Fuel Processing Technology 114 (2013) 81100

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Fuel Processing Technology

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Review

Adsorption of SOx by oxide materials: A review

Yannick Mathieu a, Lydie Tzanis a, Michel Soulard a, Jol Patarin a,,
Matthieu Vierling b, Michel Molire b
a
Univ de Haute Alsace (UHA), CNRS, Equipe Matriaux Porosit Contrle (MPC), Institut de Science des Matriaux de Mulhouse (IS2M), UMR CNRS 7361, 3 bis rue Alfred Werner, F-68093
Mulhouse, France
b
GE Energy Products France SNC, 20 avenue du Marchal 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: This paper is an attempt to provide a review as extensive as feasible of the literature devoted to the wide
Received 2 April 2012 variety of sorbent systems that are currently either in use or under laboratory investigation for the removal of
Received in revised form 16 November 2012 the SOx (SO2 + SO3) from ue gases. From an industrial perspective and besides any economic consideration,
Accepted 14 March 2013
the ideal SOx sorbent candidate must ally four essential qualities some of which may appear contradictory
Available online 18 April 2013
to some extent: a strong afnity of the sorbent towards SOx along with fast kinetics; a large specic surface; a
Keywords:
high physical/thermal/chemical stability and the capability for multiple regenerations at a reasonable tem-
SO2 adsorption perature and with performance recoveries close to 100%.
Single oxides In this paper, the sorbent are classied in four categories which are: (i) single oxides; (ii) mixed oxides (in-
CuO/-Al2O3 cluding spinels and alumina supported oxides); (iii) oxides supported on carbonaceous materials and (iv)
Zeolites oxides supported on zeolites and mesoporous materials. A noteworthy outcome of this review lies in the
Carbonaceous materials promising prospects offered by porous silica-based materials as desulfurization (DeSOx) candidates and
Regeneration the interest of elaborating in this direction.
2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2. Singles oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.1. CaO and MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.2. Other single oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3. Mixed oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.1. The CuO/-Al2O3 system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.2. Use of others oxides/metals in association with -Al2O3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.3. Spinels and mixed oxides derived from hydrotalcites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.4. Other mixed oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4. Oxides supported on carbonaceous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5. Oxides supported on microporous and mesoporous silica-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
6. Regeneration by thermal decomposition of the metal sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7. Conclusion and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95

1. Introduction
SOx are known to be a major source of atmospheric pollution leading
in particular to acid smog formation and acid rain. This category of
pollutant is strongly harmful towards human beings leading to asthma,
respiratory diseases and is associated with increased mortality and
Corresponding author. Tel.: +33 3 89 33 68 80.
E-mail address: joel.patarin@uha.fr (J. Patarin).
morbidity [14]. Therefore, many countries and the World Bank have
enacted or are enacting increasingly stringent regulations limiting the
emissions of SOx into the atmosphere. For instance, new standards for
sulfur dioxide emissions were taken in 2010 by the EU; the Industrial
Emission Directive (IED) applicable to new large combustion plants
above 300 MWth has set emission limit values (ELVs) as stringent as
35 mg/Nm3 for gaseous fuels and 150 mg/Nm3 for liquid and solid
fuels (25% lower than the previous ELVs). Similarly, in the USA, the
SOx budgets are called to be reduced by ca. 40% between 2011 and

0378-3820/$ see front matter 2013 Elsevier B.V. All rights reserved.
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82 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100

