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Contents lists available at ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Development and testing of an interconnected multiphase CFD-model

for chemical looping combustion
H. Kruggel-Emden a,b,n, S. Rickelt c, F. Stepanek a, A. Munjiza b
a

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

Noorman et al., 2009), moving (Gnanapragasam et al., 2009; Fan

et al., 2008) or uidized beds (Lyngfelt et al., 2001; Son and Kim,
2006) in which the oxygen necessary for the combustion is provided
by a solid carrier. A basic outline of the process is shown in Fig. 1.
Two steps are required: an initial oxidation and a subsequent
reduction step of the oxygen carrier. Currently implemented
systems are mostly based on the uidized bed technology due to
the fact that solid fuels are addressable, a good mixing of gas and
solid carrier is provided and the circulation and replacement of
the carrier material become easy. The process is usually realized
through the combination of a bubbling uidized bed operated as
the fuel reactor in combination with a high velocity riser operated
as air reactor as originally proposed by Lyngfelt et al. (2001).
Intensive research has been performed over the past decade
involving chemical looping combustion (Hossaina and de Lasa,
2008), but it is still away from being a commercially available
technology. In the current state of development, laboratory scale
systems can be operated with different types of fuel up to
140 kWth (Abad et al., 2006; De Diego et al., 2007; Berquerand
and Lyngfelt, 2008; Berguerand and Lyngfelt, 2008; Adanez et al.,
2009; Kolbitsch et al., 2009) with the aim to realize systems of up
to 1 MWth (Epple and Stroehle, 2008) in the near future. In this
context robust and reliable simulation methods will become
important for the detailed design and scale up.
Simulations of chemical looping combustion can be performed
on different levels of accuracy with differing methodologies and
varying related computational costs (Mahecha-Botero et al., 2009).

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Fig. 1. Outline of an interconnected uidized bed chemical looping combustion

system.

The simulation approaches can be categorized as particle based

methods, macroscopic balance models and multi-phase uid
dynamics models. Particle based methods offer a high level of
detail but are computationally very demanding and limited in the
number of particles they can address (Zhu et al., 2007). In case
that realistic particle sizes are used (De Diego et al., 2007) the
system size that can be simulated is also restricted. On currently
available computer systems a modeling of real size vessels even
on laboratory scale becomes impracticable. In contrast to the high
level of detail resolvable through particle based methods,
macroscopic balance models (Noorman et al., 2007; Xu et al.,
2007; Bolhar-Nordenkampf et al., 2009; Kolbitsch et al., 2009;
Abad et al., 2010) allow for a coarse modeling at low computational cost. However, the formation of internal structures
within the domain like bubbles or the development of gradients
within different regions of the model can often not be resolved
satisfactorily.
Multi-phase uid dynamics modeling forms a suitable compromise between coarse and detailed modeling possible through
the previously discussed approaches with respect to both
computational cost and level of detail. Within multi-phase uid
dynamics modeling the particles and uid phase are modeled in
the framework of the NavierStokes equations using averaged
quantities. Closure equations for the solid phase pressure and the
solid phase viscosity have to be provided derived from the kinetic
theory of granular ow (Ding and Gidaspow, 1990). The kinetic
theory of granular ow is an extension of the classical kinetic gas
theory (Patil et al., 2004; Patil et al., 2004). Although these models
have been frequently used for bubbling uidized beds (Enwald
and Almstedt, 1999), mixing (Cooper and Coronella, 2005),
downow reactors (Vaishali et al., 2008) and spouted beds
(Gryczka et al., 2009), Jung and Gamwo (2008) were the rst to
apply multi-phase CFD modeling for chemical looping combustion processes followed by (Deng et al., 2008; Deng et al., 2009)
and Jin et al. (2009). They restricted their considerations to the
fuel reactor operated as a bubbling bed in batch mode
(Fig. 1grey line). This perspective leaves the air reactor and
the complex interaction between both vessels unconsidered.
In this study a coupled model of both air and fuel reactors is
developed using a multi-phase uid dynamics framework
(Fig. 1black line). Methane is used as gaseous fuel and Mn3O4
supported on MgZrO2 (Zafar et al., 2007) is applied as oxygen
carrier.

