Ultimate Analysis of Fuels

Fuels and Combustion

By- 1.) Meet Oza-14BME065

2.) Alay Patel-14BME073
3.) Prakash Parghi-14BME153D
Batch- Mechanical, 2014
Guided By- Mr. Abhinaya Srinivas
 Introduction

The composition of fuels vary widely and hence it is

necessary to analyse and interpret the results for:
Commercial classification
Price fixation
Proper industrial utilization

The quality of fuels is ascertained by the following two

types of analysis:
Proximate Analysis and Ultimate Analysis
Ultimate Analysis
Ultimate analysis refers to the determination of weight
percentage of carbon, hydrogen, nitrogen, oxygen and
sulphur.
This analysis gives the elementary, ultimate
constituents of the fuel.
This analysis is essential for calculating heat balances
in any process for which the fuel is employed.
It is useful to the designing of fuel burning
equipments and auxiliaries.
Carbon and Hydrogen:
A known amount of coal is burnt in presence of oxygen
thereby converting carbon and hydrogen into-
1. CO2 (C +O2 = CO2)
2. H2O (H2 + O2 = H2O)
The products of combustion CO2 and H2O are passing
over weighed tubes of anhydrous CaCl2 and KOH
which absorb H2O and CO2 respectively.
The increase in the weight of CaCl2 tube represents the
weight of water formed while the increase in the weight
of KOH tube represents the weight of CO2 formed.
 In the ASTM standard method, a 0.2 gram sample is
normally used.
A combustion tube contains a section of heated copper
oxide in wire form to complete the combustion.
Lead chromate or silver are specified for removing
oxides of sulfur, and silver for removing chlorine.
A temperature of 850 to 900 C is specified for
burning the sample.
For the high-temperature combustion method, a coal
sample of approximately 0.5 gram (accurately
weighed) is used, and combustion is accomplished,
without copper oxide, with a rapid flow of oxygen at a
temperature of from 1250 to 1350 C.
 The percentage of carbon and hydrogen in coal can
be calculated in the following way-

The weight of coal sample taken = x g

The increase in the weight of KOH tube = y g
The increase in the weight of CaCl2 tube = z g

a.) Carbon:
Consider the following reaction,
C (12) + O2 = CO2 (44)
44 g of CO2 contains 12 g of carbon
Therefore y g of CO2 contains = (y * 12/44) g of carbon.
And, x g of coal contains = 12*y/44 g carbon
% of carbon in coal = (12*y/44*x) * 100
b.) Hydrogen:

Consider the following reaction,

H2 (2) + O2 = H2O(18)

18 g of water contains 2 g of hydrogen

Therefore, z g of water contains = 2 z/18 g of hydrogen
And, X g of coal contains = 2 z/18 g of hydrogen

% of hydrogen in coal = (2*z) / (18*x) * 100

Significance of Total Carbon:
It is the sum of fixed carbon and the carbon present in
the volatile matters like CO, CO2, hydrocarbons.
Thus, total carbon is always more than fixed carbon in
any coal.
High total carbon containing coal will have higher
calorific value.

Significance of Hydrogen:
It increases the calorific value of the coal.
It is associated with the volatile matter of the coal.
When the coal containing more of hydrogen is heated,
it combines with nitrogen present in coal forming
ammonia. Ammonia is usually recovered as
(NH4)2SO4, a valuable fertilizer.
Uses of Carbon and Hydrogen Data:
Carbon and hydrogen values are used as parameters in
certain proposed classification systems.
They are also used in the calculation of heat values for
checking determined calorific values and for calculating heat
balances in boiler efficiency tests.
They are probably most often used, however, in research
investigations.

Limitations:
Incomplete combustion.
Inclusion of the hydrogen of moisture and water of
hydration.
The temperature of the furnace section covering the lead
chromate and/or the silver must be maintained carefully and
must not be too high.
Determination of Nitrogen:
This is done by Kjeldhals method.
A known amount of powdered coal is heated with
concentrated sulphuric acid in the presence of K2SO4
and CuSO4 in a long necked Kjeldhals flask. This
converts nitrogen of coal to ammonium sulphate.
When the clear solution is obtained (ie., the whole of
nitrogen is converted into ammonium sulphate), it is
heated with 50 % NaOH solution and the following
reaction occurs:

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

 The ammonia thus formed is distilled over and is
absorbed in a known quantity of standard 0.1 N H2SO4
solution.
The volume of unused 0.1 N H2SO4 is then determined
by titrating against standard NaOH solution.
Thus, the amount of acid neutralized by liberated
ammonia from coal is determined using the formula:

% Nitrogen in coal
= 1.4*volume of acid used*normality/x

The current ASTM standard method specifies mercury

as the catalyst and is known as the Kjeldahl-Gunning
method.
Significance:
Presence of nitrogen decreases the calorific value of the
coal.
However, when coal is carbonized, its N2 and H2
combine and form NH3. Ammonia is recovered as
(NH4)2SO4, a valuable fertilizer.

