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Prepared by: Addisu D. May, 2018
Introduction
Any matter that is a source of heat is called fuel.
Fuel releases its energy either through a chemical reaction, such
as during combustion, or via nuclear fission or fusion.
An important property of a useful fuel is that its energy can be
stored and released only when needed, and that the release is
controlled in such a way that the energy can be harnessed to
produce the desired work.
Fuels are broadly classified as fossil or organic or chemical fuel,
nuclear fuel, and rocket fuel.
Fossil fuels are hydrocarbons, primarily coal and petroleum
(liquid petroleum or natural gas), formed from the fossilized
remains of dead plants and animals by exposure to heat and
pressure in the earth’s crust over hundreds of millions of years.
Fossil fuels generate substantial quantities of heat per unit of
mass or volume by reacting with an oxidant in a combustion
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process.
Introduction
In most practical applications including combustion in a steam
generator, air is used as the oxidant, although in certain processes
oxygen, oxygen-enriched air and other chemicals are used as the
oxidant.
Energy generation by a nuclear fuel takes place either by the
process of nuclear fission of heavy fissile elements in a nuclear
reactor resulting in chain reactions or by the process of nuclear
fusion, in which simple atomic nuclei are fused together to form
complex nuclei, as in case of fusion of hydrogen isotopes to form
helium.
The process of nuclear fusion is also known as a thermonuclear
reaction, which is difficult to control even today. As a result, the
main source of nuclear energy presently available is mainly from
nuclear fission.
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Introduction
The most common fissile radioactive heavy metals are naturally
occurring isotope of uranium, U235, artificial isotope of uranium,
U233, and artificial element plutonium, P239.
In a nuclear reactor plutonium, P239, is produced from naturally
occurring isotope of uranium, U238, and U233 is produced from the
naturally occurring element thorium, Th232.
Nuclear fission of 1 kg of U235 generates about 85*106 MJ of heat,
which is equivalent to the heat generated by combustion of about
5106 kg of coal with a high heating value (HHV) of 17 MJ/kg.
In nuclear reactions, the product is either isotopes of the reactants
or other nuclei.
Unlike fossil fuel, rocket fuel does not depend on its surroundings
for the oxidant. The oxidant is carried by the rocket itself. The
propellant is the chemical mixture burned to produce thrust in
rockets and consists of a fuel and an oxidizer.
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Introduction
The increasing worldwide demand for energy has focused
attention on fuels, their availability and environmental effects.
The fuels available to utility industry are largely nuclear and
fossil, both essentially nonrenewable. Nuclear fuels originated
with the universe, and it takes nature millions of years to
manufacture fossil fuels.
Fossil fuels originate from the earth as a result of the slow
decomposition and chemical conversion of organic material. They
come in three basic forms: solid (coal). liquid (oil), and natural
gas.
Coal represents the largest fossil-fuel energy resource in the
world.
According to IEA report in 2015, coal is responsible for about 40
percent of electric-power generation in the world. Oil and natural
gas are responsible for another 27 percent. The remaining
5 percentage is mostly due to nuclear and hydraulic generation.
Introduction
Most widely used fossil fuels for the production of steam in
relation to power are available in all the states of matter.
Gaseous
✓ natural gas, blast furnace gas, coke-oven gas, refinery gas,
liquefied petroleum gas or (LPG), etc.
Liquid
✓ high-speed diesel (HSD), light diesel oil (LDO), heavy fuel
oil (HFO), furnace oil (FO), low sulfur heavy stock (LSHS),
naphtha, liquefied natural gas (LNG), etc.
Solid
✓ bituminous coal, anthracite, lignite, peat, oil shale, biomass,
rice husk, bagasse etc.
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Introduction
Fossil fuels consist of a large number of complex compounds of
five elements: carbon (C), hydrogen (H), oxygen (O), sulfur (S),
and nitrogen (N). Besides these elements, all fuels contain mineral
matter (A) and moisture (M) to some extent.
However, there are just three combustible elements of
significance in a fuel, e.g., carbon, hydrogen, and sulfur, of which
carbon is the principal combustible element with a HHV of
32.780 MJ/kg.
Hydrogen has a very high HHV of 141.953 MJ/kg, but its content
in solid fuel is quite low, about 2 - 4%.
The HHV of sulfur is only 9.257 MJ/kg, hence as a source of heat
its presence is insignificant, although it is more so since its
presence in coal is small in quantity.
Major concern regarding sulfur is that it promotes corrosion and
creates atmospheric pollution problems.
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Introduction
Contrary to solid and liquid fuels, gaseous fuels are mixtures of
combustible and non-combustible gases.
