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H I G H L I G H T S
G R A P H I C A L
A B S T R A C T
art ic l e i nf o
a b s t r a c t
Article history:
Received 20 June 2013
Received in revised form
19 August 2013
Accepted 2 September 2013
Available online 14 September 2013
Keywords:
Chemical-looping
Heterogeneous modeling
Oxygen carrier
Diffusion
1. Introduction
The reliance of burning fossil fuels to meet the world's increasing energy demand has contributed to the dramatic rise in global
carbon dioxide (CO2) concentration from about 280 ppm during the
pre-industrial era to 379 ppm in 2005, the highest in over 450,000
n
Correspondence to: Department of Chemical & Biomolecular Engineering,
University of Connecticut, 191 Auditorium Road Unit 3222, Storrs,
CT 06269-3222, USA. Tel.: 1 860 486 4602.
E-mail address: george.bollas@uconn.edu (G.M. Bollas).
0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.09.021
234
(o1200 1C) without ame (Hossain and De Lasa, 2008; Ishida and
Jin, 1996).
Research in the CL process has been largely focused on the
development and testing of suitable oxygen carriers. The desired
characteristics include high rates of oxidation and reduction, high
melting point temperature, low tendency of attrition and fragmentation, low toxicity, low cost of raw materials and production,
and high combustion efciency (Hossain and De Lasa, 2008).
Oxygen carriers are formulated by depositing an active component, can be Cu, Fe, Ni, or Mn, onto an inert material, such as Al2O3
(IPCC, 2005; Johansson et al., 2006c). A signicant part of the
experimental testing has been performed in laboratory batch
reactors, where particles are subjected to alternating cycles of
oxidizing and reducing conditions (Adnez et al., 2004; Dueso
et al., 2012; Ishida et al., 1996; Mattisson et al., 2008). The CLC
technology has been successfully demonstrated for methane or
natural gas combustion in different prototypes of interconnected
uidized beds, ranging from 0.3 to 50 kWth with over several
hundred combined hours of operation (Abad et al., 2006; Adnez
et al., 2009, 2006; Johansson et al., 2006a, 2006b; Linderholm
et al., 2010, 2008; Rydn et al., 2008a, 2006; Ryu et al., 2003;
Sedor et al., 2008; Son and Kim, 2006; Zafar and Mattisson, 2005;
Zafar et al., 2006). Oxygen carriers for CLC and CLR have also been
tested in xed-bed reactors and thermogravimetric analyzers
(TGA), for measuring the intrinsic kinetics and diffusion limitations (Garcia-Labiano et al., 2006; Iliuta et al., 2010; Ishida et al.,
1996; Jin, 2002; Jin et al., 1999; Noorman et al., 2011a, 2011b,
2007; Ryu et al., 2003). In addition, CLR studies have been
performed in continuous circulating-uidized bed reactor systems
(De Diego et al., 2009; Rydn et al., 2006) and xed-bed units
(Jin 2002). Potential drawbacks of implementing chemical-looping
in xed-bed reactors include low oxygen carrier utilization, high
pressure drop, and large temperature uctuations, as well as the
inability to operate using solid fuels (Zhou et al., submitted for
publication). With repeated cycles of oxidation and reduction, the
reactivity of oxygen carriers have been shown to change, as a
result of pore opening, surface restructuring, and spinel formation
(Jerndal et al., 2009; Linderholm et al., 2009; Shulman et al., 2009;
De Diego et al., 2009). It is of scientic importance to understand
how the gradual chemical and/or physical changes in the oxygen
carrier from continuous usage affect the reactivity of the oxygen
carriers and the overall performance of chemical-looping systems,
which will be the subject of interest of the second part of
this work.
Different mathematical models have been developed to simulate
CLC systems. Ishida et al. (1996) applied the unreacted shrinking core
model to interpret the experimental results on kinetics of the NiO
mixed with yttria-stabilized zirconia (YSZ) particle. Comparison of
model prediction with experimental results indicated that the
reduction reaction was controlled by chemical reaction, while oxidation was controlled by both chemical reaction and ash-layer diffusion
(Ishida et al., 1996; Mattisson et al., 2006). Iliuta et al. (2010) used an
isothermal dynamic plug-ow model to estimate kinetic parameters
2. Model description
Flow in xed-bed reactors can be modeled by the motion of
gaseous bulk uid through the gaps between and within the oxygen
carriers that constitute the solid phase (Avci and Ilsen, 2011). Heat and
mass transfer resistances can occur within the solid phase (intraparticle resistance) or between the solid and the bulk uid (interfacial or
interparticle resistance). Intraparticle resistance is related to the pore
size and can be controlled by the dimensions of the oxygen carrier.
