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MEE374 PROCESS PLANT UTILITIES

Dr. S. K. Behera
School of Chemical Engineering
VIT, Vellore, TN, India – 632 014.
Module 7

Solid Fuels – Coal & Coke


Classification of coal:
• Coal is classified on the basis of following characteristics :
– Less hydrogen, nitrogen, oxygen, sulphur contents and more
carbon content

– Less moisture content

– High calorific value

– Moderately hard

– Less volatile matter

The successive stages of transformation of vegetable matter into coal


are wood, peat, lignite, bituminous and anthracite.
Classification of coal:
Peat
• It is found as brown fibrous jelly like material. It is considered that it is
the first stage of wood coalification.

• It is not an economical fuel. Peat variety contains 80-90% water


(moisture).

• The average composition of air dried peat coal is as follows : C = 57%,


H = 6%, O = 35% and ash content 2 to 6%.

• The calorific value of this coal is about 5500 kcal/kg (on air dry basis).
In India, it is found in Nilgiri Hills (South India).
Classification of coal:
Lignite:
• It is considered as the second stage of coalification of wood. It
contains less moisture than peat coal.

• It is soft and brown coloured variety of coal. It is in compact texture


and gets broken down in small pieces easily.

• In India, it is found in Kashmir, Rajasthan, Assam and in Tamil Nadu


(at Neyveli).

• The average composition of lignite (on air dry basis) is as C = 60 to


70%, O = 20%, H = 5% and ash = 2%.

• Lignite coal is a very good domestic fuel. It is mainly used in the


manufacture of producer gas and in steam generation as boiler fuel.
On air dry basis, its calorific value ranges between 6400-7150
kcal/kg.
Classification of coal:
Bituminous Coal:
• These coals are available in pitch black to dark grey colors. These
are good quality coals.

• The average composition of bituminous coals (on air dry basis) is as


follows : C = 88%, H = 4.5 and O (N, S) 13.5%.

• Their calorific value is higher than peat and lignite coals. This value
varies from 7000 to 8500 kcal/kg.

• The bituminous coal deposits are found in Madhya Pradesh, Orissa,


Bihar and West Bengal.

• These coals are very much used in industries, household needs and
in the manufacturing of metallurgical coke and coal gas.
Classification of coal:
Anthracite:
• Anthracite is the coal of the highest rank. It is considered as the
purest form of the coal.

• It contains (on air dry basis) 92-96% carbon and has the lowest
amount of volatile matter.

• It is the hardest form of coal and has good lustrous appearance. It


gives intense local heating.

• It gives no smoke during burning. It provides high calorific value of


8700 kcal/kg.

• In India, its deposits are found in Kashmir and in eastern Himalayan


region .
Selection of coal:
The selection of coal is carried out on the basis of following seven points:
• Calorific Value:
The coal should have high calorific value so that its small quantity may
provide a large amount of heat. High calorific value coal reduces the
cost of its transportation and storage.

• Coking Quality
Coke is obtained by high carbonization process of coal which is heated
in large size ovens in the absence of air (pyrolysis). Then coal is
converted into soft, plastic and tube of large coherent masses which
are known as coking coals.

• Moisture Content
A good quality coal should have low percent of moisture to prevent the
heat loss.
Selection of coal:
• Ash Content
The ash content of coal should be low so that cost of coal
transportation and disposal of ash is less. Low ash content coal gives
more heating value.

• Size of Coal
To give maximum heat, the size of the coal should be uniform.

• Sulphur and Undesirable Contents


The sulphur and undesirable contents in the coal should be low.
During the combustion of coal, these substances produce unpleasant
odor as well as pollute the environment.
Selection of coal:
• Calorific intensity

The calorific intensity may be defined as the maximum temperature


obtainable on the complete combustion of a fuel in the presence of
excess air.

If any fuel burns without flame then it is of high calorific intensity. On


the other hand, if it burns with a flame then total heat is distributed to
a large area which decreases the calorific intensity.
Analysis of coal:
• There are two methods of analysis of coal: (i) ultimate analysis and
(ii) proximate analysis.

Proximate analysis of coal


 Determines only fixed carbon, volatile matter, moisture and ash
 Useful to find out heating value (GCV)

Ultimate analysis of coal


 Determines all coal component elements: carbon, hydrogen, oxygen,
nitrogen and sulphur
 Useful for furnace design (e.g. flame temperature, flue duct design)
Analysis of coal:
Proximate analysis:
• Proximate analysis of coal gives good indication about heating and burning
properties of coal. The test gives the composition of coal with respect to
fixed carbon, moisture, volatile matter, ash percentages.

