Fuel Processing Technology 99 (2012) 3542

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Fuel Processing Technology

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Mesoporous materials for the removal of SO2 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 r t i c l e i n f o a b s t r a c t

Article history: A MCM-41 sorbent containing two metal oxides (CuO, CeO2) and an alkaline additive (LiCl) was prepared to
Received 17 August 2011 remove SO2 from gas streams at 673 K. Two impregnation methods i.e. the template-ion exchange and the
Received in revised form 23 November 2011 two solvents impregnation method were employed yielding a high dispersed state of the metal oxides inside
Accepted 11 February 2012
the porosity of the MCM-41 sorbent. The MCM-41 sorbent was found to have a high adsorption capacity of
Available online 9 March 2012
130 mg SO2/g at 673 K. During the adsorption process, cerium oxide partially oxidized SO2 into SO3 which
Keywords:
was further chemically adsorbed on active sites (CuO, Li2O). The formation of CuSO4 and Li2SO4 was observed
SO2 adsorption by X-ray diffraction after the reaction.
Mesoporous MCM-41 2012 Elsevier B.V. All rights reserved.
CuO
CeO2
LiCl

1. Introduction mainly with CuO/-Al2O3 sorbents [10]. However, CuO/-Al2O3 sor-

Sulfur oxide (SOx = SO2 + SO3) 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 SOx
is of primary importance. SOx 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/-Al2O3), mixed oxides derived from spinels 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 SO2 sor-
bents. These studies showed that porous silica materials are promising
sorbents for the removal of SO2 at low temperatures within physical
sorption processes. However, increasing the adsorption temperature
often results in a strong decrease of the SO2 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 SO2. Copper oxide was found to be one of
the most active metal oxides to capture SO2 or SO3 as copper sulfates
Corresponding author. Tel.: + 33 3 89 33 68 80.
E-mail address: joel.patarin@uha.fr (J. Patarin).
bents have only textural porosity and moderate specic surface area
(b200 m 2/g) in contrast to porous silica based materials. Furthermore,
the -Al2O3 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 -Al2O3 support as SOx sorbent [1214]. The SOx adsorption
on CuO/-Al2O3 leads to the formation of CuSO4 and Al2(SO4)3. As it
was showed by Centi et al., the sulfation reaction involves the decom-
position of CuSO4 leading to the formation of SO3 which is further
chemically adsorbed on Al sites [10]. Thus, an oxidation catalyst
such as cerium which promotes the oxidation of SO2 into SO3 can sig-
nicantly enhance the sulfation process. A few studies mentioned a
signicant increase of the SOx adsorption capacity for sorbents pre-
pared in the presence of cerium oxide [15,16]. For instance, Palomares
et al. [15] showed that Ce-doped mixed oxides derived from hydrotal-
cites exhibits higher SO2 removal efciency than the corresponding
mixed oxides alone. Wey et al. [16] showed that activated carbon -
bers (ACs) containing CuO and CeO2 have improved performance in
SO2 adsorption in contrast to ACs that do not contain metal oxides.
Additions of alkaline metals are known to increase the SO2 adsorp-
tion capacity. As it has been showed by Jeong et al. [17], the adsorp-
tion capacity of CuO/-Al2O3 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 SOx which combines an inert silica mesoporous sup-
port (MCM-41) having a high specic surface area (~ 1000 m 2/g)

