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Solid Fuels
Thermal Systems/Fuels
Coal classification
Anthracite: hard and geologically the
oldest
Bituminous
Lignite: soft coal and the youngest
Further classification: semi- anthracite,
semi-bituminous, and sub-bituminous
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UNEP 2006
Type of Fuels
Solid Fuels
Thermal Systems/Fuels
Physical properties
Heating or calorific value (GCV)
Moisture content
Volatile matter
Ash
Chemical properties
Chemical constituents: carbon, hydrogen,
oxygen, sulphur
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UNEP 2006
Type of Fuels
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UNEP 2006
Type of Fuels
Moisture content
% of moisture in fuel (0.5 10%)
Reduces heating value of fuel
Weight loss from heated and then cooled powdered
raw coal
Volatile matter
Methane, hydrocarbons, hydrogen, CO, other
Typically 25-35%
Easy ignition with high volatile matter
Weight loss from heated then cooled crushed coal
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UNEP 2006
Type of Fuels
Ash
Impurity that will not burn (5-40%)
Important for design of furnace
Ash = residue after combustion
Fixed carbon
Fixed carbon = 100 (moisture + volatile matter +
ash)
Carbon + hydrogen, oxygen, sulphur, nitrogen
residues
Heat generator during combustion 11
UNEP 2006
Type of Fuels
Proximate analysis
Typical proximate analysis of various coals
(%)
Indian Indonesian South African
Coal Coal Coal
Moisture 5.98 9.43 8.5
Ultimate analysis
Typical ultimate analysis of coal (%)
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Usage
Used extensively in industrial applications
Examples
Furnace oil
Light diesel oil
Petrol
Kerosine
Ethanol
LSHS (low sulphur heavy stock)
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Density
Ratio of the fuels mass to its volume at 15 oC,
kg/m3
Useful for determining fuel quantity and quality
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Specific gravity
Ratio of weight of oil volume to weight of same
water volume at a given temperature
Specific gravity of water is 1
Hydrometer used to measure
Liquid Fuels
Thermal Systems/Fuels
Viscosity
Measure of fuels internal resistance to flow
Most important characteristic for storage and use
Decreases as temperature increases
Flash point
Lowest temperature at which a fuel can be
heated so that the vapour gives off flashes when an
open flame is passes over it
Flash point of furnace oil: 66oC
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Pour point
Lowest temperature at which fuel will flow
Indication of temperature at which fuel can be
pumped
Specific heat
kCal needed to raise temperature of 1 kg oil by
1oC (kcal/kgoC)
Indicates how much steam/electricity it takes to
heat oil to a desired temperature
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Calorific value
Heat or energy produced
Gross calorific value (GCV): vapour is fully
condensed
Net calorific value (NCV): water is not fully
condensed
Liquid Fuels
Thermal Systems/Fuels
Sulphur content
Depends on source of crude oil and less on the
refining process
Furnace oil: 2-4 % sulphur
Sulphuric acid causes corrosion
Ash content
Inorganic material in fuel
Typically 0.03 - 0.07%
Corrosion of burner tips and damage to
materials /equipments at high temperatures
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Carbon residue
Tendency of oil to deposit a carbonaceous solid
residue on a hot surface
Residual oil: >1% carbon residue
Water content
Normally low in furnace oil supplied (<1% at
refinery)
Free or emulsified form
Can damage furnace surface and impact flame
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Storage of fuels
Store in cylindrical tanks above or below
the ground
Recommended storage: >10 days of
normal consumption
Cleaning at regular intervals
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UNEP 2006
Type of Fuels
Liquid Fuels
Thermal Systems/Fuels
Gaseous Fuels
Thermal Systems/Fuels
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UNEP 2006
Type of Fuels
Gaseous Fuels
Thermal Systems/Fuels
Gaseous Fuels
Thermal Systems/Fuels
Calorific value
Fuel should be compared based on the net
calorific value (NCV), especially natural gas
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UNEP 2006
Type of Fuels
Gaseous Fuels
Thermal Systems/Fuels
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UNEP 2006
Type of Fuels
Gaseous Fuels
Thermal Systems/Fuels
Natural gas
Methane: 95%
Remaing 5%: ethane, propane, butane,
pentane, nitrogen, carbon dioxide, other gases
High calorific value fuel
Does not require storage facilities
No sulphur
Mixes readily with air without producing smoke or
soot
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UNEP 2006
Type of Fuels
Comparing Fuels
