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Scheme of the reacting mechanism for CH4 reduction with the Fe20cAl oxygen carrier.
a r t i c l e
i n f o
Article history:
Received 26 May 2014
Received in revised form 15 July 2014
Accepted 16 July 2014
Available online 25 July 2014
Keywords:
CO2 capture
Chemical Looping Combustion
Oxygen carrier
Iron
Reaction kinetic
Impregnated
CH4
CH4
Fe2O3
CO2 + H2O
O FeAl2O4
CO2 + H2O
CH4
O
FeAl2O4
Fe2O3
Fe2O3
Al2O3
Al2O3
Al2O3
1. Fresh parcle
2. Kinec control
3. Diusion control
a b s t r a c t
The objective of this work was to determine the kinetic parameters for reduction and oxidation reactions
of a highly reactive Fe-based oxygen carrier for use in Chemical Looping Combustion (CLC) of gaseous
fuels containing CH4, CO and/or H2, e.g. natural gas, syngas and PSA-off gas. The oxygen carrier was prepared by impregnation of iron on alumina. The effect of both the temperature and gas concentration was
analyzed in a thermogravimetric analyzer (TGA).
The grain model with uniform conversion in the particle and reaction in grains following the shrinking
core model (SCM) was used for kinetics determination. It was assumed that the reduction reactions were
controlled by two different resistances: the reaction rate was controlled by chemical reaction in a rst
step, whereas the mechanism that controlled the reactions at higher conversion values was diffusion
through the product layer around the grains. Furthermore, it was found that the reduction reaction mechanism was based on the interaction of Fe2O3 with Al2O3 in presence of the reacting gases to form FeAl2O4
as the only stable Fe-based phase. The reaction order values found for the reducing gases were 0.25, 0.3
and 0.6 for CH4, H2 and CO, respectively, and the activation energy took values of between 8 kJ mol1 (for
H2) and 66 kJ mol1 (for CH4). With regard to oxidation kinetics, the reacting model assumed a reaction
rate that was only controlled by chemical reaction. Values of 0.9 and 23 kJ mol1 were found for reaction
order and activation energy, respectively.
Finally, the solids inventory needed in a CLC system was also estimated by considering kinetic parameters. The total solids inventory in the CLC unit took a minimum value of 150 kg MW1 for CH4 combustion, which is a low value when compared to those of other Fe-based materials found in the literature.
2014 Elsevier B.V. All rights reserved.
Abbreviations: CGSM, Changing Grain Size Model; CLC, Chemical Looping Combustion; SCM, shrinking core model; DRM, Diffusion Reaction Model; ICP-AES, inductively
coupled plasma atomic emission spectroscopy; MVM, Modied Volumetric Model; TGA, thermogravimetric analyzer; TPR, temperature-programmed reduction; VM,
Volumetric Model; XRD, X-ray diffraction.
Corresponding author. Tel.: +34 976 733 977; fax: +34 976 733 318.
E-mail address: abad@icb.csic.es (A. Abad).
http://dx.doi.org/10.1016/j.cej.2014.07.083
1385-8947/ 2014 Elsevier B.V. All rights reserved.
266
Nomenclature
Ci
i
C
Ci,0
D
dp
Dpl
Dpl,0
Eact
Ech
Epl
EX
Fg
ks
ks,0
kX
kX,0
m
_c
m
_ OC
m
mOC
mOC;j
mox
mred
MO
N
0
Rg
RO
ROC
R0OC
T
T
Vg,Xg=0
Vg,Xg=1
xMeO
Xg
Xg,in
1. Introduction
The Intergovernmental Panel on Climate Change [1] concluded
in 2013 that climate change is unequivocal and that its main cause
is human activity. In order to avoid an excessive increase in the
average temperature in the Earth, which could lead to unpredictable consequences, it is necessary to apply mitigation measures
Xg,out
gas conversion at the reactor outlet
XS
conversion of solids
XS,ox in AR oxidation conversion of solids at the inlet of the air reactor
X0 S,ox in AR normalized oxidation conversion of solids at the inlet of
the air reactor when the reaction kinetics is controlled
by chemical reaction
XS,ox in FR oxidation conversion of solids at the inlet of the fuel
reactor
X0 S,ox in FR normalized oxidation conversion of solids at the fuel
