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Contents
Fuel types
Coal: its classification, and analysis
Coal properties
Combustion reactions
Mechanism of Coal combustion
Enthalpy of combustion and Flame temperature
Coal firing : Stoker, Pulverized, Cyclone and Fluidized bed.
Coal gasification.
Fuels
Fuels are substances which, when heated, undergo chemical reaction with an
oxidizer, typically oxygen, to liberate heat.
Fuels may be solid, liquid or gaseous
Fuels may be fossil (non-renewable) or biomass (renewable)
Fossil fuels may be coal, petroleum-crude derived or natural gas.
Biomass fuels may be wood, refuse or agricultural residues.
Solid fuel embraces a wide variety of combustibles, ranging from wood, peat and
lignite, through refuse and other low calorific value substances, to coal and other
solid fuels derived from it.
Coal represents by far the largest component of the worlds fossil fuel reserves.
The carbon: hydrogen ratio of coal is the highest of the fossil fuels, hence the
calorific values of coals are principally determined by the carbon in the fuel.
1 BTU = 1.055 KJ
Ash
Volatile matter
Fixed carbon
Typically 25-35%
Coal classification
It is usual to consider coals in terms of their rank: in general, a high ranking coal
will have a high carbon content.
The other major coal constituent element, hydrogen, is present in hydrocarbons
which are released as volatile matter when the coal is heated.
As the rank of a coal increases, its carbon content increases from 75% to about 93%
(by weight), the hydrogen content decreases from 6% to 3%, and the oxygen content
decreases from 20% to 3%.
A useful method for analyzing a coal is the proximate analysis.
Coal Analysis
Proximate analysis of coal
Determines only fixed carbon, volatile matter, moisture and ash
Useful to find out heating value (GCV)
Simple analysis equipment
Ultimate analysis of coal
Determines all coal component elements: carbon, hydrogen, oxygen, sulphur,
other
Useful for furnace design (e.g flame temperature, flue duct design)
Laboratory analysis
Coal Analysis
Proximate analysis:
Sample of known mass, to determine:
Moisture dried at 105 to 110oC in an oven
Volatile combustible matter heated to 900oC in a covered crucible
Fixed carbon heated to 750oC in an open crucible
Ash the final residue
Coal Ranking
1.
2.
3.
4.
5.
6.
Peat
Lignite
Bituminous
Coal
Anthracite
Carbon
Volatile
matter
Moisture
Ash
44
57
82
65
50
25
20
15
2
4
4
5
90
Indonesian
Coal
South African
Coal
Moisture
5.98
9.43
8.5
Ash
38.63
13.99
17
Volatile
matter
20.70
29.79
23.28
Fixed
Carbon
34.69
46.79
51.22
Parameter
Moisture
Mineral Matter (1.1 x Ash)
Carbon
Hydrogen
Nitrogen
Sulphur
Oxygen
GCV (kCal/kg)
Indian Coal, %
5.98
38.63
41.11
2.76
1.22
0.41
9.89
Indonesian Coal, %
9.43
13.99
58.96
4.16
1.02
0.56
11.88
4000
5500
Coal properties
There are a number of properties which are important in identifying the suitability
of a coal for any given application:
Size
Some common size groups, together with their rather picturesque names, are given
in Table 1 (next slide).
Heating Value or Calorific value
Coal fuels generally have a range of values from 21 to 33 MJ/kg (gross).
Ash Fusion Temperature
Sulphur Content
Size
Table 1 Size distribution for coals
Name
Large Cobbles
Cobbles
Trebles
Doubles
Singles
>150
100-150
63-100
38-63
25-38
75
50-100
38-63
25-38
13-18
Heating Value
It is the heat transferred when the products of combustion of a
sample of coal are cooled to the initial temperature of air and
fuel.
The higher heating value (HHV) assumes that the water vapor
in the products condenses and includes the latent heat of
vaporization of the water vapor.
The lower heating value (LHV) assumes that the water vapor
formed by combustion leaves as vapor itself.
HHV of anthracite and bituminous coals approximately
determined from Dulong and Petit formula:
HHV = 33.83 C + 144.45 (H O/8) + 9.38 S in MJ/Kg;
where C, H, O are mass fractions in coal.
