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Modeling of Oxidation and Reduction of a Copper-Based Oxygen

Juan C. Maya and Farid Chejne*
School of Chemical and Petroleum, National University of Colombia, Medelln, Crr 80 Number 65-223, Medelln 050001, Colombia
ABSTRACT: A mathematical model that describes the conversion and the temperature prole trough time of a copper-based
oxygen-carrier particle was developed. The model describes the reaction rate based on an initial distribution of grain, permitting a
better adjustment to the experimental data than the classic changing grain size model and it can be used to modeling the chemical
looping combustion process at real scale. On other hand, two oxygen carriers were synthesized using wet-impregnation and
incipient impregnation techniques, and they were characterized with scanning electron microscopy (SEM), energy-dispersive
X-ray spectroscopy (EDX), BET supercial area, porosimetry, and X-ray diraction (XRD). Kinetic parameters of the
synthesized materials were calculated by thermogravimetry.

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

propose a mathematical model describing the reduction and

oxidation reactions of a copper-based oxygen carrier that occur
in a CLC process.

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
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
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II. The resulting solution was ltered under vacuum.

III. The material was dried for 24 h in an oven.
IV. The solid was calcined in air for 10 h at 600 C to
decompose the Cu(NO3)2 to CuO.
Incipient Impregnation. In incipient impregnation, the
alumina support is contacted with the minimum volume of
solution necessary to wet the whole surface. The concentration
of the solution should be adjusted depending on the amount of
metal to be impregnated. The detailed procedure is described
I. The alumina was maintained under vacuum at 65 C for
2 h, to remove air and any adsorbed compounds on the
support and facilitate contact of the solution of Cu(NO3)2
II. The solution of Cu(NO3)2 was added to saturation and
waited for 20 min.
III. The material at 100 C for 3 h was dried in an oven to
achieve complete solvent evaporation.
IV. The material was calcined in air for 10 h at 600 C
to decompose the Cu(NO3)2 to CuO. A temperature
ramp of 1 K/min was used until it reached the desired
Finally, six oxygen carriers were obtained (see Table 1). The
following nomenclature is used: The rst letter symbolizes the

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

Table 1. Composition of Oxygen Carriers


concentration Cu(NO3)2 (M)

%w CuO




type of impregnation which was obtained material (H = wet

impregnation, I = incipient impregnating) and the number that
follows the letter represents the approximate percentage of
CuO that has the oxygen carrier.
The H9, H10, I20, I23, and I21 are black materials such
as CuO, with some small light spots that are probably due to
not being fully calcined. The H12 sample kept the light color it
had before calcination, indicating that the Cu(NO3)2 did not
decompose, so it was discarded from the study. Furthermore,

Figure 2. SEM micrography of oxygen carrier H9.

particles are smaller than the original size alumina, which is

due to attrition in the agitation during the synthesis process.
In Figure 2c and d, the copper oxide grains are observed in the

Figure 1. SEM micrography of Al2O3.

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Figure 3. SEM micrography of oxygen carrier H10.

Figure 5. SEM micrography of oxygen carrier I23.

surface of the particle. However, they are areas of greatest

accumulation of grains.
Figure 3a, b, c, and d shows the oxygen carrier H10 micrographs. Particle sizes below that of the alumina particle and
stratication was noted. Higher attrition of this transporter
compared with H9 was also noted.
SEI and BES oxygen carrier I20 micrographs are presented
respectively in Figure 4a and b, respectively. In this case, particles

Table 2. Chemical Analysis of Oxygen Carriers


O (% W)

Al (% W)

Cu (% W)





carrier I23 presents a high concentration of Cu. However, this

high concentration can also cause pore blockage; as observed in
SEM images (Figure 5).
Surface Area (BET). The specic surface area and porosimetry of oxygen carriers were determined with the ASAP
2020 (Accelerated Surface Area and Porosimetry System)
equipment by nitrogen adsorption and desorption. All samples
decreased its surface area (see Table 3) with respect to the
Table 3. Specic Surface Area of Oxygen Carriers