2. Multiphase uid dynamics modeling framework

The interconnected multi-phase framework was implemented
as a two-phase Euler-model into the commercial computational

4733

uid dynamics software FLUENT 12.1.4. Balance equations are

solved for each individual phase regarding the exchange of
momentum, heat and mass transfer. The solid phase is modeled
through the kinetic theory of granular ow. Air and fuel reactor
are modeled in separate uid dynamics simulations allowing for
an exchange of solid ow through time-dependent boundary
conditions and sinks. The chosen approach is computationally
much less demanding than a full three dimensional transient
model as suggested e.g. in the case of circulating uidized beds
(Zhang et al., 2008). The lower computing time allows using the
interconnected framework for sensitivity studies for which many
simulation runs have to be performed. The effect of a cyclone and
siphons as necessary for a real chemical looping process is not
represented in the interconnected framework proposed here. All
governing equations are given in the following subsections.
Details on the interconnected model and the model setup are
discussed in the section thereafter.
2.1. Continuity and momentum equations
In the Eulerian two-phase model the volume fractions for both
gas eg and solid phase es sum up to one. The continuity equations
for gas and solid phase are
@eg rg
@t

!
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

with h being the enthalpy, l the thermal conductivity, Qgs  Qsg

the inter-phase heat transfer and Sg, Ss the heat released due to
chemical reactions. The inter-phase heat transfer can be calculated based on
Qsg asg Ts Tg

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where asg is the heat transfer coefcient derivable from the

Nusselt-number which can be obtained from empirical correlations e.g. Gunn (Gunn, 1978)

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.

The exchange of uctuation energy due to particle uid

interaction fYs dened in Eq. (16) is given following an approach
by Ding and Gidaspow (1990) with

fYs 3bYs :

The diffusion of uctuation energy kYs can be calculated

according to Lun et al. (1984) with
thin
kYs kdense
Ys kYs ,

kdense
Ys

2.3. Species transport equations

The conservation of species j is realized through the following
equation within an arbitrary phase i:

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.

The solid pressure Ps can be dened according to Lun et al.

(1984) as

2.4. Inter-phase momentum transfer coefcient

Ps 1 21 ees g0 es rs Ys :

The inter-phase momentum transfer coefcient b, can be

derived from different empirical approaches. A widely used model
was suggested by Gidaspow (1994) which is a combination of the
equations of Wen and Yu (1966) and Ergun (1952) reading

Most of the above equations rely on the radial distribution

function which is a measure of how close the particle distribution
is to uniform. A suitable model was proposed by Ding and
Gidaspow (1990)
" 
 #1

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

2.5. Kinetic theory of granular ow

15

Through introduction of the granular temperature Ys 1=3

!!
us0 us0 a balance equation for the uctuation energy within the
particle phase can be derived (Ding and Gidaspow, 1990)


3 @es rs Ys
!
rUes rs us Ys Ps I ts
2
@t
!
16
: r us rUkYs rYs gYs fYs :
Within this equation gYs is the dissipation of the uctuation
energy due to particle collisions given by Lun et al. (1984) as
s

gYs 121e2 e2s rs

Y3s

pd2p

where e is the coefcient of restitution.

es
es,max

1=3

24

The bulk viscosity li for the solid phase can be calculated

according to Lun et al. (1984) from the kinetic theory of granular
ow as
r
4
Ys
ls es rs dp g0 1 e
:
25
p
3
The solids shear stress tensor is arising due to contributions from
particle collisions, particle motion (Gidaspow et al., 1992) and due to
frictional effects (Schaeffer, 1987). All contributions are added up as

ms ms,col ms,kin ms,fr

In order to solve the NavierStokes equations for the solid

phase, equations for the granular pressure Ps, the granular shear
viscosity ms and the bulk viscosity ls have to be provided which
are linked to the rheology of the particle phase. Information on
the rheology of the particle phase can be derived by the theory
of kinetic granular ow. Thereby the particle phase velocities can
!
be separated into a local mean velocity us and a uctuating
!
velocity us0 .
! ! !0
us us us :

g0 3=5 1

23

17

26

with its single components being

r

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

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the two one step reactions

4Mn3 O4 CH4 -12MnO CO2 2H2 O with DH 100:4 kJ=mol

1

30
1

6MnO O2 -2Mn3 O4 with DH 451:4 kJ=mol

31

where DH is the reaction enthalpy.

