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Fuel 87 (2008) 11151126

www.fuelrst.com

Thermogravimetric studies on the eect of support in

sorbent-materials applied to ue gas desulfurization
Roberto Flores *, Arturo Rodas, Cinthya Palma, Yuliana I. Melendez, Xochitl S. Melendez,
Laura L. Gonzalez
Instituto de Investigaciones Electricas, Calle Reforma 113, Colonia Palmira, Cuernavaca, Morelos 62490, Mexico

Received 16 March 2007; received in revised form 11 July 2007; accepted 12 July 2007
Available online 7 August 2007

Abstract

Mexican thermal power plants typically use heavy fuel oil with high sulfur content as feedstock, so ue gases with high amounts of
sulfur oxides (SOx) are continuously emitted to the environment. On the other hand, stringent environmental restriction will be world-
wide implemented in the near future; therefore, modications or installation of new technologies in the thermal power plants are
mandatory in order to decrease these emissions. The present work shows the eect of support, composition, and temperature in sor-
bent-materials based on CuO applied to the abatement of SOx from ue gases. CuO supported on alumina, titania, and zirconia were
prepared using the wet impregnation method. The SO2 adsorption capacity of the dierent materials was analyzed using thermogravi-
metric analysis (TGA). The eciency of the sorbents was statistically analyzed using the factorial design. The results show a direct rela-
tionship between the adsorption capacity of the sorbents and the surface area of the support. Also, the capacity and eciency of the
materials was directly related to the CuO content. Finally, increasing the temperature enhanced the adsorption capacity and the eciency
of the sorbents.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Cupric oxide sorbent materials; TGA; Thermal power plant; Flue gas desulfurization; Factorial design; Parameter estimation

1. Introduction sulfur (Claus Process) or sulfuric acid (Contact Process) [4

In Mexico, most of the thermal power plants are oper-
ated by burning heavy fuel oil. This heavy fuel oil contains
around 4 wt% of sulfur [1], so huge amounts of sulfur oxi-
des (SOx: SO2 + SO3) are emanated from the thermal
power plants during power generation. The concentration
in the ue gases can reach up to 30004000 ppm [2]. For
that, a great environmental challenge in these plants is to
decrease the SOx emissions in the ue gases [3]. One option
is the hydrodesulfurization of the heavy fuel oil before
being feeding to the power plant. In this process, organic
sulfur is eliminated from the fuel oil in the form of H2S,
which could be further treated to either produce elemental
*
Corresponding author. Tel.: +52 777 362 3811x7028.
E-mail address: rfv@iie.org.mx (R. Flores).
9]. However, considering the nal purpose of the product,
this process has many disadvantages in order to eliminate
considerable amounts of sulfur in the heavy fuel oil, such
as, the use of stringent operating conditions (above
450 C and 100 bar), the use of huge amounts of hydrogen,
which is an expensive raw material, and fast catalyst foul-
ing due to the heavy compounds and high metal content in
the heavy fuel oil. Therefore, most of the eorts in this eld
have been directed to the abatement of SOx from the ue
gases after the combustion of the heavy fuel oil [3,7,8].
One of the emerging technologies is the use of selective
sorbent-materials in xed or uidized bed reactors. Unfor-
tunately, there are several problems related to the thermo-
mechanical stability of the support, low supercial area,
and low dispersion of the active phase, among others
[3,9,10]. One relatively cheap DeSOx/DeNOx process is
based on cupric oxide (CuO) supported on alumina,