To address these major limitations, many studies were devoted to the

Nomenclature development of supported metal oxide sorbents that are not only ca-
pable of an efcient SO2 removal but also exhibit a large surface area
Cads SO2 adsorption capacity, mg SO2/g sorbent and high textural stability; this has led to the development of alterna-
SV space velocity, h 1 tive sorbent products in terms of oxides, textures and supports. In this
SBET specic surface, m 2/g respect, there has been and there is still at the time being a large
FR ow rate, ml/min place for works to address the challenges created by SOx abatement
technologies based on adsorption systems.
In this paper, the oxide materials intended for SO2 removal will be
Greek letters split in four categories:
a kind of structure for AlOOH, Al2O3 and MnO2
a kind of structure for Al2O3 1. Single oxides
2. Mixed oxides including spinels and alumina supported oxides
3. Oxides supported on carbonaceous materials (active coal and car-
bon bers)
Acronyms
4. Oxides supported on porous silica-based materials (zeolites,
AC Activated Carbon
mesoporous or clay minerals).
ACF Activated Carbon Fiber
DAY Dealuminated Y
All these sorbent types present some advantages and some draw-
DTA Differential Thermal Analysis
backs that will be discussed in this review. In the literature, the con-
EU European Union
ditions employed in the adsorption tests are extremely diverse, thus
FCC Fluid Catalytic Cracking
leading to serious difculties to compare the efciency of the differ-
FGD Flue Gas Desulfurization
ent active materials, which represents a major challenge in such a re-
GC Gas Chromatography
view work. For instance, basic parameters such as the temperature,
GHG Green-House Gas
ow rate (FR) or space velocity (SV) and gas composition (concentra-
HT Hydrotalcite
tion of SO2, presence of other gases such as H2O or NOx), strongly af-
IR Infrared
fect the adsorption performances.
NSR NOx-Storage Reduction
In this review, the term of adsorption will be systematically
RFCC Residue Fluid Catalytic Cracking
employed to designate the capture process although in the case of
SCR Selective Catalytic Reduction
massive sorbents (non-supported, single or mixed oxides), in which
TEA Triethanolamine
bulk-reactions are developed, the use of the term absorption might
TGA Thermogravimetric Analysis
be more appropriate. The SO2 adsorption capacities will be expressed
TPD Temperature Programmed Desorption
in milligrams of SO2 captured per gram of sorbent. The gas composi-
USEPA United States Environmental Protection Agency
tion and the SV when available in the literature will be given in
XPS X-ray Photoelectron Spectroscopy
vol.% and in h 1, respectively. The gas vector will be designated as
XRD X-ray Diffraction
the balance. The sorbents which are described in this review will be
designated as follows: heteroelements (including metal, metal oxides,
salts, etc.) which are supported on the sorbent/name of the sorbent
2014 in average in the twenty most emitting states. SOx are also corro- (for instance LiClCuO/-Al2O3). The purpose of this review is to
sive towards many materials especially those used in thermal power shed light on the various types of sorbents, with an emphasis placed
plants, leading to important increases in operational and maintenance on supported-oxide materials, to compare their characteristics and
costs. elaborate on the optimum set of properties required to develop a
The focus of this paper will be mainly stationary applications high performance SO2 sorbent.
among which the combustion of coal, oil or sour gases in thermal
power plants and the rening of crude oils represent typical cases. 2. Singles oxides
The past decades have seen the development of a number of desulfur-
ization techniques, some of them reaching end-use applications but 2.1. CaO and MgO
most staying at the laboratory level. As far as combustion plants are
concerned, several routes are used to control SOx emissions including Calcium oxide based sorbents such as limestone, hydrated lime or
precombustion, in-ame and postcombustion controls [5]. While in lime (CaO), are among the most used materials for industrial desul-
the oil sector, the increasing rate of desulfurization of gasoline and furization with most FGD processes relying on two major techniques:
gasoils achieved in reneries represents a form of precombustion the wet and dry-scrubbing. Since the seventies, intensive studies have
treatment, in the coal sector, however, the major technologies to con- been devoted to limestone as sorbent [624]. In the wet-scrubbing
trol SOx emissions are based on postcombustion controls. Historically, technique, an aqueous suspension of limestone is sprayed into towers
the most common method employed to abate SOx is to have it cap- where it contacts the sulfur oxides present in the ue gas and forms
tured by basic oxide materials. Based on this concept, wet and dry gypsum (CaSO42H2O). Approximately 95% of SO2 is generally re-
Flue Gas Desulfurization (FGD) processes represent the major indus- moved. The following overall reaction (1) occurs:
trial routes used to control SO2 emissions in atmosphere. Despite the
SO2 CaCO3 s 1/2O2 2H2 OCaSO4 2H2 Os CO2 : 1
relatively low cost and efciency of these techniques, these processes
suffer from major drawbacks. Wet scrubbing methods consume large Despite its high efciency, this process is essentially non-
amounts of water and entail large volumes of waste liquids. Both the regenerative. Therefore, it has as major economic inconvenience,
dry and wet FGD processes also generate important quantities of gyp- the large consumptions of slurry and water and as strong environ-
sum as a by-product. Finally, the thermal regeneration of gypsum mental drawbacks, the release of CO2 leading to green-house gas
poses a major issue due to the high temperature level required for (GHG) effect and the generation of both large volumes of waste
its desulfation, moreover resulting in a strong sintering effect (inten- water and high heaps of low grade gypsum that cannot be always
sive recrystallization with a dramatic loss of porosity and reactivity). commercialized. With such strong drawbacks, this throw-away
 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100
process is clearly not in line with current and future environmental
trends. Other calcium-based, natural materials such as dolomites
were also studied for the removal of SO2 [2528]. The second route
is the dry-FGD technique in which a calcium hydroxide slurry (gener-
ally quicklime mixed with water) is introduced into a spray dryer
tower [2934]. This slurry is atomized and injected close to saturation