As the heterogeneous reaction models the linear and spherical
shrinking core approaches are used. The conversion X is dened as
the unreacted molar solid amount divided by the overall reactive
molar particle amount. The conversion X of chemical reaction (30) is
equal to (1 X) of chemical reaction (31). Later in this paper the solid
conversion X of the reduction reaction (30) is referred to as XOX and
used as a measure for the degree of reduction of the solid in the
overall system. At XOX 1 the carrier material is fully reduced; at
XOX 0 the carrier is fully oxidized. The conversion rates for both
linear and spherical shrinking core models can be derived as


E
32
C n 1X2=3 ,
dX=dtSSC 3bk exp 
RT gas


E
Cn ,
dX=dtLSC bk exp 
RT gas

4735

Both models (32) and (33) are adjusted to the experimental

data provided by Zafar et al. (2007) by a genetic algorithm in
combination with a LevenbergMarquardt algorithm (KruggelEmden et al., submitted for publication) used for renement.
Results for the conversion rate plotted over the degree of
conversion are given in Fig. 2. The spherical shrinking core
model leads to reasonable agreement between experimental and
model data; the linear shrinking core model gives good agreement
only when applied over a narrow range of conversion degrees.
The kinetic parameters derived from the adjustment procedure
are outlined in Table 1.
For all applied models the heterogeneous reaction rate is
important for the determination of the mass transfer between solid
and uid phase and for the species transport equation given as
Rhe 1=b dX=dtCMe0 ,

34

where CMe0 is the oxygen carrier bulk concentration.

3. Interconnected chemical looping model

33

with the stoichiometric coefcient of the solid reactant b and Cgas the
bulk concentration of the gaseous reactant.

In the interconnected model both air and fuel reactors are

implemented as seperate CFD-simulations coupled through the
inlet and outlet conditions. The interconnected model setup is

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).

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outlined in Section 3.1 followed by a detailed description of the

considered base case and base case variations.
3.1. Model setup
The combined model setup is spatially 2D. A schematic
drawing of it is shown in Fig. 3. The fuel reactor is designed as a
bubbling bed uidized from the bottom through a velocity inlet
and equipped with a weir. At the lower sidewall an inow for the
solid phase is realized through a velocity inlet boundary
condition. The solid phase can exit the vessel at the left of the
fuel reactor through a cell row in which mass, momentum, heat
and species sinks are applied. Through the weir a constant lling
level is enforced in the fuel reactor. The gas phase leaves the fuel
reactor through the top, implemented as a pressure outlet. The air
reactor is modeled as a high velocity riser. Solid and gas phase
enter the vessel at the bottom through a combined velocity inlet.
At the top of the air reactor both phases leave the vessel through a
pressure outlet.
In order to ensure a sufcient lling level in the bubbling bed a
buffer is introduced into the coupled system. Two different
designs are considered. The buffer can be placed upstream
(Fig. 3a) or downstream (Fig. 3b) from the bubbling bed. The
buffer is not implemented as an entity in the CFD-framework
though, its purpose is to even out possible uctuations in the

_ s,feed is fed into the buffer in

solids owrate. A solid phase stream m
_ s,red in Fig. 3b from the
_ s,ox in Fig. 3a or m
case that the inow m
upstream situated vessel drops below the target solid phase
_ s,feed
_ s,buf between both vessels. The solid feed m
circulation rate m
_ s,ox or m
_ s,red is
is compensating for any lacking ow. In case that m
exceeding the desired inter-vessel solid circulation rate, mass is
stored in the buffer and discharged at a later point in time. The
buffer is assumed as an ideal mixer. The degree of conversion X
_ s,buf
within the buffer and therewith in the leaving solid stream m
is calculated from the degrees of conversion X of the inlet streams
_ s,ox , m
_ s,red . All vessels are assumed to be adiabatic.
_ s,feed and m
m
3.2. Base case model parameters
Within the CFD-software FLUENT version 12.1.4 the set of
partial differential equations outlined in Section 2 is solved
through the nite volume method. The pressurevelocity coupling for both uid and solid phase is achieved through a phase
coupled SIMPLE algorithm. The second-order QUICK-scheme is
employed. A time step of Dt0.0002 s is used for the temporal
discretization. A convergence criterion of 10  3 is chosen for all
quantities. In each time step 20 iterations are performed.
The bubbling bed fuel reactor is discretized through 2500
quadrilateral cells and the air reactor designed as a riser through
1500 quadrilateral cells. Grid renement was tested and has only

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

Apparent reaction order (n)

Reaction preexponential factor (k)
Reaction activation energy (E)
Linear shrinking core model
Apparent reaction order (n)
Reaction preexponential factor (k)
Reaction activation energy (E)
Stoichiometric coefcient (b)

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.

