Chapter - 7 - Combustions of Fuels

CHT 2502.
Fundamentals of Fluid Flow and Heat Transfer
CHT 2501
MATERIALS & ENERGY BALANCE

CHAPTER-7
Combustion of Fuels
Dr D. Mandal
dmandal10@gmail.com
8/31/2019
Dr D Mandal 1
CHT 2502. Fundamentals of Fluid Mechanics and Heat Transfer
FUELS AND COMBUSTION
₡ Because of the universal use of the combustion of fuels for the generation of
heat and power, special techniques and methods have been developed for
establishing the material and energy balances of such processes.
₡ Each problem should be pursued independently and as rigorously as the

available experimental data permit, using the chemical principles involved
and not empirical equations.
Heating Values of Fuels
₡ The most important property of a fuel is its heating value, which is

numerically equal to its standard heat of combustion but of opposite sign.
₡ ‘Heating value’ property is usually determined by direct experimental

measurements, although methods are also given for its estimation.
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Products from Combustion
₡ The major products of complete combustion from practically all fuels are
carbon dioxide and water.
₡ Two methods of expressing heating values are in common use, differing in

the state selected for the water present in the system after combustion.
₡ The total heating value of a fuel is the heat evolved in its complete
combustion under constant pressure at a temperature of 18°C when all
the water formed and originally present as liquid in the fuel is condensed
to the liquid state.
₡ The net heating value is similarly defined except that the final state of the
water in the system after combustion is taken as vapor at 18°C.
₡ The total heating value is also termed the " higher " or " gross " heating
value; the net is often termed the " lower " heating value.
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Products from Combustion
Ӝ The net heating value is obtained from the total heating value by subtracting
the latent heat of vaporization at 18°C of the water formed and vaporized in
the combustion.
Coke and Carbon
₡ The combustible constituents of cokes and charcoals are practically pure

carbon.
₡ The heating value of such a fuel may be predicted with accuracy sufficient for
most purposes by simply multiplying its carbon content by the heating value
per unit weight of carbon.
₡ The heats of combustion of the various forms of amorphous carbon differ by

the same amounts as do their heats of formation.
₡ For combustion calculations the value of the heat of combustion of carbon is

taken as 404.30 kJ (96,630 calories) per gram-atom or 33715.37 kJ/kg (14,495
Btu/pound).
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Coal Analyses
₡ Coal consists chiefly of organic matter of vegetable origin which has been
altered by decomposition, compression, and heating during long ages of
inclusion in the earth's crust.
₡ In addition to organic matter it contains mineral constituents of the plants

from which it was formed and also inclusions of other inorganic materials
deposited in it during its geological formation.
₡ Two types of analysis are in common use for expressing the composition of
coal.
• Ultimate Analysis: In an ultimate analysis, determination is made of

each of the major chemical elements.
• Proximate Analysis: In a proximate analysis four arbitrarily defined

groups of constituents are determined and termed moisture, volatile
matter, fixed carbon, and ash.
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Ultimate & Proximate Analysis
• Following are the ultimate and proximate analyses of a typical coal

Ultimate Proximate
Moisture :…………………………………… 9.61 Moisture :…………………………………… 9.61
Ash (corrected) :………………………… 9.19 Ash :…………………………………………… 9.19
Carbon:……………………………….…….. 66.60 Volatile matter:…………………………… 30.68
Net hydrogen: …………………………… 3.25 Fixed carbon:…………………….. ……. 50.34
Sulfur: ……………………………………….. 0.49 TOTAL: 100.00
Nitrogen: ……………………………………… 1.42
Combined H2O : …………………………..9.44

TOTAL: 100.00
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₡ The proximate analysis of coal should be carried out according to an

arbitrarily standardized procedure which has been recommended by the
United States Bureau of Mines.
₡ The details of this method are described in most books on methods of

technical analysis.
₡ The determinations may be rapidly and easily carried out, and the majority
of the contracts and specifications for the purchase of coal are based on this
analysis.
₡ The tedious methods of ultimate analysis are completely acarried out only
when necessary to serve as a basis for energy and material balance
calculations.
₡ However, the sulfur content is of particular interest, and determination of

this element frequently accompanies the proximate analysis.
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₡ In both schemes of analysis ‘moisture‘ represents the loss in mass on

heating the finely divided coal at 105°C for one hour.
₡ The material termed ‘ash’ in the proximate analysis is the residue from
complete oxidation of the coal at a high temperature in air.
₡ This quantity is needed for calculating the quantity of refuse formed in the
ordinary combustion of the coal.
₡ The ash determined in this manner does not accurately represent the
mineral content of the original coal because of the changes which take place
during combustion.
₡ An important mineral component of many coals is iron pyrites, FeS2.
₡ In combustion this is oxidized to form Fe203, which is weighed in the residual