0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2012.02.005
36 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542
with two metal oxides (CuO, CeO2) and an alkaline additive (LiCl).
Metal loaded MCM-41 sorbents for the removal of SOx 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
C16TMA + 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 N2 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 -MnO2 [21], Co3O4 [22] or
-Fe2O3 [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 (CeO2, 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 SO2 adsorption of the different samples at a high
space velocity (SV) of 25,000 h 1, in particular the adsorption capac-
ity (milligram of SO2 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 C16TMABr (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.% SiO2, 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 CeO2-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 CeO2-MCM-41. The color of the CeO2-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 CeO2-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/CeO2-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/CeO2-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 SOx. The
MCM-41 sorbent containing CeO2, 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 LaB6 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 SO2 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 SO2, 10 v.%
O2 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 SO2 outlet concentration was continuously moni-
tored by a Rosemount NGA 2000 analyser based on UV absorption
(range 01000 ppm). Before the SO2 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 N2 (gas ow rate of 100 Nl/h) and the
temperature was maintained at 673 K for 1 h. The adsorption capacity
(Cads) was calculated by integration of the breakthrough curve via the
following formula:
C SO2
in C out dt
SO2
SO2 SO2
C ads m where Cin and Cout are the inlet and outlet con-
centrations of SO2 and m is the mass of the hydrated sample. The
amount of water in the hydrated sample was carefully determined
 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542 37

by TG measurements. The temperature programmed desorption was Table 1

performed under pure N2 by heating the sulfated samples from Structural and textural properties of the calcined MCM-41 and metal oxides containing
MCM-41 samples.
room temperature to about 1173 K at a heating rate of 10 K/min.
Sample 2 (100) d100 a0a SBET Pore Pore
() (nm) (nm) (m2/g) volumeb sizeb
(cm3/g) (nm)
3. Results and discussion
MCM-41 2.41
3.66 4.23 1020 0.87 2.42.5
CeO2-MCM-41 2.45
3.60 4.15 915 0.66 2.02.2
3.1. Characterization of the sorbent
CuO/CeO2-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
The calcined MCM-41 (reference) and metal oxides loaded MCM- a
p
Wall thickness calculated as a0 = 2 d100/ 3.
41 samples were rst characterized by low angle X-ray diffraction. b
Pore-size distributions and pore volumes were determined from N2 adsorption iso-
The XRD pattern of the calcined MCM-41 is a characteristic of a well therms at 77 K.
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- Further, the CeO2-MCM-41 sample and the Li-doped MCM-41 sor-
tensities of the (100) reection is strongly decreased for the metal ox- bent were studied by TEM. The two samples show an ordered meso-
ides containing MCM-41 samples (Fig. 1bd). In addition, the other porous structure. For the CeO2-MCM-41 sample, CeO2 nanoparticles
reections (110), (200) and (210) disappear suggesting a loss of of highest electron density appear as black areas on the silica grains