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minor effect on the ow behavior. Mass ow rates, temperatures

and compositions of both solid and gas phases are only minimally
affected. The k  e model is used for both uid and solid phase
with a standard wall function to model for turbulence. The mass
exchange between the vessels as well as the reaction model is
achieved within FLUENT through user-dened functions. Mass,
temperature and composition of the solid phase are exchanged

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

Fuel reactor specications

Width of vessel (m)
Height of vessel (m)
Weir height (m)
Initial bed height (m)
Initial solids packing (  )
Initial temperature (K)
Initial state of reduction Xox ( )
Grid number (  )
Inlet gas temperature (K)
Inlet gas velocity (m/s)
Inlet gas composition (kg/kg)

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

Air reactor specications

Width of vessel (m)
Height of vessel (m)
Grid number (  )
Inlet gas temperature (K)
Inlet gas velocity (m/s)
Inlet gas composition (kg/kg)

0.15
4.0
1500
300
1.45
N2: 0.77; O2: 0.23

4. Computational results and discussion

Table 3
Applied base case alterations.
Variant

Specications

1
2

 Buffer is placed upstream from the air reactor

 Buffer is placed upstream from the air reactor
 Initial buffer feed state of reduction Xox 0.6
 Initial fuel reactor state of reduction Xox 0.4
 Specications as in variant 2
 Linear shrinking core model applied
 Specications as in variant 2
 Mass ow m_ s,buf 3.0 kg/s
 Specications as in variant 2
 Mass ow m_ s,buf 4.0 kg/s
 Specications as in variant 2
 Mass ow m_ s,buf 4.5 kg/s
 Specications as in variant 2
 Mass ow m_ s,buf 5.0 kg/s
 Specications as in variant 2
 Height of air reactor h 5 m
 Specications as in variant 2
 Height of air reactor h 6 m

3
4
5
6
7
8
9

The base case conguration of the chemical looping system as

outlined in the previous section will be systematically modied.
An overview of the applied changes can be found in Table 3.
Modications imply a change of the buffer position within the
system. A partially oxidized feed stream is injected into the buffer
and initially available in the fuel reactor. A different kinetic model
in the form of the linear shrinking core approach is used in both
air and fuel reactors. The circulating solid mass ow is varied from
3.0 up to 5.0 kg/s. The riser length is altered from 4 m in the base
case to 5 m and later 6 m.

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

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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.

from the riser is subject to strong variations due to the weir in

the bubbling bed. Temporarily the mass ow reaches values of
up to 35 kg/s. The outlet stream from the buffer is xed at
3.5275 kg/s. Up to t 7 s the mass ow from the buffer is
_ s,feed . Up to 15 s
completely sustained through the feed stream m
into the simulation it is constantly necessary to add mass through
_ s,feed into the system to reach the desired
the feed stream m
circulation rate. At later points in time it is only occasionally

necessary to compensate for any deciencies in the mass ow

from the riser.
The evolution of the solid temperature over time of the
inow and outow from the buffer and of the solid inside the
buffer itself is shown in Fig. 5b. Up to 7 s into the simulation
the solid from the buffer is fully originating from the feed
_ s,feed being at 1223 K. Later the regenerated solid
stream m
carrier temperature is varying strongly being usually lower than

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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.

the temperature of the feed stream. Temperature minima in

the solid ow from the riser are balanced out through the solid
mass which is stored in the buffer. With less feed stream needed
at later points in time the solid temperature in the buffer agrees
well with the outlet stream leaving the buffer. From t 40 s
onwards the degree of reduction increases sufciently positively
affecting the reactivity in the air reactor which results in a
temperature increase of the solid stream released.
The degree of reduction within the inow and outow of the
buffer is plotted in Fig. 5c. In all ows the degree of reduction is
continuously increasing. The rise in its conguration as used in
the base case does not provide for sufcient regeneration of the
carrier material. Peaks in the degree of reduction of the outlet
stream from the buffer result from the addition of fully oxidized
carrier through the feed stream.
The degree of reduction and the temperature of the solid
inow and outow from the air and the fuel reactor as well as the
gas outow temperature of both air and fuel reactors are given in

