Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
a r t i c l e
i n f o
Article history:
Received 4 September 2013
Accepted 10 June 2014
Available online 10 July 2014
Keywords:
CFD simulation
Chemical looping combustion
Fuel reactor
Kinetic theory of granular ow
Eulerian method
a b s t r a c t
This study investigates the temporal development of bubble hydrodynamics in the fuel reactor of a
hydrogen-fueled chemical looping combustion (CLC) system by using a computational model. The model
also investigates the molar fraction of products in gas and solid phases. The study assists in developing a
better understanding of the CLC process, which has many advantages such as being a potentially promising candidate for an efcient carbon dioxide capture technology.
The study employs the kinetic theory of granular ow. The reactive uid dynamic system of the fuel
reactor is customized by incorporating the kinetics of an oxygen carrier reduction into a commercial computational uid dynamics (CFD) code. An Eulerian multiphase treatment is used to describe the continuum two-uid model for both gas and solid phases. CaSO4 and H2 are used as an oxygen carrier and a fuel,
respectively. The computational results are validated with the experimental and numerical results available in the open literature. The CFD simulations are found to capture the features of the bubble formation,
rise and burst in unsteady and quasi-steady states very well. The results show a signicant increase in the
conversion rate with higher dense bed height, lower bed width, higher free board height and smaller oxygen carrier particles which upsurge an overall performance of the CLC plant.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
The concern about the effect of greenhouse gases on the global
climate changes is growing worldwide. Anthropogenic carbon
dioxide (CO2) emissions are the major contributor and a signicant
part of it is due to the combustion of various carbonaceous fuels in
power generating plants. Accordingly, the development of novel
technologies to control CO2 emissions with minimum energy
losses has become a topic of strategic interest for researchers. In
addition to developing renewable energy conversion technologies,
the use of CO2 capture and storage (CCS) with the use of fossil fuels
will make a signicant contribution to the reduction of CO2 emissions. Many CO2 capture methods such as amine scrubbing, oxyfuel combustion, and decarbonization of fuels, are currently under
investigation. Chemical looping combustion (CLC) introduced by
Richter and Knoche [1] is an efcient technology in which CO2 is
inherently separated during the combustion process.
A CLC system consists of two separated reactors (air and fuel
reactors). A suitable oxygen carrier is oxidized (storing oxygen)
in the air reactor and is transported to the fuel reactor using a
Corresponding author. Tel.: +971 (2) 810 9158; fax: +971 (2) 810 9901.
E-mail address: tshamim@masdar.ac.ae (T. Shamim).
http://dx.doi.org/10.1016/j.enconman.2014.06.027
0196-8904/ 2014 Elsevier Ltd. All rights reserved.
cyclone. In the fuel reactor, the metal oxide is reduced and the
released oxygen reacts with the fuel. Carbon-dioxide and water
(H2O) vapors are the two ue gases generated in the fuel reactor.
Afterwards, H2O is condensed from the ue gases and an uncontaminated stream of CO2 is captured and stored for later use.
Fig. 1 shows a schematic of CLC process. The abbreviations
MeO/Me represent the metal oxide in oxidized/reduced forms,
respectively. In the recent past, this novel technology has been
studied extensively [213] focusing on different distinct aspects
such as technical feasibility, economic assessments, incorporation
of the CLC system in power generation cycles, numerical simulation of the system with solid and gas fuels, and the experimental
improvement of the CLC system.