reactor inlet when the reaction kinetics is controlled
by chemical reaction
XS,ox min minimum oxidation conversion of solids when the reaction kinetics is controlled by chemical reaction
XS,red in FR reduction conversion of solids at the inlet of the fuel
reactor
X0 S,red in FR normalized reduction conversion of solids at the fuel
reactor inlet when the reaction kinetics is controlled
by chemical reaction
Greek symbols
e
porosity of particles
eg
coefcient of expansion of the gas mixture
DH
variation of enthalpy for reduction or oxidation reactions (kJ mol1)
DH0C
standard heat of the gas fuel combustion (kJ mol1)
DXg
variation of gas conversion
DXS
variation of solids conversion between fuel reactor and
air reactor
DX0 S
normalized variation of solids conversion between fuel
reactor and air reactor when the reaction kinetics is
controlled by chemical reaction
DXS,red ch variation of solids conversion between fuel reactor and
air reactor when the reaction kinetics is controlled by
chemical reaction
sch
time for complete conversion when the chemical reaction controls the process (s)
so
time for complete conversion of particles in the air reactor (s)
spl
time for complete conversion when the diffusion
through the product layer controls the process (s)
sr
time for complete conversion of particles in the fuel
reactor (s)
s0r
time for complete conversion of particles in the fuel
reactor when the reaction kinetics is only controlled
by chemical reaction (s)
Uj
characteristic reactivity in the reactor j
U0j
characteristic reactivity in the reactor j when the reaction kinetics is only controlled by chemical reaction
Subscripts
I
gas (CH4, H2, CO)
J
reactor (AR = air reactor, FR = fuel reactor)
Ox
oxidation
Red
reduction
267
268
Table 1
Summary of kinetic data for Fe-based oxygen carriers.
Oxygen carrier
Method of preparation
Experimental
conditions
Kinetic model
Redox system
Reference
Fe2O3
dp = 125 lm
ROC = 10.0%
TGA; T = 7731173 K
CH4
Diffusion control
n = n.a.; Eact = 271 kJ/mol
Fe2O3/FeO
[30]
Fe2O3
dp = 300425 lm
ROC = 3.310.0%
Mechanical mixing
DRM
n = 1.0; Eact = 75 kJ/mol
n = 1.0; Eact = 94 kJ/mol
Fe2O3/Fe3O4
Fe3O4/FeO
[31]
Multi-crystal Fe
dp = n.a.
ROC = 30.0%
n.a.
TGA; T = 9731173 K
0.075.25 vol.% O2
Fe2O3/Fe
[32]
94 wt.% Fe2O3
dp = 60100 lm
ROC = 9.4%
TGA; T = 9731098 K
1535 vol.% CH4
Fe3O4/FeO
Fe2O3/Fe3O4
[33]
Impregnation
TGA; T = 7731273 K
Total pressure: 1
30 atm
570 vol.% H2
570 vol.% CO
521 vol.% O2
CGSM
n = 0.8; Eact = 24 kJ/mol
n = 1.0; Eact = 20 kJ/mol
n = 1.0; Eact = 14 kJ/mol
Fe2O3/Fe3O4
[13]
Mechanical mixing
TGA; T = 10731123 K
2070 vol.% CH4
2070 vol.% H2
2070 vol.% CO
SCM with Fg = 3
n = 0.2; Eact = 45 kJ/mol
n = 0.85; Eact = 22 kJ/mol
n = 1.0; Eact = 19 kJ/mol
Fe2O3/Fe3O4
FeAl2O4
[34]
Freeze granulation
TGA; T = 8731223 K
570 vol.% CH4
570 vol.% H2
570 vol.% CO
521 vol.% O2
SCM with Fg = 3
n = 1.3; Eact = 49 kJ/mol
n = 0.5; Eact = 24 kJ/mol
n = 1.0; Eact = 20 kJ/mol
n = 1.0; Eact = 14 kJ/mol
Fe2O3/Fe3O4
FeAl2O4
[14,29]
Mechanical mixing
TGA; T = 9731273 K
10 vol.% CH4
10 vol.% O2
TGA; T = 9731098 K
520 vol.% CH4
Fe2O3/Fe3O4
[21]
Fe2O3/Fe3O4
Fe3O4/FeO
[35]
Solid-state mixing
TGA; T = 8731223 K
3 vol.% H2 in Ar
Air
Fe2O3/Fe3O4
FeOFe
[36]
Pre-oxidized ilmenite
(Fe2TiO5)
dp = 150300 lm
ROC = 4.0%
Thermal treatment
TGA; T = 10731123 K
550 vol.% CH4
550 vol.% H2
550 vol.% CO
521 vol.% O2
SCM with Fg = 3
n = 1.0; Eact = 165 kJ/mol
n = 1.0; Eact = 109 kJ/mol
n = 1.0; Eact = 113 kJ/mol
n = 1.0; Eact = 12 kJ/mol
Fe2O3TiO2/
FeOTiO2
[37]
Thermal treatment +
activation in a uidized
bed
TGA; T = 10731123 K
550 vol.% CH4
550 vol.% H2
550 vol.% CO
521 vol.% O2
SCM with Fg = 3
n = 1.0; Eact = 136 kJ/mol
n = 1.0; Eact = 65 kJ/mol
n = 0.8; Eact = 80 kJ/mol
n = 1.0; Eact = 25 kJ/mol
Fe2O3TiO2/
FeOTiO2
[37]
98 wt.% Fe2O3
dp = 50200 lm
ROC = 3.2%
TGA; T = 10731223 K
33 vol.% CH4
Fe2O3/Fe3O4
[38]
the oxygen carrier particles are shown in Table 2. This oxygen carrier is hereafter referred to as Fe20cAl.