4739

Fig. 6. The degree of reduction of the solid entering and leaving

the air reactor is constantly inclining. The ability of the air
reactor to regenerate the solid phase is evidently too small
(Fig. 6a). The difference in the degree of reduction between the
inow and outow of the air reactor is increasing. This is due to
the growing ability of the air reactor to regenerate the solid
oxygen carrier at larger degrees of reduction. The degree of
reduction of the air reactor inow is subject to nearly no
uctuations; the degree of reduction at the outow, however, is
very intermittent which is a result of the varying solid mass in the
riser. The temperatures of the solid phase at the inow of the air
reactor decline smoothly down to 1100 K at t 40 s. Later in the
simulation it increases again, due to the growing heat generation
in the air reactor resulting out of the larger degree of reduction.
The outow temperature of the solid reveals strong uctuations
(Fig. 6b). In the beginning of the simulation, the temperatures are
lower than the initial solid temperature of 1223 K; further into
the simulation temperatures reach peak values larger than
1300 K. The gas outow temperature in the air reactor is equal
to the solid outow temperature. The peaks in the evolution of the
degree of reduction and in the temperature entering the fuel
reactor as displayed in Fig. 6c and d are a result of freshly added
solid to the buffer which is at T 1223 K and Xox 0. The evolution
of the temperature and the evolution of the degree of reduction
in the solid stream from the fuel reactor are smoother than those
of the stream entering the fuel reactor from the buffer as plotted
in Fig. 6c and d.
The evolution of the mass fraction of O2 at the outow in
contrast to that at the inow gives insight into the operation of
the air reactor (Fig. 7a). In the beginning of the simulation the
mass fraction of O2 decreases only marginally. Later in the
simulation the decrease is more pronounced, which indicates a
stronger regeneration of the oxygen carrier passing through the
air reactor. The evolution of the mass fraction of O2 is very
unsmooth. The mass fraction of CH4 at the gas outlet of the fuel
reactor increases over time with decreasing reactivity of
the oxygen carrier material in the bubbling bed. This is due to
the increasing degree of reduction in the system and dropping
solid temperatures. However, peak values remain below 3%. The
mass distribution in the different vessels including air and fuel
reactor as well as the virtual buffer over time is outlined in Fig. 7b.
The mass in the fuel reactor is linearly inclining in the rst 7 s
of the simulation. At this point in time the rst solid reaches
the air reactor. The mass in the buffer and the air reactor are
both uctuating strongly not reaching values larger than 10 kg.
The mass in the bubbling bed reaches a saturation level of
around 60 kg.

4.2. Results for the base case variations

In the following the base case alterations are discussed.
Simulations are performed for a duration of at least t 50 s.
Case 1: Buffer placed upstream from the air reactor
In order to prevent the strong variations in mass ow passing
through the air reactor which also result in uctuating solid and
gas temperatures at the outow of the air reactor the buffer is
placed upstream from the air reactor in the alteration 1. This
conguration leads to a constant mass ow entering the air
reactor. The mass ow leaving the air reactor is subject to minor
uctuations as indicated in Fig. 8a. The overall variations as well
as the peak values in the mass ow rate from the fuel reactor
decrease in contrast to the base case. The overall solid
temperature in the system is constantly decreasing over time.
Especially in the beginning of the simulation up to 30 s this
decrease is most signicant. Solid temperature drops below

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H. Kruggel-Emden et al. / Chemical Engineering Science 65 (2010) 47324745

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.

1000 K after 60 s of simulation time. This strong decrease in

temperature is a result of the feed entered fully oxidized directly
through the buffer into the air reactor. In contrast to the base case
no carrier material is reacting with oxygen in the early state of the
simulation within the air reactor because the carrier is fully
regenerated. With no reaction heat released, temperatures drop
rapidly. Solid temperatures at the outlet of the air reactor are even
smaller than the temperature of the solid from the bubbling bed

entering the air reactor as outlined in Fig. 8b. In contrast to the

base case the temperature evolution is much smoother. Peaks
are occasionally originating from fresh feed material entering the
buffer. The degree of reduction of the solid streams both upstream
and downstream of the air reactor is continuously increasing.
Similar to the development of the temperatures, the evolution of
the degrees of reduction is smoother. With increasing simulation
time and increasing overall degree of reduction the slope of the