In a CLC system, the distribution of solidgas particles in the
reactors (which are generally based on the uidized bed reactor
design) is highly complex and can be better understood by using
computational uid dynamics (CFD) models based on the uid
dynamics and reaction kinetic mechanisms. The CFD models can
be used to simulate the behavior of the reactants and the products
in the reactors during unsteady and quasi-steady states by using
the conservation principles of mass, momentum, energy and species. The difculties of capturing the ow physics in a relatively
complex circulating uidized bed (CFB) require signicantly large
1011
Nomenclature
CD
Di,mix
Dturb
egg
F
~
Fa
~
F lift;a
~
F v m;a
g0,gg
G
I2S
~
J ai
Kgl
_ ab
m
_ ab
m
P
~
Rab
Rai
Reg
Sa
Sai
Scturb
tg
u0g
vr,g
~
va
~
v ab
drag function
diffusion coefcient of the mixture
turbulent diffusivity
coefcient of restitution for particle collision
factor that depends on CD and Reg
external body force
lift force
virtual mass force
radial distribution function
acceleration due to gravity
second invariant of the stress tensor
diffusion ux of species i
multi-phase exchange coefcient
mass transfer from phase a to phase b
mass transfer source between phases
pressure
interaction force between phases
net rate of production of homogeneous species i by
chemical reaction for phase a
relative Reynolds number
source term in continuity equation
rate of creation
turbulent Schmidt number
particulate relaxation time
uctuating velocity of the particles
terminal velocity correlation for the granular phase
velocity of phase a
inter-phase velocity
Y ai
Greek Symbols
a
volume fraction
bgd
inter-phase momentum transfer for calculating drag between solid phase and gas phase
cg
dissipation of uctuating energy due to inelastic collision
Hg
granular temperature
ka
bulk viscosity of phase a
la
shear viscosity of phase a
lg
granular shear viscosity
lg,col
granular collisional shear viscosity
lg,fr
granular frictional viscosity
lg,kinetic granular kinetic viscosity
lturb
turbulent viscosity
q
density
sa
ath phase stressstrain tensor
/f
internal friction angle
Subscripts
a,b
phases (solid and gas)
dg
diameter of particles in solid phase
g
granular phase
gas
gas phase
i, j
species
l
liquid phase
The reactions described in Eqs. (1) and (2) are both exothermic in
nature with low level energy releases at low-temperature region
1012
@
aa qa~
ma r aa qa~
ma~
ma aa rp r sa aa qa~
g
@t
n
X
~
_ ba~
Rba m
mba m_ ab~
mab
b1
~
Fa ~
F lift;a ~
F mm;a
2
3
2. Mathematical model
The study employs the kinetic theory of granular ow with an
Eulerian approach. The continuity, momentum and energy equations are solved for each phase whereas a single pressure is shared
by all the phases.
solid particles. These forces are more substantial for bigger particles. In the present model, the lift forces on solid particles are insignicant due to their smaller resisting surface area and in
comparison to larger drag forces. So, these forces are not included
in the model. The virtual mass force (~
F v m;a ) is considered when a
solid phase (secondary, b) moves faster relative to the gas phase
(primary, a). The solid particles are likely to experience a virtual
mass force due to the inertia of gas phase caused by the fast moving particles (bubbles or droplets). As the gas phase is denser than
the solid phase, this force is not very important and is not incorporated in the present model. Furthermore, the adhesive forces
between particles were not considered for the present simulations.
2.1.3. Species transport equations
The local mass fraction (Y ai ) of ith species in a multiphase ow is
predicted by the species conservation equation, which is described
as:
@ a a a
q a Y i r qa aa~
ma Y ai r aa~Jai aa Rai aa Sai
@t
n
X
_ bi aj m
_ aj bi R
m
b1
~
J ai qDi;mix
lturb
Scturb
rY ai
@
aa qa ha r aa qa ua ha rka rT a Q ab Sab hab
@t
1013
Q ab hab T a T b
where
A a4:14
l
(
and B
tg
2.1.5. Kinetic theory of granular ow
A random granular motion of particles is likely to occur due to
the collisions of solid particles inside the reactor. The transport
equation for the solid phase [23] is described by the following
equation:
@
2
g : r~
ug r:kg rHg
ag qg Hg r:ag qg Hg ug pgI ag s
@t
3
10
c 3bggas Hg
Here, Hg is the granular temperature and is given by: Hg 13 u0g u0g ,
where u0g is the uctuating velocity of the particles and can be
derived from u0g V g ug , and pg is the solid pressure. bggas is the
interphase momentum transfer for calculating the drag between
two phases. The well-known Ergun equation [24] is considered for
agas < 0.8 to describe the dense region in the reactor:
bggas 150
1 agas r g lgas
agas d2g
1:75
qgas ag jugas ug j
dg
11
If agas > 0.8, the drag coefcient is calculated by the equation proposed by Wen and Yu [25]:
bggas
3 jugas ug j 2:65
Cd
agas
4
dg
12
where
Cd
24
1
Re
0:15Re0:687 ; Re 6 1000
0:44;
and Re
Re > 1000
lgas
13
14
K gl
f
ag qg f
15
tg
C D Reg al
24m2r;g
16
where f is a factor that depends on the drag function (CD) and relative Reynolds number (Reg) [26].