Figure 4. SEM micrography of oxygen carrier I20.


specic surface area (m2/g)



original alumina which suggests a blockage of pores as in

Cortes work.17
Porosimetry. The mesopore size distribution, pore volume
and area distribution were calculated with the BJH method
(Barrett, Joyner, and Halenda).18 It was observed that the H9,
H10, and I20 carriers conserved pore size distribution similar to
the original alumina, whereas I23 carrier porosity decreased
sharply (see Figure 6), indicating a block of pores by CuO,
which conrms the results obtained by the BET specic surface
area analysis.
The average pore size (see Table 4) was similar for all oxygen
carriers. However, the porosity and, hence, the total pore
volume was reduced for each carrier, especially for I23 as
mentioned above.
The density of the oxygen carriers is presented in Table 5.
Note that the real density of I23 is greater than in the other

retained approximately the alumina size, which is because in this

method of synthesis is not required agitation. In Figure 4c and d,
CuO grains are observed in the surface of the particle, which
have a uniform dispersion across the surface with no signs of
stratication, contrary to what happened with the wet
SEI and BES oxygen carrier I23 micrographs are presented in
Figure 5a and b, respectively; particles retained approximately
the alumina size, which had a particle size similar to the oxygen
carrier I20. In Figure 5c and d, a large accumulation of grains is
observed uniformly dispersed on the surface of the alumina
particle, which can generate blocking of internal pores.
Chemical Analysis. From chemical analysis (see Table 2) of
carriers which are still being studied, it appears that the oxygen
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Figure 6. Pore size distributions of Al2O3, H9, H10, I20, I23.

O2 + Cu CuO
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

Table 4. Oxygen Carriers Porosimetry


total pore volume (cm3/g)

average pore size ()






Table 5. Oxygen Carriers Density


bulk density (kg/m3)

real density (kg/m3)




Scheme 1. Scheme of Shrinking Core Model in the Grain

samples. This indicates that CuO was accumulated on the initial

alumina particle.
X-ray Diraction. The technique of X-ray diraction allows
the identication of crystalline phases qualitatively and quantitatively. The equipment used for the XRD analysis was an
X-ray diractometer XPert PRO Brand Panalytical reference
MPD with Cu anode and Ni lter. In all samples, the presence of CuO, alumina, and copper aluminate was observed;
however, quantitative data are inaccurate because the samples
are amorphous.
For all the features discussed in this chapter, it can be
concluded that more oxygen carriers suitable for use in CLC
are H9 and I20, and therefore, these two are with those who
worked from here.

in the grain considers there is no resistance to mass transfer in

the lm, pores and product layer, whereby the controlling step
is the reaction in the grain.
Equations required to employ this model are listed
= 1 (1 X )1/3

mR rg
bkC n


The kinetic model developed requires input parameters (reaction
order, activation energy, and pre-exponential factor) and
also requires validation. For this, a thermogravimetric balance
LINSEIS STA PT160019 using hydrogen and air as reducing
and oxidizing atmospheres were used, respectively. The reactions
were taken into account are
H 2 + CuO H 2O + Cu

rg =

3(%wR )

k = k 0e(Ea / RT )

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Figure 7. Calculation complete conversion times at 800 C (reduction).

To determine the conversion of oxygen carrier from the data

provided by the TGA, eqs 7 and 8 are used.