2.2. Characterization techniques
Different techniques were used to physically and chemically
characterize fresh particles of the Fe20cAl material. The total
Fe2O3 content was determined by inductively coupled plasma
atomic emission spectroscopy (ICP-AES) with a Jobin Ybon 2000
spectrometer. The mean particle size was measured by means of
size particle distribution, via laser diffraction technique, according
to the ISO 13320 Standard with LS 13 320 Beckman Coulter equipment. The skeletal density of the particles was determined with a
269
201
0.02
200400
3950
1.5
50.5
39.1
Fe2O3, a-Al2O3
Determined by ICP-AES.
DH1223K
348:7 kJ=mol
red
DH1223K
135:5 kJ=mol
red
DH1223K
168:1 kJ=mol
red
2.3. Experimental setup and procedure
The kinetics of reduction and oxidation reactions with the Febased oxygen carrier was determined from experiments at atmospheric pressure in a TGA, CI Electronics type, described elsewhere
[37]. Three different gases were used as reducing agents, i.e., CH4,
CO and H2, whereas O2 was used for the oxidation reactions. In all
cases, the redox agents were diluted in N2.
The samples of approximately 50 mg of oxygen carrier were
loaded in a platinum basket, and a gas ow of 25 LN/h was fed into
the reactor of the TGA system. External and interparticle diffusion
have low relevance under these conditions [14]. Furthermore,
Garca-Labiano et al. [49] found that oxygen carrier particles can
be considered isotherm under usual operating conditions, and that
mass transfer inside them is negligible.
The oxygen carrier particles were heated to the operating temperature in an air atmosphere. When the sample weight was stabilized, the oxygen carrier was exposed to a reduction and an
oxidation cycle. In order to prevent the mixing of fuel and air, a
2-min ow of N2 was fed between the reducing and oxidizing period. This material showed excellent stability in redox reactivity
over hundreds of cycles [17]. Data obtained during the rst redox
cycle were selected for kinetic determination.
Different fuel gas (CH4, CO and H2) concentrations ranging from
5 to 60 vol.% were used to determine the kinetics of the reduction
reaction. In order to prevent carbon deposition, 20 vol.% of H2O or
CO2 were added to the reacting mixture when CH4 or CO were used
as fuel gases, respectively. To analyze oxidation reactivity, it was
initially necessary to reduce the sample to FeAl2O4, simulating
the behavior expected in a CLC process when iron oxide (Fe2O3)
supported on Al2O3 is considered as the oxygen carrier. In this case,
as mentioned in the introduction section, it was possible to reach
complete fuel combustion to CO2 and H2O, obtaining FeAl2O4 as
the reduced form of the oxygen carrier. For this reason, the previous reducing periods were conducted at 1223 K in a 15 vol.%
CO + 20 vol.% CO2 (N2 to balance) atmosphere. Under these conditions and with the addition of CO2, the reduction of Fe2O3 was
stopped at FeAl2O4, and no further reduction to metallic iron was
produced. This fact was also conrmed by XRD analysis of reduced
samples. The oxygen carrier particles were subsequently ready to
be subjected to the oxidizing period. The O2 concentration for oxidation was varied from 5 to 21 vol.%.
To study the effect of the temperature on reduction and oxidation reaction rates, this parameter was varied between 973 and
1323 K. When the reduction reaction was studied, the fuel gas
DH1223K
227:1 kJ=mol
ox
4
The conversion of solids, XS, was calculated with Eqs. (5) and (6)
for the reduction or oxidation period, respectively.
