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1. INTRODUCTION
Currently, the generation and use of energy sources is one of
the human activities that produces the greatest impact on the
environment due to the continuing depletion of the natural
resources needed to meet the growing demand of our cities and
industries and the need of modern societies in developing
countries to have a better lifestyle. The processes of energy
transformation from fossil fuels reect this reality, which release
a lot of CO2 into the atmosphere, estimated to represent onethird of the total CO2 emitted by human activity.1 In order to
solve this problem, several technologies have been developed,
such as precombustion, postcombustion, and oxy-combustion,
which require signicant energy expenditure, as a consequence
reducing process eciency considerably. However, in recent
years, a new technology known as chemical looping combustion (CLC) has emerged, allowing the inherent separation of
carbon dioxide at low cost.1
Despite the advantages of CLC with respect to the inherent
CO2 capture, this technology still has limitations, mainly due to
the problems with oxygen carriers during the cycles. Therefore,
the approach that has been given to research is mainly based on
the synthesis and characterization of oxygen carriers, leaving the
theoretical aspects and modeling behind. Among the investigations addressed the development of oxygen carriers are the by
Linderholm et al.2 and to Mattisson et al.,3 where they worked
with oxygen carriers based on nickel and iron, which are the
most used in the CLC process.
In other research, such as Chuang et al.,4 was tested copperbased oxygen carriers that have advantages over conventional
materials, such as high reactivity and the exothermicity in the
reactions of reduction and oxidation.5 These oxygen carriers
agglomeration problems arose because of the low melting point
of copper, and only until recently, with works by authors such
as Diego et al.6 and Gayan et al.,7 it was possible to optimize
the preparation of such transporters, reviving the interest of
researchers for these materials.
On the other hand, it can be said that has not been carried
out extensive research focused on the modeling of oxidation
and reduction reactions of particles of a copper-based oxygen
carrier.8,9 Therefore, the general objective of this work was to
2014 American Chemical Society
2. EXPERIMENTAL SECTION
2.1. Preparation of Oxygen Carriers. For the synthesis of
copper-based oxygen carriers have been employed dierent
synthetic methods such as coprecipitation, mechanical mixing,
and spray drying impregnation. The most commonly used
support is SiO2, which shows a good reactivity with copper and
inertia; however, the CuO decomposed to Cu2O.10,11 TiO2 was
also tested as support, but showed a strong tendency to form
CuTiO4.1
It has been found that the best method of preparation of
copper-based oxygen carriers is impregnation of -alumina,
-alumina, MgAl2O4, or NiAl2O4Al2O3 with contents of CuO
under 20 wt % to avoid agglomeration.12
In this paper, two methods of impregnation were used, the
rst was excess wet impregnation based on the work of Celaya13
and the second was the incipient impregnation was used in the
work of Jimenez14 for impregnating metals in carbonaceous
materials. In both methods, solution Cu(NO3)23H2O was used
at dierent concentrations as precursors and -alumina Puralox
NWa-155 was used as support, and also, a single impregnation
to obtain each carrier was made with dierent concentrations
of the precursor solution. This is to nd the maximum concentration at which the impregnation was successful without
causing blockage of pores, poor dispersion, or excessive
reduction of the surface area.
Excess Wet Impregnation. In this method, an excess of the
precursor solution was used. The steps followed for the
preparation of materials by this technique are shown below:
I. The alumina powder Puralox NWa-155 was immersed in
the solution of Cu(NO3)23H2O with stirring for 12 h at
room temperature.
