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abstract
Article history:
Received 1 February 2009
Received in revised form
10 January 2010
Accepted 15 January 2010
Available online 21 January 2010
In the present study heat and mass transfer related to the chemical conversion of limestone to
quicklime in a shaft kiln are investigated by means of a coupled numerical scheme for gas and solid
phase transport. The three-dimensional transport of mass, momentum and energy in the gas phase is
modelled by computational uid dynamics (CFD), while a discrete element method (DEM) is employed
for the mechanical movement and the conversion reactions of the solid material. The DEM simulation
readily describes the mechanical and thermal particle-to-particle interactions of a large number of
differently sized particles. Novel aspects addressed in this work are the simultaneous effects of inner
particle heat-conduction and pore-diffusion of the gaseous product of the calcination reaction (CO2)
modelled by a shrinking core approach. Simulations of laboratory scale experiments of single reacting
spheres show good agreement with the measured conversion rates. Simulations of an idealised vertical
shaft kiln including pressure drop calculations demonstrate the suitability of the proposed approach for
the modelling of industrial scale systems.
& 2010 Elsevier Ltd. All rights reserved.
Keywords:
Shaft kiln
Discrete element method
Heat transfer
Granular materials
Porous media
Powder technology
Mass transfer of the gaseous CO2 from the reaction front to the
1. Introduction
In lime industry natural limestone is taken from a quarry and
granulated. Subsequently it is calcined in an endothermic process
within a lime kiln. The main component of limestone calcite
(calcium carbonate) is dissociated at high temperatures according
to the following reaction (Stark and Wicht, 2000):
CaCO3 s-CaOs CO2 g
2. Particle-ow coupling
To illustrate the various interactions of a limestone particle
with its surroundings, Fig. 2 outlines the processes taking place on
an exemplary particle track through a shaft kiln.
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CO2
mGas,out
TGas,out
H2O
CaCO3
Tp
CaO
CO2
Qexternal
Tp
mGas,in
TGas,in
Fig. 2. Example of a particle track in a shaft kiln with heat, mass and momentum
transfer.
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T. Bluhm-Drenhaus et al. / Chemical Engineering Science 65 (2010) 28212834
DEM
Transfer Grid
2823
CFD
particle
sources
fluid
properties
Table 1
Parameters inuencing the coupled DEM-CFD simulation.
Solid phase (DEM)
Phenomenon
Particle heating
Evaporation of water
Chemical conversion
Gas cooling
Flow distribution
Pressure drop
Interphase feedback
Energy sink
Mass source (CO2, H2O)
Solid/void fraction
Gas temperature
Gas composition
Relative velocity
3. Submodels
The submodels described in the following sections have been
chosen to account for a sufcient representation of the underlying
phenomena, while being simple enough to limit the computational effort for systems with large numbers of particles.
A major simplication is the assumption that the limestone
particles are of spherical shape. This simplication is justied to a
certain extend by the fact that the surface of lime stones particles
is smoothed and rounded during their travelling time within a
shaft kiln (typically several hours) due to mechanical interaction
of the particles with each other and hence approach a spherical
shape. The consideration of shape details would have led to an
unacceptable numerical effort.
Note that the pressure drop correlations used here are adapted
to non-spherical particles by a shape factor. The inuence of
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2824
N
X
d2~
xi
~
g;
F ij mi ~
2
dt
j1
Ji
N
X
~i
d2 j
~ ij
M
2
dt
j1
3
n
fe 1 1; 51e
In Eq. (6) e is the void fraction of the packed bed and it is valid in
the range 0.26o e o1. The result is a mean Nusselt number for a
region of constant void fraction, which yields the mean heat
transfer coefcient:
am
Nubed lg
dp
a dp
lp
Rth;i
Rth;a
Only for Biot numbers much less than unity, which holds true for
small particle diameters or high thermal conductivities, the heat
transfer is dominated by the outer thermal resistance due to
convection (1/a) and a uniform temperature throughout the
particle can be assumed (Baehr and Stephan, 2006). For porous
lime particles typically present in shaft kilns with an effective
relative gas velocity of about 9 m/s, the Biot number is larger than
unity, as can be seen in Table 2.
The Biot number effect could be taken into account by
calculating a temperature distribution as a function of the radius.
This would require a detailed discretization of the particle which
is very time consuming, when large numbers of particles are of
interest as in technical systems. A simplied approach for the
radial temperature distribution, which can be applied in DEM
simulations based on an analytical approach, has been presented
by Rickelt et al. (2009). However, because for real scale lime shaft
kilns the calculation of several hundred thousands of particles is
nally required, we decided to neglect the Biot number effect in a
rst step and concentrate on modelling of the travelling reaction
front within the particle as the dominating effect for the heat
balance within the particle. A shrinking core approach is applied
in the current work.
As there are two distinct shells, calcium carbonate and calcium
oxide, which each possess constant material properties, we
assume that a combined energy balance for each shell (S1, S2) is
suitable for the description of the thermal behaviour.