Interfacial resistance is proportional to the thickness of the boundary
235
C
b i i b Dax;i i b Ri ;
1
z
t V
z
b C p;f C T
T
T
T
C p;f F T
b
b H i Ri
ax
t
V
z
z
U
4 T T w ;
dt
b Dax;i
C i
j
F i jz 0 yi;f eed F in =Ac ;
z z 0
T
z
C i
T
j
j
0:
z z L z z L
2.1.2. Two-dimensional
Advancing in complexity, the two-dimensional model takes
into account radial diffusion of bulk uid and temperature.
Reaction rates along the reactor diameter can be affected by
effective thermal diffusivity and conductive heat transfer at the
wall, which are determined by ow characteristics. The twodimensional pseudo-homogeneous model is
C F
C
C
rDrad;i i b Ri ;
b i i b Dax;i i b
6
z
t V
z
r r
r
b C p;f C T
T
T
T
C
C p;f F T
b
b
r rad i
ax
t
V
z
z
r r
r
b H i Ri ;
236
T
r
b rad jr R hw Tjr R T w ;
phase are
C i F i
C
C
Dax;i i b
rDrad;i i kc;i av C c;i jRp C i ;
b
z
t V
z
r r
r
17
C
b i i b Dax;i i kc;i av C c;i jRp C i ;
10
z
t V
z
b C p;f C T
T
T
T
C p;f F T
b
hf av T c jRp T;
ax
t
V
z
z
11
12
T c
s
T c
rc 2
2
1 c s C p;s c C p;c C T;c
s H i Ri :
t
r c
r c r
13
The boundary conditions for the particle phase are
C c;i
T c
j
j
0;
r c rc 0 r c rc 0
De;i
s
14
C s;i
jRp kc;i C c;i jRp C i ;
r
T s
j hf T s jRp T;
r Rp
15
16
and for the uid phase the boundary conditions are equivalent to
the one-dimensional homogeneous model (Eqs. (3)(5)).
2.2.2. Two-dimensional
The two-dimensional heterogeneous model includes radial
dispersion in the uid phase. The design equations for the uid
b C p;f C T
T
T
T
C
C p;f F T
b
b
r rad i
ax
t
V
z
z
r r
r
hf av T c jRp T;
18
19
T c
s
T c
rc 2
2
s H i Ri ;
t
r c
r c r
20
with Eqs. (19) and (20) as boundary conditions for the solid phase
and Eqs. (3)(5) for the bulk phase.
2.3. Momentum balance
The momentum balance assumes pseudo-steady state and is
dominated by the friction factor. The pressure drop correlation
using the Ergun friction factor for gas ow through a packed
tubular reactor is written as (Wilkes, 1999)
2
u0 150
dP
1 b
1:75
21
3
dz
Rep
Dp
b
where P is the total pressure in the bed and Rep is the particle
Reynolds number, dened as
Rep
u 0 dp
:
1 b
22
23
24
25
In general, for gases with Rep 4 1, Per 10 and Pea 1, and for
gases with Rep o1, Per Pea which approach 0.7 (Davis and Davis,
2003). Dispersion is usually more dominant in the radial direction,
and consequently very small radial variations of concentration can
be expected in the reactor. However a high dependency of reaction
rates on temperature can lead to pronounced differences between
the one-dimensional and two-dimensional models.
The effective radial and axial thermal conductivity can be
estimated by Eqs. (26) and (27), respectively, by Yagi and Wakao
(1959) and Yagi et al. (1960) for metal spheres. The static
0
contribution, e , is assumed to be 0.01 W/m K.
rad
13 0:11 Pr Rep ;
m
26
ax 0e
0:7Pr Rep :
m m
27
28
4er
:
D=2
29
The resistances to the radial heat transfer in the bed and at the
wall can be combined to dene the overall heat transfer coefcient
to be used in the one-dimensional models:
1
1
1
:
U hbed hw
30
0:357
hf 1:37
C p;f G Re 0359 Sc 2=3 :
32
1:0
Dt =Dp 2
0:375;
av 61 b =Dp :
33
34
S g s
1 yi
:
j a i yj =Dij
Table 1
Binary gas phase diffusivities for component pairs (Marrero and Mason, 1972).