Received: February 25, 2014
Revised: July 28, 2014
Published: July 28, 2014
5434
Article
the oxygen carrier I21 was not studied further because despite
a 1.18 M solution was used, almost the same amount of
CuO impregnated was obtained with the carrier I20, which was
synthesized with a solution 0.94 M. Therefore, it can be deduced
that the impregnation is not satisfactory in concentrations of the
precursor that exceed a limit value, probably because a blocking
of the pores of the material and poor dispersion occurs, by
which, if higher amounts are to be impregnated is it necessary to
repeat the impregnation process several times at moderate
concentrations of the precursor solution.6,7,15,16
2.2. Oxygen Carriers Characterization. SEM (EDX)
Analysis. SEM JEOL JSM 5910 LV equipment with BES and
SEI detectors was used, for image generation and EDS and
WDS detectors for qualitative and quantitative chemical analysis
on conductive and nonconductive samples.
Scanning Electron Microscopy (SEM). Initially, it can be
seen in the Figure 1a and b micrographs SEI and BES of Al2O3,
respectively, which shows that particles have irregular shapes
with rounded edges and varying particle sizes.
In Figure 2a and b, the oxygen carrier H9 micrographs SEI
and BES, respectively, are shown. One can notice that the
%w CuO
H9
H10
H12
I20
I23
I21
1.60
2.40
3.60
0.94
1.41
1.18
8.62
9.88
11.76
20.32
22.96
20.66
Article
O (% W)
Al (% W)
Cu (% W)
Al2O3
H9
H10
I20
I23
37.6
46.2
35.5
39.3
35.6
62.4
46.8
47.6
49.2
37.6
0.0
7.0
16.9
11.5
26.8
sample
Al2O3
H9
H10
I20
I23
144
107
96
49
14
Article
Oxidation
1
O2 + Cu CuO
(2)
2
3.1. Determination of Kinetic Parameters. To determine the kinetic parameters of dierent reactions with oxygen
carriers shrinking core model in the grain was used. This model
considers the constant size particle formed by nonporous grains
initially. The grain reacts, leaving a porous layer of the reaction
product that becomes a means of transport of reactants and
products (see Scheme 1). However, the shrinking core model
porosity
Al2O3
H9
H10
I20
I23
0.43
0.40
0.37
0.32
0.05
92.20
105.46
103.41
78.51
99.90
0.56
0.53
0.49
0.42
0.07
Al2O3
H9
H10
I20
I23
1300.00
1412.07
1428.47
1564.17
1598.53
577.63
669.87
732.55
904.63
1489.87
mR rg
=
(4)
bkC n
rg =
3(%wR )
SR MR mR
k = k 0e(Ea / RT )
5437
(5)
(6)
dx.doi.org/10.1021/ef5012403 | Energy Fuels 2014, 28, 54345444
Article
X red =
mox m
mox mred
Xox = 1 X red
(7)
(8)
where
m = instantaneous mass of oxygen carrier
mox = mass of fully oxidized oxygen carrier
mred = mass fully reduced oxygen carrier
To determine the kinetic parameters is necessary to avoid
diusion problems, which was achieved using a very small
amount of sample (10.23 mg), and a gas velocity sucient to
overcome the resistance to external mass transfer (200 cm3
STP/min). The H2 passes for 3 min and then purged with He
for 5 min to ensure that no explosions were presented. After
that, the O2 was allowed to ow for 3 min completing the cycle.
3.2. Determination of Reaction Order (H9). First, it is
necessary to determine the time of complete conversion
reactions H9 transporter from eq 3. This is achieved by plotting
1 (1 X )1/3 vs t. The slope of the line formed will be equal
to 1/. Figure 7 shows 1 (1 X )1/3 vs t at concentrations of
10%, 20%, and 40% of hydrogen.
For concentrations of 10%, 20%, and 40% complete conversion
times of 22.7, 12.7, and 8.9 s, respectively, were obtained.
Now, using eq 4 can calculate the reaction order. If the
natural logarithm is applied to each side of the equation ln
= ln((mRrg)/(bk)) n*ln C is obtained.Therefore, if ln vs
ln C is plotted, the slope of the line is form is equal to the
reaction order. Figure 8 shows the graph of ln vs ln CH2 to
concentrations of 10%, 20%, and 40% of hydrogen.