The energy balance for the innermost shell (core, S1) holds:
mS1 cS1
dTS1
kS12 TS2 TS1 DHR
dt
The change of the inner energy of the core results from conductive
transfer from the outer shell and the reaction enthalpy of the
endothermic calcination reaction. A threshold value is applied for
the minimum core mass to eliminate the singularity when the
particle is completely converted to calcium oxide. The heat
Table 2
Biot number of typical lime particles.
a
lp,CaO
dp
Bi
W m2 K1
W m1 K1
m
227.5
0.7
0.01
3.25
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lS1
1
rS1
4plS1 lS2
1
1
rS2;m
r1S1
lS2 rS1;m
10
3.3. Reactions and interphase mass transfer
The difference between the mean radii of each shell, see Fig. 4, is a
measure for the mean path length of conductive transfer.
The energy balance for the outer shell (S2) is accordingly:
mS2 cS2
2825
dTS2
am Ap TG TS2 kS12 TS2 TS1
dt
11
rS2
rS2m
CaO
rS1
rS1m
12
pCO2 ;eq
R Ts1
13
CaCO3
R1;C
15
CO2 ;CaO
Fig. 4. Shrinking core model for heat transfer with mean radii indicated.
16
i;CaO
Dmol;i DKn;i
t
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1.00E+06
1.00E+05
1.00E+04
1.00E+03
1.00E+02
1.00E+01
1.00E+00
200
300
400
500
600
700
Temperature [C]
800
900
1000
r pore;CaO 2
eCaO
SCaO r0CaO
18
d2s1
Sh dp DCO2 ;Gas
19
L
FD d p 2 e3
FD d p e3
20
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T. Bluhm-Drenhaus et al. / Chemical Engineering Science 65 (2010) 28212834
Table 3
Particle properties.
dp
SCaO
mm
m2 kg 1
W m1 K1
W m1 K1
t
eCaO
lCaO
eCaCO3
lCaCO3
2827
107 0.2
16 000
1.41
0.56
0.7
0.04
2.26
Table 4
Gas phase conditions for the experimental runs (Hills, 1968).
Run
Temperature (1C)
CO2 mole fraction (-)
26
877
0
28
876
0.106
30
874
0.154
35
877
0.323
41
902
0
Run 35 meas.
Run 30 meas.
Run 28 meas.
Run 26 meas.
Run 35 sim.
Run 30 sim.
Run 28 sim.
Run 26 sim.
45
829
0
52
720.5
0
1
0.9
0.8
0.7
r* [-]
0.6
0.5
0.4
0.3
0.2
0.1
0
0
10
20
30
40
50
Time [min.]
60
70
80
Run 35 meas.
Run 30 meas.
Run 28 meas.
Run 26 meas.
Run 35 sim.
Run 30 sim.
Run 28 sim.
Run 26 sim.
90
1
0.9
0.8
0.7
c* [-]
0.6
0.5
0.4
0.3
0.2
0.1
0
0
10
20
30
40
50
Time [min.]
60
70
80
90
Fig. 6. Runs conducted at constant temperature and different CO2 concentrations (see Table 4), A: dimensionless radius (r*), B: calcination degree (c*), measured data
shown as symbols, simulation data as lines.
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2828
These plots would show straight lines, if the reaction was only
controlled by a chemical step proportional to the surface area of
the reaction front. Mass conservation considerations lead to the
molar reaction rate:
n_ const 4pr 2
dr
dt
25
23
dt
const 4pr 2
m0 mt
m0 m1
24
Run 45 meas.
Run 41 meas.
Run 26 meas.
Run 52 sim.
Run 45 sim.
Run 41 sim.
Run 26 sim.
1
0.9
0.8
0.7
r* [-]
0.6
0.5
0.4
0.3
0.2
0.1
0
0
10
20
30
40
50
Time [min.]
60
70
80
Run 52 meas.
Run 45 meas.
Run 41 meas.
Run 26 meas.
Run 52 sim.
Run 45 sim.
Run 41 sim.
Run 26 sim.
90
1
0.9
0.8
0.7
c* [-]
0.6
0.5
0.4
0.3
0.2
0.1
0
0
10
20
30
40
50
Time [min.]
60
70
80
90
Fig. 7. Runs conducted at different temperatures in pure air (see Table 4), A: dimensionless radius (r*), B: calcination degree (c*), measured data shown as symbols,
simulation data as lines.
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2829
880
Ts1 sim.
Ts2 sim.
T core meas.
Temperature [C]
860
840
820
800
780
760
0
10
20
30
40
Time [min.]
50
60
70
80
Fig. 8. Simulated core (Ts1) and shell (Ts2) temperature during the decomposition of a 10 mm sample in a furnace held at 863 1C, measurement data (core) as symbols.
The feed stone contains 98.5 wt% calcite (CaCO3) and 1.5 wt%
moisture.
The heat transfer between gas and solid in the packed bed is
dominated by convection.
