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Mesoporous materials for the removal of SO

2
from gas streams
Yannick Mathieu
a
, Michel Soulard
a
, Jol Patarin
a,
*, Michel Molire
b
a
Equipe Matriaux Porosit Contrle, Institut de Science des Matriaux de Mulhouse, LRC 7228 CNRS, Universit de Haute Alsace, ENSCMu 3, rue Alfred Werner,
68093 Mulhouse Cedex, France
b
GE Energy, 20 avenue du Marechal Juin, 90007 Belfort Cedex, France
a b s t r a c t a r t i c l e i n f o
Article history:
Received 17 August 2011
Received in revised form 23 November 2011
Accepted 11 February 2012
Available online 9 March 2012
Keywords:
SO
2
adsorption
Mesoporous MCM-41
CuO
CeO
2
LiCl
A MCM-41 sorbent containing two metal oxides (CuO, CeO
2
) and an alkaline additive (LiCl) was prepared to
remove SO
2
from gas streams at 673 K. Two impregnation methods i.e. the template-ion exchange and the
two solvents impregnation method were employed yielding a high dispersed state of the metal oxides inside
the porosity of the MCM-41 sorbent. The MCM-41 sorbent was found to have a high adsorption capacity of
130 mg SO
2
/g at 673 K. During the adsorption process, cerium oxide partially oxidized SO
2
into SO
3
which
was further chemically adsorbed on active sites (CuO, Li
2
O). The formation of CuSO
4
and Li
2
SO
4
was observed
by X-ray diffraction after the reaction.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Sulfur oxide (SO
x
=SO
2
+SO
3
) emissions stemming from human
activities including fossil fuel combustion in thermal power plants,
petroleum renery or on-road vehicles are major source of atmo-
spheric pollution leading to acid rain, smog and health problems.
Therefore, the development of new sorbents for the removal of SO
x
is of primary importance. SO
x
sorbents are numerous and can be clas-
sied in different categories such as porous silica-based oxides, single
oxides materials (CaO, MgO, etc.), alumina-supported oxides (mainly
CuO/-Al
2
O
3
), mixed oxides derived fromspinels or hydrotalcites and
oxides supported on carbonaceous materials. Among these sorbents,
porous silica-based materials including zeolites, mesoporous mate-
rials or clay minerals are interesting sorbents due to their high specif-
ic surface area and fair thermal stability.
Numerous zeolites including silicalite-1 [1,2], Y [3,4], clinoptilolite
[5], mordenite or ZSM-5 [6,7] and clay minerals such as bentonite [8]
or montmorillonite [9] have been investigated as potential SO
2
sor-
bents. These studies showed that porous silica materials are promising
sorbents for the removal of SO
2
at low temperatures within physical
sorption processes. However, increasing the adsorption temperature
often results in a strong decrease of the SO
2
removal capacity [1,2,4].
Thus, as the ue gas temperature is generally ranging from 523 to
873 K, it is necessary to combine the porous silica support with metal
oxides to chemically adsorb SO
2
. Copper oxide was found to be one of
the most active metal oxides to capture SO
2
or SO
3
as copper sulfates
mainly with CuO/-Al
2
O
3
sorbents [10]. However, CuO/-Al
2
O
3
sor-
bents have only textural porosity and moderate specic surface area
(b200 m
2
/g) in contrast to porous silica based materials. Furthermore,
the -Al
2
O
3
support is not inert as aluminum sulfate species are often
observed by X-ray diffraction after bulk sulfation [11].
Numerous studies were devoted to the use of copper oxide dis-
persed in -Al
2
O
3
support as SO
x
sorbent [1214]. The SO
x
adsorption
on CuO/-Al
2
O
3
leads to the formation of CuSO
4
and Al
2
(SO
4
)
3
. As it
was showed by Centi et al., the sulfation reaction involves the decom-
position of CuSO
4
leading to the formation of SO
3
which is further
chemically adsorbed on Al sites [10]. Thus, an oxidation catalyst
such as cerium which promotes the oxidation of SO
2
into SO
3
can sig-
nicantly enhance the sulfation process. A few studies mentioned a
signicant increase of the SO
x
adsorption capacity for sorbents pre-
pared in the presence of ceriumoxide [15,16]. For instance, Palomares
et al. [15] showed that Ce-doped mixed oxides derived fromhydrotal-
cites exhibits higher SO
2
removal efciency than the corresponding
mixed oxides alone. Wey et al. [16] showed that activated carbon -
bers (ACs) containing CuO and CeO
2
have improved performance in
SO
2
adsorption in contrast to ACs that do not contain metal oxides.
Additions of alkaline metals are known to increase the SO
2
adsorp-
tion capacity. As it has been showed by Jeong et al. [17], the adsorp-
tion capacity of CuO/-Al
2
O
3
materials is signicantly enhanced by
alkaline salts, in particular LiCl. Two effects were clearly observed
by the authors. First, the required temperature for bulk sulfation is
down to about 353 K and the melting of LiCl increases the ionic mo-
bility and reagents diffusion.
The strategy followed in this study was to develop a sorbent for
the removal of SO
x
which combines an inert silica mesoporous sup-
port (MCM-41) having a high specic surface area (~1000 m
2
/g)
Fuel Processing Technology 99 (2012) 3542
Corresponding author. Tel.: +33 3 89 33 68 80.
E-mail address: joel.patarin@uha.fr (J. Patarin).
0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2012.02.005
Contents lists available at SciVerse ScienceDirect
Fuel Processing Technology
j our nal homepage: www. el sevi er . com/ l ocat e/ f upr oc
with two metal oxides (CuO, CeO
2
) and an alkaline additive (LiCl).
Metal loaded MCM-41 sorbents for the removal of SO
x
can be pre-
pared following two methods, i.e. the template-ion exchange (TIE)
and the two solvents impregnation (TSI) methods, respectively. The
TIE is a recognized method to provide a high dispersed state of
metal nanoparticles inside the porosity of mesoporous materials,
which is useful, for instance to prepare Cr-, Ni- or Co-MCM-41
[1820]. In this method, a cationic exchange occurs in which the
C
16
TMA
+
surfactant molecules located inside the mesopores of the
as-synthesized MCM-41 are substituted by the metallic cations in
the precursor solution. In the TSI method, a volume of a highly con-
centrated aqueous solution of the metal salt (typically 2 or 3 M) is
set equal to the pore volume of the silica support previously deter-
mined by N
2
sorption. The calcined and dehydrated silica support is
previously dispersed in an organic solvent poorly miscible with