Pair
Eq.
H2CO
H2CO2
COCO2
CO2H2O
H2CH4
ArH2
ArCH4
ArCO
ArCO2
N2H2O
15.39E 3
3.14E 5
0.577E 5
9.24E 5
3.13E 5
23.5E 3
0.784E 5
0.904E 5
1.74E 5
0.187E 5
1.548
1.75
1.803
1.5
1.765
1.519
1.785
1.752
1.646
2.072
0.316E8
0.488e8
2.80
11.7
0
307.9
0
39.8
0
0
89.1
0
1067
1
2
2
2
2
1
2
2
2
2
36
AT B
P
2
ln CT
Table 2
Binary gas diffusivities for component pairs (Poling et al., 2000; Sattereld, 1981).
Pair
H2N2
CON2
H2H2O
CH4H2O
H2Ar
CH4CO2
6.007E 3
0
0
0
9.625E 3
0
0.99311
0.322
0.927
0.361
2.287804
0.153
Note D12 D21. Parameters below are for the expressionDij AT B=P.
Note: T is in K, P is in atm, and Dij is in cm2/s.
Table 3
Gas phase heat capacity constants for relevant species, corresponding to the
equation C p;i A BC=T sinh C=T2 DE=T sinh E=T2 (Aspen, 2007).
35
237
CH4
H2
H2O
CO
CO2
Ar
N2
33,298
27,617
33,363
29,108
29,370
20,786
29,105
79,933
9560
26,790
8773
34,540
8614.9
2086.9
2466
2610.5
3085.1
1428
1701.6
41,602
3760
8896
8455.3
26,400
103.47
991.96
567.6
1169
1538.2
588
909.79
Table 4
Gas phase viscosity constants for selected species, corresponding to the equation
mi AT B =1 C=T D=T 2 (Aspen, 2007).
CH4
H2
H2O
CO
CO2
Ar
N2
5.255E 07
1.797E 07
1.710E 08
1.113E 06
2.148E 06
9.212E 07
6.5592E 07
0.59006
0.685
1.1146
0.5338
0.46
0.60529
0.6081
105.67
0.59
0
94.7
290
83.24
54.714
0
140
0
0
0
0
0
238
NoComp
i1
yi i
p:
NoComp
yj M j =M i
j1
38
NoComp
yi i
i1
NoComp
yj Aij
j1
210
T c M3
!1=6
42
P 4c
1 f v;i
:
s;i
43
39
2.6. Kinetic scheme
40
81 M i =M j 1=2
41
Table 5
Gas phase thermal conductivity constants for species, corresponding to the
equation AT B =1 C=T D=T2 (Aspen, 2007).
CH4
H2
H2O
CO
CO2
Ar
N2
8.398E 06
2.653E 03
6.204E 06
5.988E 04
3.69
6.33E 04
3.31E 04
1.4268
0.7452
1.3973
0.6863
0.3838
0.6221
0.7722
49.654
12
0
57.13
964
70
16.323
0
0
0
501.92
1.86E 06
0
373.72
The main reduction reactions in CLC of NiO with CH4 fuel are
shown in Table 7 (Zhou et al., 2013). The reducing gases that are
active in the oxygen carrier reduction reactions (R1R4) comprise
CH4, H2, and CO. In the work by Zhou et al. (2013) and Iliuta et al.
(2010), non-catalytic gassolid reactions have been analyzed using
the shrinking core model and a modied volumetric model.
Because the modied volumetric model has been found to
improve the model predictions, the kinetics based on the modied
volumetric model is used in this work. The kinetic expressions for
the four NiO reduction reactions are shown below, where a0 is the
initial oxygen carrier surface area, X is the oxygen carrier conversion, ks1ks4 are the Arrhenius rate constants, and C denotes the
concentration of the gas species and solid weight fraction of NiO
and Ni.
r 1 a0 1 Xk1 C CH4 C NiO C Ni
44
r 2 a0 1 Xk2 C H2 C NiO
45
r 3 a0 1 Xk3 C CO C NiO
46
47
48
Table 6
Physical properties of solids (Garca-Labiano et al., 2005).
