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Chemical Engineering Science 65 (2010) 47324745
Department of Chemical Engineering, South Kensington Campus, Imperial College London, SW7 2AZ London, UK
Department of Engineering, Queen Mary, University of London, Mile End Road, E1 4NS London, UK
c
Department of Mechanical Engineering, Ruhr-University Bochum, Universitaetsstrasse 150, 44801 Bochum, Germany
b
a r t i c l e in f o
a b s t r a c t
Article history:
Received 27 February 2010
Received in revised form
11 May 2010
Accepted 14 May 2010
Available online 24 May 2010
An interconnected multi-phase CFD model is developed capable of describing the transient behavior of
a coupled chemical looping combustion systems comprising of both air and fuel reactors. The air reactor
is modeled as a high velocity riser, the fuel reactor as a bubbling uidized bed. The models of both
reactors are implemented as separate CFD simulations allowing for an exchange of solid mass through
time-dependent inlet and outlet boundary conditions as well as mass, momentum, heat and species
sinks. The developed framework is applied to a chemical looping combustion system based on Mn3O4 as
carrier material in combination with CH4 as fuel gas. Starting from a base case, different system
congurations are investigated. The results indicate clearly that interconnected multi-phase CFD
models are well suited for the design process of coupled chemical looping systems.
& 2010 Elsevier Ltd. All rights reserved.
Keywords:
Chemical looping combustion
Interconnected model
Dynamic simulation
Multiphase ow
Multiphase reactions
Fluidization
1. Introduction
Many scientic studies come to the conclusion that a prompt
reduction of greenhouse gas emissions is important to limit the
effects of global warming (IPCC Fourth Assessment Report, 2007).
Different greenhouse gases can be identied whereas carbon
dioxide emissions from power generation and other industrial
processes represent the most dominant sources.
Due to the fact that a change in energy production towards
fully carbon neutral sources is not likely in the near future,
combustion of fossil fuels in combination with carbon capture and
sequestration appears as a suitable interim solution (Herzog et al.,
2000; Lyngfelt and Lecker, 1999). Among possible technologies
like pre-combustion, oxy-fuel combustion or post-combustion,
chemical looping combustion is a method which has a good
potential to become an important capture technology. It has a low
energy penalty due to the fact that the carbon dioxide from the
combustion process is inherently not diluted with nitrogen which
would otherwise require energy intensive processing (Rao and
Rubin, 2002; Naqvi et al., 2007).
The process of chemical looping combustion may be utilized with
either solid or gaseous fuels involving static (Noorman et al., 2007;
n
Corresponding author at: Department of Chemical Engineering, South
Kensington Campus, Imperial College London, SW7 2AZ London, UK
E-mail address: kruggel-emden@leat.rub.de (H. Kruggel-Emden).
0009-2509/$ - see front matter & 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2010.05.022
4733
!
rUeg rg ug Sgs ,
@es rs
!
rUes rs us Ssg ,
@t
with Sgs Ssg is the mass transfer between both phases due to
!
heterogeneous reactions, u the velocity and r the density. The
momentum equations for the gas phase and the solid phase can
be obtained as
!
@eg rg ug
!!
!
rUeg rg ug ug eg rp rUtg eg rg g
@t
! !
!
b ug us Sgs ug ,
3
!
@es rs us
!!
!
rUes rs us us es rp rUts rPs eg rg g
@t
! !
!
b ug us Ssg us ,
!
with the inter-phase momentum transfer coefcient b, gravity g ,
the gas pressure p, the solid pressure Ps and the stressstrain
tensor ti calculated for both gas and solid phase as
!
!
ti ei mi r!
ui r ui T ei li 2=3mi rU ui I,
with the viscosity mi, the bulk viscosity li which is assumed zero
for the gas phase and I the unit tensor.
2.2. Energy equations
The conservation of energy of the gas and solid phase is
governed through the equations
@eg rg hg
@t
!
rUeg rg ug hg rUlg rTg Qgs Sg ,
@es rs hs
!
rUes rs us hs rUls rTs Qsg Ss ,
@t
asg
6kg eg es Nus
dp
9
0:2
1=3
1=3
2
1:332:4 g 1:2 2g Re0:7
,
p Pr
g 1 0:7Rep Pr
Nus 710eg 5e
10
with Pr the Prandtl-number, Rep the particle Reynolds-number
and dp the particle diameter.
fYs 3bYs :
kdense
Ys
kthin
Ys
!