Uses of Nitrogen data:

Nitrogen data are used in comparing coals and in
research.
When the oxygen content of coal is estimated by
difference, it is necessary to make a nitrogen
determination.
Nitrogen data probably have no other important uses.
Limitations:
Certain combinations of nitrogen do not respond to the
Kjeldahl methods. For example, nitro-nitrogen is not
included unless provision is made to reduce the nitro
group to ammonia.
Incomplete conversion of the nitrogen to ammonium
sulfate will lead to low results.
In the distillation step, a too-rapid distillation rate may
result in carry-over of the alkaline digestion mixture,
which will ruin the determination.
Pyridine carboxylic acids may be formed that are
resistant to decomposition.
Determination of Sulphur

A known amount of coal is burnt completely in Bomb

calorimeter in presence of oxygen.
Ash thus obtained contains sulphur of coal as sulphate
which is extracted with dil. HCl.
The acid extract is then treated with BaCl2 solution to
precipitate sulphate as BaSO4.
The precipitate is filtered, washed, dried and weighed.
 From the weight of BaSO4, the percentage of sulphur
in coal is calculated in the following way:
The weight of coal sample taken = x g
The weight of BaSO4 precipitate = y g
Consider the following equations,

S (32) + 2O2 = SO4 (+ BaCl2) = BaSO4 (233)

233 g of BaSO4 contains 32 g of sulphur

Therefore, y g of BaSO4 contains = 32*y/233 g sulphur.
Therefore x g of coal contains = 32*y/233 g sulphur.

% of sulphur in the coal = (32*y/233*x)*100.

Significance:
It increases the calorific value of the coal, yet it has the
following undesirable effect- The oxidation products of
sulphur (SO2, SO3) especially in presence of moisture
forms sulphuric acid which corrodes the equipment and
pollutes the atmosphere.

Uses of Total Sulfur Data:

Purpose of cleaning coal is to reduce the total sulfur
content. Sulfur values, therefore, must be available for use
as a guide to successful commercial processing of coal.
Sulfur is converted to oxides that may contribute to
corrosion in the equipment, to slagging of the combustion
or boiler equipment, and to atmospheric pollution. Sulfur
data are therefore necessary for evaluation of coals to be
used for combustion purposes.
Limitations:

Due to the non uniform distribution of the pyritic

portion of total sulfur in coal, adequate sampling is
complicated.
Failure to completely convert all the sulfur to sulfate
will result in erratic values.
As sulfur normally is first oxidized to sulfur dioxide
during analysis, some of it may be lost if precautions
are not taken.
Determination of oxygen
According to the ASTM standards, the oxygen value
has been obtained by subtracting the sum of the
percentages of carbon, hydrogen, nitrogen, chlorine,
total sulfur, and ash from 100 percent.
It is calculated indirectly in the following way-
% of oxygen in coal = 100 - % (C + H + N + S + ash)

Significance:
The less the oxygen content, the better is the coal. As the
oxygen content increases, its moisture holding capacity
also increases.
Uses of Oxygen Data:

In calculating heat balances for boiler efficiency studies.

In carbonization, a coal of high oxygen content is judged
to be less suitable for making good metallurgical coke
than one with a lower oxygen content.
In gasification and liquefaction of coal, higher oxygen
(lower rank) coals may be more reactive and thus easier
to gasify or liquefy.
In research, oxygen data, as a part of the ultimate
analysis, help to characterize coal reserves and are
useful in various technical investigations.
Numericals for fun
1. A coal sample was subjected to ultimate analysis, 0.6 g
of coal on combustion in a bomb calorimeter produces
0.05 g of BaSO4. Calculate the percentage of S in the
sample.
2. 1.56 g of coal was kjeldahlized and NH3 gas thus
evolved was absorbed in 50 ml of 0.1 N H2SO4. After
absorption, the excess acid required 6.25 ml of 0.1 N
NaOH for exact neutralization. 2.6 g of coal sample in
a quantitative analysis gave 0.1755 g of BaSO4.
Calculate the % of N and S in the sample.
References
Chemistry, Uses and Limitations of coal analyses by
O.W. Rees, Illinois State Geological Survey,
Department of Registration and Education, State of
Illinois.
Fundamentals for analysis and calculation of energy and
environmental performance, Applied industrial energy
and environmental management by Z. K. Morvay, D. D.
Gvozdenac.
Jain and Jain, Engineering Chemistry, Dhanpat Rai
Publication
James G. Speight, Fuel Science and Technology Hand
Book, Marcel Dekker, New York.
Thank You