Thermal conductivity
(W/m K)
Active material
Co
CoO
Cu
CuO
Cu2O
Fe
FeO
Fe2O3
Fe3O4
MnO
Mn2O3
Mn3O4
Ni
NiO
Inert
Al2O3 ()
MgO
SiO2
TiO2 (rutile)
ZrO2
Cp1
Cp2
Cpb
Melting temperature
(kg/m )
(K)
40
5
350
6
636
751
382
430
5.13E 01
1.06E 01
7.46E 03
4.26E 01
5.03E 04
1.03E 04
6.76E 05
1.53E 04
761
775
460
705
8860
6440
8920
6400
30
5
5
6
3
3
3
75
13
433
623
860
2009
546
498
490
347
790
1.45E 01
2.72E 01
2.96E 03
1.77
3.12E 01
5.08E 01
4.90E 02
2.71E 01
2.06E 01
1.66E 06
6.62E 05
1.57E 05
6.70E 04
8.80E 05
1.29E 04
1.28E 04
5.52E 05
1.43E 04
613
856
887
847
796
926
358
596
752
6980
5700
5240
5180
5430
4500
4840
8900
6670
1768
2078
1358
NDPT 1397
1516
1809
1650
NDPT 1735
1870
2115
NDPT 1350
1835
1726
2228
7
8
2
4
3
843
1013
953
785
482
5.40E 01
3.47E 01
2.91E 01
2.12E 01
1.74E 01
1.61E 04
8.96E 05
7.82E 05
5.97E 05
4.09E 05
1263
1304
1192
955
634
3965
3580
2260
4260
5600
2290
3105
1996
2130
2950
Note: Cpa Cp0 Cp1 T Cp2 T 2 ; Cpb at Tref 1223 K (expect for Cu based OC where Tref 7073 K); NDPT normal decomposition point.
239
Table 7
CLC reduction reactions using NiO oxygen carrier selected by Zhou et al. (2013).
Oxygen carrier reduction reactions
Partial CH4 oxidation
H2 oxidation
CO oxidation
Partial CH4 oxidation
(R1)
(R2)
(R3)
(R4)
CH4 H2O23H2 CO
CO H2O2H2 CO2
CH4 CO222CO2H2
CH422H2 C
C H2O2CO H2
C CO222CO
(R5)
(R6)
(R7)
(R8)
(R9)
(R10)
Table 8a
Summary of independent variables in the one-dimensional model for a spherical oxygen carrier.
Variable
C(z,i)
F(z,i)
T(z)
P(z)
Cc(z,rc,i)
Tc(z,rc)
Unit
3
mol/m
mol/s
K
bar
mol/m3
K
Description
Dimension
Nz Ns
Nz Ns
Nz
Nz
Nz Nrc Ns
Nz Nrc
Table 8b
Summary of independent variables in the two-dimensional model for a spherical oxygen carrier.
Variable
Unit
Description
Dimension
C(z,r,i)
F(z,r,i)
T(z,r)
P(z,r)
Cc(z,r,rc,i)
Tc(z,r,rc)
mol/m3
mol/s
K
bar
mol/m3
K
Nz Nr Ns
Nz Nr Ns
Nz Nr
Nz
Nz Nr Nrc Ns
Nz Nr Nrc
49
55
50
2
P CO2 P CO
P CO2
k10
= 1 K CO;10 P CO
r 10
K CO;10 K CO2 ;10 P CO K 10
P CO K CO;10 K CO2 ;10
51
P H P CO2
k6
P CO P H2 O 2
P H2
K6
=1 K CO;5 P CO K H2 ;5 P H2 K CH4 ;5 P CH4 K H2 O;5 P H2 O =P H2 2
r 8 k8 K CH4 ;8 P CH4
!
P 2CO P 2H2
=1 K CH4 ;7 P CH4
K7
!