0016-2361/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.07.014
1116 R. Flores et al. / Fuel 87 (2008) 11151126
titania, zirconia or mixtures of these oxides, and sometimes
doped with magnesia, ceria, and chromia. Previous reports
have shown good performance in the chemisorption of sul-
fur dioxide and in the reduction of nitrogen oxides
(NOx = NO + NO2), as well as in the adsorption of H2S
in fuel gasication processes [1118].
On the other hand, the relative acidity of the supports
commonly used in DESOx/DeNOx processes is an impor-
tant characteristic which can inuence the performance of
the sorbent material due to support-active phase interac-
tions that occurs after calcination procedure. Therefore,
sorbent materials could lose their SO2 sorption capacity
if these interactions are stronger or weaker. The relative
acidity of industrial supports used commonly in catalytic
processes decreases in the following order: titania
(TiO2) > zirconia (ZrO2) > alumina (Al2O3) [19].
In the present report is showed the eect of support in
the sorbent-materials based on CuO applied to the ue
gas desulfurization in thermoelectrical plants. The study
is based on the thermogravimetrical behavior of dierent
materials formed by CuO supported on commercial alu-
mina, titania, and zirconia.
2. Experimental
Sorbent-materials were prepared using the classical wet
impregnation method by adding a known amount of cupric
nitrate solution to alumina, titania, and zirconia. After
impregnation, the solids were dried at 100 C for 12 h
and calcined at 450 C during 4 h under a continuous air
ow. In this way, materials were prepared with dierent
cupric oxide composition. After calcination, the sorbent-
materials were chemically digested and analyzed by atomic
absorption spectroscopy to determine the real composition
of cupric oxide in the sorbent materials. Table 1 presents
the composition of the dierent materials.
The surface area of the supports was determined accord-
ing to the one-point BET method. The estimated values for
alumina, zirconia, and titania were 107, 12.5, and 9.3 m2/g,
respectively.
The sulfation of the materials was carried out in a ther-
mogravimetric balance (TA Instruments 2050) by passing a
Table 1
CuO load in the supported materials
Sorbent material Label CuO load (wt%)
CuO/Al2O3 CuAl(4) 27.77 0.05
CuAl(3) 22.18 0.05
CuAl(2) 14.32 0.05
CuAl(1) 6.94 0.02
CuO/TiO2 CuTi(4) 30.47 0.05
CuTi(3) 23.57 0.05
CuTi(2) 15.83 0.05
CuTi(1) 8.25 0.02
CuO/ZrO2 CuZr(4) 29.50 0.05
CuZr(3) 22.70 0.05
CuZr(2) 16.26 0.05
CuZr(1) 8.07 0.02
stream of certied 3600 ppm SO2 with balance N2 (PRAX-
AIR) through 20 mg of sorbent material. The gas ow rate
was 97 mL/min, which is the maximum ow of the thermo-
balance. The gain of weight in the material was assigned to
the chemisorption of SO2 on the active sites. Experimental
temperatures were selected based on technical restrictions
considering the place, where the DeSOx technology could
be implemented in a typical Mexican thermal power plant:
before the preheaters, where the temperature reach up to
500 C; after the preheaters, where the ue gases tempera-
ture has decreased to near 400 C, and before arriving to
the chimney, where the ue gases have temperatures
between 150 and 200 C.
3. Results and discussion
First, the sulfation of the dierent materials was ana-
lyzed using a temperature program from room temperature
up to 850 C with a heating rate of 10 C/min in the TGA
instrument in order to determine at with temperature inter-
val the SO2 adsorption process is preferred. The experimen-
tal results are shown in Figs. 13. It can be observed that
the chemisorption of SO2 on the sorbent materials started
around 300 C, as it has been reported elsewhere [1317],
producing an increase in the weight of the sorbent materi-
als. The chemisorption process continues, and therefore the
gain of weight in the sample, up to certain temperature.
After this temperature, the chemisorbed sulfur species
become unstable, so they decompose and begin to desorb
SO2 from the surface of the sorbent material. This is
noticed in the TGA due to the loss of weight of the sample.
According to these results, the temperature at which the
chemisorbed species are still stable is between 500 and
600 C in materials supported on alumina and zirconia;
on the other hand, for the sorbent supported on titania,
this interval is slightly higher between 600 and 700 C.
Some studies have shown the formation of supercial
sulfates during the sulfation of supported CuO, and in
the presence of O2 [10,18,20,21]. Then, the reaction can
be written as follows:
CuO + SO2 + 0.5O2 ! CuSO4 1
When O2 is not presented, the SO2 is converted in super-
cial sulte, as it has been observed by spectroscopic infra-
red techniques [22,23].
Therefore, it can be proposed that a temperatures below
600700 C the supercial sulte formation is achieved
through a chemisorption process, and a temperatures over
700 C the sulte is decomposed, and SO2 is desorbed from
the surface of the sorbent material according to the follow-
ing equations:
CuO SO2 ! CuOSO2 2
T1
CuOSO2 ! CuO SO2 3
T2
where T1 < T2.
 R. Flores et al. / Fuel 87 (2008) 11151126 1117

103.5

103.0

102.5

102.0

Weight (%) 101.5

101.0

100.5

100.0

99.5

99.0

98.5

98.0
0 100 200 300 400 500 600 700 800

Temperature (C)

Fig. 1. Sulfation of the Cu/Al2O3 adsorbent-catalysts at temperature programmed: 4 CuAl(1); j CuAl(2); s CuAl(3);  CuAl(4).