The data obtained from the above graph shows that the
reaction order for the reduction reaction is equal to 0.7.
For the oxidation reaction concentrations of 5%, 13%, and 21%
were used (the maximum concentration at which the oxygen
working is 21% because it is in the air having approximately) and
complete conversion time of 63.5, 23.8, and 20.4 s, respectively.
From these data, it was concluded that the reaction order for the
oxidation of oxygen carrier is equal to 0.8.
3.3. Determination of Pre-Exponential Factor and
Activation Energy (H9). To nd the values of pre-exponential
factor and activation energy of reduction reaction complete
Article
pre-exponential factor
(mol1n m3n2 s1)
activation energy
(J/mol)
reduction H9
oxidation H9
reduction I20
oxidation I20
0.7
0.8
0.7
0.9
0.031
0.000554
0.042
0.000727
35879
11345
40512
16789
Reduction
H2 + CuO H2O + Cu
Oxidation
1
O2 + Cu CuO
2
Spatially isothermal particle.
Pseudosteady state is considered.
No sintering occurs.
Mass Balance. The gassolid reaction can be represented
according to the following equation:
A (g ) + b B(s) cC(s) + d D(g )
5439
(9)
Article
0=
X = 3
(10)
cp
(12)
when t = 0
(21)
r ,i2
v
r0,i3 i
rCu
= 2rO 2 = 3k(1 )CO2 n
1+
(20)
T
= ( rCu
)Hr ,Cu
t
T (R , t ) = Tb
(11)
CO2(RP , t ) = CO2,b
(19)
when T 0
=0
R=0
RP 3
0 P R2X dR
(1 )
k
r
Ds , i
r ,i
r1, i
(13)
r 2
,i 3 vi
r
i 0, i
(14)
bkCO2 n
m ,Cu
(15)
(16)
where
Z=
m ,Cu /b
m ,CuO /c
(17)
r , i(R , t ) 3
vi
r0, i
i
vw , i =
(18)
5440
Vp , i
i Vp , i
(23)
dx.doi.org/10.1021/ef5012403 | Energy Fuels 2014, 28, 54345444
Article
Figure 12. Grain size distribution of active phase in the sample H9 and I20.
Article
Figure 13. Conversion vs time for the reduction in kinetic control (H9).
To check the operation of the new model in dierent conditions of kinetic control, experimental tests in which the diusion
resistance is not negligible were performed. These measurements were performed at a temperature of 800 C, 20% H2, and
a ow of 50 cm3 STP/min and are shown in Figure 15.
It may be noted that as in the conditions of kinetic control,
the proposed model shows good t to the experimental results
better than the classical model, which demonstrates once again
the importance of an initial distribution of grain.
Many gassolid reactions show concave curves of conversion
vs time,34 so the classics grain model has been widely used, but
for the reactions of oxygen carriers based on copper, results do
not t the experimental data, which is better to use other
models as proposed in this work.
Simulation of the Oxidation (I20). Similar to what
happened with the oxygen carrier H9, the results of the new
model is better adjusted to this type of quasilinear kinetic.
Figure 16 shows the graph of the average conversion time for
the oxidation reaction of I20 under conditions of kinetic control.
O2 concentration is 21% at 800 C and with a gas ow of
200 cm3 STP/min.
The temperature prole vs time (see Figure 17) needs to
be validated again, although it is remarkable to note that both
Article
AUTHOR INFORMATION
Corresponding Author
*fchejne@unal.edu.co.
Notes
ACKNOWLEDGMENTS
The authors wish to thank the Departamento Administrativo
de Ciencia Tecnologia e InnovacionCOLCIENCIAS
(Administrative Department of Science, Technology and
Innovation from Colombia) through the project Research on
advanced combustion innovation in Industrial use, code no.
1115-543-31906 contract no. 0852-2012 and the Universidad
Nacional de Colombia.