X S;red
mox m
mox m
X S;ox
m mred
mox m
1
ROC mox
mox mred
270
1.0
CO
8.5
H2
9.0
CH4
0.8
0.6
0.6
Conversion, Xs,red
Conversion, Xs,red
H2 concentration (vol. %)
0.8
0.4
0.4
0.2
9.5
0.2
0.0
0
10
15
20
25
30
Time (s)
0.0
0
10.0
400
500
600
700
800
900
1000
1100
1200
Temperature (K)
Fig. 1. TPR prole of fresh particles of the Fe20cAl oxygen carrier.
1300
100
200
300
400
500
600
Time (s)
Fig. 2. Conversion vs time curves during reduction period with CH4, CO and H2.
Testing conditions: T = 1223 K; reducing gas mixtures: 15 vol.% H2 + 20 vol.% H2O;
15 vol.% CO + 20 vol.% CO2; and 15 vol.% CH4 + 20 vol.% H2O (N2 to balance).
varied from 0 to 48 vol.%. When H2O was not added to the reducing
gas mixture, the oxygen carrier was reduced beyond FeAl2O4,
although it could not be completely reduced to metallic iron. When
H2O was added to the reducing gas, the reaction rate stopped after
50 s of reduction at a solids conversion of 0.75 approximately. A
further increase in the amount of H2O slightly changed the oxygen
carrier reactivity and the reaction rate with H2. This means that the
reduction of FeAl2O4 to Fe0 is prevented if H2O is present in the
reducing gas mixture.
On the other hand, Fig. 3b shows the conversion vs time curves
obtained with 5 vol.% CO when the CO2 concentration was
increased from 0 to 50 vol.%. In all cases, the reaction rate was very
fast up to a solids conversion value of 0.75 approximately. This
degree of conversion was obtained after 30 s of reduction reaction.
For higher times, the reaction rate was considerably decreased, but
the oxygen carrier particles were able to be reduced completely to
FeAl2O4. When CO2 was not added to the reducing gas mixture, the
oxygen carrier was reduced beyond FeAl2O4. When CO2 was added
together with the reducing gas, the behavior of the oxygen carrier
was practically the same, regardless of the CO2 concentration used.
Thus, the reduction reactivity with CO was hardly affected when
the amount of CO2 was varied from 10 to 50 vol.% in the reaction
gas mixture.
From the results obtained in this section it can be concluded
that the presence of different concentrations of H2O and CO2, the
1.0
(a)
Conversion, Xs,red
0.8
0.6
0.4
0 vol.% H2O
10 vol.% H2O
271
main products of the combustion reaction, in the reacting gas mixtures affected neither the reaction rate nor the reactivity of the
oxygen carrier. Only the avoidance of these gases in the reaction
gas mixture increased the reaction rate during the reaction at high
solids conversion values, characterized by slow reactivity. However, H2O and CO2 are considered to be in the gas reacting in the
fuel reactor because they would be quickly generated in the fuel
reactor, or can even be present in uidizing gases, e.g. in the fuel
gas itself or in gases introduced into loop seals. Therefore, kinetic
determination was obtained considering the presence of H2O or
CO2 in the reacting gas mixture.
3.2.3. Effect of gas concentration
The concentration of fuel gases inside a fuel reactor varies with
height along the uidized bed. The oxygen carrier is usually in contact with high fuel concentration values at the bottom, whereas the
concentration of fuel gases decreases dramatically at the top of the
bed in such a way that the gaseous mixture is mainly composed of
CO2 and H2O.
The effect of fuel gas concentration on the reduction of the
Fe20cAl oxygen carrier was determined by carrying out experiments in a TGA with different concentrations of CH4, CO and H2
at a temperature of 1223 K. In the cases of CH4 and H2, the fuel
gas concentration was varied from 5 to 30 vol.%, while the concentration of CO was increased up to 60 vol.%. The conversion vs
time curves corresponding to the three fuel gases are shown in
Fig. 4(ac). An increase in the reaction rate was noticed during
the rst part of the reduction period as the fuel gas concentration
was increased. At the beginning of the period, the reaction rate was
very fast for all the fuel gases (for 10 s for CH4 and H2 and for 20 s
for CO, respectively), however it decreased immediately, continuing at a very low rate for the rest of the period. In this second period, characterized by a low reaction rate, the fuel gas concentration
barely affected the reduction rate of the oxygen carrier with the
different fuel gases. This behavior indicates that the corresponding
reduction reactions are controlled by two different resistances. The
change in controlling mechanism happens at conversion values of
0.45 for CH4 and H2 and at 0.7 for CO.