Natural gas is gaseous fuel occurring in nature and consisting
mostly of organic compounds, normally methane (CH4), ethane
(C2H6), propane (C3H8), and butane (C4H10).
The calorific value of natural gas varies between 26.1 and 55.9
MJ/m3, the majority averaging 37.3 MJ/m3.
Natural gas on average contains 80 - 90% methane, 6 - 9% ethane,
and 2 - 5% propane. Noncombustible gases present in minor
quantities in natural gases are nitrogen (0.5 - 2.0%) and carbon
dioxide (0.1 - 1.0%).
LPG is a material composed predominantly of the following
hydrocarbons or mixtures of them: propane, propylene, n-butane,
isobutene, and butylenes. The mixture is liquefied at room
temperature at very high pressure. An average mixture of LPG is
8 comprised of about 80% butane and about 20% propane.
Coal
Fossil solid fuels are available in almost all countries but are distributed
unevenly.
The majority of countries is not rich in coal production. There are around
70 countries that contain recoverable coal reserves.
The world currently consumes over 7,700 Mt of coal which is used by a
variety of sectors including power generation, iron and steel production,
cement manufacturing and as a liquid fuel.
Coal is the major fuel used to generate over 40% of the world’s electricity
demand and provides 30% of global primary energy needs. Coal is also
used in the production of 70% of the world’s steel.
According to World Energy Council Report in 2016 the largest producer
of coal is the People’s Republic of China (about 3747 million tons of coal
was produced in the year 2015) followed by the United States (813
million tons) , India (677 million tons), Australia (485 million tons),
Indonesia (392 million tons). Russia, South Africa, Germany, Poland, and
Kazakhstan also contribute to global coal production to some extent.
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Coal
According to geological order of formation, coal may be of the
following types: (1) Peat, (2) Lignite, (3) Subbitumioous, (4)
Bituminous, (5) Subanthracite, and (6) Anthracite, with increasing
percentages of carbon. After anthracite, graphite is formed.
Anthracite contains more than 86% fixed carbon (in amorphous
form) and less volatile matter. Volatile matter helps in the ignition of
coal. So, it is often difficult to bum anthracite.
Bituminous coal is the largest group containing 46-86% of fixed
carbon and 20-40% of volatile matter. It can be low-volatile,
medium-volatile and high-volatile. The lower the volatility, the
higher the heating value.
Lignite is the lowest grade of coal containing moisture as high as
30% and high volatile matter.
According to ASTM (American Society of Testing and Materials),
peat is not regarded as a rank of coal. Peat contains up to 90%
moisture and is not attractive as a utility fuel.
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Coal Analysis
There are two methods
➢ ultimate analysis and
➢ proximate analysis.
The ultimate analysis determines all coal component elements,
solid or gaseous and the proximate analysis determines only
the fixed carbon, volatile matter, moisture and ash percentages.
The ultimate analysis is determined in a properly equipped
laboratory by a skilled chemist, while proximate analysis can
be determined with a simple apparatus.
It may be noted that proximate has no connection with the
word “approximate”.
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Coal Analysis: Proximate Analysis
Measurement of Moisture
When 1 g sample of coal is subjected to a temperature of about
105oC for a period of 1 hour, the loss in weight of the sample
gives the moisture content of the coal.
Significance of Moisture:
High moisture content of the coal is undesirable for the following
reasons:
1) Reduces the calorific value of coal
2) Increases the consumption of coal for heating purpose.
3) Lengthens the time of heating.
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Coal Analysis: Proximate Analysis
Measurement of Volatile Matter
When 1 g sample of coal is placed in a covered platinum crucible and
heated to 950 oC and maintained at that temperature for about 7 min,
there is a loss in weight due to the elimination of moisture and volatile
matter. The latter may now be determined since moisture has been
calculated from the previous test.
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Coal Analysis: Proximate Analysis
Measurement ash in coal
By subjecting 1 g sample of coal in an uncovered crucible to a
temperature of about 720 oC until the coal is completely burned,
a constant weight is reached, which indicates that there is only
ash remaining in the crucible. Complete combustion of coal is
determined by repeated weighing of the sample.
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Coal Analysis: Proximate Analysis
Measurement of fixed carbon
Fixed carbon is the difference between 100% (original sample) and
the sum of the percentages of moisture, ash and volatile matter.
However, this difference does not represent all the carbon that was in
the coal. Some of the carbon may have been in the form of
hydrocarbons which may have been distilled off while determining
the volatile matter. It is also possible that some of this fixed carbon
may include Sulphur, nitrogen and oxygen.