!2
3=2
PH
P 2H2
= 1 2 K CH4 ;8 P CH4
K8
K H2 ;8
!2
3=2
P H2
P H2 O P CO
P H2 O
r9
= 1 K CH4 ;9 P CH4
K H2 O;9 P H2
K9
P H2 K H2 O;9 K H2 ;9
k9
56
2.7. Integration strategy
The dynamic model was implemented and solved in the
equation-based process modeling platform gPROMS 3.6.0
(Process Systems Enterprise Limited, 2012). The nite difference
method is used for the discretization of partial differential equations along the xed-bed axial (Nz nodes) and radial (Nr nodes)
direction, and along the solid radial and/or axial directions (Nrc
and Nzc nodes). The number of species is denoted as Ns. A
summary of independent variables can be found in Tables 8a
and 8b. In the proceeding sections, the results are presented and
discussed.
52
3. Results and discussion
53
54
The developed pseudo-homogeneous and heterogeneous models are applied to published chemical-looping xed-bed experiments. In Section 3.1, the model predictions are shown against the
experimental data, where the differences in estimated kinetic
parameters will be discussed based on the importance of various
240
1D homogeneous model
1D heterogeneous model
k1
k2
k3
k4
k5
k6
k7
k8a
k9
k10
1.63E 05
2.29E 05
1.42E 05
2.29E 05
3.54E 03
1.64E 05
5.41E 05
5.10E 05
5.40E-07
1.35E-04
8.16E 06
2.26E 05
1.32E 05
2.13E 05
5.44E 03
1.68E 05
9.37E 05
6.07E 05
5.40E-07
1.07E-04
Table 11
Estimated kinetic rate constants for modeling CLR experimental data reported by
Jin (2002) at 600 1C.
Frequency factors
2D homogeneous model
2D heterogeneous model
k1
k2
k3
k4
k5
k6
k7
k8a
k9
k10
1.46E 05
4.38E 07
2.05E 07
1.61E 08
4.70E 07
8.56E 04
7.35E 09
0.00E 00
1.06E 08
2.38E 04
5.84E 06
1.26E 07
6.41E 07
8.50E 08
1.82E 06
3.10E 02
7.34E 06
1.62E 03
8.71E 04
1.96E 04
Table 9
Oxygen carrier physical properties and experimental conditions of chemical-looping xed-bed units studied in this work.
OC properties
Lbed (mm)
Dreactor (mm)
Q (ml/min)
U (W/(m2 K))
(kg/m3)
(1e5 Pa s)
Cpf (J/(kg K))
m, ax, rad [1E2 W/(m K)]
Dax, Drad, De (1E5 m2/s)
Re
Sc
Pea, Per
Pr [x1E2]
Sh
a
b
Jin (2002)
1D homogeneous model
2D homogeneous model
k1
k2
k3
k4
k5
k6
k7
k8a
k9
k10
3.65E 04
2.93E 05
2.20E 05
3.49E 06
6.30E 04
2.41E 01
1.59E 04
1.14E 02
5.56E 06
1.92E 02
3.39E 04
2.89E 05
3.21E 05
3.60E 06
5.58E 04
2.41E 01
1.59E 04
1.37E 02
5.65E 06
2.38E 02
Fig. 2. 1D model predictions of the experimental data reported by Iliuta et al. (2010).
2.25
5
R1 and R4
R2
R3
R5
R6 (reverse)
R7
R8
R9
R10
Effectiveness factor
Effectiveness factor
1.75
1.5
1.25
10
241
Time (seconds)
10
10
Time (seconds)
Fig. 3. Effectiveness factors for R1R10 from the 1D heterogeneous model for the xed-bed reactor reported by Iliuta et al. (2010).
242
reactions are kinetically-controlled because the calculated effectiveness factors are one or higher. The negligible effect of diffusional limitations inside the small particle supports the close
agreement between the homogeneous and heterogeneous simulations in terms of exit concentration proles (Fig. 2) and estimated
kinetic parameters (Table 10).
In comparison, resistance to mass and heat transfer is important for large particles (Dp 4 0.2 mm), where the local concentration and temperature inside the particle deviate from the surface.