water before adding the inorganic precursors. During the drying
step performed at room temperature, the inorganic precursors ll
the mesopores by capillarity. This method was proposed by Davidson
et al. to incorporate metal oxides such as -MnO
2
[21], Co
3
O
4
[22] or
-Fe
2
O
3
[23] inside the mesopores of SBA-15 materials.
In our study, the TIE and TSI methods were used to prepare the
MCM-41 sorbent containing the metal oxides (CeO
2
, CuO) and the al-
kaline additive (LiCl). The samples were fully characterized by X-ray
diffraction (XRD), transmission electron microscopy (TEM), thermal
analysis and nitrogen adsorption. A main part of this work was devot-
ed to the study of SO
2
adsorption of the different samples at a high
space velocity (SV) of 25,000 h
1
, in particular the adsorption capac-
ity (milligram of SO
2
captured by gram of sorbent). The sulfated sam-
ples were also characterized by XRD and temperature programmed
desorption (TPD).
2. Experimental
2.1. Synthesis of MCM-41
The synthesis procedure of MCM-41 includes the dissolution of
3.35 g of C
16
TMABr (hexadecyltrimethylammonium bromide, Al-
drich, 99%) in 70 g of distilled water at 313 K (=solution A) and
the dissolution of 10.50 g of sodium silicate (Riedel de Han,
27 wt.% SiO
2
, 10 wt.% NaOH) in 11 g of distilled water at room tem-
perature (=solution B). After cooling solution A at room tempera-
ture, solutions A and B were mixed leading to the formation of a
white precipitate and the resulting mixture was mechanically stirred
at room temperature for 5 min. An aqueous solution of hydrogen
chloride (1 M) was added slowly to decrease the pH up to 8.5 and
the mixture was stirred for 5 more minutes. The resulting mixture
was then transferred in a polypropylene bottle and heated under stat-
ic conditions at 363 K for 24 h. The solid obtained after the hydrother-
mal treatment was recovered by ltration, washed three times with
500 ml of distilled water and dried at 343 K for one night.
2.2. Preparation of CeO
2
-MCM-41 (Template Ion Exchange)
The incorporation of cerium was performed following the TIE
method. A mass of 2.70 g of cerium nitrate hexahydrate (Aldrich,
99.9%) was dissolved in a solution containing 60 ml of absolute etha-
nol and 300 ml of distilled water. After dissolution, 3 g of as-
synthesized MCM-41 was added and the mixture was stirred at
333 K for 24 h. The Ce-MCM-41 material was then recovered by ltra-
tion, washed three times with 500 ml of distilled water and dried at
room temperature for 24 h. The Ce-MCM-41 material was further cal-
cined at 873 K for 6 h (heating rate of 1.7 K/min) yielding the forma-
tion of CeO
2
-MCM-41. The color of the CeO
2
-MCM-41 sample was
slightly yellow.
2.3. Preparation of the MCM-41 sorbent (Two Solvents Impregnation)
The incorporation of copper and lithium chloride was performed
by the TSI method. The anhydrous CeO
2
-MCM-41 (1.70 g) was dis-
persed in 100 ml of n-hexane and stirred for 20 min. Then, 700 l of
a 3 M aqueous solution of copper nitrate (Carlo Erba, 99.5%) was
added and the mixture was stirred for 10 min. The powder was
then recovered by ltration, crushed in a mortar for 10 min and
dried 24 h at ambient temperature. The material was further calcined
at 873 K for 6 h (heating rate of 1.7 K/min) leading to the formation of
CuO/CeO
2
-MCM-41. A pronounced gray color was observed. A similar
procedure was applied for the incorporation of lithium chloride (Al-
drich, 99%). A mass of 1.80 g of CuO/CeO
2
-MCM-41 was dispersed
in 100 ml of n-hexane and stirred for 20 min. Then, 680 l of an aque-
ous solution of lithium chloride 5 M was added and the mixture was
stirred for 10 min. Finally, the powder was recovered by ltration,
crushed in a mortar for 10 min and dried 24 h at room temperature
leading to the formation of the sorbent for the removal of SO
x
. The
MCM-41 sorbent containing CeO
2
, CuO and LiCl will be designated
in this work as Li-doped MCM-41 sorbent.
2.4. Characterization
X-ray powder diffraction was performed in a reection mode on a
Philips X'Pert diffractometer (Cu K radiation, =1.54 ) equipped
with a X'Celerator detector. Diffractograms were recorded with a 2
scan range of 370 with a step of 0.02 per 20 s at 35 kV tube voltage
and 55 mA tube current. A glass support was used to record the XRD
at low angles. Thermal (TG/DTA) analyses were performed under air
on a Setaram Labsys thermoanalyzer with a heating rate of 5 K/min
up to 1273 K. Chemical analyses were performed on the MCM-41 sor-
bent using an X-ray uorescence apparatus (PHILIPS MagiX). Nitro-
gen adsorption measurements were carried out on a Micromeritics
Tristar surface area analyzer after outgassing the samples for 15 h at
423 K. Specic surface areas and pore size distributions were deter-
mined by the BET and BJH methods, respectively [24]. The adsorption
branch was used for pore size calculations. Transmission electron mi-
croscopy images were collected on a Philips CM200 microscope
equipped with a LaB
6
lament. The accelerating voltage was 200 kV.
Samples were previously dispersed in water and sonicated for
10 min. Then, ve to ten drops of the solution were deposited onto
Cu grids coated with a thin (5 nm thickness) holey carbon support
lm.
The SO
2
adsorption tests were performed on the metal oxides con-
taining MCM-41 samples. The materials were previously pelletized,
crushed and sized to obtain grains with a size ranging from 250 to
450 m. The experimental set-up was carried out using a xed-bed
ow quartz reactor (16.5 mm inner diameter) designed to allow ex-
periments over a wide range of space velocities. The experiment
was performed at 673 K using a gas mixture of 250 ppm SO
2
, 10 v.%
O
2
and nitrogen as the carrier gas. The gasses were preheated before
entering the reactor. The gas ow rate was 53 Nl/h and the mass of
the material deposited over the glass-frit was 1.0 g yielding a SV of
25,000 h
1
. The SO
2
outlet concentration was continuously moni-
tored by a Rosemount NGA 2000 analyser based on UV absorption
(range 01000 ppm). Before the SO
2
experiment, in order to get a
dry sample, the material was heated from 298 to 673 K at a heating
rate of 10 K/min under pure N
2
(gas ow rate of 100 Nl/h) and the
temperature was maintained at 673 K for 1 h. The adsorption capacity
(C
ads
) was calculated by integration of the breakthrough curve via the
following formula:
C
ads