% of fixed carbon in coal =
100 - % (moisture + volatile matter + ash)
Fixed carbon is the pure carbon present in coal. Higher the fixed
carbon content of the coal, higher will be the calorific value of the
sample.
So, the proximate analysis of coal gives
FC + VM + M+ A = 100% by mass
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Coal Analysis
Ultimate Analysis
The ultimate analysis indicates the various elemental chemical
constituents such as Carbon, Hydrogen, Oxygen, Nitrogen,
Sulphur of pure dry coal. This analysis gives the elementary,
ultimate constituents of coal.
It is useful in determining the quantity of air required for
combustion and the volume and composition of the combustion
gases.
This analysis is essential for calculating heat balances in any
process for which coal is employed as a fuel.
It is useful to the designing of coal burning equipment and
auxiliaries. This information is required for the calculation of
flame temperature and the flue duct design etc.
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Coal Analysis: Ultimate Analysis
a) Determination of carbon and hydrogen in coal:
A known amount of coal is burnt in presence of oxygen thereby
converting carbon and hydrogen of coal into-
(i) CO2 (C + O2 → CO2) and (ii) H2O (H2 + ½ O2 → H2O)
respectively.
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.
The percentage of carbon and hydrogen in coal can be calculated in
the following way-
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Coal Analysis: Ultimate Analysis
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Coal Analysis: Ultimate Analysis
(b) Determination of hydrogen:
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Coal Analysis: Ultimate Analysis
(c) Determination of nitrogen:
This is done by Kjeldhal’s method.
A known amount of powdered coal is heated with concentrated
sulphuric acid in the presence of potassium sulfate (K2SO4) and
copper sulfate (CuSO4) in a long necked Kjeldhal’s flask.
This converts nitrogen of coal to ammonium sulphate. When the
clear solution is obtained (i.e., the whole of nitrogen is converted
into ammonium sulphate), it is heated with 50 % sodium
hydroxide (NaOH) solution and the following reaction occurs:
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Coal Analysis: Ultimate Analysis
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Coal Analysis: Ultimate Analysis
e) Determination of oxygen in coal:
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.
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Coal Analysis
Table : Proximate and ultimate analysis of some U.S. coals
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HEATING VALUE
The heating value, J/kg of fuel, is the heat transferred when the
products of complete combustion of a sample of coal or other
fuel are cooled to the initial temperature of air and fuel.
It is determined in a standard test in a bomb calorimeter.
There are two determinations:
The higher heating value (HHV) or gross calorific value
(GCV), assumes that the water vapor in the products
condenses and thus includes the latent heat of vaporization
of the water vapor in the products;
When the latent heat of vaporization of water vapor
contained in the combustion products is subtracted from the
HHV we get the lower heating value (LHV) or net calorific
value (NCV) of fuel.
Therefore,
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HEATING VALUE
LHV = HHV − 𝑚𝑤 ℎ𝑓𝑔
where mw is the mass of water vapour formed given by
𝑚𝑤 = 𝑀 + 9𝐻 + 𝛾𝐴 𝑤𝐴
where M and H are the mass fractions of moisture and hydrogen
in the coal, 𝛾𝐴 is the specific humidity of atmospheric air and 𝑤𝐴
is the actual amount of air supplied per kg of coal.\
If the ultimate analysis is known, the HHV of anthracite and
bituminous coals can be determined approximately by using
Dulong and Petit formula as given below:
O
HHV = 33.83 C + 144.45 H − + 9.38 S, in MJ/kg
8
where C, H, 0 and S are mass fractions of carbon, hydrogen,
oxygen and sulphur in coal.
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HEATING VALUE
Assuming the latent heat of vaporization hfg at the partial pressure
of water vapour in the combustion products as 2.395 MJ/kg, the
lower heating value of coal is given by
LHV = HHV − 2.395 𝑚𝑤 in MJ/kg
For lower-rank fuels the Dulong and Petit formula usually
underestimates the HHV.
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COMBUSTION REACTIONS
Combustion is the high temperature oxidation of the combustible
elements of a fuel with heat release.
In combustion reactions, rapid oxidation of combustible elements
of the fuel results in energy release as combustion products are
formed.
The three major combustible chemical elements in most common
fuels are carbon, hydrogen, and sulfur. Sulfur is usually a
relatively unimportant contributor to the energy released, but it
can be a significant cause of pollution and corrosion problems.
Combustion is complete when all the carbon present in the fuel is
burned to carbon dioxide, all the hydrogen is burned to water, all
the sulfur is burned to sulfur dioxide, and all other combustible
elements are fully oxidized. When these conditions are not
fulfilled, combustion is incomplete.