into the ue gases, where the calcium-laden droplets react with SO2
as they evaporate in the tower. The resulting dry by-product is col-
lected in the bottom of the spray dryer using separation systems
such as electrostatic precipitators or bag lters. The by-product is a
dry mixture of calcium sulte/sulfate. The following reactions (25)
are developed in the dry-FDG system, for a temperature below
400 C and both in the presence and in the absence of oxygen:
CaO H2 OCaOH2 2 decomposition of non-porous limestone (7), followed by the sulfation
CaOH2 SO2 CaSO3 H2 O 3
CaO SO2 CaSO3 4
CaSO3 1=2 O2 CaSO4 : 5
Dry scrubbing boasts a lower operation cost than the wet scrub-
bing method as less energy is required and no waste water is pro-
duced. However, both the wet and dry-FGD techniques are by
essence non-regenerative methods due to the high decomposition
temperatures of calcium sulfate/sulte and the sintering phenome-
non of the regenerated CaO, characteristics that lead to a signicant
decrease of the adsorption capacity. Nevertheless, lime has attracted
much interest for the removal of SO2 from ue gas and has been the
subject of numerous studies [3546].
Muoz-Guillena et al. [38] studied the adsorption of SO2 on CaO
samples obtained by calcination of different limestone qualities at
high temperature (800 C) and showed that the adsorption capacity
tends to decrease in the presence of oxygen due to the formation of
a calcium sulfate layer that tends to surround the calcium oxide and
limit the diffusion of the SO2 molecules inside CaO particles. After
the saturation is reached and depending on the nature of the precur-
sor limestone, adsorption capacities ranging from 590 to 990 mg/g
were obtained at 800 C for a gas feed containing 0.3% SO2 in He (de-
termined from TG-DTA, FR = 60 ml/min). The decomposition of cal-
cium sulte via thermal treatment occurred between 700 and 800 C
thus giving rise to a potential regeneration of the CaO adsorbent via
the following reaction (6):
CaSO3 CaO SO2 : 6 formances of several commercial oxide systems at room temperature
In order to improve the removal rate of SO2, several studies report
about the possibility of adding various oxides and especially y ashes
to Ca(OH)2 or CaO [29,3234,4760]. The so called pozzolanic reac-
tions between Ca(OH)2/CaO and silica/alumina contained in y
ashes lead to highly hydrated materials, particularly calcium
alumino-silicate hydrated compounds, having high specic surface
areas thus improving the SO2 adsorption capacity [61]. Bueno-Lpez
et al. [41] studied the capture of SO2 at 300 C by several sorbents
prepared from a mixture of 80 wt.% Ca(OH)2 and 20 wt.% of inorganic
solids such as Al2O3, SiO2, MgO, TiO2 or SiC. The SO2 retention exper-
iment was performed by TG/DTA at 300 C using 0.3% SO2, 5% O2 in N2
(FR = 90 ml/min), the samples were previously heated at 450 C
during 10 min at a heating rate of 20 C/min under N2 to decompose
Ca(OH)2 into CaO. Similar adsorption capacities ranging from 310 to
330 mg/g were obtained. However, after regeneration (performed
under N2 by heating the sample at 880 C during 10 min at a heating
rate of 20 C/min), a loss of activity from 68 (with SiC added) to 82%
(with SiO2 or TiO2 added) was observed. In contrast, additions of car-
bonaceous materials entail limited activity losses. As shown by
Garca-Martnez et al. [42], the adsorption capacity of CaO measured
83
by TG-DTA at 300 C using 0.3% SO2 in N2, strongly decreases from
250 to 42 mg/g after the thermal regeneration step (performed at
500 or 880 C). This loss of activity is explained both by a dispropor-
tionation of CaSO3 in CaSO4 and CaS during the heat treatment and an
increase of the CaO particle size. Dasgupta et al. [43] showed that the
sorption performance of CaO sorbents was related to the particle size
of the precursor limestones or hydrated limes. As expected, smaller
particles lead to a longer breakthrough time and a larger conversion
into sulfate. The desulfurization activity of CaO sorbents prepared
from Ca(OH)2/y ash mixtures was also found to increase as a func-
tion of the specic area [44]. Siriwardane et al. [62,63] showed that
the adsorption of SO2 on CaO was improved by the presence of alka-
line ions.
Another way to remove SO2 from ue gas is based on the thermal
reaction (8) [64,65].
CaCO3 CaO CO2 7
CaO SO2 1=2 O2 CaSO4 : 8
In summary, despite the proven efciency of calcium-based sor-
bents, the fatal drawback of these materials lies in the difculty to re-
generate them.
Some studies also report the use of magnesia in spray dryer sys-
tems [66]. Magnesia is hydrated in the slurry and reacts with SO2 to
form magnesium sulte (reactions 9 and 10).
MgO H2 OMgOH2 9
MgOH2 SO2 MgSO3 H2 O: 10
The magnesium sulte obtained can be dried and decomposed at
higher temperatures yielding MgO for potential recycling.
2.2. Other single oxides
Various single oxides such as TiO2, CeO2 and MnO2 were also tested
for the removal of SO2.
Based on thermodynamic analysis, Lowell et al. [67] investigated nu-
merous metal oxides as potential sorbents to remove SO2 from ue gas.
The decomposition temperatures of several sulfates in air or in an inert
gas were also studied. A comparative study of the SO2 adsorption per-
was carried out by Waqif et al. [68]. Adsorption capacities of pure SO2
gas were measured at room temperature by thermogravimetric analysis
(TGA, McBain thermobalance). Desorption was performed with the
same method by increasing the temperature from room temperature
up to 500 C. The best performances were obtained with MgO
(140 mg/g), Al2O3 (7778.5 mg/g) and Al2O3 in the presence of
3 wt.% Na (107110 mg/g). The adsorption capacity of TiO2 (anatase)
was lower around 36 mg/g. However it should be noted that, for all
the metal oxides studied, large amounts of SO2 remained adsorbed
after evacuation at room temperature at 100 or 240 C. Stark et al.
[69] showed that, at low pressure (20 Torr), MgO nanoparticles
adsorbed more SO2 molecules per nm2 than microscale particles. But
at higher pressure, the multilayers of SO2 were weakly adsorbed thus
leading to a higher adsorption capacity for the MgO microscale particles.
Luo and Li [70] studied the adsorption of SO2 on anatase nanoparticles
at 120 C under a gas stream of 0.25% SO2 in N2. The TiO2 nanoparticles
were obtained from a mixture of nitric acid, butyl titanate and isopropyl
alcohol after a hydrothermal treatment in two steps (80 C12 h and
120 C24 h). Polyethylene alcohol was also used to control the size
and the morphology of the nanoparticles. Samples were further cal-
cined at 340, 440, 540 and 640 C during 30 min. The best temperature
84 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100