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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

degree of reduction of the solid leaving the air reactor becomes

atter than the slope of the degree of reduction of the solid
leaving the fuel reactor. This indicates an increasing regeneration
of the carrier material in the air reactor despite declining
temperatures which is only stimulated by the increasing overall
degree of reduction (Fig. 8c).
The mass fractions of CH4 and O2 at the inow and outow of
the air and fuel reactor are plotted in Fig. 9a. Up to 10 s into the
simulation the oxygen mass fraction does not decline which
indicates that no reaction takes place in the air reactor. Further
into the simulation the consumption of oxygen increases
continuously. The evolution of the mass fraction of CH4 at the
outlet is zero up to 10 s into the simulation. Later it inclines
continuously up to values of 16% at t60 s (Fig. 9b). The
comparatively large loss in CH4 results from the low
temperatures in the fuel reactor which slows down the reaction
of methane with the oxygen carrier signicantly. A larger bed
mass would be needed at these temperatures. The evolution of
the mass in the air and fuel reactor and the riser are outlined in
Fig. 9b. The solid mass in the riser reaches a constant level after it
is fully charged. Very well visible is the order in which air and fuel
reactor are lled. The overall mass in the chemical looping system
is larger when the buffer is placed upstream from the air reactor
as done here compared to the base case conguration. The buffer
mass uctuations are smaller than encountered for the base case.
Case 2: Usage of partly reduced carrier material
The modication in Case 1 where the buffer is placed upstream
from the air reactor can be identied as more feasible than the
base case setup due to the more constant properties in the air
reactor. However it must be tried to compensate for the decline in
temperature in the system. Therefore in a new simulation case
partly reduced material is placed in the fuel reactor with XOX 0.4
and the feed stream enters the buffer with XOX 0.6. Mass ow
rates and masses in the different vessels of the system are not
affected by this variation and therefore not addressed in the
following.
The development of the temperatures over time is outlined in
Fig. 10a. In the beginning of the simulation the solid leaving the
air reactor which is initially partly reduced with XOX 0.6 at
the inlet reaches temperatures of up to T 1280 K. After a certain
time the system is lled and the solid material from the bubbling
bed is recirculated into the air reactor. This material is less
reduced (Fig. 6b). Therefore temperatures of the solid leaving the
air reactor drop after some time. With increasing simulation time
the overall level of reduction increases. This automatically

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.

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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.

triggers increasing temperatures of the solid in the system. The

temperatures in the air reactor increase faster than the
temperatures in the fuel reactor. Peaks in the temperature or
degree of reduction prole for the solid stream leaving the buffer
are originating from solid feed occasionally entered into the
system. Sometimes temperature peaks in the solid stream leaving
the fuel reactor can be detected which originate from larger mass
releases over the spill way. The mass fraction of O2 at the outlet
plotted in Fig. 10c indicates that with increasing temperature and
reduction more oxygen is consumed. At t 60 s half of the oxygen
provided through the inlet air is consumed. Due to the large
temperature of the solid only minor fractions of methane are
released uncombusted from the fuel reactor despite the large
level of reduction in the system.
Case 3: Linear shrinking core model applied
In order to investigate the effect of different kinetic models in
interconnected chemical looping systems, Case 2 studied in the
previous section relying on a spherical shrinking core model (32)

for the reaction kinetics is modeled through a linear shrinking

core model (33). Kinetic parameters are used according to Table 1.
Results on the solid temperatures are shown in Fig. 11a. The
general temperature level within the system is declining.
Temperatures of the solid leaving the air reactor are at
T1190 K at t 55 s and solid leaving the fuel reactor is at
T1150 K. This temperature trend is completely opposite to that
encountered for the case where the spherical shrinking core
model was applied. The evolution of the degree of reduction over
time is plotted in Fig. 11b. Larger overall levels of reduction are
obtained in the system compared to Case 2 for the spherical
shrinking core model. In contrast to the previous investigation the
evolution of the degree of reduction of the solid leaving and
entering the air reactor is not developing apart. This is a direct
result of the linear shrinking core model that is insensitive to the
overall degree of reduction. In Fig. 11c results for the mass
fraction of O2 and CH4 are shown. The consumption of O2 is
constant and not affected signicantly by the decrease in