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COMBUSTION REACTIONS
The combustible elements in coal and fuel oil are carbon, hydrogen and
sulphur. The basic chemical equations for co1nplete combustion are
C + O2 → CO2
2H2 + O2 →2H2O
S + O2 → SO2
When insufficient oxygen is present, the carbon will be burned incompletely
with the formation of carbon monoxide.
2C + O2 → 2CO
When dealing with chemical reactions, it is necessary to remember that mass
is conserved, so the mass of the products equals the mass of the reactants.
The total mass of each chemical element must be the same on both sides of
the equation, even though the elements exist in different chemical
compounds in the reactants and products.
However, the number of moles of products may differ from the number of
moles of reactants. for example. . . consider the complete combustion of
hydrogen with oxygen
1
29 1H2 O
+ 2 2
→ 1H2 O
COMBUSTION REACTIONS
In this case, the reactants are hydrogen and oxygen. Hydrogen is
the fuel and oxygen is the oxidizer. Water is the only product of the
reaction.
The numerical coefficients in the equation, which precede the
chemical symbols to give equal amounts of each chemical element
on both sides of the equation, are called stoichiometric
coefficients. In words,
1
1 kmol H2 + kmol O2 → 1 kmol H2 O
2
Note that the total numbers of moles on the left and right sides of
are not equal. However, because mass is conserved, the total mass
of reactants must equal the total mass of products.
Since 1 kmol of H2 equals 2 kg, 1 kmol of O2 equals 16 kg, and 1/2
kmol of H2O equals 18 kg, the above equation can be interpreted
as stating
30 2 kg H2 + 16 kg O2 → 18 kg H2 O
COMBUSTION REACTIONS
ln order to bum a fuel completely, four basic conditions must be
fulfilled:
1. Supply enough air for complete combustion of fuel.
2. Secure enough turbulence for thorough mixing of fuel and air.
3. Maintain a furnace temperature high enough to ignite the
incoming fuel air mixture.
4. Provide a furnace volume large enough to allow time for
combustion to be completed.
Apart from adequate air supply, the three T's, viz., time,
temperature and turbulence have to be kept in mind while
designing a furnace.
Since the complete mixing of the fuel and air is virtually
impossible, excess air must be supplied to ensure complete
combustion. The greater is the rate of mixing or turbulence, the
lower would be the excess air required.
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FUELS
A fuel is simply a combustible substance.
In this chapter emphasis is on hydrocarbon
fuels, which contain hydrogen and carbon.
Sulfur and other chemical substances also
may be present.
Hydrocarbon fuels are denoted by the
general formula CnHm.
Hydrocarbon fuels exist in all phases, some
examples being coal, gasoline, and natural
gas
Liquid hydrocarbon fuels are commonly
derived from crude oil through distillation
and cracking processes. Examples are
gasoline, diesel fuel, kerosene, and other
types of fuel oils.
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FUELS
Most liquid fuels are mixtures of hydrocarbons for which
compositions are usually given in terms of mass fractions. For
simplicity in combustion calculations, gasoline is often modeled as
octane, C8H18, and diesel fuel as dodecane, C12H26.
Gaseous hydrocarbon fuels are obtained from natural gas wells or
are produced in certain chemical processes. Natural gas normally
consists of several different hydrocarbons, with the major
constituent being methane, CH4. The compositions of gaseous fuels
are usually given in terms of mole fractions.
The main constituent of coal is carbon. Coal also contains varying
amounts of oxygen, hydrogen, nitrogen, sulfur, moisture, and ash.
It is difficult to give an exact mass analysis for coal since its
composition varies considerably from one geographical area to the
next and even within the same geographical location.
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FUELS
For combustion calculations, the composition of coal is usually
expressed as an ultimate analysis.
The ultimate analysis gives the composition on a mass basis in terms
of the relative amounts of chemical elements (carbon, sulfur,
hydrogen, nitrogen, oxygen) and ash.
Most liquid hydrocarbon fuels are a mixture of numerous
hydrocarbons and are obtained from crude oil by distillation.
The most volatile hydrocarbons vaporize first, forming what we
know as gasoline. The less volatile fuels obtained during distillation
are kerosene, diesel fuel, and fuel oil.
The composition of a particular fuel depends on the source of the
crude oil as well as on the refinery.
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FUELS
Although liquid hydrocarbon fuels are mixtures of many different
hydrocarbons, they are usually considered to be a single
hydrocarbon for convenience.