C
SO2
in
C
SO2
out dt
m
where C
in
SO2
and C
out
SO2
are the inlet and outlet con-
centrations of SO
2
and m is the mass of the hydrated sample. The
amount of water in the hydrated sample was carefully determined
36 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542
by TG measurements. The temperature programmed desorption was
performed under pure N
2
by heating the sulfated samples from
room temperature to about 1173 K at a heating rate of 10 K/min.
3. Results and discussion
3.1. Characterization of the sorbent
The calcined MCM-41 (reference) and metal oxides loaded MCM-
41 samples were rst characterized by low angle X-ray diffraction.
The XRD pattern of the calcined MCM-41 is a characteristic of a well
ordered hexagonal mesoporous structure with the main diffraction
peak (100) at 2.4 2 and other diffraction peaks (110), (200) and
(210) having lower intensities between 4 and 6.5 2 (Fig. 1a). The in-
tensities of the (100) reection is strongly decreased for the metal ox-
ides containing MCM-41 samples (Fig. 1bd). In addition, the other
reections (110), (200) and (210) disappear suggesting a loss of
long range crystallographic order. The formation of metal oxide parti-
cles inside the mesopores after calcination of the Ce-MCM-41 and Cu/
CeO
2
-MCM-41 samples may also explain this effect. The interplanar
spacing d
100
and the hexagonal lattice parameter a
0
of the calcined
MCM-41 and metal oxides containing MCM-41 samples are listed in
Table 1. It is observed that, the diffraction peak (100) is shifted from
2.41 (d
100
=3.66 nm) to 2.57 2 (d
100
=3.44 nm) leading to a de-
crease of the unit cell size from 4.23 to 3.97 nm. Such a decrease
may be explained by the successive calcination steps. The X-ray dif-
fraction patterns at wide angles of the metal oxides containing
MCM-41 samples are shown in Fig. 2. After calcination of the Ce-
MCM-41 material, large diffraction peaks suggesting small crystallite
size and corresponding to the cerium oxide are observed at 28.4,
47.5 and 56.8 2 (Fig. 2a). The Scherrer equation was used to calcu-
late the size of the CeO
2
crystallites using the diffraction peaks (111),
(220) and (311), respectively (Table 2). The calculated values are
consistent with CeO
2
particles located inside MCM-41 mesopores.
Other sharp peaks are attributed to copper oxide which is formed
during the calcination of the Cu/CeO
2
-MCM-41 sample (Fig. 2b). A
typical X-ray diffraction pattern of the Li-doped MCM-41 sorbent is
shown in Fig. 2c. After incorporation of lithium chloride, diffraction
peaks corresponding to copper oxide are less intense in the Li-
doped MCM-41 sorbent than in the CuO/CeO
2
-MCM-41 sample indi-
cating that chloride anions from LiCl reacted with copper oxide yield-
ing the formation of a hydrated copper chloride which was identied
as Cu
2
(OH)
3
Cl (atacamite). It is also important to note that no lithium
chloride peaks are observed by XRD.
Further, the CeO
2
-MCM-41 sample and the Li-doped MCM-41 sor-
bent were studied by TEM. The two samples show an ordered meso-
porous structure. For the CeO
2
-MCM-41 sample, CeO
2
nanoparticles
of highest electron density appear as black areas on the silica grains
(Fig. 3a and b). As it can be seen, empty and lled mesopores with
CeO
2
nanoparticles are observed. Furthermore, no isolated or external
CeO
2
nanoparticles attached on MCM-41 grains are evidenced. For the
Li-doped MCM-41 sorbent, lled and empty mesopores are also found
to coexist (Fig. 3c and d). No signicant modications of the meso-
porous structure are observed.
The nitrogen adsorption/desorption isotherm of the calcined
MCM-41 is a typical type-IV isotherm with a vertical step at a relative
pressure around P/P
0
=0.30 which is characteristic of capillary con-
densation in mesopores having a diameter lower than 35 (Fig. 4a)
[25]. A narrow and uniform pore size distribution around 2425 is
observed (Fig. 5a). After the loading of CeO
2
, the shape of the iso-
therm is slightly modied (Fig. 4b). However, a less pronounced ver-
tical step slightly shifted toward lower P/P
0
values (0.250.30) is
observed indicating a decrease of the mesoporous organization. A de-
crease of the porous volume and the specic surface area is also ob-
served. The corresponding BJH pore-size analysis shows a pore size
distribution around 2022 (Fig. 5b). For the CuO/CeO
2
-MCM-41
and the Li-doped MCM-41 sorbent, no inection point is visible (Fig.
4cd). The specic surface area and the pore volume are found to de-
crease from 1020 to 453 m
2
/g and from 0.87 to 0.28 cm
3
/g, respec-
tively throughout the preparation process (Table 1). As it was
shown by TEM observations, no metal oxide particles were found to
plug the mesopore's entrance. Thus, the decrease of specic surface
area and pore volume is attributed to the lling of the pores by
metal oxide particles (CeO
2
and CuO) and atacamite. Accordingly,
broad pore size distributions centered around 20 , characteristics
of a secondary microporosity, are observed for the CuO/CeO
2
-MCM-
41 and the Li-doped MCM-41 sorbent (Fig. 5cd).
The as-synthesized MCM-41, the Ce-MCM-41 sample and the Li-
doped MCM-41 sorbent were characterized by TG/DTA. For the as-
2 4 6 8 2(Cu
K
)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
(100)
(110)
(200)
(210)
(b)
(c)
(d)
(a)
Fig. 1. Low angle XRD patterns of calcined (a) MCM-41, (b) CeO
2
-MCM-41, (c) CuO/CeO
2
-
MCM-41 and (d) Li-doped MCM-41 sorbent.
Table 1
Structural and textural properties of the calcined MCM-41 and metal oxides containing
MCM-41 samples.
Sample 2 (100)
()
d
100
(nm)
a
0
a
(nm)
S
BET
(m
2
/g)
Pore
volume
b
(cm
3
/g)
Pore
size
b
(nm)
MCM-41 2.41 3.66 4.23 1020 0.87 2.42.5
CeO
2
-MCM-41 2.45 3.60 4.15 915 0.66 2.02.2
CuO/CeO
2
-MCM-41 2.55 3.45 3.98 465 0.29 2.02.1
Li-doped MCM-41 sorbent 2.57 3.44 3.97 453 0.28 1.92.1
a
Wall thickness calculated as a
0
=2d
100
/