20 vol.% H2O
30 vol.% H2O
0.2
40 vol.% H2O
48 vol.% H2O
0.0
0
50
100
150
200
250
300
Time (s)
1.0
(b)
Conversion, Xs,red
0.8
0.6
0.4
0 vol.% CO2
10 vol.% CO2
20 vol.% CO2
0.2
30 vol.% CO2
40 vol.% CO2
50 vol.% CO2
0.0
0
20
40
60
80
100
120
Time (s)
Fig. 3. Effect of H2O and CO2 presence on the reduction conversion of the Fe20cAl
oxygen carrier with H2 (a) and CO (b). Testing conditions: T = 1223 K; reducing
gases: 5 vol.% H2 and 5 vol.% CO.
272
1.0
(a)
Conversion, Xs,red
0.8
0.6
0.4
5 vol.% CH4
10 vol.% CH4
15 vol.% CH4
0.2
20 vol.% CH4
30 vol.% CH4
0.0
0
10
20
30
40
50
60
Time (s)
1.0
(b)
Conversion, Xs,red
0.8
0.6
0.4
5 vol.% H2
10 vol.% H2
0.2
15 vol.% H2
20 vol.% H2
30 vol.% H2
0.0
0
10
20
30
40
50
60
Time (s)
(c)
Conversion, Xs,red
0.8
0.6
0.4
5 vol.% CO
0.2
15 vol.% CO
30 vol.% CO
60 vol.% CO
0.0
0
20
40
60
80
100
120
Time (s)
Fig. 4. Effect of fuel gas concentration on the reduction reaction for CH4 (a), H2 (b)
and CO (c). T = 1223 K. The continuous lines are results predicted by the model
using kinetic parameters obtained in this work.
273
1.0
1.0
15 vol.% CH4
1073 K
1123 K
1173 K
0.6
0.4
0.2
0.6
0.4
1073 K
1123 K
1073 K
1223 K
0.2
0.0
0.0
0
10
20
30
40
50
60
20
40
60
Time (s)
1.0
80
100
120
Time (s)
1.0
15 vol.% H2
(c)
0.6
0.4
1073 K
5 vol.% H2
973 K
1073 K
1123 K
1173 K
0.8
Conversion, Xs,red
0.8
Conversion, Xs,red
(b)
0.8
1223 K
1273 K
Conversion, Xs,red
Conversion, Xs,red
0.8
15 vol.% CO
(a)
(d)
1223 K
1273 K
0.6
1323 K
0.4
1123 K
0.2
0.2
1173 K
1223 K
1273 K
0.0
0.0
0
10
20
30
40
50
60
10
20
30
Time (s)
40
50
60
Time (s)
1.0
1.0
0.8
0.8
Conversion, Xs,ox
Conversion, Xs,ox
Fig. 5. Effect of the temperature on the reduction reaction of the Fe20cAl oxygen carrier. Reducing gas mixtures: (a) 15 vol.% CH4 + 20 vol.% H2O; (b) 15 vol.% CO + 20 vol.%
CO2; (c) 15 vol.% H2 + 20 vol.% H2O; and (d) 5 vol.% H2 + 48 vol.% H2O. The continuous lines are results predicted by the model using kinetic parameters obtained in this work.
0.6
0.4
0.6
0.4
1073 K
1123 K
1173 K
1223 K
1273 K
5 vol.% O2
0.2
0.2
10 vol.% O2
15 vol.% O2
21 vol.% O2
0.0
0.0
0
10
20
30
40
50
60
Time (s)
10
20
30
40
50
60
Time (s)
Fig. 7. Effect of temperature on the oxidation reaction of the Fe20cAl oxygen carrier
with O2 (10 vol.%). The continuous lines are results predicted by the model using
kinetic parameters obtained in this work.
reaction still takes place on the grain surface, but the reaction rate
is now limited by oxygen diffusion through the product layer. A
third step, based on the reaction of FeAl2O4 with H2 or CO in a
highly reducing atmosphere to form metallic iron, was not
considered for the reacting model since this step must not take
place in a CLC process if complete combustion of the fuel gas is
desired, because of thermodynamic restrictions for H2 or CO conversion when FeAl2O4 is reduced to Fe0 [9].
274
Taking the above comments and conditions in the TGA into consideration, the dependence of solids conversion with time for this
Fe-based oxygen carrier is described by the following equation
[55]:
where sch and spl are the times for complete reduction conversion of the particle owing to the chemical reaction and the diffusion through the product layer. sch is calculated as follows:
sch
-2.5
nCH4= 0.25
ln (1/ch)
-2.0
-3.0
nH2= 0.3
nCO= 0.6
1
ks C ni
CH4
-3.5
H2
nO2 = 0.9
CO
ks ks;0 e Rg T
spl
1
Dpl C ni
O2
-4.0
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
ln (Ci)
Fig. 9. Plot of ln (Ci) vs ln (1/sch) to obtain the reaction order with respect to CH4, H2,
CO and O2.