and C D
Reg
mr;g
4:8
0:63 p
Reg =mr;g
ql dg j~
mg ~
ml j
ll
19
!2
0:8a1:28
; al 6 0:85
l
a2:65
;
al > 0:85
l
qg d2g
18ll
21
F gasg F ggas
q
2
3lgas ag agas
0:63 Reg =mr;g 4:8
2
4mr;g dp
18
23
g0
"
#1
3
ag 1=3
1
5
ag;max
24
q
0:5 A 0:06Reg 0:06Reg 2 0:12Reg 2B A A2
22
20
lg;kinetic
lg;fr
ag dg qg Hg p
63 egg
pg sin /f
p
2 I2S
25
1=2
ag
2
1 1 egg 3egg 1ag g 0;gg
5
26
27
28
1014
/ and I2D are the angle of internal friction and second invariant of
the stress tensor respectively.
2.2.6. Granular temperature
The diffusion coefcient for granular energy kg is given by:
kg
2
150qg dg Hg p
6
1 ag g 0 1 e 2qg c2g dg g 0 1 e
5
3841 eg 0
r
Hg
29
p
"
cg 31 e2 a2g qg dg g 0 Hg
4
dg
r!
Hg
#
rug
30
the reactor inlet and outlet respectively. In the CFB reactor, the
soliduid mixture behaves as a uid medium due to introduction
of pressurized uid through the particulate medium. For simplicity, no-slip condition at wall was used for both the phases. However, the case of solid particulate having some nite slip along
the wall can also be simulated by employing different values of
specularity coefcient in the numerical model. The convective
terms are evaluated by using a second order QUICK scheme. The
model parameters used for the base case in the present study are
similar to those used by Deng et al. [15].
1015
Fig. 4. Mole fractions in gas phase along the centerline of the reactor (x = 0 cm) and (a) at a height of 30 cm from the inlet (y = 30 cm) (dense bed region) and at (b) the outlet.
bubbles are formed. The smaller bubbles are noticed to trail behind
the larger ones. Due to a low pressure zone created at the wake of
the larger bubbles, the trailing smaller bubbles accelerate upward
and coalesce with the larger bubbles. Also, the upward moving larger bubbles, having higher velocity than the smaller ones, coalesce
with the neighboring smaller bubbles. In the process, the bubble
sizes grow quickly in the narrow ow passage area of the reactor
and slugs are formed. Thus, the solid particles are pushed upward
by the rising slugs. Later, the solid particles are pushed down into
the bed along the central core of the reactor as well as along the
walls of the reactor due to gravity and the differential density of
gassolid particles. These phenomena are noticeable from 0.5 s to
1.0 s. At 1.0 s, a core-annulus region is formed similar to that
observed experimentally by Clift and Grace [29] for slug ow reactors. This study used the reactors of different heights and widths
for different supercial velocities. The cross-section of the reactor
used by Clift and Grace [29] was also rectangular (similar to the
present simulation) where solid particles were pushed upward
by the rising slugs which subsequently moved back down along
the walls of the reactor forming a core-annulus section.
Fig. 6 shows the development of solid volume fraction proles
beyond 1.0 s. The bubbles and slugs have low solid volume fractions (nearly equal to zero). Due to the difference in gas velocities
inside the bubbles and the slugs, the reaction rates are different in
the respective regions. They are signicantly higher in the emulsion region due to larger concentration of solid particles. The reaction rates are lower in the fast moving bubbles. This transient
behavior of bubble dynamics is observed within the rst 1.0 s after
which the quasi-steady state condition is attained. The continuous
supply of the feed fuel gas through the distributer ensures the global mixing of gassolid particles in the reactor with the continuous
bubble formation, rise and burst. However, the core-annulus feature as observed during the unsteady period does not prevail for
longer time. This salient feature of bubble dynamics is clearly
noticeable up to 1.6 s after which the core-annulus structure bursts
into intimate mixing of gassolid particles and the quasi-steady
state condition is achieved.