Thermal Systems/Fuels
Sulphur 3 0.41 -
Oxygen 1 9.89 Trace
Nitrogen Trace 1.22 0.75
Ash Trace 38.63 -
Water Trace 5.98 -
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UNEP 2006
Performance Evaluation
Principles of Combustion
Thermal Systems/Fuels
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UNEP 2006
Performance Evaluation
Principles of Combustion
Thermal Systems/Fuels
1T) Temperature
2T) Turbulence
3T) Time
Principle of Combustion
Thermal Systems/Fuels
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Bureau of Energy Efficiency, India, 2004 UNEP 2006
Performance Evaluation
required
Stochiometric air needed for combustion of
furnace oil
Theoretical CO2 content in the flue gases
Actual CO2 content and % excess air
Constituents of flue gas with excess air
Theoretical CO2 and O2 in dry flue gas by
volume
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UNEP 2006
Performance Evaluation
Draft System
Thermal Systems/Fuels
Mechanical draft:
Artificially produced by fans
Three types a) balanced draft, b) induced draft and
c) forced draft
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UNEP 2006
Energy Efficiency Opportunities
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UNEP 2006
Energy Efficiency Opportunities
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UNEP 2006
Energy Efficiency Opportunities
Temperature Control of
Thermal Systems/Fuels
Combustion Oil
To prevent overheating
With reduced or stopped oil flow
Especially electric heaters
Using thermostats
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UNEP 2006
Energy Efficiency Opportunities
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UNEP 2006
Energy Efficiency Opportunities
Conditioning of coal:
Coal fines cause combustion problems
Segregation can be reduced by
conditioning coal with water
Decrease % unburnt carbon
Decrease excess air level required
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UNEP 2006
Energy Efficiency Opportunities
Blending of coal
Used with excessive coal fines
Blending of lumped coal with coal
containing fines
Limits fines in coal being fired to <25%
Ensures more uniform coal supply
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UNEP 2006
Energy Efficiency Opportunities
Combustion Controls
Thermal Systems/Fuels
48
(U2 U1) + (P2V2 P1V1) + g(Z2 Z1) +
(C22-C12) = Q-W
The terms on the left-hand side are
respectively the change in internal energy of
the fluid (u), the flow work involved in
propelling the fluid through the system (pv),
the change in potential energy of the fluid (z)
and finally its change in kinetic energy (c).
The work done by the system (W), in the
case of a boiler, is zero, so the right-hand
side of the equation represents the amount
of heat transferred into the system (Q).
49
The changes in potential and kinetic
energy of the fluid can be considered
negligible, so equation (1) simplifies to:
(U2 - U1) + (P2V2 P1V1) = Q
The enthalpy of the fluid, H, is given by
H = U+PV
leading to a final form of the steady flow
equation:
H2 H1 =Q (2)
50
This simple expression relates the heat
transferred across the boundary of the
system to the change in enthalpy of the
fluid as it enters and leaves the system.
We will see later how it leads to a very
convenient method of measuring the
efficiency of a boiler.
We can approach this problem by
considering separately the enthalpies of
the reactants and the products. 51
3. Enthalpy of a Mixture of
Gases
A change in the enthalpy of the reactants
can be calculated by summing the enthalpy
changes of each of the constituent gases.
The change in enthalpy of a gas as a
function of temperature is given by
H = cp (t)
Which would at first sight appear to give a
straight line relationship between enthalpy
change and temperature difference.
52
The temperature changes which occur in
combustion are considerable; nitrogen, for
example, could enter the combustion system at
ambient temperature (25) and be heated in
the flame to around 2,000.
At the lower temperature nitrogen has a specific
heat at constant pressure of 1.04 kJ/kg/K, rising
to 1.30 kJ/kg/K at flame temperature.
All gases have values of cp which increase with
temperature, hence a property diagram relating
the enthalpy of the reactants HR to their
temperature will be curve similar to that in Fig.
3.2 (next slide).
53
The enthalpy change of the mixture can be
obtained by summing the changes of each of
its constituents, an equation describing the
curve is
H25
At any given temperature, the vertical
distance between the two curves in Fig.
3.3 represents the enthalpy released by
the combustion process.
In general the magnitude of this quantity
will depend on the temperature chosen.
The standard temperature adopted is 25
and the quantity H25 is the enthalpy of
combustion for the fuel in question.