For example, gasoline is treated as octane, C8H18, and the diesel
fuel as dodecane, C12H26. Another common liquid hydrocarbon
fuel is methyl alcohol, CH3OH, which is also called methanol and
is used in some gasoline blends. The gaseous hydrocarbon fuel
natural gas, which is a mixture of methane and smaller amounts of
other gases, is often treated as methane, CH4, for simplicity.
Natural gas is produced from gas wells or oil wells rich in natural
gas. It is composed mainly of methane, but it also contains small
amounts of ethane, propane, hydrogen, helium, carbon dioxide,
nitrogen, hydrogen sulfate, and water vapor.
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COMBUSTION AIR
Oxygen is required in every combustion reaction. Pure oxygen is
used only in special applications such as cutting and welding.
In most combustion applications, air provides the needed oxygen.
On a mole or a volume basis, dry air is composed of 20.9 percent
oxygen, 78.1 percent nitrogen, 0.9 percent argon, and small amounts
of carbon dioxide, helium, neon, and hydrogen.
In the analysis of combustion processes, the argon in the air is
treated as nitrogen, and the gases that exist in trace amounts are
disregarded.
Then dry air can be approximated as 21 percent oxygen and 79
percent nitrogen by mole numbers. Therefore, each mole of oxygen
entering a combustion chamber is accompanied by 0.79/0.21 = 3.76
mol of nitrogen.
The coefficient 2 before the term (O2 + 3.76N2) is the number of moles
of oxygen in the combustion air, per mole of fuel, and not the amount
of air. The amount of combustion air is 2 moles of oxygen plus 2 x 3.76
moles of nitrogen, giving a total of 9.52 moles of air per mole of fuel.
Thus, for the reaction given, the air–fuel ratio on a molar basis is 9.52.
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THEORETICAL AIR
The air–fuel ratio on a mass basis can be calculated as
Normally the amount of air supplied is either greater or less than the
theoretical amount.
The amount of air actually supplied is commonly expressed in terms of
the percent of theoretical air. For example, 150% of theoretical air
means that the air actually supplied is 1.5 times the theoretical amount
of air.
The amount of air supplied can be expressed alternatively as a percent
excess or a percent deficiency of air. Thus, 150% of theoretical air is
equivalent to 50% excess air, and 80% of theoretical air is the same as
a 20% deficiency of air.
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THEORETICAL AIR
for example.. . consider the complete combustion of methane with
150% theoretical air (50% excess air). The balanced chemical
reaction equation is
In this equation, the amount of air per mole of fuel is 1.5 times the
theoretical amount determined previously. Accordingly, the air–fuel
ratio is 1.5 times higher.
Since complete combustion is assumed, the products contain only
carbon dioxide, water, nitrogen, and oxygen. The excess air supplied
appears in the products as uncombined oxygen and a greater amount of
nitrogen than the equation based on the theoretical amount of air.
The equivalence ratio is the ratio of the actual fuel–air ratio to the
fuel–air ratio for complete combustion with the theoretical amount
of air. The reactants are said to form a lean mixture when the
equivalence ratio is less than unity. When the ratio is greater than
unity, the reactants are said to form a rich mixture.
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E X A M P L E 1. Determining the Air–Fuel Ratio
Determine the air–fuel ratio on both a molar and mass basis for the
complete combustion of octane, C8H18, with (a) the theoretical
amount of air, (b) 150% theoretical air (50% excess air).
Analysis:
(a) For complete combustion of C8H18 with the theoretical amount of
air, the products contain carbon dioxide, water, and nitrogen only.
That is
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E X A M P L E 1. Determining the Air–Fuel Ratio
46
Example 2
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Dew Point Temperature
The saturation temperature at the partial pressure of water vapour is
called the dew point temperature (d.p.t.).
The partial pressure of water vapour in the mixture of gases
constituting the flue gas is given by
𝑃𝐻2 𝑂 = 𝑥𝐻2 𝑂 𝑃
where P is the total pressure of the exhaust gas mixture and is 𝑥𝐻2 𝑂 is
the mole fraction of water vapour in the exhaust gas mixture
𝑛𝐻2 𝑂
𝑥𝐻2 𝑂 =
𝑛𝑡𝑜𝑡𝑎𝑙
The flue gases arc cooled in heat exchangers like economizer and air
preheater so as to minimize the exhaust losses through chimney. These
gases, however, should never be cooled below the dew point
temperature. If cooled below the d.p.t., the water vapour condenses
into liquid droplets which react with S02 or S03 to form acid. This acid
corrodes the metal surfaces of the ducts through which the flue gas
48 flows
Example 3
Ethane (C2H6) is burned with 20 percent excess air during a
combustion process, as shown in Fig. below. Assuming complete
combustion and a total pressure of 100 kPa, determine (a) the air–
fuel ratio and (b) the dew-point temperature of the products
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Example 3
(a) The air–fuel ratio is determined by taking the ratio of the mass
of the air to the mass of the fuel,
That is, 19.3 kg of air is supplied for each kilogram of fuel during
this combustion process.