Fig. 7 shows the quasi-steady state distribution of (a) solid volume fraction, and the gas phase mole fractions of (b) reactants and
(c) products at 10 s. A global mixing of the gas and particles is
observed. The qualitative representation of the bubble hydrodynamics is shown in Fig. 7(a) where the blue color1 represents the
pure gas and the red color denotes the dense gassolid mixture.
The reactant (H2) prole, shown in Fig. 7(b), implies that the H2 mole
fraction decreases linearly from about 1.0 around the distributor
(inlet) to 0.65 at the interface between the dense uidized and the
free-board regions. A sudden increase in its magnitude to a constant
value of 0.7 has been observed in the free-board region. As expected,
the reverse characteristics are observed for the product (H2O) prole
as shown in Fig. 7(c). Similar observations were also observed by
Deng et al. [15] and the proles presented in Fig. 7 are in qualitative
agreement with their results.
The study also investigated the effects of reactor geometric
dimensions and particle size on the bubble hydrodynamics and
1
For interpretation of color in Fig. 7, the reader is referred to the web version of
this article.
1016
1017
Fig. 6. Unsteady development of solid volume fraction contour with quasi-steady reaction rate.
Fig. 7. (a) Solid volume fraction, (b) mole fraction of H2 and (c) mole fraction of H2O at the quasi-steady state conditions (t = 10 s).
widths (w) for different cases are selected as 10, 15, 20, 25 and
30 cm. The ow Reynolds numbers in all the cases are kept similar
to the base case. The global mixing of gassolid particles is
observed to be more prominent for the reactors with smaller
widths. The velocities of gas and emulsion in these reactors are relatively higher than the reactors with the higher widths. Thus, the
gas and the emulsion tend to grow over the entire span of the reactor. Alternate layers of gas and emulsion are noticed in the smaller
1018
Fig. 8. Solid volume fraction contour with different dense bed heights (H) at the quasi-steady state conditions (t = 10 s).
Fig. 9. (a) Mole fraction of H2 and (b) conversion rate for different dense bed heights of the reactor at the quasi-steady state conditions (t = 10 s).
width reactors. However, for a bed width of 10 cm, the characteristics of volume fraction contours are somewhat different as no
core-annulus region was formed and many bubbles were observed
with most of the oxygen carrier particles accumulated near the
wall. Moreover, the upper portions of the reactors with high widths
are predominantly covered by the gas particles. This causes the net
reaction rate to be lower due to unavailability of oxygen carrier
particles.
Fig. 11 shows the temporal variations of H2 mole fractions at the
outlet and the conversion rate of the feed fuel gas at the quasisteady state (t = 10.0 s) for different reactor bed widths. The results
depict that the H2 mole fraction at the outlet increases and consequently the fuel conversion rate decreases with an increase in the
reactor bed width. The H2 molar fraction at the outlet and the fuel
conversion rate become nearly constant for reactors with bed
widths P20 cm.
3.3. Effect of free board heights
Fig. 12 shows the variations of solid volume fraction contours
for different heights of free board region at the quasi-steady state
(t = 10.0 s). For these simulations, the static bed height and the
bed width of the reactor are kept xed at 40 cm and 25 cm, respectively. The heights of the free board region for different cases are
selected as 40, 60, 80, 100 and 120 cm. The results show that an
increase in the height of the free board region increases the mixing
of gassolid mixture and reduces the bubble size. This increases
the H2 conversion rate in the reactor. The reactor free board height
also affects the gas concentration prole in the fuel reactor mainly
due to differences in the uid dynamics of the dense bed and the
free board regions. The metal oxide particle concentration in the
free board region decreases with an increase in the reactor height.
However, this increases the reaction rate in this region due to a
better gassolid contact than in the dense bed.
Fig. 13 shows the temporal variations of H2 mole fractions at the
outlet and the conversion rate of the feed fuel gas at the quasisteady state (t = 10.0 s) for different reactor free board heights.
The results show that the H2 mole fraction at the outlet decreases
with an increase in the reactor free board region height. As
expected, the H2 molar fraction decreases rapidly from unity to
certain constant values. These observations are also similar to the
experimental results reported by Kolbitsch et al. [31] and Abad
1019
Fig. 10. Solid volume fraction contour with different bed widths: (a) w = 10 cm, (b) w = 15 cm, (c) w = 20 cm, (d) w = 25 cm, (e) w = 30 cm at the quasi-steady state conditions
(t = 10 s).