ash, and SO2 gas.
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₡ In the oxidation of pyrites 4 gram-atoms (128 grams) of sulfur are replaced

by 3 gram-atoms (48 grams) of oxygen, a loss in mass equal to 3Τ8 times
the mass of pyrite sulfur present.
₡ In order to determine the actual mineral content of the coal, including the
pyritic sulfur, it is necessary to add to the ash-as mass, a correction equal to
3Τ8 times of the pyritic sulfur content.
₡ To determine the actual mineral content, not including the pyritic sulfur, a
correction equal to 3Τ8 of the pyritic sulfur must be subtracted from the
ash-as-mass.
₡ Other less important corrections may also be applied to the ash. Unless
otherwise designated, " ash " refers to ash as-mass.
₡ Unless otherwise designated, " ash " refers to ash as-mass.
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₡ To obtain the ultimate analysis, direct determinations are made of

• Carbon,
• Sulphur,
• Nitrogen, and
• Hydrogen
by the usual analytical methods.
₡ The moisture and ash are determined by the standardized procedures of the
proximate analysis.
₡ The percentage oxygen content is then taken as the difference between 100
and the sum of the percentages of carbon, hydrogen, sulfur, nitrogen, and
corrected sulfur-free ash.
₡ It is recommended that, for this calculation, the corrected ash be estimated

by assuming that all sulfur in the coal is present in the pyritic form.
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% 𝒐𝒇 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒆𝒅 𝒂𝒔𝒉 = % 𝒂𝒔𝒉 𝒂𝒔 𝒎𝒂𝒔𝒔 − 𝟑Τ𝟖 % 𝑺
= % 𝒎𝒊𝒏𝒆𝒓𝒂𝒍 𝒄𝒐𝒏𝒕𝒆𝒏𝒕 − % 𝑺
where % S = percentage sulfur content of coal.
₡ This correction represents only an approximation, since not all sulfur is

pyritic and other changes in the mineral constituents may take place in
combustion.
₡ More refined methods for estimating oxygen content are not ordinarily
justified.
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₡ In reporting the ultimate analysis it is convenient to consider that all oxygen

is in combination with hydrogen to, form moisture and ‘combined water.’
₡ The surplus hydrogen, above that required to combine with the oxygen, is
termed ‘net‘ or ‘available ‘ hydrogen.
₡ This represents the hydrogen present in the form of hydrocarbons and

available for further oxidation.
Applicable standards for Proximate analysis
₡ Moisture (ASTM D3173, ISO 11722, AS1038.3)
Moisture is the water that exists in the coal at the site, time, and under the
conditions it is sampled. SGS experts determine the amount of moisture in your
samples by measuring the loss in mass between an as-mined sample and a
sample that has been heated under controlled conditions to drive off the water
that is not contained within the chemical structure of the coal.
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₡ Sulfur (ASTM D4239, ISO 351, AS1038.6)
It is important to measure the sulfur content in coal samples to evaluate the

potential sulfur emissions from coal combustion, or for contract specifications
purposes.
₡ Calorific Value (ASTM D5865, ISO 1928, AS1038.5)
The calorific value of coal or coke is the heat liberated when the solid fuel
undergoes complete combustion in oxygen. In order to obtain accurate results, it
necessary to burns fuel sample in a bomb calorimeter and measures the total
heat energy.
₡ Volatile Matter (ASTM D3175, ISO 562, AS1038.3)
Volatile matter includes the components of coal, except for water, which are
liberated at high temperature in the absence of oxygen. Volatile matter is a key
health and safety concern as coals high in volatiles have an increased risk of
spontaneous combustion. The volatile matter in coal sample is determined by
measuring the mass of volatiles before and after weight analysis under strictly
controlled conditions.
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₡ Fixed Carbon (ASTM D5142, ISO 17246)
The fixed carbon content of coal is determined by subtracting the

percentages of moisture, volatile matter and ash from the original mass of
the coal sample: the solid combustible residue that remains after a coal has
had the volatiles driven off. SGS experts conduct a fixed carbon test to
estimate of the amount of coke your coal sample will yield.
₡ ASH
Ash content of coal is very important to know and a variety of fundamental