Heating Value
LHV = HHV mwhfg = HHV 2.395mw MJ/Kg
Where mw is the mass of water vapor formed given by
mw = M + 9H + gawa
Where M and H are the mass fractions of moisture and hydrogen
in the Coal, ga is the specific humidity of atmospheric air, and
wa is the actual amount of air supplied per Kg of coal.
For Energy balance, HHV is considered in the USA and LHV
in Europe.
Coal properties
Principles of combustion
Nitrogen: (a) reduces the combustion efficiency (b) forms NOx at high
temperatures
Water vapor is a by-product of burning fuel that contains hydrogen and this robs
heat from the flue gases
Combustion
When a solid fuel particle is exposed to a hot gas flowing stream it undergoes
three stages of mass loss
i.
Drying
ii.
Devolatilization
iii.
Char combustion
The relative significance of these three is indicated by proximate analysis of coal
homogeneous
combustion
volatiles
coal particle
p-coal, d=30-70m
char
heterogeneous
combustion
CO2, H2O,
CO2, H2O,
devolatilization
tdevolatile=1-5ms
tvolatiles=50-100ms
tchar=1-2sec
Drying
DEVOLATILIZATION
Occurs in the temperature range between 400 600 deg C.
Devolatilization or pyrolysis is the process where a wide range of gaseous
products are released through the decomposition of fuel.
The volatile matter (VM) comprises a number of hydrocarbons, which are
released in steps
Since the volatiles flow out of the solid through the pores, external oxygen
cannot penetrate into the particle, hence the devolatilization is referred to as the
pyrolysis stage.
A high yield of volatiles produces enough heat to ignite coke particles.
CHAR COMBUSTION
The combustion of a char particle generally starts after the evolution of volatiles
from the parent fuel particle, but sometimes the two processes overlap.
The char, being a highly porous substance, has a large number of internal pores of
varying size
Oxygen diffuses into the pores and oxidizes the carbon on the inner walls of the
pores.
The oxygen then undergoes an oxidation reaction with the carbon on the char
surface to produce CO.
The rate of diffusion of oxygen per unit surface area of the particle is given by Ficks
law:
rds max = kg cb
The burning rate or rate of reaction is given as
rsr = k cs
The maximum reaction rate will occur at cs = cb
rsr max = k cb
For rsd = rsr = rs
rsr
1
rs k g (c b )
c b
k
1/k 1/k g
Combustion Reactions
The basic chemical equations for complete combustion of coal
are
C O 2 CO 2
2H 2 O 2 2H 2 O
S O 2 SO2
With insufficie nt oxygen,
2C O 2 2CO
Stoichiometric Air
CO 2
12 kg
32 kg
44 kg
1kg
2.67 kg
3.67 kg
C kg
2.67 C kg
O2
2H 2
3.67 C kg
2H 2 O
4 kg
32 kg
36 kg
1 kg
8 kg
9 kg
H kg
8 H kg
9 H kg
O2
SO 2
32 kg
32 kg
64 kg
1 kg
1kg
2 kg
S kg
2 S kg
S kg
O2
Stoichiometric Air
Air contains 23.2 % oxygen by mass. Therefore, stoichiometric air required for
complete combustion of 1 kg of fuel is
Wt = WO2 / 0.232 = 11.5 C + 34.5 (H - O/8) + 4.3 S
where C, O, S, H are mass fractions of respective components.
The % excess air varies between 15 to 30 % for most large utility boilers.
Combustion equation
60
4
3.2
4.8
C H2
S
O2 aO2 3.76aN 2
12
2
32
32
bCO2 dCO eSO2 fO2 gN 2 hH 2 O
By equating the coefficients,
Carbon: b+d = 60/12 = 5 Hydrogen: h=2
Oxygen: b+d/2+e+f+h/2 = 4.8/32 + a
Actual Air
be
d
0.12;
0.02
bd e f g
bd e f g
f
g
0.04;
0.82
bd e f g
bd e f g
By solving these equations, the coefficients a,b,d,e,f, g and h are
determined and given to be d=0.73, b=4.27, f=1.46, a =7.045 and g =
26.49
Actual air supplied per kg coal = 32a/(0.232X100) = 9.72 kg.