Fig. 11. (a) Mole fraction of H2 and (b) conversion rate at for different bed widths of the reactor at the quasi-steady state conditions (t = 10 s).
1020
Fig. 12. Solid volume fraction contour with constant bed width (w = 25 cm) and different free board heights: (a) h = 40 cm, (b) h = 60 cm, (c) h = 80 cm, (d) h = 100 cm, (e)
h = 120 cm at the quasi-steady state conditions (t = 10 s).
Fig. 13. (a) Mole fraction of H2 and (b) conversion rate for different free board heights of the reactor at the quasi-steady state conditions (t = 10 s).
Fig. 14. Solid volume fraction contour with different particle sizes: (a) Dp = 0.1 lm, (b) Dp = 0.2 lm, (c) Dp = 0.3 lm, (d) Dp = 0.4 lm, (e) Dp = 0.5 lm at the quasi-steady state
conditions (t = 8 s).
1021
Fig. 15. (a) Mole fraction of H2 and (b) conversion rate for different particle sizes in the reactor at the quasi-steady state conditions (t = 8 s).
4. Conclusions
References
A CFD model has been developed and employed for the simulations of the fuel reactor in a chemical looping combustion (CLC)
system. The model included the reaction kinetics of fuel and metal
oxide. The governing equations were solved by using a commercial
CFD code. The numerical model was employed to investigate the
temporal development of the bubble hydrodynamics and the
unsteady aspects of bubble formation, rise and burst in the fuel
reactor of a hydrogen-fueled CLC system. The molar fractions of
the product in gas and solid phases were also investigated by the
numerical model.
The computational results were validated qualitatively and
quantitatively with the numerical results of Deng et al. [15] and
the experimental results of Clift and Grace [29]. The bubble
dynamics and the ow patterns were in good agreement with
the literature results. A low conversion rate of the feed fuel gas
was obtained which is due to combined effect of low bed temperature, bigger particle size, smaller dense bed height and larger bed
width of the reactor. All these parameters led to fast and large bubbles in the reactor which reduced the reaction rate and hence the
conversion rate of the feed fuel gas. The low fuel conversion can
be improved by (i) the use of an oxygen carrier with small particle
sizes and high reactor temperature; (ii) the use of a different oxygen carrier material, for example Ni; and (iii) the recirculation of
the unutilized hydrogen to the fuel reactor.
The paper also presents the results of a parametric study based
on the reactor dimensions and particle sizes. The results show that
a signicant increase in the fuel conversion rate can be obtained
with a higher dense bed height, a lower bed width, a higher free
board height and smaller oxygen carrier particles. However, additional cost must be considered for larger dense bed and higher free
board heights. The smaller oxygen carrier particles (preferably of
nano-size) are a preferred option for enhancing the overall performance of CLC plant as they do not generate large bubbles and a
proper mixing of gassolid particles can very well be established.
The direct numerical simulation of the present multiphase reactive model will be considered for the future work in order to get
better bubble hydrodynamics.
[1] Richter HJ, Knoche KF. Reversibility of combustion processes. ACS Symposium
Series 1983;235:7185.
[2] Abad A, Mattison T, Lyngfelt A, Ryden M. Chemical looping combustion in a
300 W continuously operating reactor system using a manganese based
oxygen carrier. Fuel 2006;85:117485.
[3] Johansson E, Mattisson T, Lyngfelt A, Thunman H. A 300 W laboratory reactor
system for chemical-looping combustion with particle circulation. Fuel
2006;85:142838.
[4] Mattisson T, Garcia-Labaiano F, Kronberger B, Lyngfelt A, Adanez J, Hofbauer H.
Chemical-looping combustion using syngas as fuel. Int J Greenhouse Gas
Control 2007;1(2):15869.
[5] Song Q, Xiao R, Deng Z, Zhang H, Shen L, Xiao J, et al. Chemical-looping
combustion of methane with CaSO4 oxygen carrier in a xed bed reactor.
Energy Convers Manage 2008;49(11):317887.
[6] Forero CR, Gayan P, de Diego LF, Abad A, Garcia-Labiano F, Adanez J. Syngas
combustion in a 500 Wth chemical-looping combustion system using an
impregnated Cu-based oxygen carrier. Fuel Process Technol 2009;90(12):
14719.