ash analysis tests including ash elemental tests, ash fusion tests and coal ash
analysis are generally performed.
Accurate and precise calculations are vital to the success of your coal
operation. These calculations are used to calculate various skeleton
parameters including ash and calorific value that let you determine the
grades of your coal.
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Ultimate Analysis Tests
₡ Ultimate analysis tests produce more comprehensive results than the

proximate analyses.
₡ The ultimate analysis tests are carried out to determine the elemental
composition of the coal including moisture, ash, carbon, hydrogen, nitrogen,
sulfur, and oxygen (by difference).
₡ Each element are normally determined through chemical analysis and

express it as a percentage of the total mass of the original coal or coke
sample.
Coal petrography is a microscopic technique used to determine a coal’s

rank (degree of coalification) and type (amount and category of macerals
(softness or breakup))
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Rank of Coal
₡ The sum of the fixed carbon and volatile matter of a coal is termed the
combustible.
₡ The Bureau of Mines has published extensive tables' of the ultimate analyses
of coals representing hundreds of coal deposits throughout the United
States.
₡ If the source of a coal is known the ultimate analysis of its combustible

matter can be obtained with fair reliability from these tables since the
composition of combustible material in any one coal bed is nearly constant.
₡ In every coal sample it is necessary, however, to make separate

determinations of ash and moisture contents.
₡ The fuel ratio of a coal is defined as the ratio of its percentage of fixed
carbon to that of volatile matter.
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Rank of Coal
₡ The rank of the coal, whether bituminous, or anthracite, may be estimated

from the fuel ratio.
₡ The generally accepted classification of coals and the corresponding ranges

of fuel ratios are as follows:
Rank Fuel Ratio The classification of coals on

Anthracite between 10 and 60 the basis of fuel ratio is not
entirely satisfactory for many
Semi-anthracite between 6 and 10 purposes. Several other
methods have been
Semi-bituminous between 3 and 7
developed which give more
Bituminous Between 1 and 3 nearly exact differentiation.
₡ Fuels of lower rank than bituminous, namely, sub-bituminous and lignite,

may have fuel ratios within the bituminous range but are characterized by
higher water or oxygen contents.
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Heating Value of Coal
₡ The total heating value of a coal may be determined by direct calorimetric

measurement and is usually expressed in kJ per kg (Btu per pound).
₡ The net heating value is obtained by subtracting from the total heating value
the heat of vaporization at 18°C of the coal.
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Example # 1: A city gas has the following composition by volume:

CO2 2.6%
C2.73 H4.72 ( unsaturated) 8.4%
O2 0.7%
H2 39.9%
CO 32.9%
C1.14 H4.28 ( paraffin) 10.1%
N2 5.4%
TOTAL 100%
(a) Calculate the theoretical number of moles of oxygen which must be supplied
for the combustion of 1 mole of the gas.
(b) Calculate the heating value of the gas in kJ per gram-mole per standard cubic
meter of the fuel
Given: Heat of combustion of hydrogen: 285.35 kJ/mol, carbon−monoxide:282.04

kJ/mol, unsaturated Hydrocarbon : 1678.65 kJ/mol, paraffin: 983 kJ/mol
8/31/2019 Dr D Mandal 19
Solution # 1: (a) Basis: 100 gram-moles of gas.
Oxygen required for:
Unsaturateds = 8.4(2.73 + 4.72/4) =32.8

Hydrogen =39.9/2 =19.95
𝐶𝑎𝑟𝑏𝑜𝑛 𝑚𝑜𝑛𝑜𝑥𝑖𝑑𝑒 = 32.9/2 =16.45
4.28 =22.3
𝑃𝑎𝑟𝑎𝑓𝑓𝑖𝑛 = 10.1(1.14 + )
4
TOTAL 91.5
Oxygen to be supplied per mole of gas = 0.915 — 0.007 = 0.908 mole.
8/31/2019 Dr D Mandal 20
(b) Basis: 1.0 gram-mole of gas.
Heating value of:
Hydrogen = 0.399 x 285.35 kJ = 113.855 kJ

𝐶𝑎𝑟𝑏𝑜𝑛 𝑚𝑜𝑛𝑜𝑥𝑖𝑑𝑒 = (0.329𝑥 282.04) kJ = 92.792 kJ
Unsaturateds = (0.084 * 1678.65 )kJ =141.0 kJ
𝑃𝑎𝑟𝑎𝑓𝑓𝑖𝑛 = (0.101 𝑥 983) 𝑘𝐽 =99,28 kJ
TOTAL = 446.93 kJ
kJ per std. m3 ?
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(b) Basis: 1.0 gram-mole of gas.
Heating value of:
Hydrogen = 0.399 x 285.35 kJ = 113.855 kJ