@ei ri Yi,j
!
rUei ri ui Yi,j rUei J i,j Rhe
@t
where
11
18
19
p
15rs ds es Ys p
12
16
1
Z4Z3
4133Z Zes g0 ,
44133Z
5
15p
20
p
25rs ds Ys p
12 2
1
Z 4Z3es g0 ,
16g0 Z4133Z
5
Z 0:51 e:
21
22
!
where Yi,j is the mass fraction of species j in phase i, J i,j the
diffusive mass ux and Rhe the heterogeneous reaction rate.
Ps 1 21 ees g0 es rs Ys :
3 eg 1eg
!
rg 9!
ug us 9eg 2:65 for eg 4 0:8,
C
dp
4 d
8
h
i
>
< 24 1 0:15Rep 0:687 ,
Re
p
Cd
>
: 0:44
b 150
Rep r1000
12
13
Rep 41000
rg ! !
mg 1eg 2
1:751eg 9 ug us 9 for eg r0:8:
dp
eg dp 2
14
15
Y3s
pd2p
es
es,max
1=3
24
g0 3=5 1
23
17
26
ms,col 4=5es rs g0 dp 1 e
27
p
10ds rs Ys p
1 5=4es g0 1 e2 ,
96es 1 eg0
28
Ps sin x
p ,
2 I2D
29
ms,kin
ms,fr
Ys
where x is the angle of internal friction and I2D the second invariant
of the deviatoric stress tensor.
2.6. Modeling of the reaction kinetics
The oxygen carrier used in the investigation here is Mn3O4
supported on MgZrO2 (Zafar et al., 2007). Manganese has the
advantage to provide a medium oxygen carrier capacity combined
with quick kinetics when used with methane as fuel gas (Hossaina
and de Lasa, 2008). It is chosen because it is expected to reveal
insights into the dynamics of the interconnected uidized bed
system on small time scales (Kruggel-Emden et al., submitted for
publication). Reduction and oxidation of the carrier are described by
1
30
1
31
4735
34
33
with the stoichiometric coefcient of the solid reactant b and Cgas the
bulk concentration of the gaseous reactant.
Fig. 2. Conversion rate of: (a,b) Mn3O4 with CH4 and (c,d) MnO with O2 for different molar fractions Z and temperatures T: () Best t spherical shrinking core model, (- - -)
best t linear shrinking core model and (J) experimental data by Zafar et al. (2007).
Table 1
Kinetic parameters of the applied oxygen carrier material Mn3O4 supported on MgZrO2 with a diameter distribution of dnp 125180 mm (Zafar et al., 2007).
Spherical shrinking core model
Reduction
Oxidation
0.9344
1935.8 m3n 2 mol1 n s 1
124.88 kJ/mol
Reduction
0.85264
873.95 m3 moln s 1
111.7 kJ/mol
4
0.58052
0.17291 m3n 2 mol1 n s 1
27.156 kJ/mol
Oxidation
0.54212
0.10526 m3 moln s 1
17.184 kJ/mol
6
Fig. 3. Outline of the combined modeling framework consisting of a bubbling uidized bed used as fuel reactor and an air reactor implemented as a riser. Outlines (a) and
(b) vary in the position where the buffer is placed.
Table 2
System properties and parameters for the simulations.
4737
between the vessels after each time step. An overview over the
general simulation parameters and the specications of the base
case is provided in Table 2.
The base case is designed as outlined in Fig. 3a with the buffer
placed upstream from the bubbling bed. The inlet gas velocity for
the bubbling bed is following a ramp function reaching its
maximal velocity after 7 s. The mass inlet at maximal velocity
corresponds to 0.5 MWth. The solid circulation rate and the vessel
dimensions were chosen to match design recommendations given
by Zafar et al. (2007).
3.3. Base case variations
General parameters
Time step Dt (s)
Mean particle diameter dp (mm)
Angle of internal friction x (1)
Maximal packing limit es,max ( )
Restitution coefcient e ( )
Kinetic model
0.0002
0.1525
30
0.6
0.9
Spherical shrinking core
Buffer specications
Initial mass (kg)
Initial state of reduction Xox ( )
Initial temperature (K)
_ s,buf (kg/s)
Mass ow m
Feed temperature (K)
Feed state of oxidation Xox ( )
0
0
1223
3.5275
1223
0
0.25
0.8
0.4
0.1475
0.42
1223
0
2500
300
Min(0.061; t 0.0102 1/s+ 0.01)
CH4: 1
0.15
4.0
1500
300
1.45
N2: 0.77; O2: 0.23
Table 3
Applied base case alterations.
Variant
Specications
1
2
3
4
5
6
7
8
9
In the following, results for the base case are discussed in detail.
Results from the case alterations are discussed briey focusing on
differences in the results with respect to the base case.
4.1. Results for the base case
The base case is simulated for a duration of t 62 s. A wide
variety of properties is transiently available from the simulations.