ABBREVIATIONS
5. CONCLUSIONS
A mathematical model, which was derived from the changing
grain size model, based on the denition of a pore to sphere
factor and the prediction of an initial grain size distribution was
developed. The use of this distribution is the main contribution
of this work, as in the classic changing grain size model is
assumed that the grains are uniform at the start of the reaction,
which is a signicant simplication. The model describes the
reaction rate based on an initial distribution of grain. Results
that predict conversion over time consistent with the experimental data, both the oxidation reaction and the reduction is
obtained.
The results were considerably better than those obtained
with the classical model. The model was tested for the case of
kinetic control and for the case in which the system was not in
this regime, showing highly approximate results in the two
situations, and better adjusted than the classical model, which
is the contribution of this paper. This model can be used to
modeling the chemical looping combustion process at real.
Six copper-based oxygen carriers by incipient impregnation
and wet impregnation were synthesized. Wet impregnation
involves immersing the support in a precursor solution, and
then ltering, drying, and calcining. It was found that the
transporters prepared by wet impregnation retain almost all of
the initial surface area, although a greater amount of precursor
solution is needed.
Synthesis by incipient impregnation consists of lling the
total pore volume of the support with an exact amount of the
precursor solution and then drying and calcining. The carriers
5443
Article
t = Time, s
T = Temperature, K
vi = Volume fraction of grains, i
vw,i = Weight fraction of grains, i
Vp = Specic pore volume, m3 kg1
%w = Weight percent
X = Conversion
X = Average conversion
Z = Ratio of molar density between reactant and product
b = Bulk phase
Cu = Relating to copper
CuO = Relating to copper oxide
He = Relating to helium
ox = Oxidation
O2 = Relating to oxygen
R = Relating to reactive phase
REFERENCES
(1) Hossain, M. M.; De Lasa, H. I. Chem. Eng. Sci. 2008, 63, 4433
4451.
(2) Linderholm, C.; Jerndal, E.; Mattisson, T.; Lyngfelt, A. Chem.
Eng. Res. Des. 2010, 88, 661672.
(3) Mattisson, T.; Johansson, M.; Lyngfelt, A. Energy Fuels 2004, 18,
628637.
(4) Chuang, S. Y.; Dennis, J. S.; Hayhurst, A. N.; Scott, S. A. Combust.
Flame 2008, 154, 109121.
(5) De Diego, L. F.; Garca-Labiano, F.; Gayan, P.; Celaya, J.;
Palacios, J. M.; Adanez, J. Fuel 2007, 86, 10361045.
(6) De Diego, L. F.; Gayan, P.; Garca-Labiano, F.; Celaya, J.; Abad,
A.; Adanez, J. Energy Fuels 2005, 19, 18501856.
(7) Gayan, P.; Forero, C. R.; Abad, A.; De Diego, L. F.; GarcaLabiano, F.; Adanez, J. Energy Fuels 2011, 25, 13161326.
(8) Garca-Labiano, F.; De Diego, L. F.; Adanez, J.; Abad, A.; Gayan,
P. Chem. Eng. Sci. 2005, 60, 851862.
(9) Noorman, S.; Gallucci, F.; Van Sint Annaland, M.; Kuipers, J. A.
M. Chem. Eng. J. 2011, 167, 297307.
(10) Zafar, Q.; Mattisson, T.; Gevert, B. Energy Fuels 2006, 20, 34
44.
(11) Adanez, J.; De Diego, L. F.; Garca-Labiano, F.; Gayan, P.; Abad,
A.; Palacios, J. M. Energy Fuels 2004, 18, 371377.
(12) Adanez, J.; Abad, A.; Garcia-Labiano, F.; Gayan, P.; De Diego, L.
F. Prog. Energy Combust. Sci. 2011, 38, 215282.
(13) Celaya, J. Combustion de CH4 en lecho uidizado con separacion
de base
inherente de CO2 por medio de transportadores solidos de oxigeno
cobre, Ph.D. Thesis, Universidad de Zaragoza, 2007.