The model needs to distinguish between the uid and solid phase
to adequately account for the internal and external diffusion into
the particle. The CLR xed-bed experiment conducted by Jin
(2002), who prepared cylindrical-shaped oxygen carriers of
4.0 mm diameter and 1.5 mm length, is modeled using the
developed heterogeneous and homogeneous models. Radial variations within the structure of the xed-bed are accounted for in
Times (minutes)
Fig. 4. 2D model predictions of the experimental data reported by Jin (2002).
R1
R2
R3
R4
2.5
Effectiveness factor
2.5
Effectiveness factor
R5
R6
R7
R8
R9
R10
1.5
0.5
1.5
0.5
0
0
10
Time (minutes)
15
20
10
15
20
Time (minutes)
Fig. 5. Effectiveness factor for R1R10 from the heterogeneous model for the xed-bed reactor reported by Jin (2002).
be neglected and a heterogeneous model is more realistic at predicting the experimental results.
3.2. Effect of dispersion
The presented models are developed to describe cases of nonideal plug ow, whereby components are transported by bulk ow
and convective diffusion (or dispersion). The CLC experiment
performed by Rydn et al. (2008b) is representative of a system
where there is signicant contribution to transport by dispersion.
The low Pclet number and even lower Reynolds number, shown
in Table 9, point towards a mixed reactor. The importance of axial
dispersion can be analyzed by noticeable differences in concentration proles from the dispersive and non-dispersive models
(Fig. 6). Dispersion serves to broaden concentration and temperature gradients and is important to characterize in the direction
of bulk ow. In addition to its strongly dispersive ow,
particle effects are negligible, owing to the small particle size
(Dp 120 m) and large pore size. As shown in Fig. 6, the homogeneous model has been able to adequately predict the experimental data. The heterogeneous model predictions are also
satisfactory, but the model does not bring added benet in terms
900
890
880
870
860
6
4
Time (min)
2
0 0
243
8
6
4
Bed Radial Direction (mm)
870
869
868
867
0.02
0.04
0.06
Fig. 7. Radial uid and solid temperature prole predicted by the 2D heterogeneous model for the experiment conducted by Rydn et al. (2008b).
900
244
890
880
870
860
850
30
20
Time (s)
10
0
868
866
864
1.5
0.5
870
0.02
0.04
0.06
Fig. 8. Radial uid and solid temperature prole predicted by the 2D heterogeneous model for the experiment conducted by Iliuta et al. (2010).
600
580
560
540
538
536
534
532
530
0.5
1.5
540
30
20
Time (min)
10
0
Fig. 9. Radial uid and particle temperature prole predicted by the 2D heterogeneous model for the experiment conducted by Jin (2002).
The radial temperature prole for the CLR experiment conducted by Jin (2002) is shown in Fig. 9 and predicts a temperature
drop of 58 1C in the reactor and 20 1C along the radial direction of
the bed due to insufcient heat transfer rate with the wall. The
temperature inside the particle remains constant; however, the
particle temperature can be 15 1C colder than the bulk. This
temperature difference results from the interfacial heat transfer
resistance which causes a lower temperature in the particle. Due
to moderate thermal gradients and strong dependency of the
reaction rates on temperature, modelmodel discrepancy between
the one- and two-dimensional models is observed. Radial mass
dispersion limitations arise in the Jin (2002) experiment because,
even though the reactor diameters chosen by Jin (2002) and Rydn
et al. (2008b) are comparable, the radial Pclet number is much
larger than that observed for Rydn et al. (2008b) and contribute
to a smaller dispersion rate, and thus lower heat transfer.
1
{ ;
n
57
{1;
58
59
o 0:15:
60
Satisfaction of the Mears and WeiszPrater criteria are determined for each reactant and corresponding reaction. Specically,
Eqs. (57) and (59) are used for R1R4 and Eqs. (58) and (60) for
R5R10. The equilibrium concentrations are calculated from the
equilibrium constants and the corresponding species concentration at the uid or solid phase. The reaction rates of the forward
reactions are integrated over the particle volume to give the
observed rates.
A common nding by investigators is that if mass interphase
gradients occur, then mass intraparticle gradients would occur as
10
0.1
0.01
0.1
Mears number
Mears number
103
104
105
104
106
R1
R2
R3
R4
107
108
245
10
15
R5-CH4
R5-H2O
R6-CO
R6-H2O
R7-CH4
105
20
106
10
R7-CO2
R8-CH4
R9-H2O
R10-CO2
15
20
Time (minutes)
Time (minutes)
Fig. 10. Mears numbers reported for R1R7. Fixed-bed unit operated by Jin (2002) is simulated using the heterogeneous model.