[7] Dennis JS, Scott SA. In situ gasication of a lignite coal and CO2 separation
using chemical looping with a Cu-based oxygen carrier. Fuel 2010;7(89):
162340.
[8] Mahalatkar K, Kuhlman J, Huckaby ED, OBrien T. Computational uid dynamic
simulation of chemical looping fuel reactors utilizing gaseous fuels. Chem Eng
Sci 2011;66:46979.
[9] Hassan B, Shamim T, Ghoniem AF. A parametric study of multi-stage chemical
looping combustion for CO2 capture power plant. In: Proceedings of the ASME
2012 Summer Heat Transfer Conference, Puerto Rico; 2012. Paper ASME201258597.
[10] Moldenhauer P, Ryden M, Mattisson T, Lyngfelt A. Chemical-looping
combustion and chemical-looping with oxygen uncoupling of kerosene with
Mn- and Cu- based oxygen carriers in a circulating uidized bed 300 W
laboratory reactor. Fuel Processing Technol. 2012;104:37889.
[11] Wang B, Zhao H, Zheng Y, Liu Z, Yan R, Zheng C. Chemical looping combustion
of a Chinese anthracite with Fe2O3-based and CuO-based oxygen carriers. Fuel
Processing Technol 2012;96:10415.
[12] Abad A, Gayan P, de Diego LF, Garcia-Labiano F, Adanez J. Fuel reactor
modelling in chemical-looping combustion of coal: 1. model formulation.
Chem Eng Sci 2013;87:27793.
[13] Peltola P, Ritvanen J, Tynjl T, Hyppnen T. Model-based evaluation of a
chemical looping combustion plant for energy generation at a pre-commercial
scale of 100MWth. Energy Convers Manage 2013;76:32331.
[14] Jung J, Gamwo IK. Multiphase CFD based models for chemical looping
combustion process: fuel reactor modeling. Powder Technol 2008;183:4019.
[15] Deng Z, Xiao R, Jin B, Song Q. Numerical simulation of chemical looping
combustion process with CaSO4 oxygen carrier. Int J Greenhouse Gas Control
2009;3:36875.
[16] Kruggel-Emden H, Rickelt S, Stepanek F, Munjiza A. Development and testing
of an interconnected multiphase CFD-model for chemical looping combustion.
Chem Eng Sci 2010;65:473245.
[17] Shuai W, Guodong L, Huilin L, Juhui C, Yurong H, Jiaxing W. Fluid dynamic
simulation in a chemical looping process with two interconnected uidized
beds. Fuel Processing Technol 2011;92:38593.
[18] Wang X, Jin B, Zhong W, Zhang Y, So Min. Three-dimensional simulation of a
coal gas fueled chemical looping combustion process. Int J Greenhouse Gas
Control 2011;5:1498506.
Acknowledgements
The work is nancially supported by the MIT/Masdar Institute
Collaborative Research funds (grant # 10MAMA1).
1022
[25] Wen CY, Yu HY. Mechanics of uidization. Chem Eng Prog Symp Ser
1966;62:100.
[26] Syamlal M, OBrien TJ. Computer simulation of bubbles in a uidized bed.
AlChE Symp Ser 1989;85:2231.
[27] Vasquez SA, Ivanov VA. A phase coupled method for solving multiphase
problems on unstructured meshes. In: Proceedings of ASME FEDSM00: ASME
2000 Fluids Engineering Division Summer Meeting, Boston; 2000
[28] Gelderbloom SJ, Gidaspow D, Lyczkowski RW. CFD simulations of bubbling/
collapsing uidized beds for three geldart groups. AlChE J. 2003;49:84458.
[29] Clift R, Grace JR. Continuous Bubbling and Slugging. London: Academic Press;
1985.
[30] Abad A, Adanez J, Garcia-Labiano F, de Diego LF, Plata A, Gayan P. Modeling of
the chemical-looping combustion of methane using a Cu-based oxygencarrier. Combust Flame 2010;157:60215.
[31] Kolbitsch P, Proll T, Hofbauer H. Modeling of a 120 kW chemical looping
combustion reactor system using a Ni-based oxygen carrier. Chem Eng Sci
2009;64:99108.