103.5

103.0

102.5

102.0
Weight (%)

101.5

101.0

100.5

100.0

99.5
0 100 200 300 400 500 600 700 800
Temperature (C)

Fig. 2. Sulfation of the Cu/TiO2 adsorbent-catalysts at temperature programmed: 4 CuTi(1); j CuTi(2); s CuTi(3);  CuTi(4).

Even though the appreciated sulfation of the materials
started at temperatures over 300 C, according to the pre-
vious results, the isothermic sulfation of all the sorbents
was studied at 200, 300, and 400 C in the TGA instrument
because the reasons previously explained. Before doing
these experiments, the supports were submitted to the same
experimental conditions to determine if they adsorbed SO2;
nevertheless, no adsorption of SO2 was detected in the
thermogravimetric balance. It was observed that the
amount of adsorbed SO2 increased at higher CuO concen-
trations in all the supports at any temperature. Also, an
increase in the temperature allowed more chemisorption
of SO2 on the sorbent-materials regardless the support
and the CuO concentration. Finally, it was noticed that
the ability of chemisorbing SO2 of the sorbent supported
on alumina was considerably greater than those obtained
in materials supported on titania and zirconia; this has
been attributed to the greater surface area of the alumina,
which may promote a better distribution of the supported
CuO particles. From the previous results, the eciencies of
each sorbent material were estimated, and they are
reported in Fig. 4. In order to calculate the eciency, it
1118 R. Flores et al. / Fuel 87 (2008) 11151126

105

104

Weight (%) 103

102

101

100

99
0 100 200 300 400 500 600 700 800
Temperature (C)

Fig. 3. Sulfation of the Cu/ZrO2 adsorbent-catalysts at temperature programmed: 4 CuZr(1); j CuZr(2); s CuZr(3);  CuZr(4).

100

90

80

70
Efficiency [%]

60

50
CuAl(1)
CuAl(2)
40
CuAl(3)
CuAl(4)
30
CuTi(1)
20
CuTi(2)
CuTi(3)
10 CuTi(4) Catalysts
CuZr(1)
0
CuZr(2)
400 CuZr(3)
300 CuZr(4)
200
Temperature [C] 100

Fig. 4. Sulfation eciency of the CuO catalysts supported on dierent metal oxides.

was taken into account the amount of SO2 adsorbed on the The experimental eciency data were statistically evalu-
solid after 1 h of sulfation divided by the amount of active ated, using Minitab, considering the following model:
sites available in the sample of sorbent material. The active
sites are the CuO particles supported in the material. y ijk si bj ck sbij scik bcjk eijk 4
 R. Flores et al. / Fuel 87 (2008) 11151126 1119

Table 2
Analysis of variance of the experimental eciency results
Sum of squares Degrees of freedom Mean squares F0 P-value
A 9045 2 4522 64.82 0.000
B 2463 2 1231 17.65 0.000
C 2726 3 909 13.02 0.000
AB 1368 4 342 4.90 0.014
AC 4432 6 739 10.59 0.000
BC 504 6 84 1.20 0.368
Error 837 12 70
Total 21,375 35
A: Type of support (alumina, titania, zirconia); B: temperature (200, 300, 400 C); C: CuO load (7.5, 15, 23, 29 wt%).

where yijk are the experimental data; si is the eect of sup-
port; bj is the eect of temperature; ck is the eect of CuO
load; and eijk is the experimental error.
The analysis of variance is presented in Table 2. From
this table, it can be concluded that all the main factors
are statistically signicant; therefore, the eciency depends
on the type of support, temperature of the adsorption pro-
cess, and CuO load. Also, it can be observed that the only
relevant interaction is A C (A: type of support; C: CuO
load), which means that there is a synergistic eect between
the type of support and the CuO load regardless the tem-
perature. This may be related to the notorious enhance in
the eciency of those sorbent materials supported on alu-
mina at low CuO loads, which could imply that in these
particular cases, the eciency not only depends in the bet-
ter dispersion of the active sites, as previously stated, but
2 The experimental data were mathematically analyzed in
1 adsorption process. Several models were tested considering
Normal Score
also in an atomic interaction between the alumina and
the CuO that favors the adsorption of the SO2 in the active
sites. This atomic interaction is bolstered as the CuO load
decreases, and may even promote the formation of new
more active species, such as, copper aluminate (CuAl2O4)
as was reported elsewhere [24]. This species has been
reported to be even more active for the chemisoprtion of
SO2. On the other hand, the eect of temperature on type
of support and CuO load is basically additive, which means
that eciency increases linearly with temperature. The sta-
tistical model was validated by building the normal proba-
bility plot and the yijk vs eijk graph, which are presented in
Fig. 5. It can be observed from the normal probability plot
that the residuals are eectively aligned between the 25 and
75 percentiles; also, there is no tendency, and the data are
randomly distributed in the yijk vs eijk graph; therefore, it
can be concluded the proposed statistical model is ade-
quate to represent the eciency data.
order to determine the kinetic parameters that govern the