X red =

mox m
mox mred

Xox = 1 X red


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

Figure 8. Deduction of reaction order (reduction).

conversion times at 600, 700, and 800 C are found, as

performed above. In Figure 9, the graph shows1 (1 X )1/3
vs t to temperatures of 600, 700, and 800 C at hydrogen
concentration of 40%.
For temperatures of 600, 700, and 800 C complete
conversion times of 32.3, 19.2, and 8.9 s, respectively, were
obtained. Now, it is necessary to calculate the grain radius with
eq 5 which has a value of 4.01238 108 m.
k values are subsequently calculated from eq 4 for the
temperatures 600, 700, and 800 C. Now, the natural logarithm
is taken on both sides of eq 6 have ln k0 = ln k0 (Ea/RT).
Therefore, if ln k vs 1/T is obtained graph a line with intercept
and slope equal to ln k0 and Ea/R, respectively (see Figure 10).
Finally, the activation energy is calculated to be 49705.58 J/mol
and the pre-exponential factor is equal to 0.031 mol0.3 m0.1 s1.
To nd the values of the pre-exponential factor of the oxidation
reaction proceeds as in the reduction reaction, calculating
complete conversion times at dierent temperatures. At oxygen
concentration of 21% for temperatures of 600, 700, and 800 C
entire reaction time of 19.6, 18.5, and 15.1 s, respectively, were
obtained. From these data, an activation energy of 9927.48 J/mol
and a pre-exponential factor of 0.000554 mol0.2 m0.4 s1 is
obtained. Kinetic parameters for all reactions studied are shown
in Table 6.
The dierence between the oxidation reaction order of H9
and I20 (see Table 6) is due the dierent way of reaction related
to the impregnation technique and concentration of CuO. Each
impregnation technique produces oxygen carriers with a specic
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Figure 9. Calculation of complete conversion times at dierent temperatures (reduction).

Scheme 2. Scheme of Changing Grain Size Model

Figure 10. Arrhenius plot for the reduction.

reaction proceeds grain radius r1 is increased or decreased,

depending on the molar ratio of densities between the reactant and product (the molar density of the metal copper
is 140 kmol/m3 and copper oxide is 80 kmol/m3), whereas
the unreacted core radius r decreases.12 The improvement
proposed in this paper is to use an initial distribution of radius
r0 derived from the analysis of the carrier done porosimetry.
Model Assumptions. For the development of this model,
the following assumptions were:
A spherical particle made of spherical grains.
The grains are nonporous initially.
The interstices between the grains make the pores of the
The particle maintains its spherical shape and their
diameter during the course of the reaction.
At the start of the reaction, the grain sizes are not uniformly
The reactions to be considered are the following:

Table 6. Kinetic Parameters for H9 and I20 Carriers


pre-exponential factor
(mol1n m3n2 s1)

activation energy

reduction H9
oxidation H9
reduction I20
oxidation I20





In regard to particle models, the models developed by Szekelly
in the 1970s are remarkable.2127 Of these models, the most
used is the variable grain size model, which has been widely
used to study gassolid noncatalytic reactions as calcination28
and carbonation.29 In regard to modeling of the reaction into
a particle level for the oxidation and reduction of oxygen carriers
is given by CLC process, one can note the work by Garcia et al.,8
in which they evaluated the temperature proles in a particle of
oxygen carrier, and the Noorman et al. work,9 where the redox
reactions of a copper-based oxygen carrier using shirking core
model were modeled.30 However, these models consider
homogeneous the carrier particle and do not take into account
the initial characteristics of the material as is its grain size
distribution. In this work, it was developed a mathematical model
that can describe the oxidation and reduction reactions occurring
in the CLC process using a method for determining the grain
size distribution within the oxygen carrier particle.
Thus, the changing grain size model proposed by Szekelly
(see Scheme 2) is used, but given an initial grain size distribution. The classic model considers that the particle consists
of a number of nonporous grains with a characteristic length
r0 uniform among which pores are formed. As the chemical

H2 + CuO H2O + Cu


O2 + Cu CuO
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 )

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Knowing the conversion, you can nd the average particle


The complete model for the oxidation reaction arises

(1/2)O2 + Cu CuO, however, in reducing the equations
are similar. The mass balance at pseudo-steady-state for oxygen
can be expressed in the following manner, knowing that the
phenomenon under study only takes into account the diusive
term, because the ow velocity within the pores of the particle is
very low and also is considered a source term for the chemical
reaction that occurs in the solid:
De ,O2R2
( rO 2)