10
11
where
EX
kX kX;0 eRg T
12
t sch X S;ox
13
t sch X S
14
sch values are obtained at different Ci by tting each experimental curve. Thus, the following equation was deduced from expression (8).
ln
sch
ln ks n ln C i
15
Fig. 8. Scheme of the reacting mechanism for CH4 reduction with the Fe20cAl oxygen carrier.
to 23 kJ/mol. The value of the activation energy for oxidation reaction, i.e., 23 kJ/mol, was higher in comparison with other kinetic
studies conducted in the literature on Fe-based oxygen carriers
[21,29,36]. The opposite behavior was found with the activation
energies for reduction reactions with CO and H2. In these cases,
the values determined in this work were slightly lower than the
ones found in the literature, see Table 1.
As mentioned previously, diffusion through the product layer
became the limiting step that controlled the reduction reactions
at higher solids conversion values. The corresponding kinetic
parameters tting the conversion curves for different gas concentrations and temperatures were also calculated.
It was found that the reacting gas concentration had no inuence over the diffusion mechanism. Furthermore, it was observed
that the decay constant, kX, was not dependent on the reacting
temperature since there were no perceptible variations in the slope
of the conversion vs time curves when the reaction rate was controlled by the diffusion mechanism. It should be noted that parameter kX affects the intensity of the reaction rate decrease in the
second step, which was similar at all temperatures tested in this
work. Therefore, the activation energy for kX was considered to
be EX = 0 J mol1.
Fig. 10(b) illustrates a plot of ln (Dpl) vs the inverse of the temperature in order to determine the pre-exponential factor, Dpl,0, and
the activation energy, Epl, for the reduction reactions. Both parameters achieved the highest values for CH4 reduction, see Table 3.
-2.25
CH4
(a)
-2.50
H2
ECH4 = 66 kJ/mol
CO
EH2 = 8 kJ/mol
ln (ks)
-2.75
O2
-3.00
ECO = 14 kJ/mol
-3.25
-3.50
-3.75
8.0
8.5
9.0
9.5
-1
_ OC
m
CO
6
4
ln (Dpl)
4. Discussion
CH4
(b)
8
Finally, the decay constant, kX, was also calculated. This parameter
took the highest value for the reduction reaction with CH4, since
the decrease in the reaction rate with time was slightly more
noticeable with this gas than with the other reducing gases. Table 3
shows the kinetic parameters obtained in this work for reduction
of Fe20cAl material with CH4, H2 and CO, as well as for oxidation
with O2.
As can be observed in Figs. 47, the theoretical curves determined from the reaction model correctly predicted the experimental results obtained during the whole reacting time for each type of
gas, temperature and concentration considered.
EO2 = 23 kJ/mol
7.5
275
_c
m
DX s
16
-1
_c
m
-1
-2
-4
-6
7.5
8.0
8.5
9.0
9.5
2 d MO
ROC DH0C
17
276
Table 3
Kinetic parameters for reaction of Fe20cAl oxygen carrier particles with reducing (CH4, H2, CO) and oxidizing gases (O2).
n
ks,0
Ech
n0
Dpl,0
Epl
kX,0
EX
Units
CH4
H2
CO
O2
0
0
m3n moln s1
kJ/mol
kJ/mol
0.25
4.34 101
66
0
9.80 1030
672
20
0
0.3
1.45 101
8
0
1.40 1013
288
14
0
0.6
1.59 101
14
0
2.29 109
204
10
0
0.9
3.64 101
23
expresses the molar ratio between the potential ow oxygen in circulating oxygen carrier and the required ow of oxygen for fuel
combustion. Thus, the / parameter is also included in Fig. 11. It
_ OC parameter decreased as the variation of
can be observed that m
solids conversion, DXs, increased. The minimum circulation rate
for CH4 combustion with the Fe20cAl oxygen carrier at DXs = 1
was 4.0 kg s1 MW1. On the other hand, the solids circulation ow
was dependent on the operating conditions and the conguration
of the riser in the CLC unit. For usual conditions of velocity, temperature and excess of air, the maximum circulation rate in a CLC
system is established at 16 kg s1 MW1 [29]. Therefore, a solids
conversion higher than 0.25 would be necessary for this material
in order to maintain the ow of solids under the average maximum
limit of 16 kg s1 MW1 if CH4 is used as the feed gas for the CLC
unit.