that the rate of a solidgas reaction can be represented by

0 the product of two factors, where one is dependent on the

-1
Table 3
Kinetics models for the adsorption and desorption processes
-2
Model f(a)
-10 0 10 nth order an
Residual Random nucleation, unimolecular 1  a
decay law
Phase boundary controlled reaction 1  a1=2
10 (contracting area)
Phase boundary controlled reaction 1  a2=3
(contracting volume)
Two-dimensional growth of nuclei 21  a ln 1  a1=2
Residual

(AvramiErofeev)
0
Three-dimensional growth of nuclei 21  a ln 1  a2=3
(AvramiErofeev)
One-dimensional diusion, sharp 1=2a
interface
-10 Two-dimensional diusion, sharp 1= ln 1  a
interface h  i
0 50 100
Three-dimensional diusion, sharp 3= 2 1  a1=3  1
ExperimentalData interface (GingstlingBrounstein) h i.h i
Three-dimensional diusion (Jander) 31  a2=3 21  1  a1=3
Fig. 5. Validation of the proposed mathematical statistical model.
1120 R. Flores et al. / Fuel 87 (2008) 11151126

1
400C
0.9

0.8

0.7
300C
Covered Fraction 0.6

0.5

0.4
200C
0.3

0.2

0.1

0
0 10 20 30 40 50 60
Time [h]

0.25

0.2

400C
Covered Fraction

0.15

0.1

300C
0.05

200C
0
0 10 20 30 40 50 60
Time [min]

0.08

0.07
400C

0.06

0.05
Covered Fraction

0.04

300C
0.03

0.02

0.01
200C

0
0 10 20 30 40 50 60
Time [min]

Fig. 6. Adsorption isotherms for the sorbent materials with 7.5 wt% CuO composition. Supports: (a) alumina, (b) titania, (c) zirconia.  Experimental
data; s model 5; 4 model 6.
 R. Flores et al. / Fuel 87 (2008) 11151126 1121

400 C

0.8

Covered Fraction
0.6
300C

0.4

200C
0.2

0
0 10 20 30 40 50 60
Time [min]

0.3

400C
0.25

0.2
Covered Fraction

0.15

0.1

300C
0.05

200C
0
0 10 20 30 40 50 60
Time [min]

0.1
400C
0.09

0.08

0.07
Covered Fraction

0.06
300C
0.05

0.04

0.03

200C
0.02

0.01

0
0 10 20 30 40 50 60
Time [min]

Fig. 7. Adsorption isotherms for the sorbent materials with 15 wt% CuO composition. Supports: (a) alumina, (b) titania, (c) zirconia.  Experimental
data; s model 5; 4 model 6.
1122 R. Flores et al. / Fuel 87 (2008) 11151126

0.3

0.25
400C

0.2
Covered Fraction

0.15

300C
0.1

0.05
200C

0
0 10 20 30 40 50 60
Time [min]

0.25

0.2

400C
Covered Fraction

0.15

0.1

0.05
300C

0
0 10 20 30 40 50 60
Time [min]

0.08

0.07

0.06
400C
Covered Fraction

0.05

0.04

0.03

300C
0.02

0.01
200C

0
0 10 20 30 40 50 60
Time [min]

Fig. 8. Adsorption isotherms for the sorbent materials with 23 wt% CuO composition. Supports: (a) alumina, (b) titania, (c) zirconia.  Experimental
data; s model 5; 4 model 6.
 R. Flores et al. / Fuel 87 (2008) 11151126 1123

0.35

400C
0.3

0.25

Covered Fraction
300C
0.2

0.15

0.1
200C

0.05

0
0 10 20 30 40 50 60
Time [min]

0.14

0.12

400C
0.1
Covered Fraction

0.08

0.06

0.04

300C
0.02

200C
0
0 10 20 30 40 50 60
Time [min]