3
p
.
b
Pore-size distributions and pore volumes were determined from N
2
adsorption iso-
therms at 77 K.
10 20 30 40 50 60
*: CuO
+
: Cu
2
(OH)
3
Cl
: CeO
2
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
(a)
(b)
(c)
(111)
(220) (311)
2(Cu
K
)
Fig. 2. XRD patterns of (a) CeO
2
-MCM-41, (b) CuO/CeO
2
-MCM-41 and (c) Li-doped
MCM-41.
37 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542
synthesized MCM-41, two weight losses can be seen (Fig. 6a). The
rst one of about 4.7 wt.% occurring between 298 and 423 K is
coupled with a weak endothermic signal which is attributed to the
elimination of physisorbed water. The second one (~37 wt.%) takes
place in the range 423773 K and corresponds to the C
16
TMA
+
de-
composition and is associated with two exothermic peaks around
573 and 773 K, respectively. A larger loss (~17.7 wt.%) of physisorbed
water is seen for the Ce-MCM-41 after the drying and rehydration of
the sample elaborated via the TIE procedure (Fig. 6b). The second
weight loss (~1.1 wt.%) coupled with a weak exothermic peak is at-
tributed to residual C
16
TMA
+
. The residual C
16
TMA
+
comes from a
non complete exchange of the C
16
TMA
+
located inside the mesopores
by the Ce
3+
. Strydom and Van Vuuren showed that the decomposi-
tion of cerium nitrate leads to the formation of CeO
2
in the tempera-
ture range 523573 K [26]. However, it is difcult to evaluate exactly
the temperature of the CeO
2
formation in the MCM-41 since the de-
composition of residual C
16
TMA
+
occurs in the same temperature
range (473573 K). For the Li-doped MCM-41 sorbent, a loss of phy-
sisorbed water about 8.1 wt.% associated with an endothermic peak
occurs between 323 and 513 K (Fig. 6c). As it was showed by Sharkey
and Lewin, atacamite was found to decompose in two steps including
dehydration (553563 K) and the loss of halogen (713723 K)
according to the following reactions [27]:
2Cu
2
OH
3
ClCuOCuCl
2
2CuO 3H
2
O 1
CuOCuCl
2