long range crystallographic order. The formation of metal oxide parti- (Fig. 3a and b). As it can be seen, empty and lled mesopores with
cles inside the mesopores after calcination of the Ce-MCM-41 and Cu/ CeO2 nanoparticles are observed. Furthermore, no isolated or external
CeO2-MCM-41 samples may also explain this effect. The interplanar CeO2 nanoparticles attached on MCM-41 grains are evidenced. For the
spacing d100 and the hexagonal lattice parameter a0 of the calcined Li-doped MCM-41 sorbent, lled and empty mesopores are also found
MCM-41 and metal oxides containing MCM-41 samples are listed in to coexist (Fig. 3c and d). No signicant modications of the meso-
Table 1. It is observed that, the diffraction peak (100) is shifted from porous structure are observed.
2.41 (d100 = 3.66 nm) to 2.57 2 (d100 = 3.44 nm) leading to a de- The nitrogen adsorption/desorption isotherm of the calcined
crease of the unit cell size from 4.23 to 3.97 nm. Such a decrease MCM-41 is a typical type-IV isotherm with a vertical step at a relative
may be explained by the successive calcination steps. The X-ray dif- pressure around P/P0 = 0.30 which is characteristic of capillary con-
fraction patterns at wide angles of the metal oxides containing densation in mesopores having a diameter lower than 35 (Fig. 4a)
MCM-41 samples are shown in Fig. 2. After calcination of the Ce- [25]. A narrow and uniform pore size distribution around 2425 is
MCM-41 material, large diffraction peaks suggesting small crystallite observed (Fig. 5a). After the loading of CeO2, the shape of the iso-
size and corresponding to the cerium oxide are observed at 28.4, therm is slightly modied (Fig. 4b). However, a less pronounced ver-
47.5 and 56.8 2 (Fig. 2a). The Scherrer equation was used to calcu- tical step slightly shifted toward lower P/P0 values (0.250.30) is
late the size of the CeO2 crystallites using the diffraction peaks (111), observed indicating a decrease of the mesoporous organization. A de-
(220) and (311), respectively (Table 2). The calculated values are crease of the porous volume and the specic surface area is also ob-
consistent with CeO2 particles located inside MCM-41 mesopores. served. The corresponding BJH pore-size analysis shows a pore size
Other sharp peaks are attributed to copper oxide which is formed distribution around 2022 (Fig. 5b). For the CuO/CeO2-MCM-41
during the calcination of the Cu/CeO2-MCM-41 sample (Fig. 2b). A and the Li-doped MCM-41 sorbent, no inection point is visible (Fig.
typical X-ray diffraction pattern of the Li-doped MCM-41 sorbent is 4cd). The specic surface area and the pore volume are found to de-
shown in Fig. 2c. After incorporation of lithium chloride, diffraction crease from 1020 to 453 m 2/g and from 0.87 to 0.28 cm 3/g, respec-
peaks corresponding to copper oxide are less intense in the Li- tively throughout the preparation process (Table 1). As it was
doped MCM-41 sorbent than in the CuO/CeO2-MCM-41 sample indi- shown by TEM observations, no metal oxide particles were found to
cating that chloride anions from LiCl reacted with copper oxide yield- plug the mesopore's entrance. Thus, the decrease of specic surface
ing the formation of a hydrated copper chloride which was identied area and pore volume is attributed to the lling of the pores by
as Cu2(OH)3Cl (atacamite). It is also important to note that no lithium metal oxide particles (CeO2 and CuO) and atacamite. Accordingly,
chloride peaks are observed by XRD. broad pore size distributions centered around 20 , characteristics
of a secondary microporosity, are observed for the CuO/CeO2-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-