(b) The dew-point temperature of the products is the temperature at
which the water vapor in the products starts to condense as the
products are cooled at constant pressure.
The dew-point temperature of a gas–vapor mixture is the saturation
temperature of the water vapor corresponding to its partial pressure.
Therefore, we need to determine the partial pressure of the water
vapor Pv in the products first. Assuming ideal-gas behavior for the
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combustion gases, we have
Example 3
52
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air
A certain natural gas has the following volumetric analysis: 72
percent CH4, 9 percent H2, 14 percent N2, 2 percent O2, and 3
percent CO2. This gas is now burned with the stoichiometric
amount of air that enters the combustion chamber at 20°C, 1
atm, and 80 percent relative humidity. Assuming complete
combustion and a total pressure of 1 atm, determine the dew-
point temperature of the products.
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EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air
Assumptions 1 The fuel is burned completely and thus all the carbon in
the fuel burns to CO2 and all the hydrogen to H2O. 2 The fuel is burned
with the stoichiometric amount of air and thus there is no free O2 in the
product gases. 3 Combustion gases are ideal gases.
Properties The saturation pressure of water at 20oC is 2.3392 kPa
Analysis We note that the moisture in the air does not react with
anything; it simply shows up as additional H2O in the products.
Therefore, for simplicity, we balance the combustion equation by using
dry air and then add the moisture later to both sides of the equation.
54
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air
55
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air
56
EXAMPLE 4. Combustion of a Gaseous Fuel with Moist Air
57
DETERMINING PRODUCTS OF COMBUSTION
Combustion is the result of a series of very complicated and rapid
chemical reactions, and the products formed depend on many factors.
When fuel is burned in the cylinder of an internal combustion engine,
the products of the reaction vary with the temperature and pressure in
the cylinder.
In combustion equipment of all kinds, the degree of mixing of the fuel
and air is a controlling factor in the reactions that occur once the fuel
and air mixture is ignited.
Although the amount of air supplied in an actual combustion process
may exceed the theoretical amount, it is not uncommon for some
carbon monoxide and unburned oxygen to appear in the products. This
can be due to incomplete mixing, insufficient time for complete
combustion, and other factors.
When the amount of air supplied is less than the theoretical amount of
air, the products may include both CO2 and CO, and there also may be
58
unburned fuel in the products.
DETERMINING PRODUCTS OF COMBUSTION
The products of combustion of an actual combustion process and
their relative amounts can be determined only by measurement.
Among several devices for measuring the composition of products
of combustion are the Orsat analyzer, gas chromatograph, infrared
analyzer, and flame ionization detector. Data from these devices
can be used to determine the mole fractions of the gaseous products
of combustion.
The analyses from these devices are often reported on a “dry” basis.
In a dry product analysis, the mole fractions are given for all
gaseous products except the water vapor.
If the gaseous products of combustion are cooled at constant
mixture pressure, the dew point temperature is reached when water
vapor begins to condense. Since water deposited on duct work,
mufflers, and other metal parts can cause corrosion, knowledge of
the dew point temperature is important
59
Example 5
A natural gas has the following molar analysis:
CH4, 80.62%; C2H6, 5.41%; C3H8, 1.87%; C4H10, 1.60%; N2, 10.50%.
The gas is burned with dry air, giving products having a molar
analysis on a dry basis:
CO2, 7.8%; CO, 0.2%; O2, 7%; N2, 85%.
(a) Determine the air–fuel ratio on a molar basis.
(b) Assuming ideal gas behavior for the fuel mixture, determine the
amount of products in kmol that would be formed from 100 m3 of
fuel mixture at 300 K and 1 bar.
(c) Determine the percent of theoretical air.
60
Example 5
Analysis:
(a) The solution can be conducted on the basis of an assumed amount
of fuel mixture or on the basis of an assumed amount of dry products.
Let us illustrate the first procedure, basing the solution on 1 kmol of
fuel mixture. The chemical equation then takes the form
giving a = 2.892.