0.06

0.05

400C

0.04
Covered Fraction

0.03

300C
0.02

0.01

200C
0
0 10 20 30 40 50 60
Time [min]

Fig. 9. Adsorption isotherms for the sorbent materials with 29 wt% CuO composition. Supports: (a) alumina, (b) titania, (c) zirconia.  Experimental
data; s model 5; 4 model 6.
1124 R. Flores et al. / Fuel 87 (2008) 11151126

temperature, and the other on the concentration, as is indi- out the proposed models are empirical equations; there-
cated in the following equation: fore, they do not have any physical meaning; however,
da the selection of the back reaction equations was made con-
kT  f a  f pSO2 5 sidering the opposing process of the forward reaction; for
dt
example, Eq. (9) considers a contracting volume reaction
where a is the degree of conversion of the solid reactant; t is for the forward reaction which is a three-dimensional con-
the time; T is the temperature; and pSO2 is the SO2 partial traction from the outside to the nuclei, the opposite is a
pressure. three-dimensional growth of the nuclei. The same analogy
The above equation can be further reduced considering was done to establish Eq. (8).
the pSO2 remains essentially constant through the process Figs. 69. show the experimental data with the tted
given the operating conditions previously explained: curves. As it can be observed, the model tted curves are very
da similar, and no distinction can be performed between them;
kT  f a 6 therefore, the method of nonintrisic parameters was applied
dt
to determine the best model [25]. This method supposes that
Table 3 presents the f(a) functions that were tested for a selection between two nonlinear models must be made
modeling the experimental data. The estimation of the ki-
netic parameters was achieved using the acslXtreme soft- Ey f1 x; b1 10
ware developed by AEgis Technologies. None of them Ey f2 x; b2 11
adjusted well the data; therefore, it was considered the
adsorption process reached and equilibrium state, and the A new dependent variable is dened
kinetic model was modied to 1
z y  ^y 1 ^y 2 12
da 2
k f T  ff a  k r T  fr a 7
dt where ^y i is the prediction of the dependent variable under
where the subscripts f refers to the forward reaction, and r model i.
to the reversible reaction. After some mathematical steps, the following equation
Many combinations were tested, and the better were the is obtained:
following: Ez k^y 1  ^y 2 13
da 1=2 1=2
k f 1  a  2k r 1  a ln 1  a 8 If model 1 is correct, k tends a value of +0.5, but if model 2
dt is correct, its value is 0.5. Regression on ^y 1  ^y 2 deter-
da 2=3 2=3
k f 1  a  3k r 1  a ln 1  a 9 mines which model is best. The results are presented in
dt Fig. 10. Doing a linear regression, the slope was estimated
Eq. (8) assumes a contracting area controlled reaction for to be 0.24(0.054). Since the k value tends to 0.5, mod-
the forward reaction, and the two-dimensional growth of el 2 is preferred; therefore, the selected model is Eq. (9).
nuclei for the back reaction. On the other hand, Eq. (9) The numeric values of the kinetic parameters are
considers a contracting volume controlled reaction for reported in Figs. 11 and 12. From these gures, it can be
the forward reaction, and the three-dimensional growth observed that, in general, as the CuO load increases, the
of nuclei for the back reaction. It is important to point ks values (both forward and reversible) reduce. This can

0.06

0.05

0.04

0.03

0.02
y-1/2(y 1+y 2)

0.01

0
-0.06 -0.04 -0.02 0 0.02 0.04 0.06
-0.01

-0.02

-0.03

-0.04

-0.05
(y 1-y 2)

Fig. 10. Application of the method of nonintrisic parameters for model discrimination.
 R. Flores et al. / Fuel 87 (2008) 11151126 1125

0.0014 0.0009 0.0003

0.0008
0.0012
0.00025
0.0007
400C 400C
0.001
0.0006 0.0002
400C
0.0008

kf [min ]
kf [min-1] 300C

kf [min ]
-1
0.0005

-1
0.00015
0.0006 0.0004

0.0003 0.0001
0.0004 300C 200C
300C 0.0002
0.0002 200C 0.00005
0.0001
200C
0 0
0
5 10 15 20 25 30 5 10 15 20 25 30
5 10 15 20 25 30
CuO Load [wt%] CuO Load [wt%] CuO Load [wt%]

Fig 11. Rate constants for the forward reaction in the selected model. Support: (a) alumina, (b) titania, (c) zirconia.