1
/
2O
2
2CuO Cl
2
2
Therefore, the broad endothermic peak observed around 593 K
should correspond to the loss of water coming from atacamite. The
interpretation of the exothermic signals above 673 K is more difcult.
A XRD performed on the calcined sorbent at 923 K revealed the pres-
ence of small amounts of quartz and lithium silicate (Li
2
SiO
3
). Thus,
the exothermic signals visible above 673 K might correspond to the
loss of halogen and/or the formation of quartz and lithium silicate
due to the loss of order of the MCM-41 sorbent but it is difcult to
clearly assign them. Moreover, no sharp endothermic peak corre-
sponding to the melting of LiCl is observed around 873883 K [28].
It is worth mentioning that the structure of a classical MCM-41 with-
out any metal oxides is thermally stable up to 1073 K.
Table 3 summarizes the chemical analyses for the Li-doped MCM-
41 sorbent. The Si/Ce molar ratio is found to strongly increase from
4.8 (TIE procedure) to 35 as cerium nitrate is introduced in large ex-
cess during the TIE procedure. The mother liquid recovered by
Table 2
Crystallite size L () in different directions evaluated from the width at half-maximum
intensity of the (111), (220) and (311) diffraction peaks of the CeO
2
-MCM-41 sample.
Diffraction peak Position (2) L ()
(111) 28.2 25.4
(220) 47.2 24.3
(311) 56.3 24.5
Fig. 3. TEM micrographs of (a, b) CeO
2
-MCM-41 sample and (c, d) Li-doped MCM-41 sorbent.
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0
0
100
200
300
400
500
600
(a)
(b)
(c)
(d)
P/P
0
V
a
d
s