X = 3




Chemical Reaction. An equation is necessary to determine

the speed of the chemical reaction, which must take into
account the resistance to mass transfer in the product layer
formed around the grains27

when t = 0


Scheme 3. Scheme of Oxygen Carrier Particle Formed by


r ,i2

r0,i3 i

= 2rO 2 = 3k(1 )CO2 n


Pore to Sphere Factor. According to the distribution

model of grain raised by Heesink et al.,32 a porous particle is
composed of a collection of spherical grains of various sizes,
and the pores are in the interstices of these grains as shown in
Scheme 3.

The second boundary condition expresses the external mass

transfer, that is, the molar ux on the outer surface of the
oxygen carrier particle. This condition is shown below
in t 0

= ( rCu
)Hr ,Cu

T (R , t ) = Tb


CO2(RP , t ) = CO2,b


To solve eq 20, an initial condition is necessary to indicate

that in the initial state, oxygen temperature inside the particle is
equal to the temperature in the bulk and is given by8

when T 0


RP 3

Energy Balance. In the energy balance, the transition state

is not considered the convective term because it can be
assumed that the ow velocity is low in the inside of the pores
of the particle, and it also takes into account the diusive term
because for being such a small particle, it can be said that the
temperature does not vary radially. It allows for a source term
due to the heat produced by the reaction

For the solution of this dierential equation, it is necessary to

consider two boundary conditions.8 There are typical boundary
conditions for this type of problems that have been worked
extensively in catalytic31 processes. The rst condition indicates
that there is symmetry about the center of the particle and is
expressed as

0 P R2X dR

(1 )

Ds , i

r ,i

r1, i


where Ds is diusivity in the product layer which is formed

around the grain. However, for very small grain sizes (4.01238
108 m), Ds , therefore, the equation is as follows:
= 2rO 2 = 3k(1 )CO2

r 2

,i 3 vi
i 0, i


The unreacted core size variation grain can be calculated with

eq 15
dr , i

According Frevel and Kressley,33 who studied mercury

porosity diagrams of microspheres packages and concluded
that the pore size depends only on the size of microspheres.
Thus, there is a proportional relationship between the size of
the pores and grains that is known as the pore to sphere
factor F, which can be expressed by eq 22

bkCO2 n
m ,Cu


whose initial condition is r,i = r0,i. Grain radius is given by

r1, i = [Zr0, i 3 + (1 Z)r , i 3]1/3



m ,Cu /b
m ,CuO /c

In this paper, the method of Frevel and Kressley33 was used

to determine the grain size distribution from the porosity
diagrams of oxygen carriers that were studied. The weight
fraction occupied by grains of size i can be calculated with
eq 23


Finally, we can obtain an equation for the conversion in the

interior of the particle
X (R , t ) = 1

r , i(R , t ) 3

r0, i

vw , i =


Vp , i
i Vp , i

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Figure 11. Grain size distribution of oxygen carriers.

Figure 12. Grain size distribution of active phase in the sample H9 and I20.

Simulation of Reduction (H9). To validate the data

provided by the model developed in this work, a comparison
with experimental data obtained in the thermobalance was
performed. In addition, we also compared our data with the data
provided by the classical model using a average initial grain size.
In Figure 13, H9 average conversion is plotted over time for the
reduction reaction with hydrogen under conditions of kinetic
control to the experimental data, the new model, and the classical
model of Szekelly explained above. The concentration of H2 is
20% to 800 C and with a gas ow of 200 cm3 STP/min.
One can observe that the experimental graph tends to be
linear with a very slight curvature, which fails to describe the
classical model; however, the model proposed here achieves
considerably closer to the actual behavior of the phenomenon
because the reaction considered each type of grain. In Figure 14,
the temperature prole predicted by the classical model and
the new model is presented. Both models show similar trends,
but there is no experimental data to compare these results.

the temperature must reach a

According to Garcia-Labiano,
maximum and then go down to the temperature of the bulk
phase; however, because the model of this study does not take
into account the diusive and convective terms in equation 20,
energy can not observe this behavior, and the maximum
temperature is reached when the conversion is too.