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temperature in the system. Over time signicant amounts of CH4

are released. At t 55 s nearly 10% of CH4 is leaving the fuel
reactor unreacted. The results above clearly indicate that the use
of a different reaction kinetic model can have signicant effects on
the simulation outcome, especially if the degree of reduction in
the chemical looping system is varying over time. An accurate
representation of the real reaction kinetics in a model is therefore
essential.
Cases 47: Modication of the solid circulation rate
Based on the simulation Case 2 a variation of the solid
circulation rate is performed. The solid ow is considered with
dm/dt{3, 4, 4.5, 5} kg/s. Investigated are the temperatures and
degrees of reduction of the solid ow entering and leaving the air
reactor.
The temperature of the solid entering and leaving the air
reactor is plotted in Fig. 12a. For a circulation rate of 3 kg/s the
temperature of the solid ow entering the air reactor is decreasing
although the temperature of the ow leaving the air reactor is
increasing. With increasing mass ow the temperatures of both
solid entering and leaving the air reactor are increasing. The
temperature difference at t 45 s for 3 kg/s and 5 kg/s solid
circulation rate is 200 K. Increased circulation rates also affect the
overall degree of reduction in the system. With an increased solid
circulation rate the increase in the degree of reduction for the
considered system can be softened (Fig. 12b).

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Cases 89: Altered air reactor length

The effect of an altered air reactor length is shown in Fig. 13. An
increased length of the air reactor leads to larger solid outlet
temperatures at the top of the reactor. The overall temperature
level in the chemical looping system also increases. The relative
temperature gain resulting from an elongation of the air reactor from
4 to 5 m is larger than that for an elongation from 5 to 6 m. The level
of oxygen towards the top of the air reactor is decreasing. In a leaner
oxygen atmosphere the reactivity gain becomes smaller. Therefore an
extension of the vessel length as a constructive measure is limited in
its effect when also not adjusting the inlet air ow. For the degree of
conversion in the system, an increased reactor length dampens the
overall increase of the degree of reduction over time (Fig. 13b).

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.

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The developed framework is tested for chemical looping

operated with methane as fuel gas and Mn3O4 as oxygen carrier.
Simulations of up to 60 s were performed addressing the start-up
period of the system. In theory simulations of up to several
minutes can be performed with reasonable effort on modern
computer systems taking advantage of e.g. parallel computing.
Starting from a base case different system variations were
considered including alterations of the position of the buffer,
the initial degree of reduction of the solid, the kinetic model, the
solid circulation rate and the air reactor length.
A wide variety of properties related to chemical looping
combustion can be resolved transiently in the performed interconnected CFD-simulations. Among them are volume fractions,
masses and mass ow, velocities, temperatures and species
distributions of gas and solid phase just to mention a few. A
coupled CFD-framework accounts transiently for the interconnected nature of air and fuel reactor in chemical looping
combustion. The interdependence of both reactors cannot be
addressed through CFD-batch simulations of individual vessels as
performed so far in literature. Furthermore, a coupled CFDframework resolves more details than macroscopic modeling
(Mahecha-Botero et al., 2009) and therefore qualies to be used as
a potent design tool for chemical looping systems. In contrast to
fully three dimensional full-loop modeling in case of circulating
uidized beds (Zhang et al., 2008) the proposed interconnected
framework offers much faster computation and qualies especially for sensitivity studies in which many simulation runs have
to be performed. A disadvantage however is that siphons and
cyclones which are of importance in the chemical looping process
are not modeled. They could either be realized as entities in the
CFD-framework or as virtual equipment similar to the buffer
already in use.
The different cases investigated in the study here rather
represent design examples than operational chemical looping
setups. They are not capable of regenerating sufcient oxygen
carrier and do not release enough heat through the gas leaving the
air reactor for a stable operation of the system. In an operational
setup the air reactor needs to be broadened, extended in length
and eventually equipped with additional cooling. A comparison of
simulation results with experimental investigations is desirable
for the future. The use of a two buffer system is advisable to
reduce mass ow uctuations. For a better comparison of the
different cases longer simulations have to be performed to reach a
steady state in the systems. This and the elaboration of the
stability of operation points, the test of appropriate control
strategies and the analysis of the part-load behavior of chemical
looping systems are of interest for future investigations utilizing
the coupled CFD-framework developed here.

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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