(
c
m
3
.
g
-
1

S
T
P
)
Fig 4. Nitrogen adsorptiondesorption isotherms for the calcined (a) MCM-41,
(b) CeO
2
-MCM-41, (c) CuO/CeO
2
-MCM-41 and (d) Li-doped MCM-41 sorbent.
38 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542
ltration of the Ce-MCM-41 sample after the TIE procedure was ana-
lyzed by
1
H liquid NMR spectroscopy (spectra not shown here) and
conrmed the presence of C
16
TMA
+
. Thus, a cationic exchange be-
tween C
16
TMA
+
molecules and Ce
3+
cations was found to occur dur-
ing the TIE procedure. Some preliminary experiments were
performed to adjust the duration of the TIE procedure in order to
reach a high cerium content in the MCM-41. The optimal time was
found to be between 12 and 24 h. The Si/Li molar ratio is close to 11
even though no lithium phase was observed by XRD.
3.2. SO
2
adsorption
The CeO
2
-MCM-41 sample exhibits no particular SO
2
removal ca-
pacity (breakthrough curve not presented here) as the SO
2
adsorption
-5
0
5
10
15
20
-5
0
5
10
15
20
Exo
TG
DTA
Exo
TG
DTA
350 450 550 650 750 850 950 1050
Temperature(K)
350 450 550 650 750 850 950 1050
Temperature(K)
350 450 550 650 750 850 950 1050
Temperature(K)
Exo
TG
DTA
-5
0
5
10
15
20
25
30
35
40
45
W
e
i
g
h
t

l
o
s
s
(
%
)
W
e
i
g
h
t

l
o
s
s
(
%
)
W
e
i
g
h
t

l
o
s
s
(
%
)
b
c
a
Fig. 6. TG/DTA curves of (a) the as-synthesized MCM-41, (b) Ce-MCM-41 sample and
(c) Li-doped MCM-41 sorbent.
Table 3
Chemical composition of the Li-doped MCM-41 sorbent.
Chemical composition (in wt.%) Weight loss %
from TG
b
Molar ratio
Si/Ce Si/Cu Si/Li
Si O Cu Ce Li
a
Cl 18.3 35 11.5 11.3
36.5 44.6 7.2 5.2 0.8 5.7
a
Determined by ICP (inductively coupled plasma).
b
Under air up to 1073 K.
0
50
100
150
200
250
0 3000 6000 9000 12000 15000 18000
Time (s)
[
S
O
2
]