Furthermore, it must be taken into consideration that temperature greatly affected the reduction conversion degree of the oxygen
carrier, and, consequently, the solids circulation rate. It can be
inferred from Fig. 5 that, depending on the operating temperature
in the CLC system, the maximum variation of reduction conversion
reached by this material in the fuel reactor would be different. As a
rst approximation, it was assumed that the oxygen carrier would
only be reduced in a real CLC system up to solids conversion values
within the range at which the reaction kinetics was controlled by
chemical reaction. Therefore, the maximum variation of reduction
conversion was determined from experimental results for the different reacting gases in a usual range of operating temperatures,
see Fig. 12. From the results shown in Figs. 11 and 12, important
conclusions regarding adequate operating temperatures in the fuel
_c
mOC;FR m
sr
18
UFR
40
2.5
1.67
1.25
1.0
0.8
Xs,red ch
30
20
1100
825 CK
16
10
0.6
0.4
0.2
1000
1273CK
CH4
H2
CO
0.0
1050
0
0.0
0.2
0.4
0.6
0.8
1100
1150
1200
1250
1300
1.0
Xs
Fig. 11. Solids circulation rate vs variation of solids conversion in the fuel reactor
using the Fe20cAl material as oxygen carrier. Reducing gas: CH4.
Temperature (K)
Fig. 12. Variation of reduction conversion in chemically controlled reaction for
Fe20cAl material reached in the fuel reactor for CH4, H2 and CO combustion in a
usual range of operating temperatures for CLC.
277
_c
mOC;AR m
so
19
UAR
i
C
R
DX g C ni;0
h
in
Xg;out
Xg;in
1eg X g
1X g
20
dX g
eg
V g;Xg 1 V g;Xg0
V g;X g 0
21
where V g;Xg0 and V g;Xg1 are the volumes of the gas mixture at Xg = 0
and Xg = 1, respectively. This parameter changes its value depending
on the fuel gas considered for the CLC process. For example, eg takes
a value of 2 for CH4, 0 for H2 and CO and 0.21 for the oxidation
reaction with air.
The average concentrations were determined at 1223 K in both
reactors taking into consideration the reaction order, n, shown in
Table 3. When 100 vol.% fuel gas concentration at the fuel reactor
inlet and a nal gas conversion of 0.999 was considered, the average CH4, H2 and CO concentrations in this reactor were 15.7, 30.7
and 24.6 vol.%, respectively. On other hand, for an oxidation reaction in the air reactor with 21 vol.% O2 and 20 vol.% excess air,
the resulting average O2 concentration was 11.2 vol.%. The times
for complete conversion of the particles in the fuel reactor, considering a temperature of 1223 K, were 13.7, 11.0 and 14.2 s for CH4,
H2 and CO combustion, respectively. In the case of oxidation
reaction, the time for complete conversion of the Fe20cAl oxygen
carrier particles in the air reactor at 1223 K was 23.9 s.
Eqs. (18) and (19) are also dependent on parameters UFR and UAR
which are the characteristic reactivity in the fuel reactor and air
reactor respectively. Assuming perfect mixing of the solids in both
reactors, Uj can be expressed as a function of the variation of solids
conversion and as a function of the solids conversion in the inlet of
each reactor. For the kinetic model used in this work, the expressions
for Uj are the following and take a value between 0 and 1:
UFR 1 exp
UAR 1 exp
1 X S;red in FR
UFR
DX S
1 X S;ox in AR
UAR
DX S
22
23
24
s0r DX s;red ch sr
the kinetic model used in this work, the highest value of parameter
Uj is 1. The minimum solids inventories for CH4, H2 and CO combustion were 149, 116 and 109 kg MW1, respectively, see Table 4.
A comparison between the expected performance of different oxygen carriers can easily be made by contrasting the minimum solids
inventory values. The minimum solids inventories obtained for the
Fe20cAl material were compared to the ones found for the Fe45Al
oxygen carrier prepared by freeze granulation [29] or ilmenite [37].
In fact, the high reactivity of Fe20cAl with CH4 resulted in a lower
solids inventory in the fuel reactor for Fe20cAl (54 kg/MWth) compared to that of Fe45Al (950 kg/MWth) and of activated ilmenite
(272 kg/MWth), even when the iron content in these materials
was higher. Thus, it can be concluded that the Fe20cAl oxygen carrier, prepared by the incipient impregnation method, presents
much higher reactivity with CH4, and hence the minimum solids
inventory needed in the CLC unit reactor is lower in comparison
with the other Fe-based material.