58
Some examples of enthalpy of
combustion for gaseous fuels are given in
Table 3.1.
Table 3.1 Standard enthalpies of combustion
Fuel H25 (kJ/kmol)
Hydrogen (H2) -241,800
Methane (CH4) -802,300
Propane (C3H8) -2,045,400
Acetylene (C2H2) -1,256,400
59
The combustion of all the above fuels will
produce water in the flue gases, which can
be considered as existing in either the
liquid or vapor phases.
All the figures quoted for the enthalpy of
combustion given above are for water in
the vapor phase.
Should the enthalpy of combustion be
required with water in the liquid phase,
then the latent heat of evaporation for the
water vapor produced in the combustion
products (Hfg) must be accounted for:
60
(H ) = (H ) n H
The latent heat at 25 has a value of 44,000
kJ/kmol of water produced.
Example 1:
the value of H25 for methane is -802,300 kJ/kmol
with water in the vapor phase. Calculate H25 for
the case when all the water vapor is condensed.
Solution:
the relevant stoichiometric combustion equation
for methane is:
CH4 + 2 O2 CO2 + 2 H2O
i.e. 2 kmoles of water vapor are produced for
each kmole of fuel burnt.
(H25 )f = (H25 )g 2 Hfg
= -802,300 2 44,000
= -890,300 kJ/kmol
61
5. Constant-volume
Combustion
The heat released when a solid or liquid
fuel is burnt is measured by burning a
sample of the fuel at constant volume,
hence it is important to look at the
thermodynamics of this process as well as
that of combustion at constant pressure.
Internal combustion engine (vehicles) is a
constant-volume combustion system.
62
6. Internal Energy of
Combustion
The combustion of a mixture of fuel and air at
constant volume is most easily envisaged as taking
place inside a rigid closed container.
The First Law energy equation for a closed system is:
(U2 U1) = Q W (3)
As the system boundary is fixed, no work can cross
it, hence equation (3) becomes:
(U2 U1) = Q
The change in internal energy can be related to
temperature rise by: U = cV (t)
Thus we can plot an internal energy-temperature
diagram for the reactants and products of
combustion in the same way as an enthalpy-
temperature plot was made in section 3. (Fig. 3.4,
63
next slide)
internal
U25
energy
The curves of Fig. 3.4 are described by:
U R (m cv ) R (t ) and
U P (m cv ) P (t )
Once again, at any given temperature the
internal energy of the products must be less than
that of the reactants (since heat has left the
system).
The difference between the two curves at the
reference temperature of 25 is referred to as
the internal energy of combustion for that fuel.
65
Each fuel will have two values for
internal energy of combustion: one
for water in the vapor phase and one
for water in the liquid phase.
The two values will differ by the
internal energy of evaporation (Ufg) of
water at 25, which is 37,602
kJ/kmol.
66
7. Relationship between H25 and
U25
These two quantities are associated with
fuel types, because calorific measurements
are usually performed at constant pressure
for a gaseous fuel, and at constant volume
for liquid and solid fuels.
As all types of fuels are burned at constant
pressure in heating plants, the question
naturally arises as to the nature and
magnitude of the difference between the
two values.
67
H 25 ( H P H R ) 25 and
H U PV
We get H 25 (U P U R ) ( PV ) P ( PV ) R
R
H 25 (U P U ) U
25
( PV) P ( (PV
PV ))R
P ( PV ) R
U 25 ( PV ) P ( PV ) R
The (PV) terms for solids and liquids are
very small, so for any reactant or product
in the gas phase:
PV = nRT
hence:
H25 = U25 + RT (nP - nR)
where nP and nR represent the total
number of kmoles of combustion68 products
If nP = nR, then H25 and U25 will have the same
value.
Example 2:
H25 for propane (C3H8) is -2,045,400 kJ/kmol with
water in the vapor phase. Calculate the
corresponding internal energy of combustion.
Solution:
We can write the stoichiometric equation for
propane ignoring the presence of nitrogen and any
excess oxygen as they will appear in both the
reactants and the products:
H25 =CU + RT (nP -3nCO
3H825+ 5 O2 R ) 2 + 4 H2 O
So -2,045,400
nP n= U25 + (8.314 298 1)
R = 7 6 = 1
U25 = -2,047,878 kJ/kmol
In conclusion, there is normally little numerical
difference between the enthalpy and internal energy
of combustion of a fuel.