(
p
p
m
)
(a)
(b)
Fig. 7. SO
2
breakthrough curves of (a) the CuO/CeO
2
-MCM-41 sample and (b) Li-doped
MCM-41 sorbent. Conditions: T=673 K, SV=25,000 h
1
, 53 Nl/h, gas composition:
250 ppm SO
2
, 10% O
2
in N
2
. The breakthrough curve of the CeO
2
-MCM-41 sample is
not shown since the SO
2
adsorption capacity is very small (b5 mg SO
2
/g). According
to this result, the breakthrough curves of the MCM-41 sample and the empty reactor
were not performed.
Fig. 5. BJH pore size curves for (a) the calcined MCM-41, (b) CeO
2
-MCM-41, (c) CuO/
CeO
2
-MCM-41 and (d) Li-doped MCM-41 sorbent.
10 20 30 40 50 60
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
++
+
+
+
+
+
+
+
++
+
+ +
+
O
*
*
*
*
* *
* *
*
(a)
(b)
2 4 6 8 2 (Cu
K
)
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
(a)
(b)
2(Cu
K
)
Fig. 8. XRD pattern of (a) the sulfated CuO/CeO
2
-MCM-41 sample and (b) Li-doped
MCM-41 sorbent. (Inset) Corresponding low angle XRD patterns.
39 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542
capacity was found lower than 5 mg SO
2
/g. The SO
2
breakthrough
curve of the CuO/CeO
2
-MCM-41 sample is shown in Fig. 7a. The sor-
bent is found to completely adsorb SO
2
for 460 s. The SO
2
adsorption
capacity measured by integration of the breakthrough curve is 15 mg
SO
2
/g. As it can be seen, the saturation is reached around 220 ppm
after 6000 s. However, the inlet SO
2
concentration of 250 ppm is not
retrieved after the saturation of the sorbent. This suggests that a frac-
tion of SO
2
reacts with oxygen and/or is oxidized by CeO
2
yielding the
formation of SO
3
which is not seen by the UV analyzer. A signicant
increase of the SO
2
removal performance is observed for the Li-
doped MCM-41 sorbent (Fig. 7b). The adsorption capacity is 96 mg
SO
2
/g which is more than 6 times higher than the CuO/CeO
2
-MCM-
41 sample and all the SO
2
is completely adsorbed for 75008000 s.
The saturation is reached after 18,000 s with around 220 ppm SO
2
detected at the reactor outlet. This result clearly shows that the com-
bination of copper oxide, cerium oxide, atacamite and lithium ap-
pears to be necessary to reach a high SO
x
removal activity.
3.3. Characterization of the sulfated sorbents
The XRD pattern of the sulfated CuO/CeO
2
-MCM-41 sample ex-
hibits no particular modications as characteristic peaks of CeO
2
and CuO are still observed (Fig. 8a). This shows a lack of reactivity
of the metal oxides towards SO
x
in this sample under these experi-
mental conditions (673 K, SV=25,000 h
1
). However, for the sulfat-
ed Li-doped MCM-41 sorbent, several peaks of chalchantite
(CuSO
4
5H
2
O) and lithium sulfate (Li
2
SO
4
H
2
O) are observed (Fig.
8b). The presence of hydrated sulfates could be explained by the ex-
position of the sample to moisture after the tests. Furthermore, the
CeO
2
and CuO peaks completely disappear suggesting a high activity
of the metal oxides towards SO
x
in this sorbent. No cerium sulfates
are observed conrming that CeO
2
only acts as an oxidation promot-
er. The mesoporous organization is not affected conrming the stabil-
ity of both the CuO/CeO
2
-MCM-41 sample and Li-doped MCM-41
sorbent at 673 K after sulfation (Fig. 8, inset).
The sulfation reaction induces some morphological changes in the
Li-doped MCM-41 sorbent as several grains are surrounded by
Fig. 9. TEM micrographs of the sulfated Li-doped MCM-41 sorbent.
0
200
400
600
800
1000
1200
0 1000 2000 3000 4000 5000 6000 7000
Time (s)
T
e
m
p
e
r
a
t
u
r
e

(
K
)
0
200
400
600
800
1000
1200
[
S
O


]