*: CuO
+: Cu (OH) Cl
Intensity (a.u.)

2 3
(d) : CeO2
Intensity(a.u.)

(c)
(c)

(100) (b) (b)

(111)
(110)
(200) (220) (311)
(210)
(a) (a)

2 4 6 8 2(CuK) 10 20 30 40 50 60 2(CuK)

Fig. 1. Low angle XRD patterns of calcined (a) MCM-41, (b) CeO2-MCM-41, (c) CuO/CeO2- Fig. 2. XRD patterns of (a) CeO2-MCM-41, (b) CuO/CeO2-MCM-41 and (c) Li-doped
MCM-41 and (d) Li-doped MCM-41 sorbent. MCM-41.
38 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542

Table 2
600
Crystallite size L () in different directions evaluated from the width at half-maximum (a)
intensity of the (111), (220) and (311) diffraction peaks of the CeO2-MCM-41 sample. 500
(b)

Vads (cm3.g-1 STP)

Diffraction peak Position (2) L ()
400
(111) 28.2 25.4
(220) 47.2 24.3
(311) 56.3 24.5 300

200 (c)
(d)
100
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
0
coupled with a weak endothermic signal which is attributed to the 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
elimination of physisorbed water. The second one (~37 wt.%) takes P/P0
place in the range 423773 K and corresponds to the C16TMA + de-
composition and is associated with two exothermic peaks around Fig 4. Nitrogen adsorptiondesorption isotherms for the calcined (a) MCM-41,
573 and 773 K, respectively. A larger loss (~17.7 wt.%) of physisorbed (b) CeO2-MCM-41, (c) CuO/CeO2-MCM-41 and (d) Li-doped MCM-41 sorbent.
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 CuOCuCl2 1 2O2 2CuO Cl2
/
2
weight loss (~1.1 wt.%) coupled with a weak exothermic peak is at-
tributed to residual C16TMA +. The residual C16TMA + comes from a Therefore, the broad endothermic peak observed around 593 K
non complete exchange of the C16TMA + located inside the mesopores should correspond to the loss of water coming from atacamite. The
by the Ce 3+. Strydom and Van Vuuren showed that the decomposi- interpretation of the exothermic signals above 673 K is more difcult.
tion of cerium nitrate leads to the formation of CeO2 in the tempera- A XRD performed on the calcined sorbent at 923 K revealed the pres-
ture range 523573 K [26]. However, it is difcult to evaluate exactly ence of small amounts of quartz and lithium silicate (Li2SiO3). Thus,
the temperature of the CeO2 formation in the MCM-41 since the de- the exothermic signals visible above 673 K might correspond to the
composition of residual C16TMA + occurs in the same temperature loss of halogen and/or the formation of quartz and lithium silicate
range (473573 K). For the Li-doped MCM-41 sorbent, a loss of phy- due to the loss of order of the MCM-41 sorbent but it is difcult to
sisorbed water about 8.1 wt.% associated with an endothermic peak clearly assign them. Moreover, no sharp endothermic peak corre-
occurs between 323 and 513 K (Fig. 6c). As it was showed by Sharkey sponding to the melting of LiCl is observed around 873883 K [28].
and Lewin, atacamite was found to decompose in two steps including It is worth mentioning that the structure of a classical MCM-41 with-
dehydration (553563 K) and the loss of halogen (713723 K) out any metal oxides is thermally stable up to 1073 K.
according to the following reactions [27]: 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-
2Cu2 OH3 ClCuOCuCl2 2CuO 3H2 O 1 cess during the TIE procedure. The mother liquid recovered by

Fig. 3. TEM micrographs of (a, b) CeO2-MCM-41 sample and (c, d) Li-doped MCM-41 sorbent.
 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542 39

Table 3
Chemical composition of the Li-doped MCM-41 sorbent.

Chemical composition (in wt.%) Weight loss % Molar ratio

from TGb
Si/Ce Si/Cu Si/Li
a
Si O Cu Ce Li 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.

ltration of the Ce-MCM-41 sample after the TIE procedure was ana-
lyzed by 1H liquid NMR spectroscopy (spectra not shown here) and
conrmed the presence of C16TMA +. Thus, a cationic exchange be-
tween C16TMA + molecules and Ce 3+ cations was found to occur dur-
ing the TIE procedure. Some preliminary experiments were
Fig. 5. BJH pore size curves for (a) the calcined MCM-41, (b) CeO2-MCM-41, (c) CuO/
performed to adjust the duration of the TIE procedure in order to
CeO2-MCM-41 and (d) Li-doped MCM-41 sorbent.
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.

a -5
0 TG 3.2. SO2 adsorption
Exo
5
The CeO2-MCM-41 sample exhibits no particular SO2 removal ca-
Weight loss(%)

10
pacity (breakthrough curve not presented here) as the SO2 adsorption
15
20
25
250
30 (a) (b)
35 DTA
200
40
45
[SO2] (ppm)

350 450 550 650 750 850 950 1050

150
Temperature(K)

100
b -5

50
0 Exo
Weight loss(%)

DTA 0
5 0 3000 6000 9000 12000 15000 18000
Time (s)

10 Fig. 7. SO2 breakthrough curves of (a) the CuO/CeO2-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 SO2, 10% O2 in N2. The breakthrough curve of the CeO2-MCM-41 sample is
15 not shown since the SO2 adsorption capacity is very small (b 5 mg SO2/g). According
TG to this result, the breakthrough curves of the MCM-41 sample and the empty reactor
were not performed.
20
350 450 550 650 750 850 950 1050
Temperature(K)

O
c
Intensity (a.u.)