However, the phase of any water produced by 69
8. Calorific
Values
The terms enthalpy of combustion and internal
energy of combustion have precise
thermodynamic definitions.
However, in more practical situations engineers
generally use calorific values as a measure of the
heat released when unit quantity of a fuel is
burned.
The calorific value for a liquid fuel measured at
constant volume differs from its internal energy of
combustion.
Such discrepancies are small.
70
The calorific value of a fuel is normally expressed
as kJ (or MJ) per m3 (gaseous fuels) or kJ (MJ) per
kg which is applicable to all types of fuel.
If the calorific value includes the latent heat of
condensation of the water produced it is usually
referred to as the gross calorific value, where as
if the water is in the vapor phase, the term net
calorific value is used.
The expressions higher calorific value and
lower calorific value are also in use.
71
A fuel can have four calorific values:
(1)gross calorific value at constant volume;
(2)gross calorific value at constant pressure;
(3)net calorific value at constant volume;
(4)net calorific value at constant pressure.
The numerical values of (1) and (3) correspond
closely to the two values of U25 while the values
of (2) and (4) are close to the two values for H25.
72
The value for hfg for water at 25 is 2,442 kJ/kg.
Example 3:
A liquid fuel consists of 86% carbon and 14%
hydrogen (by mass). Its gross calorific value is 43.5
MJ/kg. calculate the net calorific value.
Solution:
H2 + O2 H2O
hence 2 kg hydrogen produce 18 kg water vapor. The
mass of water vapor produced by the combustion of 1
kg fuel is thus
0.14 9 = 1.26 kg
the net calorific value of the fuel is then
43.5 1.26 2.442 = 40.42 MJ/kg
73
On a per kilogram basis, hydrogen has a much higher
calorific value than carbon. Carbon has a calorific
value of 32.8 MJ/kg whereas molecular hydrogen has a
net calorific value of 120.9 MJ/kg.
The calorific value of a hydrocarbon fuel cannot be
predicted with any degree of accuracy from these
figures, but there is an implicit suggestion that the
calorific value of a fuel may be roughly related to the
relative quantities of carbon and hydrogen from which
it is made up.
The broad trend is illustrated in Fig. 3.5 (next slide).
The C:H ratio range runs from anthracite and
bituminous coal (the highest C:H ratio) to natural gas
(the lowest).
74
A much more consistent trend is exhibited by the
liquid and gaseous fuels, which have a much
higher proportion of hydrogen than do coals.
Fig. 3.6 (next slide) show the gross calorific
values of these fuels as a function of their C:H
ratio.
Residual fuel oils (H, M, and Z)
Distillate oil (G and K)
Propane (P)
Natural gas (N)
76
It is possible to obtain a rough estimate of the
calorific value of a solid or liquid fuel from its
ultimate analysis and the calorific values of its
combustible constituents.
For this purpose, the relevant gross calorific
values are:
carbon 33.9 MJ/kg
hydrogen 144.4 MJ/kg
sulfur 9.4 MJ/kg
O
CV 33.9C calorific
The estimated 9.4is
144.4 H - value S given by
8
79
When Steady-State conditions are
obtained, the heat released by
burning the fuel is calculated from
the temperature rise of the cooling
water and its mass flow rate.
The apparatus is designed so that
the average of the starting and
finishing gas temperatures is close to
the reference value of 25.
80
This temperature is well below the dew
point of the combustion products, so
the value measured is the gross
calorific value of the fuel.
Not all the water vapor generated in
the combustion of the fuel may
condense out in the calorimeter, but
this can be corrected for by supplying
the calorimeter with near-saturated air.
81
The calorific value of a liquid or solid fuel
is measured in the bomb calorimeter (Fig.
3.8,).
This device consists of a spherical vessel
containing a small sample of the fuel in an
atmosphere of pressurized oxygen.
The bomb is immersed in an isolated
water bath which acts as the calorimeter
for the heat released when combustion is
initiated.
82
The temperature change in the water is
measured by a sensitive thermometer,
and knowing the thermal capacity of the
apparatus the heat released can be
determined.
Once again, the temperature rise is
arranged to take place from just below, to
just above the reference temperature of
25 with a maximum rise of about 4.
84
In practice, the thermal capacity of
the apparatus is evaluated
experimentally by burning a known
quantity of a reference fuel, typically
benzoic acid, in the device.
A quantity of water is introduced into
the bomb to ensure saturation,
hence the condensation of all the
water produced by combustion of the
fuel. 85