𝐶𝑎𝑟𝑏𝑜𝑛 𝑚𝑜𝑛𝑜𝑥𝑖𝑑𝑒 = (0.329𝑥 282.04) kJ = 92.792 kJ
Unsaturateds = (0.084 * 1678.65 )kJ =141.0 kJ
𝑃𝑎𝑟𝑎𝑓𝑓𝑖𝑛 = (0.101 𝑥 983) 𝑘𝐽 =22.3 kJ
TOTAL = 369.947 kJ
kJ per std. m3 ?
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Example # 2: A stack gas contains 60.0 mole % N2, 15.0 °/o C02 , 10.0°/o 02, and
the balance H20.
Calculate the molar composition of the gas on a dry basis.
Solution# 2
Basis: 100 mol Wet Gas
Nitrogen 60 mol
𝐶𝑎𝑟𝑏𝑜𝑛 𝑑𝑖𝑜𝑥𝑖𝑑𝑒 15 mol
Oxygen 10.0 mol
𝐷𝑟𝑦 𝑔𝑎𝑠 85 mol
mol nitrogen 60
So, x 100 = x100 =70.6 %
𝑚𝑜𝑙 𝐷𝑟𝑦 𝑔𝑎𝑠 85
𝐶𝑎𝑟𝑏𝑜𝑛 𝑑𝑖𝑜𝑥𝑖𝑑𝑒 15
x 100 = x100 = 17.6 %
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mol oxygen 10
x 100 = x100 = 11.8 %
Example # 3: An Orsat analysis (a technique for stack analysis) yields the

following dry basis composition:
Nitrogen 65 %
𝐶𝑎𝑟𝑏𝑜𝑛 𝑑𝑖𝑜𝑥𝑖𝑑𝑒 14 %
𝐶𝑎𝑟𝑏𝑜𝑛 𝑚𝑜𝑛𝑜𝑜𝑥𝑖𝑑𝑒 11 %
Oxygen 10 %
A humidity measurement shows that the mole fraction of H20 in the stack gas is
0.07.
Calculate the stack gas composition on a wet basis.
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Example # 4: A sample of medium-grade bituminous coal analysis is as

follows:
Component Percent
S 2
N 1
O 6
Ash 11
Moisture 3
The residuum is C and H in the mole ratio H/C = 9. Calculate the mass
fraction composition of the coal with the ash and the moisture omitted.
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Solution # 4
Take as a basis 100 kg of coal, for then percent = kilograms.

Basis: 100 kg of coal
The sum of the S + N + 0 + ash + water is 2 + 1 + 6 + 11 + 3 = 23 kg
Hence, the C + H must be 100 - 23 = 77 kg.
To determine the kilograms of C and H, we have to select a new

basis. Is 77 kg satisfactory?
No. Why? Because the H/C ratio is in terms of moles, not mass.
Pick instead:
Basis: 100 kg mol of C + H
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Solution # 4 Contd...
Basis: 100 kg mol of C + H
Component Mole-fraction Kg-mol Mol. mass Kg

H 9
= 0.9
1+9 90 1.008 90.7
C 1
= 0.1
1+9 90 12 120
TOTAL 1.0 100 - 210.7
Finally, to return the original basis, we have
77 𝑘𝑔 90.7 𝑘𝑔
H: = 33.15 kg
1 210.7 𝑘𝑔 𝑡𝑜𝑡𝑎𝑙
8/31/2019 Dr D Mandal 27
Solution # 4 Contd...
77 𝑘𝑔 120 𝑘𝑔
C: = 43.85 kg
1 210.7 𝑘𝑔 𝑡𝑜𝑡𝑎𝑙
and we can prepare a table summarizing the results.
Component Kg mass-fraction
C 43.85 0.51
H 33.15 0.39
S 2 0.02
N 1 0.01
O 6 0.07
TOTAL 86.0 1.00
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Problem # 5 A city gas has the following composition by volume:

Component Volume %
CO2 2.6
C2.72H4.72 (unsaturated) 8.4
O2 0.7
H2 39.9
CO 32
C1.14H4.28 (Paraffin) 10.1
N2 5.4
TOTAL 100%
(a) Calculate the theoretical number of moles of oxygen which must be

suppose for the combustion of 1 mole of the gas.
(6) Calculate the heating value of the gas in calories per gram-mole and
Btu per standard cubic foot.
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Problem # 6: A fuel oil analyzes 80% C and 20% H by mass. The standard heat of
combustion of this oil is determined in an oxygen bomb calorimeter.
(a) Calculate the correction that must be applied to get the heat of
reaction at constant pressure.
(b) Which is the greater, the heat of reaction at constant pressure, or the
heat of reaction at constant volume?
Problem # 7 : When 1.0 gram of naphthalene (C10H8) is burned in a bomb

calorimeter, the water formed being condensed, 40 kJ energy is evolved at 18°C.
Calculate the heat of combustion at constant pressure and 18°C, the water
vapor remaining uncondensed.
Problem# 8: A coal containing 81% total carbon and 6% unoxidized hydrogen is

burned in air.
(a) If air is used 30% in excess of that theoretically required, calculate the
number of pounds of air used per pound of coal burned.
(b) Calculate the composition, by weight, of the gases leaving the furnace,
assuming complete combustion.
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Chapter - 7 - Combustions of Fuels

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CHT 2502.

Fundamentals of Fluid Flow and Heat Transfer

MATERIALS & ENERGY BALANCE

FUELS AND COMBUSTION

₡ Each problem should be pursued independently and as rigorously as the

Heating Values of Fuels

₡ The most important property of a fuel is its heating value, which is

₡ ‘Heating value’ property is usually determined by direct experimental

Products from Combustion

₡ Two methods of expressing heating values are in common use, differing in

Coke and Carbon

₡ The combustible constituents of cokes and charcoals are practically pure

₡ The heats of combustion of the various forms of amorphous carbon differ by

₡ For combustion calculations the value of the heat of combustion of carbon is

₡ In addition to organic matter it contains mineral constituents of the plants

• Ultimate Analysis: In an ultimate analysis, determination is made of

• Proximate Analysis: In a proximate analysis four arbitrarily defined

Ultimate & Proximate Analysis

• Following are the ultimate and proximate analyses of a typical coal

Ash (corrected) :………………………… 9.19 Ash :…………………………………………… 9.19

Carbon:……………………………….…….. 66.60 Volatile matter:…………………………… 30.68

Net hydrogen: …………………………… 3.25 Fixed carbon:…………………….. ……. 50.34

Sulfur: ……………………………………….. 0.49 TOTAL: 100.00

Nitrogen: ……………………………………… 1.42

Combined H2O : …………………………..9.44

Ultimate & Proximate Analysis

₡ The proximate analysis of coal should be carried out according to an

₡ The details of this method are described in most books on methods of

₡ However, the sulfur content is of particular interest, and determination of

Ultimate & Proximate Analysis

₡ In both schemes of analysis ‘moisture‘ represents the loss in mass on

₡ An important mineral component of many coals is iron pyrites, FeS2.

₡ In combustion this is oxidized to form Fe203, which is weighed in the residual

Ultimate & Proximate Analysis

₡ In the oxidation of pyrites 4 gram-atoms (128 grams) of sulfur are replaced

₡ Unless otherwise designated, " ash " refers to ash as-mass.

Ultimate & Proximate Analysis

₡ To obtain the ultimate analysis, direct determinations are made of

₡ It is recommended that, for this calculation, the corrected ash be estimated

Ultimate & Proximate Analysis

% 𝒐𝒇 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒆𝒅 𝒂𝒔𝒉 = % 𝒂𝒔𝒉 𝒂𝒔 𝒎𝒂𝒔𝒔 − 𝟑Τ𝟖 % 𝑺

where % S = percentage sulfur content of coal.

₡ This correction represents only an approximation, since not all sulfur is

Ultimate & Proximate Analysis

₡ In reporting the ultimate analysis it is convenient to consider that all oxygen

₡ This represents the hydrogen present in the form of hydrocarbons and

Applicable standards for Proximate analysis

₡ Moisture (ASTM D3173, ISO 11722, AS1038.3)

₡ Sulfur (ASTM D4239, ISO 351, AS1038.6)

It is important to measure the sulfur content in coal samples to evaluate the

₡ Calorific Value (ASTM D5865, ISO 1928, AS1038.5)

₡ Fixed Carbon (ASTM D5142, ISO 17246)

The fixed carbon content of coal is determined by subtracting the

Ash content of coal is very important to know and a variety of fundamental

Ultimate Analysis Tests

₡ Ultimate analysis tests produce more comprehensive results than the

₡ Each element are normally determined through chemical analysis and

Coal petrography is a microscopic technique used to determine a coal’s

₡ If the source of a coal is known the ultimate analysis of its combustible

₡ In every coal sample it is necessary, however, to make separate

₡ The rank of the coal, whether bituminous, or anthracite, may be estimated

₡ The generally accepted classification of coals and the corresponding ranges