In real conditions, the solids inventory depends on the degree of
oxidation of the oxygen carrier particles in the inlet of both reactors and on the value of DXS. Furthermore, it must be also taken
into consideration that in real conditions, the variation of solids
conversion, DXS, is dened by the solids circulation rate established in the CLC system, see Eq. (16), and it is possible that the
oxygen carrier will not completely oxidized when it enters the fuel
reactor .
Fig. 13 illustrates the total solids inventory of the Fe20cAl oxygen carrier needed in a CLC unit for CH4 combustion as a function
of the oxidation conversion of the particles at the inlet of the fuel
reactor considering that the variation of solids conversion, DXS, is
limited to the minimum value related to the maximum solids
circulation rate of 16 kg s1 MW1. Thus, these calculations were
made for a variation of solids conversion of 0.25, see Fig. 11. This
value of DXS is adequate because it is within the optimum range
proposed by Abad et al. [29], i.e., DXS = 0.20.5, to obtain low solids
inventories and reasonable circulation rate values.
Now, the method to calculate UFR was modied from that
shown by Abad et al. [29] to consider the active Fe2O3 fraction as
being only the fraction reacting with chemical control, but the
solid fraction reacting with slow diffusional controlled reaction
was assumed to be inert; see Appendix A. Thus, to calculate UFR
by Eq. (22), a modied conversion X 0S; red was used, which ranges
from 0 to 1 when the solids conversion varies from 0 to X S; red ch .
Considering the case of CH4 combustion at 1223 K, X S;red ch was
established at 0.52 approximately (see Fig. 12), which means that
for a variation of solids conversion of DX S 0:25, DX 0S takes a value
of 0.48.
With the above considerations, the inlet conversion of solids to
the fuel reactor must fulll X S;ox in FR > DX S 1 X S;red ch because
the fraction 1 X S;red ch is considered inert for the reduction reaction. It can be observed in Fig. 13 that the minimum oxidation conversion at the inlet of the fuel reactor is X S;ox in FR 0:73 for
DX S 0:25. If the value of parameter X S;ox in FR is very close to the
aforementioned limit, the availability of oxygen for the reduction
conversion will be low because the oxygen carrier particles are
reduced to a great extent and, consequently, the required solids
inventory in this reactor will tend towards innity. At the same
Table 4
Minimum solids inventories for CH4, H2 and CO combustion in fuel and air reactors of
a CLC unit with Fe20cAl as oxygen carrier (T = 1223 K).
25
The minimum solids inventory was obtained when the variation of solids conversion in the reactors was very low (DXS ? 0)
and the characteristic reactivity reached the highest value. For
CH4
H2
CO
54
95
149
37
79
116
42
68
109
278
500
400
300
AR
Total
200
FR
100
0
0.70
0.75
0.80
0.85
0.90
0.95
1.00
Xs,ox in FR
Fig. 13. Total solids inventory of the Fe20cAl material as a function of the solids
conversion at the inlet of the fuel reactor (X S;ox in;FR ). Reducing agent: CH4. DXS = 0.25.
T = 1223 K. It is assumed that the Fe20cAl oxygen carrier is only reduced up to
solids conversion values within the range at which the reaction kinetics is
controlled by chemical reaction.
5. Conclusions
The isothermal method in a TGA was identied as the proper
method with which to obtain the reduction and oxidation kinetics
of the Fe20cAl oxygen carrier with CH4, H2, CO and O2 as reacting
A:1
279
(a)
Xs,red
(b)
X's,red
Xs,red ch
'r
'r
Fig. A1. (a) Determination of s0r and X S;red ch parameters from reduction conversion vs time curve (Fig. 5a). (b) Normalized reduction conversion vs time curve when the
reduction reaction is controlled by chemical reaction. Operating conditions: reducing gas, 15 vol.% CH4; temperature: 1223 K.
Therefore, the solid fraction reacting with slow diffusioncontrolled reaction is assumed to be inert. The solids inventory
in the fuel reactor can be calculated in these conditions as follows:
mOC;FR
2 d MO
DH0C
s0r 1
R0OC U0FR
A:2
s0r DX s;red ch sr
A:3
sr
ROC
s0r
A:4
R0OC
mOC;FR
2 d MO
DH0C
sr 1
ROC U0FR
A:5
The characteristic reactivity in the fuel reactor was also redened according to the following expression:
U0FR 1 exp
1 X 0S;red in FR
DX 0S
U0FR
A:6
X 0S;red in FR
DX 0S
X S;red in FR
;
X S;red ch
DX S
;
X S;red ch
DX S < X S;red ch
A:7
A:8
X 0S;ox in FR
A:9
A:10
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