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Table 5
Particle properties.
dp
SCaO
t
eCaO
lCaO
eCaCO3
lCaCO3
mm
m2 kg 1
W m1 K1
W m1 K1
17y45
5000
1.41
0.56
0.7
0.04
2.26
Fig. 9. Geometry of the simulated vertical shaft kiln with input streams.
Table 6
Operating conditions.
Height
Diameter
Angle of cone
Input (100% CaCO3)
Residence time
Air ow rate
Stone inlet temperature
Air inlet temperature
Thermal input
m
m
1
t d1
h
m3/h STP
1C
1C
kW
Run 1 (base)
2
0.64
60
3.29
8
233.5
20
20
80
2
0.64
60
3.29
8
233.5
20
350
80
Table 7
Results for the gas phase.
Run 1
(base)
Run 2
(preheated air)
m s1
m s1
4.02
0.73
8.55
0.88
Pa
2135
4064
5.2. Results
The main characteristics of the resulting gas ow are
summarised in Table 7 for both runs.
The mean supercial gas velocity magnitude at the air inlet is
much lower in run 1 than in run 2, due to the different densities at
the respective inlet temperatures. The velocity in the lower part of
the calcination zone is quite similar in both cases, because the
temperature levels are almost the same in this position. The
pressure drop resulting from the overall ow pattern in run 2 is
almost doubled compared to run 1. It is mainly determined by the
high velocity at the tip of the cone (air inlet).
Fig. 10 shows the particle residence times in steady state
operation. The mean residence time of approximately 8 h
(28,800 s) is met by most of the particles. Some at the outer
wall have longer and some in the core of the granular ow have
shorter travelling times through the kiln.
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2831
Fig. 13. Particle calcium oxide mass fraction (A: run 1, B: run 2).
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content evaporates, while the particles fall into the kiln. In the
calcination zone the shell temperatures are substantially higher
than the core temperatures of the particles. The temperature at
the reaction interface develops from energy consumption by the
calcination reaction and energy supply by convection through the
boundary layer to the shell surface and conduction through the
outer shell. In the lower part of the kiln the particles are again in
thermal equilibrium with the cooling air.
The result of greatest interest from the current simulation is
the degree of calcination of the particles, which is proportional to
the calcium oxide mass fraction. These results are presented in
Fig. 13.
It can be seen that the kiln is operated at very poor efciency in
run 1. The temperature level in the burning zone is generally too
low to achieve complete conversion, see Fig. 14. Nevertheless the
ue gases still contain a high amount of energy. The overall mass
based degree of calcination (c*) is only 55% in run 1.
100%
CaO
CaCO3
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
17.0
22.4
31.5
particle diameter [mm]
45.0
100%
CaO
90%
CaCO3
80%
70%
60%
50%
40%
30%
20%
10%
0%
17.0
22.4
31.5
particle diameter [mm]
45.0
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6. Conclusion
Fig. 16. Proles of particle and gas temperature along the centreline of the kiln,
(A: run 1, B: run 2).
Table 8
Heat and mass balance (reference temperature 25 1C).
Run 1
Mass (kg h
INPUT
Feedstone, wet
Gas
Total
OUTPUT
Quicklime, dry
Gas
Energy source
Evaporation
Reaction
Total
Run 2
1
Mass (kg h 1)
Temperature (1C)
Energy (kJ s 1)
0.2
0.4
0.6
138.96
301.21
440.17
20.0
350.0
0.2
28.9
28.7
88.97
351.03
350.0
476.6
440.0
6.2
48.6
80.0
1.3
51.4
27.5
0.2
0.1%
1.2
1.5%
Temperature (1C)
Energy (kJ s
138.96
301.21
440.17
20.0
20.0
105.19
334.78
20.0
451.0
439.97
0.1
43.4
80.0
1.3
34.0
1.4
Imbalance
0.2
0.1%
0.8
1.0%
Calcination
55%
1
90%
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t
FD
tortuosity, dimensionless
shape factor, dimensionless
angle, 1
Acknowledgement
This work was kindly supported by Thyssen-Krupp Technologies Polysius AG, Germany.
References
Notation
A
Bi
c
ci
c*
Di
d
F
f
g
HR
J
k
kS12
L
M
Mi
mi
_
m
N
Nu
n_
p
Q_
area, m2
Biot number, dimensionless
specic heat, J/(kg K)
molar concentration, mol/m3
calcination degree
diffusion coefcient, m2/s
diameter, m
force, N
factor, dimensionless
gravitational constant, m/s2
enthalpy of reaction, J/mole
momentum of inertia, kg m2
constant of stiffness
thermal conductivity, W/K
length, m
momentum, Nm
molar mass, kg/mol
mass, kg
mass ow, kg/s
number, dimensionless
Nusselt number, dimensionless
molar reaction rate, mol/s
pressure, N/m2
heat ow, J/s
R
Rth
Ri,C
S
Sh
r
r*
T
t
u, v, w
V
x, y, z
y
Greek letters
a
g
d
D
e
l
m
m
x
r
r0