(
p
p
m
)
2
(a)
(b)
Fig. 10. TPD of (a) the sulfated CuO/CeO
2
-MCM-41 sample and (b) Li-doped MCM-41
sorbent performed under N
2
(D
v
=53 Nl/h).
10 20 30 40 50 60
: SiO
2
: Li
2
SiO
3
: CeO
2
2 4 6 8 2 (Cu
K
)
i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
2 (Cu
K
)
Fig. 11. XRD pattern of the Li-doped MCM-41 sorbent after TPD. (Inset) Corresponding
low angle XRD patterns.
40 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542
globular particles which may be attributed to the sulfated species
(Fig. 9). The aspect of the majority of MCM-41 grains is however
not changed.
The TPD curves of the sulfated CuO/CeO
2
-MCM-41 sample and Li-
doped MCM-41 sorbent are shown in Fig. 10. As it can be seen, only
one desorption peak is observed for the sulfated CuO/CeO
2
-MCM-41
sample. The maximum of desorption (~100120 ppm SO
2
) occurs be-
tween 833 and 953 K. Mu and Perlmutter clearly showed that the de-
composition of CuSO
4
5H
2
O under N
2
occurs in the same
temperature range [29]. Thus, the desorption peak in the sulfated
CuO/CeO
2
-MCM-41 sample corresponds to the decomposition of
CuSO
4
which is in a highly dispersed state in the MCM-41 and is
therefore not detectable by XRD. The adsorption capacity, calculated
by integration of the desorption peak, is about 21 mg SO
2
/g. This
value is higher than the adsorption capacity calculated by integration
of the breakthrough curve (15 mg SO
2
/g). It is worth mentioning that
the TPD is performed under a non oxidative atmosphere (no forma-
tion of SO
3
can occur). Therefore, it is likely that previously adsorbed
SO
3
molecules have been desorbed in the form of SO
2
thus leading to
a SO
2
adsorption capacity which is higher than the one measured by
integration of the breakthrough curve. For the sulfated Li-doped
MCM-41 sorbent, two distinct desorption peaks are observed. The
rst desorption peak corresponds to the decomposition of CuSO
4
and starts at around 763 K with a maximum observed around 963 K
(~700 ppm SO
2
) and nishes at 1023 K. The second desorption occurs
at higher temperature (~1153 K) and may correspond to the decom-
position of Li
2
SO
4
as reported in the literature [30]. The adsorption ca-
pacity as determined in the desorption phase is therefore 130 mg
SO
2
/g which is one of the highest values found in the current litera-
ture for porous silica supports. Again the desorption process leads
to a higher adsorption capacity than the adsorption process. An XRD
analysis performed on the MCM-41 sorbent after the TPD conrms
the complete transformation of the sorbent into SiO
2
(quartz) and
lithium silicate (Fig. 11). Several sharp peaks of CeO
2
are also
observed.
3.4. Proposed mechanism
The main crystalline phases determined by XRD and inferred from
the TPD peaks for the various samples involved in this study are sum-
marized in Table 4. As it was shown, it is necessary to combine metal
oxides (CuO, CeO
2
) in a highly dispersed state, atacamite and lithium
to reach a high SO
x
removal activity. However, the role of both ataca-
mite and lithium was not clearly established during the sulfation pro-
cess. Therefore, an intermediate MCM-41 sorbent type containing
only CuO and lithium chloride was synthesized to investigate both
the crystalline phases formed after the sulfation reaction and the de-
sorption peaks developed during the TPD. The XRD of the fresh CuO/
LiCl-MCM-41 sample exhibits CuO and atacamite crystalline phases.
However, only lithium sulfate peaks are observed by XRD after sulfa-
tion. Two characteristic desorption peaks attributed respectively to
CuSO
4
and Li
2
SO
4
are observed by TPD between 673 and 1013 K and
for a temperature higher than 1073 K, respectively. The area of the
desorption peak attributed to CuSO
4
is about three times lower than
in the Li-doped MCM-41 sorbent resulting in a lower adsorption ca-
pacity of 80 mg SO
2
/g. This conrms that the highly dispersed CuO,
and therefore not detected by XRD, did react with SO
x
during the sul-
fation reaction yielding the formation of CuSO
4
despite the absence of
the corresponding XRD peaks. Thus, the presence of an oxidation pro-
moter such as cerium oxide efciently enhances the sulfation of CuO.
According to the previous observations made by Centi et al. who ob-
served that the sulfation process in CuO/Al
2
O
3
material occurs via ad-
sorption of SO
3
on CuO sites [10]. The main following reactions may
occur:
SO
2

1
/
2O
2
SO
3
catalyzed by CeO
2
3
CuO SO
3
CuSO
4
4
Li
2
O SO
3
Li
2
SO
4
5
CuO SO
2

1
/
2O
2
CuSO
4
6
Li
2
O SO
2

1
/
2O
2
Li
2
SO
4
7
It is noteworthy that Li
2
O is not a stable species in the test condi-
tions and is actually in the form of LiCl or LiOH before reacting with
SO
x
. Furthermore, the decomposition of atacamite via reaction (2)
may lead to the formation of highly active CuO sites.
4. Conclusion
A high specic surface area and thermally stable MCM-41 sorbent
was prepared for the removal of SO
x
at 673 K. The investigated for-
mulation combined a SO
x
trap (copper oxide), an oxidation promoter
(cerium oxide) and lithium chloride to assist the sulfation reaction.
This type of sorbent exhibits characteristic XRD peaks of copper and
lithium sulfate after the sulfation. A high adsorption capacity of
130 mg SO
2
/g was obtained by integration of the TPD curve which is
one of the highest values mentioned in the literature for porous silica
based sorbents. Further studies are underway, dealing with the re-
generation of the sorbent; in particular a regeneration process involv-
ing a reductive gaseous ow (hydrogen, methane) is likely to
signicantly decrease the decomposition temperature of copper and
lithium sulfates and to avoid the collapse of the MCM-41 support
that has been observed.
Acknowledgments
The authors would like to thank Sophie Dorge from the Labora-
toire Gestion des Risques et Environnement for her help in SO
2
ad-
sorption experiments and interpretations.
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Table 4
Crystalline phases observed by XRD before and after sulfation and TPD peaks of the dif-
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Sample XRD TDP peaks C
ads
b
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T (K)
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