric acid, which can be
used to absorb NH3 from the coal gas.