-5
TG Exo (b)
Intensity(a.u.)

0
(a)
Weight loss(%)

5 2 4 6 8 2 (CuK)
DTA + +
++ ++ + +
+ ++ + +
10 + + (b)

* *
15
(a)
* *
* * * * *
20
350 450 550 650 750 850 950 1050
Temperature(K) 10 20 30 40 50 60 2(Cu )
K

Fig. 6. TG/DTA curves of (a) the as-synthesized MCM-41, (b) Ce-MCM-41 sample and Fig. 8. XRD pattern of (a) the sulfated CuO/CeO2-MCM-41 sample and (b) Li-doped
(c) Li-doped MCM-41 sorbent. MCM-41 sorbent. (Inset) Corresponding low angle XRD patterns.
40 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542

Fig. 9. TEM micrographs of the sulfated Li-doped MCM-41 sorbent.

capacity was found lower than 5 mg SO2/g. The SO2 breakthrough
curve of the CuO/CeO2-MCM-41 sample is shown in Fig. 7a. The sor-
bent is found to completely adsorb SO2 for 460 s. The SO2 adsorption
capacity measured by integration of the breakthrough curve is 15 mg
SO2/g. As it can be seen, the saturation is reached around 220 ppm
after 6000 s. However, the inlet SO2 concentration of 250 ppm is not
retrieved after the saturation of the sorbent. This suggests that a frac-
tion of SO2 reacts with oxygen and/or is oxidized by CeO2 yielding the
formation of SO3 which is not seen by the UV analyzer. A signicant
increase of the SO2 removal performance is observed for the Li-
doped MCM-41 sorbent (Fig. 7b). The adsorption capacity is 96 mg
SO2/g which is more than 6 times higher than the CuO/CeO2-MCM-
41 sample and all the SO2 is completely adsorbed for 75008000 s.
The saturation is reached after 18,000 s with around 220 ppm SO2
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 SOx removal activity.
1200
1000
3.3. Characterization of the sulfated sorbents
The XRD pattern of the sulfated CuO/CeO2-MCM-41 sample ex-
hibits no particular modications as characteristic peaks of CeO2
and CuO are still observed (Fig. 8a). This shows a lack of reactivity
of the metal oxides towards SOx 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
(CuSO45H2O) and lithium sulfate (Li2SO4H2O) 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
CeO2 and CuO peaks completely disappear suggesting a high activity
of the metal oxides towards SOx in this sorbent. No cerium sulfates
are observed conrming that CeO2 only acts as an oxidation promot-
er. The mesoporous organization is not affected conrming the stabil-
ity of both the CuO/CeO2-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
1200
: SiO2
1000 : Li2SiO3
intensity (a.u.)

: CeO2
Temperature (K)

800 800
[SO2 ] (ppm)

intensity (a.u.)

600 600
2 4 6 8 2 (CuK)

400 400

200 (b) 200

(a)
0 0
0 1000 2000 3000 4000 5000 6000 7000
Time (s) 10 20 30 40 50 60 2 (Cu )
K

Fig. 10. TPD of (a) the sulfated CuO/CeO2-MCM-41 sample and (b) Li-doped MCM-41 Fig. 11. XRD pattern of the Li-doped MCM-41 sorbent after TPD. (Inset) Corresponding
sorbent performed under N2 (Dv = 53 Nl/h). low angle XRD patterns.
 Y. Mathieu et al. / Fuel Processing Technology 99 (2012) 3542 41