• Moisture content:
About 1g of finely powdered air dried coal sample is weighed in a crucible
and is placed inside an electric hot air oven for an hour maintained at 105-
1100C. It is cooled in a desiccator and weighed. The loss in weight is the
moisture content on percentage basis.

• Volatile matter:
Fresh sample of crushed coal is weighed, placed in a covered crucible, and
heated in a furnace at 950±15 0C for 7 min. The sample is cooled and
weighed. Loss of weight represents both moisture and volatile matter.
Deducting the moisture content (as found from moisture test) would give
the amount of volatile matter in the coal.
Analysis of coal:
Proximate analysis:
• Ash content:
It is the weight of residue obtained after burning a weighed amount of dry
coal in an open crucible at 700-750 0C for 30 min in a muffle furnace. The
weight of residue remaining in the crucible is reported as ash content on
percentage basis.

• Fixed carbon:
It is the quantity of carbon in coal that can be burnt by a primary current of
air drawn through the hot bed of fuel. The percentage of fixed carbon is
determined by subtracting the value of moisture, volatile matter and ash
from 100.

FC = 100 – (% of moisture + % of volatile matter + % of ash content)


Analysis of coal:
Significance of Proximate analysis:
• Moisture content - Moisture lowers the effective calorific value because
considerable amount of heat is wasted in evaporating the moisture during
combustion. Hence lesser the moisture content, better the quality of coal
as a fuel.
• Volatile matter - It may be combustible gases (CO, CH4 etc.) or non-
combustible gases (CO2, N2). The presence of non-combustible gases is
undesirable since they do not add to the heat value.
 The volatile matter content of coal influences the furnace design. Lower
the content, smaller is the combustion space required.
 Low volatile matter and high fixed carbon is preferred for manufacture
of metallurgical coke.
• Ash - It is the non-combustible, useless matter that is left behind when all
the combustible matters burnt off from coal. Hence, lesser the ash
content better is the quality of coal.

• Fixed carbon - Fixed carbon gives a rough estimate of heating value of


coal. Higher the percentage of fixed carbon, greater is its calorific value
and better the quality of coal.
Analysis of coal:
Ultimate analysis:

• This analysis of coal precisely finds the chemical composition of


coal with respect to the elements like carbon, hydrogen,
oxygen, nitrogen, sulphur (CHONS).

• The chemical composition is very useful in combustion


calculations and in finding the composition of flue gases. This
information is required for the calculation of flame
temperature and the flue duct design.

• For most purposes the proximate analysis of coal is quite


sufficient.
Analysis of coal:
Ultimate analysis:
• Carbon and Hydrogen:
About 1-2 g of accurately weighed coal sample is burnt in a current of
oxygen in a combustion apparatus. The carbon and hydrogen of the sample
are converted into CO2 and H2O. This is absorbed by KOH and CaCl2 tubes of
known weights. The weights of CaCl2 and KOH in the bulbs are determined.
• The increase in weight of CaCl2 gives the weight of H2O formed and increase
in weight of KOH gives the weight of CO2 formed.
Increase in weight of KOH 12
% carbon  100
Weight of coal sample taken  44

Increase in weight of CaCl2  2


% hydrogen  100
Weight of coal sample taken 18
Analysis of coal:
Ultimate analysis:
• Nitrogen:
A known quantity of coal is treated with concentrated H2SO4 in
presence of K2SO4 and CuSO4.

The contents of the flask are heated in a long necked flask called
Kjeldahl’s flask till the solution becomes clear.

The nitrogen present in the coal is converted to (NH4)2SO4. This is


then boiled with sodium hydroxide solution to give ammonia.

The ammonia is absorbed in known quantity of H2SO4 solution.

The excess H2SO4 left unreacted is found by titration against NaOH


solution of known strength. This enables to find the quantity of
ammonia produced.
Analysis of coal:
Ultimate analysis:
• Nitrogen:
Knowing the weight of ammonia, the quantity of nitrogen in the coal
can be calculated.

(NH4)2SO4 + NaOH → Na2SO4 + NH4OH

Volume of acid used x Normality x 14


% nitrogen = -----------------------------------------------------X100
Weight of coal x 1000

As nitrogen has no calorific value, its presence in coal decreases the


calorific value of coal.
Analysis of coal:
Ultimate analysis:
• Sulphur:
A known quantity of coal is heated with fuming nitric acid. The sulphur
present in coal is converted to sulphuric acid. The solution is then
treated with BaCl2 powder when BaSO4 is formed. The BaSO4 is
filtered, washed, dried and weighed. From weight of BaSO4, amount
of sulphur in coal can be calculated.

If weight of coal = ‘m’ gm


weight of BaSO4 = ‘N’ gm
32
Sulphur in BaSO4 = -------- x N
233
32 x N
% Sulphur in coal = -------------x 100
233 x m
Analysis of coal:
Ultimate analysis:
• Oxygen:
Percentage of oxygen in the coal is calculated by subtracting the
percentage of carbon, hydrogen, nitrogen and sulphur in coal from 100.