The specic surface area can be calculated with eq 24

Cu i r0i
Thus, knowing the specic surface area of the sample, it is
possible to derive the pore to sphere that is shown in eq 25
SCu i rpi
Grain Size Distributions. To determine the grain size
distributions of oxygen carriers studied, eqs 2325 were used.
The grain size distributions of alumina and oxygen carriers can
be seen in Figure 11.
However, in the calculation of the grain size distribution
of the oxygen carrier, no dierence between the alumina
grains and the grains of the active phase is made. Therefore,
it can be assumed that the grains of the support do not change
the distribution with the impregnation, as in so small grains
attrition is unlikely. Then, the distributions of the oxygen
carrier are subtracted with the grain distribution of the alumina
to obtain the grain distribution of active phase. In Figure 12,
the grain size distribution of active phase of H9 and I20 are
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Figure 15. Conversion vs time for the reduction (H9).

Figure 13. Conversion vs time for the reduction in kinetic control (H9).

Figure 14. Temperature prole of the reduction (H9).

Figure 16. Conversion vs time for the oxidation in kinetic control

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

Figure 17. Temperature prole of the oxidation (I20).

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prepared by incipient impregnation require less precursor

solution to achieve a given composition, but a notable drop in
the surface area occurs. Oxygen carriers were characterized by
scanning electron microscopy (SEM), energy-dispersive spectroscopy X-ray (EDX), surface area (BET) porosimetry, and X-ray
diraction (XRD).
The carriers synthesized by incipient impregnation from a
certain concentration (1.41 M) are at an almost complete
blockage of pores of the surface. Additionally, all showed the
formation of copper aluminate in the calcination process. Finally,
H9 and I20 carriers for validation of the model were chosen.

models reach the same maximum temperature of particles,

which is probably due to the were not taken into account the
diusive and convective terms in the energy equation, which is
a considerable simplication.
Finally, Figure 18 shows the graph of average conversion vs
time for conditions in which the system is not in kinetic


Corresponding Author


The authors declare no competing nancial interest.

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.

Figure 18. Conversion vs time for the oxidation (I20).

control. O2 concentration is 21% at 800 C and with a gas ow

of 50 cm3 STP/min.
It is important to mention that the experimental data is not
so well accommodated in the oxidation as in reduction with the
new model, although the trend remained.


Symbols with Latin Letters

Symbol Term Unit SI

b = Stoichiometric coecient of the reactant

c = Stoichiometric coecient of the product
cp = Average specic heat at constant pressure of the particle,
J kg1 K1
C = Concentration, mol m3
De = Eective diusion coecient, m2 s1
Dg = Diusion coecient of the gas, m2 s1
DK = Knudsen diusion coecient, m2 s1
Dm = Molecular diusioncoecient, m2 s1
Ds = Diusion coecient in the product layer, m2 s1
Ea = Activation energy, J mol1
F = Pore to sphere factor
k = Reaction rate constant, mol1n m3n2 s1
k0 = Pre-exponential factor, mol1n m3n2 s1
m = Mass of the carrier, kg
m0 = Mass of the oxidized carrier, kg
mr = Mass of the reduced carrier, kg
M = Molecular weight, kg mol1
n = Reaction order
N = Number of Avogadro, particles mol1
r = Reaction rate, mol m3 s1
r0 = Initial grain radius, m
r0 = Initial average grain radius, m
r1 = Grain radius, m
r = Unreacted core radius, m
rg = Average grain radius, m
rp = Pore radius, m
R = Radial coordinate in the particle, m
R = Universal ideal gas constant, J mol1 K1
RP = Particle radius, m
S = Specic surface area per unit mass, m2 kg1
SR = Specic surface area per unit volume, m1