0.1 0.005 0.006

400C 400C 400C

0.08 0.004 0.005

300C 300C
0.004 300C
0.06 0.003
kr [min ]

kr [min ]
-1

kr [min ]
-1

-1 0.003
0.04 0.002
200C
200C 0.002
200C
0.02 0.001
0.001

0 0 0
5 10 15 20 25 30 5 10 15 20 25 30 5 10 15 20 25 30
CuO Load [wt%] CuO Load [wt%] CuO Load [wt%]

Fig 12. Rate constants for the reversible reaction in the selected model. Support: (a) alumina, (b) titania, (c) zirconia.

be explained considering that ideally the CuO particles are A2 r 1

14
spherical, and by geometrical reasons, if the total mass of A1 r 2
the spheres were constant, there is an inverse relationship
between the total surface area and the radius of the parti- where A is the total surface area, and r is the particle
cles in the following way: radius.

Table 4
Arrhenius parameters for the kinetics proposed model
Sorbent material kf kr
A0 (min1) EA (cal/mol K) A0 (min1) EA (cal/mol K)
CuAl(4) 1.0015 1.3942 1.0388 25.4481
CuAl(3) 1.0019 1.6448 1.0533 14.2959
CuAl(2) 1.0020 1.6303 1.0979 40.2905
CuAl(1) 1.0028 2.4343 1.2321 160.9831
CuTi(4) 1.0016 1.371 1.0110 8.8973
CuTi(3) 1.0020 1.7772 1.0110 8.7089
CuTi(2) 1.0017 1.4751 1.0110 8.5209
CuTi(1) 1.0019 1.7322 1.0123 9.6035
CuZr(4) 1.0003 0.2057 1.0066 4.4704
CuZr(3) 1.0003 0.1564 1.0062 3.1924
CuZr(2) 1.0004 0.2347 1.0089 5.7255
CuZr(1) 1.0005 0.3569 1.0004 1.0089
1126 R. Flores et al. / Fuel 87 (2008) 11151126
Therefore, as the CuO particle size increases, the total
surface area of the spheres decreases. Since the chemisorp-
tion occurs on the surface of the CuO particles, the number
of available active sites per unit of mass is lower as the par-
ticle grows. Finally, the Arrhenius constants for all the sor-
bent materials were estimated, and they are reported in
Table 4. It can be observed that the frequency factor, A0,
remains essentially constant regardless the support and
the CuO load. On the other hand, the activation energy,
EA, tends to increase as the CuO load diminishes. The last
reinforces the statement that the sorbent materials are
more active and temperature sensitive when lower CuO
loads are employed.
4. Conclusions
Cupric oxide supported on dierent materials was tested
for the adsorption of SO2, and the results were statistically
analyzed applying the concepts of the factorial design. It
was determined that the best operating temperature for
SO2 adsorption is between 300 and 400 C, which is the
temperature of the combustion gases before the air pre-
heaters in a typical thermal power plant. Therefore, a good
option would be to install an adsorbing bed in this place.
However, more studies must be performed since the ther-
mal deactivation of the sorbent materials and their ease
of regeneration at these conditions are unknown. Also,
according to the statistical analysis, it was found that all
the studied factors (temperature, type of support, and
CuO load) are signicant in the performance of the sor-
bents, and the only relevant interaction was between the
CuO load and the type of support. On the other hand, sor-
bents supported on alumina presented much better activity
and eciency than those supported on zirconia and titania;
these results were attributed to a higher surface area in the
alumina compared to the other supports, and to an atomic
interaction between it and the CuO that could lead to the
formation of a new more active species. Also, decreasing
the CuO composition in sorbents supported on alumina
generally enhanced the eciency, but in materials sup-
ported on zirconia and titania this eect was minimal,
and with some exceptions practically negligible. Finally, a
reversible kinetic model was proposed to represent the
adsorption process, in which the forward reaction was
assumed to be a contracting volume controlled reaction,
meanwhile, the back reaction was considered to be a
three-dimensional growth of nuclei.
Acknowledgements
The authors acknowledge the collaboration of Georgina
Blass from IIE, Cuernavaca, Mexico for her participation
in the Atomic Absorption Analysis of the calcined sor-
bent-materials. The authors acknowledge the IIE for the
nancial support through the project 12194. The authors
acknowledge the Aegis Technologies Group Inc. for allow-
ing the use of the asclXtreme software for the kinetic
parameter estimations.
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