10
1
Weisz-Prater number
Weisz-Prater number
0.1
0.01
103
4
10
105
106
0.1
0.01
103
104
105
10
15
20
Time (minutes)
106
10
15
20
Time (minutes)
Fig. 11. WesizPrater numbers reported for R1R10. Fixed-bed unit operated by Jin (2002) is simulated using the heterogeneous model.
through the pores are generally higher than the rates of CO and
CO2 due to higher effective diffusivities. Therefore, if internal
transport resistance is signicantly controlling a reaction, it is
expected that the slower diffusing reactant will observe higher
WesizPrater numbers. By analysis of Fig. 11, the NiO reduction
reactions satisfy the WesizPrater criteria, and a few catalytic
reactions are limited by internal diffusion. The reaction most
affected by internal transport resistance is R6, with the diffusion
rate of CO to be the most limiting. This nding is expected as lm
resistance is also detected from analysis of the Mears number. R6
is close to equilibrium inside the particle and thus is controlled by
the slow rate of diffusion of CO through the particle. Other
reactions that are limited by internal limitations are the CO2
consuming reactions, R7 and R9, which exhibit slightly greater
than 1 WesizPrater numbers. This is likely due to a slow diffusion
rate CO2 leading to high concentration gradient and non-uniform
reaction rates. As shown, the internal mass transport, as determined by the WesizPrater number, plays a critical role on the
reaction rates, as concentrations deviate much from the bulk.
This analysis reveals the importance of internal and external
mass transfer in chemical-looping reduction reactions. The former
is primarily associated with the oxygen carrier properties, like
particle size and pore size, and the latter to ow characteristics. To
visualize the variation of solid concentration inside a particle at
any given time, the mole fraction of the gas is plotted with respect
246
0.21
CO2
CO
0
0...0.02
0.64
H2O
0
0.15
H2
0
0.32
CH4
Fig. 12. Solid concentration variation with particle radius at zp Lp/2. At each
radius, concentration of species is denoted by the color bar where at the surface
represents rp Rp and the center represents rp 0. Fixed-bed unit operated by Jin
(2002) is simulated using the heterogeneous model.
to the radius of the cylindrical particle (Fig. 12). The arc length at
each radial coordinate represents the fraction of each individual
gas species inside the particle (excluding inert gas). For instance, at
positions close to the inlet of the reactor, the surface concentration
is mainly H2O and CH4 because of the direct transfer with the bulk
uid. Approaching rc-0, the conversion of CH4 and H2O and
corresponding production of H2, CO, and CO2 is depicted by the
decreasing arc length of CH4 and H2O and increasing arc length for
H2, CO and CO2. As discussed, intraparticle gradients arising large
particle dimensions and slow diffusion rates lead to non-uniform
reaction rates and departure from optimum performance. In the
next section, the limits due to internal diffusion are explored
through design optimization of the oxygen carrier geometry to
meet chemical-looping standards.
S H2
F H2 ;out
2F CH4 ;in F H2 O;in
Original
Optimal size
Length (mm)
Diameter (mm)
X CH4
S H2
1.5
0.42.0
4
0.8
0.74
0.83
0.52
0.56
61
62
4. Conclusions
Table 13
Effect of particle size on X CH4 and SH2 for CLR xed-bed setup reported by Jin (2002)
at 600 1C.
X CH4
Fig. 13. Heterogeneous model predictions for the effect of particle size on the CLR
xed-bed experiment conducted by Jin (2002). Solid lines represent the reference
particle and dashed lines represent the optimal particle.