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
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 | Energy Fuels 2014, 28, 54345444

Energy & Fuels


(19) STA PT1600 TGA-DSC (STA Simultaneous Thermal

pt1600_specication.php (accessed Dec 9, 2012).
(20) Szekely, J.; Evans, J. W.; Sohn, H. Y. Gas-solid reactions;
Academic Press: Salt Lake City, UT, 1976; p 400.
(21) Szekely, J.; Evans, J. W. Chem. Eng. Sci. 1970, 25, 10911107.
(22) Szekely, J.; Evans, J. W. Chem. Eng. Sci. 1971, 26, 19011913.
(23) Sohn, H. Y.; Szekely, J. Chem. Eng. Sci. 1972, 27, 763778.
(24) Sohn, H. Y.; Szekely, J. Chem. Eng. Sci. 1973, 28, 11691177.
(25) Szekely, J.; Lin, C. I.; Sohn, H. Y. Chem. Eng. Sci. 1973, 28,
(26) Szekely, J.; Propster, M. Chem. Eng. Sci. 1975, 30, 10491055.
(27) Georgakis, C.; Chang, C. W.; Szekely, J. Chem. Eng. Sci. 1979,
34, 10721075.
(28) Garca, F.; Abad, A.; De Diego, L. F.; Gayan, P.; Adanez, J.;
Garca-Labiano, F.; Adanez, J. Chem. Eng. Sci. 2002, 57, 23812393.
(29) Yu, Y. S.; Liu, W. Q.; An, H.; Yang, F. S.; Wang, G. X.; Feng, B.;
Zhang, Z. X.; Rudolph, V. Int. J. Greenhouse Gas Control 2012, 10,
(30) Levenspiel, O. Chemical reaction engineering; 3rd ed.; Wiley:
Weinheim, Germany, 1999; p 668.
(31) Fogler, H. S. Elementos de Ingenieria de Las Reacciones Quimicas;
3rd ed.; Pearson Education: Upper Saddle River, NJ, 2001; p 968.
(32) Heesink, A. B. M.; Prins, W.; Van Swaaij, W. P. M. Chem. Eng. J.
1993, 53, 2537.
(33) Frevel, L. K.; Kressley, L. J. Anal. Chem. 1963, 1492.
(34) Bhattacharya, A.; Purohit, P. Chem. Eng. J. 2004, 102, 141149.

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

Symbols with Greek Letters

Hr = Heat of reaction, J mol1

= Porosity
= True density, kg/m3
= Average particle density, kg/m3
m = Molar density, mol m3
= Time of complete conversion, s

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


(1) Hossain, M. M.; De Lasa, H. I. Chem. Eng. Sci. 2008, 63, 4433
(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,
(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
(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.

(14) Jimenez, V. Sintesis,

activacion quimica
y aplicaciones de
nanoestructuras de carbono; Universidad de Castilla-La Mancha:
Albacete, Spain, 2011; p 399.
(15) Dueso, C.; Abad, A.; Garca-Labiano, F.; De Diego, L. F.; Gayan,
P.; Adanez, J.; Lyngfelt, A. Fuel 2010, 89, 33993409.
(16) Gayan, P.; Cabello, A.; Garca-Labiano, F.; Abad, A.; De Diego,
L. F.; Adanez, J. Int. J. Greenhouse Gas Control 2013, 14, 209219.
(17) Cortes, F. Adsorcion de agua en materiales compuestos y zeolita;
Universidad Nacional de Colombia: Bogota, Colombia, 2009; p 110.
(18) ASAP 2020 Accelerated Surface Porosimetry System Operators
Manual; Micromeritics: Norcross, GA, 2011.
5444 | Energy Fuels 2014, 28, 54345444