Percentage of oxygen = 100 – (% of C + % of H + % of N + % of S)

• The broad range in which the constituents of coal vary by weight as


determined by ultimate analysis are given below:
Significance of Ultimate analysis:
(i) Carbon & hydrogen: Greater the percentage of carbon, better is the coal
in quality and calorific value.
The hydrogen is combustible and present in combination with oxygen in
water. On heating, it changes into steam. The calorific value of any fuel
containing hydrogen is only due to hydrogen present in Free State and not in
combined form as water. So, lesser the percentage of hydrogen better is the
quality of coal.
(ii) Nitrogen: It has no calorific value and hence its presence is not desirable.
(iii) Sulphur: Sulphur adds to the calorific value of coal since the oxidation of
sulphur is an exothermic process.
But SO2 is harmful. Because it gets oxidized to SO3, which forms H2SO4 leading
to corrosion.
(iv) Oxygen: The oxygen content in coal decreases the calorific value. Hence a
good quality coal should have low percentage of oxygen.
Analysis of coal:
Proximate analysis:

Ultimate analysis:
Analysis of coal:
Relationship between Proximate analysis & Ultimate analysis:
Heating value -- CFRI Formulae --
Low Moisture Coal (M < 2% ) -- CV (Kcal/kg) = 71.7 FC + 75.6 (VM-
0.1 A) - 60 M
High Moisture Coal (M > 2%) – CV (kcal.kg) = 85.6 {100 -
(1.1A+M)} - 60 M

Where, M, A, FC and VM denote moister, ash , fixed carbon and


Volatile mater (%), respectively.
Dulong’s formula

GCV = 81 %C + 341 (%H − %O/8) + 22 %S, kcal/kg (1)


GCV = 339 %C + 1427 (%H − %O/8) + 92 %S, kJ/kg (2)

NCV = GCV – Heat of vaporization of water


• NCV = GCV – 5.84 (9 %H + %M), kcal/kg (3)
• NCV = GCV – 24.44 (9 %H + %M), kJ/kg (4)

Heat of vaporization of water at 1000C = 542 kcal/kg; whereas at 250C it


is 584 kcal/kg.
Problem 1:
A sample of coal contains C =60%, O = 33%, H = 6%, S = 0.5%, N
= 0.3%, ash = 0.2%. Calculate the higher and lower calorific
values of coal.
Ans: GCV = 5505 Kcal/kg, LCV = 5186 Kcal/kg
Problem 2:
A coal containing C – 67.9%, H – 4.4%, S – 0.8%, N – 11.6%, O -
7.9%, ash – 4.5 % and moisture – 2.9% is burnt in a furnace. The
dry product of combustion analyses CO2 – 14.5%, O2 - 4.7% and
N2 – 80.8% (v/v). Calculate (a) the theoretical volume of air used
for the complete combustion of 100 kg of coal, (b) the % excess
air used.
Coke:
• It is obtained as residue in the retorts during the dry distillation of coal.

• The good coke should have the following characteristics


i. It should possess low ash content & low moisture content.
ii. It should have high calorific value.
iii. It should be moderate in size.
iv. It should have no or low undesirable contents like S, P, N etc.
v. It should have good combustibility so that it can be easily burnt.
vi. It should have good porosity so that oxygen can pass through for
complete combustion.

• Coke is one of the prime materials to manufacture coal gas. It is also


used as a reducing agent in the manufacturing of metallurgical coke.
Metallurgical Coke:
• The metallurgical coke is manufactured in two ways:
(i) Beehive oven process, and
(ii) Otto Hoffmann’s Byproduct oven process.

Beehive Oven Process


Coal
Metallurgical Coke:
Beehive Oven Process
• The oven employed in this process is a dome shaped structure made
of bricks. It is about 4 m wide and 2.5 m high with two openings – one
at the top to feed the coal charge and other on the side to let in air as
well as for coke discharge.

• In this process, the coal is fed through the opening at the top and the
charge is leveled to provide about 0.6 m deep layer.

• The air is sent through the side opening and the coal is ignited. The
volatile matter is allowed to escape through the partly closed opening
on the side.

• Combustion is allowed to proceed in gradually low supply of air to get


slow carbonization from the top layer to bottom layer.
Metallurgical Coke:
Beehive Oven Process
• The process may last for nearly 4-5 days when the carbonization is
complete.

• The hot coke is raked out through the side and quenched with water.
The yield is about 80%.