The actual amount air supplied per kg fuel can be ascertained from the
measured volumetric composition using 1. Orsat analyser, 2) Haldane
apparatus, 3) Infra-red gas analyser 4) Gas chromatograph.
The fuel ratio of a fuel is the ratio of fixed carbon (FC) and VM contents of the
fuel.
This ratio has an important effect on the combustion efficiency of coal in a CFB
boiler
Higher ratios possibly leading to lower combustion efficiencies
A high rank fuel like anthracite has a higher fuel ratio than a low rank fuel like
lignite.
For this reason low-rank fuels (or low fuel ratio) like lignite and
bituminous have higher efficiencies than anthracite.
The fuel ratio is easily computed from the proximate analysis of a fuel
, dfg
12(CO CO)
2
C a b ( 4CO2 O2 700)
3(CO2 CO)
V fg
Wdfg WH 2O
Tg 273 101.325
X 22.4 X
X
18
pg
M dfg
273
The 1st law for the steady-state steady-flow (SSSF) for a chemically reactive
system, ignoring the changes in K.E and P.E is
HR + Q = HP + Wsf
Where HR and HP are the enthalpies of the reactants and products, evaluated at their
respective pressures and temperatures.
HR
mh(T
R,
p ); H P
mh(T
P,
p)
hf
298
p dT '
Enthalpy of Combustion
HV
(nMh(298K )) (nMh(298K ))
P
nMh(T
ad ,
p)
nMh(T
R,
p)
nMh(T
ad )
Chemical equilibrium
CO 2 O2 CO2
1
a
CO
(
1
a
)
CO
a
CO
O2
2
2
2 cold reactan ts
2 hot products
For constant U, V and m, which implies no heat and work interactions (isolated
system), the second law requires that the entropy change interior to the system:
dS 0
The composition of the system will spontaneously shift towards the point of
maximum entropy. Hence, the condition for chemical equilibrium can be written as
dS U ,V ,m 0
G H TS
At Equilibrium
dG 0
dG T , P,m 0
Gibbs function
For a mixture of ideal gases, the mole specific Gibbs function for the ith species is
given by
P
o
g i ,T g
i ,T
RuT ln io
P
g o i ,T
Where
is the Gibbs function of the pure species at the standard-state pressure
(i.e Pi=Po), and Pi is the partial pressure. The standard state pressure is taken to be 1
atm.
The Gibbs function for a mixture of ideal gas species can be expressed as
P
Gmix
N i g i ,T
N i [ g o i ,T RuT ln io ]
P
For a fixed temperature and pressure, the equilibrium condition becomes dGmix = 0.
P
P
dN i [ g o i ,T RuT ln io ]
N i d [ g o i ,T RuT ln io ] 0
P
P
The second term is zero since changes in partial pressures must sum to zero. Thus
P
dGmix
dN i [ g o i ,T RuT ln io ] 0
P
Equilibrium constant
aA bB ... eE fF ...,
The change in the number of moles of each species is directly proportional to its
dN A a
stoichiometric coefficient i.e
dN B b
dN E e
dN F f
P
P
a g o A,T Ru T ln Ao b g o B ,T Ru T ln Bo
P
P
P
e g o E ,T Ru T ln Eo
P
P
f g o F ,T RuT ln Fo
P
eg o E ,T fg o F ,T ag o A,T bg o B,T
PE PF
o o
P P
Ru T ln
a
b
PA PB
o o
P P
Equilibrium constant
The term on the LHS of the above equation is called the standard-state Gibbs
function change G o eg o fg o ag o bg o
T
E ,T
F ,T
A,T
B,T
PE PF
o o
P P
Kp
a
b
PA PB
o o
P P
With these definitions, the statement for chemical equilibrium at constant pressure
and temperature can be written as
o
K p exp( G
/ RuT )
S
T
Also
For Kp to be greater than unity, which favors products, the enthalpy change for
reaction, should be negative, i.e, the reaction is exothermic.