The balanced chemical equation is then
62
Example 5
(b) By inspection of the chemical reaction equation, the total amount
of products is b + c = 12.931 + 1.93 = 14.861 kmol of products per
kmol of fuel. The amount of fuel in kmol, nF, present in 100 m3 of fuel
mixture at 300 K and 1 bar can be determined from the ideal gas
equation of state as
63
Example 5
The theoretical air–fuel ratio on a molar basis is
64
Example 6
Octane (C8H18) is burned with dry air. The volumetric analysis of
the products on a dry basis is
65
Example 6
Analysis: Note that we know the relative composition of the
products, but we do not know how much fuel or air is used during the
combustion process. However, they can be determined from mass
balances. The H2O in the combustion gases will start condensing when
the temperature drops to the dewpoint temperature.
For ideal gases, the volume fractions are equivalent to the mole
fractions. Considering 100 kmol of dry products for convenience, the
combustion equation can be written as
66
Example 6
The O2 balance is not necessary, but it can be used to check the
values obtained from the other mass balances, as we did previously.
Substituting, we get
67
Example 6
68
Example 6
69
Enthalpy of Combustion and Enthalpy of Formation
Enthalpy of combustion hC, which represents the amount of heat
released during a steady-flow combustion process when 1 kmol (or 1
kg) of fuel is burned completely at a specified temperature and
pressure . It is expressed as
72
Enthalpy of Combustion and Enthalpy of Formation
The heating value depends on the phase of
the H2O in the products.
The heating value is called the higher
heating value (HHV) when the H2O in the
products is in the liquid form, and it is
called the lower heating value (LHV)
when the H2O in the products is in the
vapor form. The two heating values are
related by
76
FIRST-LAW ANALYSIS OF REACTING SYSTEMS
When the changes in kinetic and potential energies are negligible,
the steady-flow energy balance relation 𝐸ሶ 𝑖𝑛 = 𝐸ሶ 𝑜𝑢𝑡 can be
expressed for a chemically reacting steady-flow system more
explicitly as
77
FIRST-LAW ANALYSIS OF REACTING SYSTEMS
where Nr and Np represent the number of moles of the reactant r
and the product p, respectively, per mole of fuel. Note that Nr = 1
for the fuel, and the other Nr and Np values can be picked directly
from the balanced combustion equation.
Taking heat transfer to the system and work done by the system to
be positive quantities, the energy balance relation just discussed can
be expressed more compactly as
78
FIRST-LAW ANALYSIS OF REACTING SYSTEMS
A combustion chamber normally involves heat output but no heat
input. Then the energy balance for a typical steady-flow combustion
process becomes
79
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion
Liquid propane (C3H8) enters a combustion chamber at 25°C at a
rate of 0.05 kg/min where it is mixed and burned with 50 percent
excess air that enters the combustion chamber at 7°C, as shown in
the Fig. An analysis of the combustion gases reveals that all the
hydrogen in the fuel burns to H2O but only 90 percent of the carbon
burns to CO2, with the remaining 10 percent forming CO. If the exit
temperature of the combustion gases is 1500 K, determine (a) the
mass flow rate of air and (b) the rate of heat transfer from the
combustion chamber.
80
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion
Analysis
We note that all the hydrogen in the fuel burns to H2O but 10
percent of the carbon burns incompletely and forms CO. Also, the
fuel is burned with excess air and thus there is some free O2 in the
product gases.
The theoretical amount of air is determined from the stoichiometric
reaction to be
81
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion
82
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion
83
EXAMPLE 8. First-Law Analysis of Steady-Flow Combustion
84
ADIABATIC FLAME TEMPERATURE
In the absence of any work interactions and any changes in kinetic
or potential energies, the chemical energy released during a
combustion process either is lost as heat to the surroundings or is
used internally to raise the temperature of the combustion products.
The smaller the heat loss, the larger the temperature rise.
In the limiting case of no heat loss to the surroundings (Q = 0), the
temperature of the products reaches a maximum, which is called
the adiabatic flame or adiabatic combustion temperature of the
reaction
Fig. The temperature of a
combustion chamber becomes
maximum when combustion is
complete and no heat is lost to the
surroundings (Q = 0).
85
ADIABATIC FLAME TEMPERATURE
The adiabatic flame temperature of a steady-flow combustion
process is determined by setting Q = 0 and W = 0. It yields
Once the reactants and their states are specified, the enthalpy of
the reactants Hreact can be easily determined. The calculation of the
enthalpy of the products Hprod is not so straightforward, however,
because the temperature of the products is not known prior to the
calculations.
Therefore, the determination of the adiabatic flame temperature
requires the use of an iterative technique unless equations for the
sensible enthalpy changes of the combustion products are
available.
86
ADIABATIC FLAME TEMPERATURE
A temperature is assumed for the product gases, and the Hprod is
determined for this temperature. If it is not equal to Hreact, calculations
are repeated with another temperature. The adiabatic flame temperature
is then determined from these two results by interpolation.