• To prevent the wastage of heat, several ovens may be arranged in


series .
Metallurgical Coke:
Otto Hoffmann’s Byproduct Oven Process
• This process is beneficial than the previous one because a number
of by-products like coal gas, ammonia, tar etc. are obtained. One of
the by-products, i.e. coal gas can be used for heating.

• The structure consists of a number of narrow silica chambers, each


about 10 – 12 m in length, 3 – 4 m in height and about 0.4 – 0.5 m in
width.

• These are erected side by side with vertical flues between them to
form a sort of battery.

• To introduce the charge, every oven has a hole at the top of it and
there is a refractory lined cast iron door at each end for coke
discharge.
Metallurgical Coke:
Otto Hoffmann’s Byproduct Oven Process
Metallurgical Coke:
Otto Hoffmann’s Byproduct Oven Process
• In this process, finely powdered coal is introduced through the hole
(at the top) of oven chamber which is then tightly closed so that the
supply of air may be prevented at both ends.

• Then, the ovens are heated to about 1200 oC using producer gas.
The required air for the combustion of the coal is preheated in
regenerators flanking the retorts.

• At the same time flue gases leave their acquired heat to one
generator, the other heater is used for preheating the incoming air.

• This cycle continues until all the volatile matter gets away. It takes
nearly 18-20 hours for the carbonization of the coal on the completion
of this carbonization process.
Metallurgical Coke:
Otto Hoffmann’s Byproduct Oven Process
• The red hot coke is taken out into a truck by massive ram.

• It is then quenched with water. The coke may also be cooled down
with the help of inert gases in a separate chamber.

• The cooling with inert gases is said to be dry quenching which


provide cleaner and stronger coke.

• It also consists of less dust content than water cooled coke.

• The yield in this process is about 70-75%.


Metallurgical Coke:
Otto Hoffmann’s Byproduct Oven Process
• In this process, following byproducts are obtained.
(i) Ammonia
(ii) H2S
(iii) Naphthalene
(iv) Benzene
(v) Tar, etc.

• Recovery of Ammonia:
The gases coming out from chamber are allowed to pass through
another tower where water is sprayed. The gaseous ammonia gets
absorbed in water and becomes available as NH4OH

• Recovery of Naphthalene :
Naphthalene gets condensed when gases are allowed to come in
contact with cold water after the recovery of ammonia.
Metallurgical Coke:
Otto Hoffmann’s Byproduct Oven Process
• Recovery of H2S:
The gases are allowed to pass through a column packed with moist
Fe2O3 which retains H2S . This can be represented as follows :

When whole of Fe2O3 is converted into Fe2S3 , the purifier on


exposure to the atmosphere regenerates Fe2O3
Metallurgical Coke:
Otto Hoffmann’s Byproduct Oven Process
• Recovery of Benzene:
When the gases after above recoveries are allowed to come in
contact with petroleum, then benzene and other homologues are
taken off.

• Recovery of Tar:
The tar is recovered after ammonia recovery.
Other industrial solid fuels:

Charcoal

• Out of the mentioned various manufactured fuels, the charcoal occupies the
first place in India.
• In some parts of the country, e.g. Mysore, huge quantities of charcoal are
being used till today in blast furnaces for reducing iron ores, etc. and in many
homes charcoal is used for cooking purposes.
• Charcoal is a product derived from destructive distillation of wood, being left
in the shape of solid residue.
• Charcoal burns rapidly with a clear flame, producing no smoke and
developing heat of about 6,050 cal/kg.
Other industrial solid fuels:
Briquettes
• The term briquettes is used in respect of the dust, and other small size waste
remains of lignite, peat, coke, etc. compressed into different shapes of
regular form, with or without binder.

• The briquetting industry is an important step towards saving the fuel


economy.

• Good briquettes should be quite hard as possible. They must withstand the
hazards of weather, and must be suitable for storing and general handling in
use.

• These properties are imparted to briquettes by a correctly selected binder, or


suitable processing such as pre-heating, pressing, etc.

• Amongst the binders, asphalt and pitch are most commonly used, giving fine
results.
Other industrial solid fuels:
Bagasse
• Bagasse is the residue of sugarcane, left as waste in the sugar mill
after extraction of sugar juice.

• In weight, it is about 20% of virgin cane. By nature, it is fibrous fuel


which can be compared to wood.

• It contains 35-45% fibre, 7-10% sucrose and other combustible, and


45-55% moisture, and possesses an average calorific value of 2200
cal/kg. On moisture-fibre basis the average composition is :
C = 45%, H2 = 6%, O2 = 46% and Ash = 3%

• Bagasse is the main fuel satisfying the needs of sugar industries and
efforts are being made for decreasing the percent moisture of
bagasse with the help of flue-gas waste heat dryers.

• Bagasse is a quick burning fuel with good efficiency.