Model results reveal that the reaction rates are highly sensitive to
particle diameter, and insensitive to length. Transport resistance is
mainly associated with radial diffusion within the particle due to
good mixing in the axial direction. Therefore, a range of particle
lengths can be utilized without decreasing the oxygen carrier
The dynamic behavior of a xed-bed reactor for chemicallooping reduction is examined by a heterogeneous model, which is
shown to agree very well with literature data, for a variety of Nibased oxygen carriers, operating conditions, and reaction temperatures. As large particles are found to be affected by intra- and
j
kc,i
KCO,j
K CO2;j
K CH4;j
K H2;j
K5
K6
K7
K8
K9
K10
k1k4
k11k41
k5
k6
k7
k8
k9
k10
k51k101
L
Lp
Mi
Nu
OC
P
Pi
Pc
Pea
Per
r
rc
rj
R
Rp
Re
Rei
Rep
Sc
Sg
Sh
Sp
t
T
Tc
Tin
Tr
Ts
Tw
ui
u
u0
U
V
Vp
X
247
chemical reaction
mass transfer coefcient between bulk uid and oxygen
carrier particle [m/s]
adsorption coefcient of CO [bar 1]
adsorption coefcient of CO2 [bar]
adsorption coefcient of CH4 [bar1]
adsorption coefcient of H2 [bar1]
equilibrium constant for steam methane reforming [bar2]
equilibrium constant for water gas shift
equilibrium constant for dry reforming [bar2]
equilibrium constant for methane decomposition [bar]
equilibrium constant for carbon gasication by
steam [bar]
equilibrium constant for carbon gasication by CO2 [bar]
reaction rate constant for oxygen carrier reduction
reactions [m/s]
frequency factor for oxygen carrier reduction rate
constants
rate constant for steam methane reforming [bar0.5mol/
kgNi s]
rate constant for water gas shift [mol/bar kgNi s]
rate constant for dry reforming [mol/bar kgNi s]
rate constant for methane decomposition [bar-1]
rate constant for carbon gasication by steam [mol/
kgNi s]
rate constant for carbon gasication by CO2 [mol/kgNi-s]
frequency factor for catalytic reduction rate constants
bed length [m]
oxygen carrier particle length [m]
molar weight of species [g/mol]
uid to wall Nusselt number (hwDp/m)
oxygen carrier
reactor pressure [bar]
partial pressure of species i [bar]
critical pressure [bar]
axial Peclet number (u0Dp/Dax)
radial Peclet number (u0Dp/Drad)
reactor radial element
oxygen carrier radial element
rate of j reaction [mol/m3 s]
reactor radius [m]
oxygen carrier particle radius [m]
Reynolds number based on supercial velocity (uDp/)
Reynolds number based on interstitial velocity (uiDp/)
Reynolds number based on initial supercial velocity
(uoDp/(1 b)/)
Schmidt number (//Dm,i)
initial specic surface area of the oxygen carrier
[cm2/g OC]
Sherwood number (kc,iDp/Dm,i)
surface area of particle
time element [s]
temperature of the uid phase [1C]
critical temperature [1C]
temperature in the inlet [1C]
reduced temperature
temperature of the solid phase [1C]
temperature at the wall [1C]
interstitial velocity [m/s]
supercial velocity [m/s]
supercial velocity at the inlet [m/s]
overall heat transfer coefcient [J/m2 K s]
volume element
volume of particle
conversion of oxygen carrier
248
yi
yi,feed
z
zc
i
rad
m
s
tr,i
b
s
Acknowledgments
This material is based upon work supported by the National
Science Foundation under Grant No. 1054718.
Appendix
Mass and energy balances for transport through a cylindrical
particle are presented (Eqs. (63) and (64)).
2
C
C c;i 1 C c;i 2 C c;i
c c;i De;i
63
p Ri
2
r c r c
t
zc
r c
c C T;c C p;c 1 c p C p;s
2
T c
T c 1 T c 2 T c
s
2
2
t
r c r c r c zc
64
C c;i
j
kf ;i C c;i jrc Rc C i
r c rc Rp
C c;i
j
0
r c rc 0
65
66
De;i
C p;i
j
kf ;i C p;i jzp Lp C i
zp zp Lp
67
De;i
C c;i
j
kf ;i C c;i jzc Lp C i
zc zc Lp
68
s
T c
j
hf T p jrc Rp T
r c rc Rp
T c
j
0
r c rc 0
s
T c
j
hf T p jzc Lp T
zc zc Lp
72
These equations can be combined with the uid phase heterogeneous model equations in either the one-dimensional or twodimensional form.
Greek letters
Hj
c
b
j
ax
e0
T c
j
hf T c jzc 0 T
zc zc 0
69
70
71
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