globular particles which may be attributed to the sulfated species Table 4

(Fig. 9). The aspect of the majority of MCM-41 grains is however Crystalline phases observed by XRD before and after sulfation and TPD peaks of the dif-
ferent MCM-41 samples.
not changed.
The TPD curves of the sulfated CuO/CeO2-MCM-41 sample and Li- Sample XRD TDP peaks Cadsb
doped MCM-41 sorbent are shown in Fig. 10. As it can be seen, only (mg SO2/g)
Fresh After T (K)a Max [SO2]max
one desorption peak is observed for the sulfated CuO/CeO2-MCM-41 sulfation (K) (ppm)
sample. The maximum of desorption (~100120 ppm SO2) occurs be- CeO2-MCM-41 CeO2 c 7731073 933 35 b 10
tween 833 and 953 K. Mu and Perlmutter clearly showed that the de- CuO-MCM-41 CuO 773973 863 160
composition of CuSO45H2O under N2 occurs in the same CuO/CeO2- CeO2 CeO2 793973 873 120 15
temperature range [29]. Thus, the desorption peak in the sulfated MCM-41 CuO CuO
CuO/LiCl-MCM- CuO Li2SO4 6731013 873 225 80
CuO/CeO2-MCM-41 sample corresponds to the decomposition of 41d atacamite >1073 /e 265
CuSO4 which is in a highly dispersed state in the MCM-41 and is Li-doped MCM- CeO2 CuSO4 6731013 953 700 130
therefore not detectable by XRD. The adsorption capacity, calculated 41 sorbent CuO Li2SO4 >1073 / 510
by integration of the desorption peak, is about 21 mg SO2/g. This atacamite
value is higher than the adsorption capacity calculated by integration a
Temperature range of the desorption peak.
b
of the breakthrough curve (15 mg SO2/g). It is worth mentioning that Adsorption capacity measured by integration of the desorption peaks.
c
the TPD is performed under a non oxidative atmosphere (no forma- No XRD peaks observed.
d
Chemical composition of 4.1 wt.% Cu, 0.8% Li.
tion of SO3 can occur). Therefore, it is likely that previously adsorbed e
Not determined as the max temperature for the TPD experiment was around
SO3 molecules have been desorbed in the form of SO2 thus leading to 1123 K.
a SO2 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 CuO SO3 CuSO4 4
rst desorption peak corresponds to the decomposition of CuSO4
and starts at around 763 K with a maximum observed around 963 K
(~700 ppm SO2) and nishes at 1023 K. The second desorption occurs Li2 O SO3 Li2 SO4 5
at higher temperature (~1153 K) and may correspond to the decom-
position of Li2SO4 as reported in the literature [30]. The adsorption ca-
pacity as determined in the desorption phase is therefore 130 mg /
CuO SO2 1 2O2 CuSO4 6
SO2/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 Li2 O SO2 1 2O2 Li2 SO4 7
the complete transformation of the sorbent into SiO2 (quartz) and It is noteworthy that Li2O is not a stable species in the test condi-
lithium silicate (Fig. 11). Several sharp peaks of CeO2 are also tions and is actually in the form of LiCl or LiOH before reacting with
observed. SOx. Furthermore, the decomposition of atacamite via reaction (2)
may lead to the formation of highly active CuO sites.
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, CeO2) in a highly dispersed state, atacamite and lithium
to reach a high SOx 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
CuSO4 and Li2SO4 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 CuSO4 is about three times lower than
in the Li-doped MCM-41 sorbent resulting in a lower adsorption ca-
pacity of 80 mg SO2/g. This conrms that the highly dispersed CuO,
and therefore not detected by XRD, did react with SOx during the sul-
fation reaction yielding the formation of CuSO4 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/Al2O3 material occurs via ad-
sorption of SO3 on CuO sites [10]. The main following reactions may
occur:
/ sulfur dioxide removal from combustion gases, Industrial and Engineering Chem-
SO2 1 2O
2 SO3 catalyzed by CeO2 3 istry Research 27 (1988) 139143.
4. Conclusion
A high specic surface area and thermally stable MCM-41 sorbent
was prepared for the removal of SOx at 673 K. The investigated for-
mulation combined a SOx 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 SO2/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 SO2 ad-
sorption experiments and interpretations.
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