When the oxidant is air, the product gases mostly consist of N2, and a
good first guess for the adiabatic flame temperature is obtained by
treating the entire product gases as N2.
In combustion chambers, the highest temperature to which a material
can be exposed is limited by metallurgical considerations. Therefore, the
adiabatic flame temperature is an important consideration in the design
of combustion chambers, gas turbines, and nozzles.
The maximum temperatures that occur in these devices are considerably
lower than the adiabatic flame temperature, however, since the
combustion is usually incomplete, some heat loss takes place, and some
combustion gases dissociate at high temperatures
The maximum temperature in a combustion chamber can be controlled
87 by adjusting the amount of excess air, which serves as a coolant.
Example 9. Adiabatic Flame Temperature in Steady
Combustion
Liquid octane (C8H18) enters the combustion chamber of a gas
turbine steadily at 1 atm and 25°C, and it is burned with air
that enters the combustion chamber at the same state, as
shown in Fig. below. Determine the adiabatic flame
temperature for (a) complete combustion with 100 percent
theoretical air, (b) complete combustion with 400 percent
theoretical air, and (c) incomplete combustion (some CO in
the products) with 90 percent theoretical air.
88
Example 9. Adiabatic Flame Temperature in Steady
Combustion
89
Example 9. Adiabatic Flame Temperature in Steady
Combustion
92
Exercises
1. Propylene (C3H6) is burned with 50 percent excess air during a
combustion process. Assuming complete combustion and a
total pressure of 105 kPa, determine (a) the air–fuel ratio and
(b) the temperature at which the water vapor in the products
will start condensing.
2. One kilogram of butane (C4H10) is burned with 25 kg of air
that is at 30°C and 90 kPa. Assuming that the combustion is
complete and the pressure of the products is 90 kPa, determine
(a) the percentage of theoretical air used and (b) the dew-point
temperature of the products.
3. A certain natural gas has the following volumetric analysis: 65
percent CH4, 8 percent H2, 18 percent N2, 3 percent O2, and 6
percent CO2. This gas is now burned completely with the
stoichiometric amount of dry air. What is the air–fuel ratio for
93 this combustion process?
Exercises
4. A certain coal has the following analysis on a mass basis: 82
percent C, 5 percent H2O, 2 percent H2, 1 percent O2, and 10
percent ash. The coal is burned with 50 percent excess air.
Determine the air–fuel ratio.
5. Methane (CH4) is burned with dry air. The volumetric analysis
of the products on a dry basis is 5.20 percent CO2, 0.33 percent
CO, 11.24 percent O2, and 83.23 percent N2. Determine (a) the
air–fuel ratio and (b) the percentage of theoretical air used.
6. Liquid propane (C3H8) enters a combustion chamber at 25°C at
a rate of 1.2 kg/min where it is mixed and burned with 150
percent excess air that enters the combustion chamber at 12°C.
If the combustion is complete and the exit temperature of the
combustion gases is 1200 K, determine (a) the mass flow rate
of air and (b) the rate of heat transfer from the combustion
94 chamber.
Exercises
7. Ethane gas (C2H6) at 25°C is burned in a steady-flow
combustion chamber at a rate of 5 kg/h with the stoichiometric
amount of air, which is preheated to 500 K before entering the
combustion chamber. An analysis of the combustion gases
reveals that all the hydrogen in the fuel burns to H2O but only
95 percent of the carbon burns to CO2, the remaining 5 percent
forming CO. If the products leave the combustion chamber at
800 K, determine the rate of heat transfer from the combustion
chamber.
8. Diesel fuel (C12H26) at 25°C is burned in a steady flow
combustion chamber with 20 percent excess air that also enters
at 25°C. The products leave the combustion chamber at 500 K.
Assuming combustion is complete, determine the required
mass flow rate of the diesel fuel to supply heat at a rate of
95
2000 kJ/s.
Exercises
9. Acetylene gas (C2H2) at 25°C is burned during a steady-flow
combustion process with 30 percent excess air at 27°C. It is
observed that 75,000 kJ of heat is being lost from the
combustion chamber to the surroundings per kmol of
acetylene. Assuming combustion is complete, determine the
exit temperature of the product gases.
10. Hydrogen (H2) at 7°C is burned with 20 percent excess air that
is also at 7°C during an adiabatic steady-flow combustion
process. Assuming complete combustion, determine the exit
temperature of the product gases.
96
End of Lecture 3
Next Lecture
Lecture 4: Steam Generators (Boilers)
97