Contours plots of the instantaneous solid fraction, the solid
temperature, the state of oxidation and the mass fraction of CH4
and O2 within the bubbling bed and riser domain are shown in
Fig. 4 at t 30.01 s. At the beginning of the simulation the
bubbling bed is partially pre-loaded with solids and the system is
slowly lled to the operating level through the buffer which is
placed upstream from the bubbling bed. After a while (t 5 s)
with increasing gas ow, bubbles form within the bottom region
of the fuel reactor. A uctuating mass ow is released from the
bubbling bed due to the weir. This uctuating mass ow is
directly entering the riser and moving through it in dilute plugs.
These variations in the solid fraction can be identied in the riser
at e.g. 2 m height in Fig. 4a for t 30.01 s. Through the uidization
of both vessels with cold gas at 300 K a temperature distribution
develops which is not resolved in detail through the applied grid
(Fig. 4b). The endothermic reaction in the bubbling bed
additionally consumes heat. In the riser the solid phase heats up
due to the exothermic reaction as can be seen in Fig. 4b. The
degree of reduction of the solid in the bubbling bed is lower at the
bottom where regenerated solid phase is entered from the side. In
the riser the degree of reduction decreases along the length of the
vessel due to the exothermic reaction of the carrier with oxygen
(Fig. 4c). The selected bed height in the fuel reactor is sufcient to
ensure a nearly complete reaction of the methane with the
oxygen carrier. In the riser the contour plot of the mass fraction of
O2 indicates temporal uctuations. Only at positions where
enough solid material is available, the oxygen concentration
decreases signicantly (Fig. 4d).
The mass ow from and to the buffer which is placed upstream
_ s,ox
from the bubbling bed is outlined in Fig. 5. The mass ow m
Fig. 4. (a) Contour plots of the solid fraction, (b) the solid temperature, (c) the degree of reduction and (d) the mass fraction of CH4 in the fuel reactor and of O2 in the air
reactor for the chemical looping base case conguration at t 30.01 s.
Fig. 5. (a) Mass ow into and out of the buffer, (b) temperature and (c) degree of
reduction of the different solid ows from and into the buffer and of the buffer
itself for the base case.
4739
Fig. 6. (a) Degree of reduction and (b) solid temperature of the inow and outow from the air reactor as well as the gas outow temperature in the air reactor. (c) Degree
of reduction and (d) solid temperature of the inow and outow from the fuel reactor as well as the gas outow temperature from the fuel reactor. Results are obtained for
the base case.
Fig. 7. (a) Mass fraction of CH4 and O2 in the gas phase at the inow and outow of the air and fuel reactor and (b) mass in the buffer, air and fuel reactor for the base case
conguration.
Fig. 8. (a) Mass ow, (b) temperatures and (c) degree of reduction of the different
solid ows and the mass in the buffer of the variant 1 where the buffer is placed
upstream from the fuel reactor.
4741
Fig. 9. (a) Mass fraction of CH4 and O2 in the gas phase at the inow and outow of the air and fuel reactor and (b) mass of the solid in the buffer, air and fuel reactor for the
variant 1 where the buffer is placed upstream from the fuel reactor.
Fig. 10. (a) Temperatures, (b) degree of reduction of the solid and (c) mass fraction
of CH4 and O2 in the gas phase at the inow and outow of the air and fuel reactor
for variant 2 where the initial oxygen carrier is partly oxidized.
Fig. 11. (a) Temperature and (b) degree of reduction of the solid and (c) mass
fraction of CH4 and O2 in the gas phase at the inow and outow of the air and fuel
reactor for case 3 where a linear shrinking core model is applied for the reaction
kinetics.
4743
5. Conclusions
An interconnected CFD-framework for chemical looping
combustion was developed. The chemical looping system considered consists of an air reactor operated as a high velocity riser
and a fuel reactor operated as a bubbling bed. Mass, temperature
and composition of the solid phase circulated between both
vessels is exchanged through time-dependent boundary conditions and mass, momentum, species and heat sinks placed in the
bubbling bed equipped with a weir.
Fig. 12. (a) Temperature and (b) degree of reduction of the solid stream leaving and entering the air reactor. Solid ow is considered with dm/dt {3, 4, 4.5, 5} kg/s for the
conguration of case 2.
Fig. 13. (a) Temperature and (b) degree of reduction of the solid stream leaving and entering the air reactor. The air reactor length is changed to 5 m and 6 m for the
conguration of case 2.
Acknowledgements
The authors gratefully acknowledge the nancial support by
the Humboldt Foundation. The opportunity to use additional
computing facilities at the Department of Energy Plant Technology, Ruhr-University Bochum is appreciated.
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