was found to be between 440 and 540 C with an adsorption capacity
ranging from 34.5 to 39.5 mg/g. This result is in the same range as
those of a previous work by Waqif et al. [68]. No data was given about
a possible regeneration of these materials. The adsorption of SO2 on
TiO2 and -Al2O3 was studied by Yanxin et al. [71]. These authors
showed that SO2 interacts more strongly with TiO2 due to the presence
of lattice oxygen at a temperature around 200 C whereas -Al2O3 pro-
vides only surface adsorption sites. Kylhammar et al. [72] developed re-
generable ceria-based SOx traps for lean exhaust gases. Incorporating
platinum was found to increase signicantly the performance of these
traps. The sample containing 1 wt.% Pt showed the highest SOx storage
ability at 250 and 400 C with adsorption capacities of 18 and 27 mg/g,
respectively, for a gas containing 0.01% SO2, 7% O2 in argon (FR =
3500 ml/min, SV = 33,400 h1). The SOx adsorption on CeO2 proceeds
via the formation of surface and bulk sulfates. The samples were noted
as fully regenerated under a ow of 7% O2 in argon by increasing the
temperature up to 700 C (10 C/min). Mahzoul et al. [73] studied the
combined adsorption of SO2 and NO on a reference NOx trap (containing
Pt, Rh, Ba and La supported on a washcoat). For a gas ow without NO
containing 0.02% SO2, 7% O2 in N2 (FR = 30 ml/min), an SO2 adsorption
capacity of around 53 mg/g was obtained at 300 C, after the saturation
was reached. However, the introduction of 200 ppm of NO leads to a de-
crease of the NOx storage capacity by around 59% (in contrast to the ex-
periment where only NO was injected) whereas the SO2 removal
activity was not affected. A competition between SO2 and NO molecules
occurred to reach the adsorption sites particularly the BaO sites. How-
ever, due to the high thermal stability of the corresponding sulfates, in
particular BaSO4, high regeneration temperatures as high as
1000 C are needed. The authors also studied the SO2 adsorption of
other NOx adsorbers containing BaO, alumina and ceria. They showed
that the introduction of platinum strongly enhances the SOx storage ca-
pacity. Manganese based-oxide octahedral molecular sieves were
studied to remove SO2 from diesel engine emissions [74,75]. In
particular, cryptomelane (KxMn8O16, SBET = 74 m 2/g) was found to
have a high adsorption capacity of 700 mg/g at 325 C for a gas feed
containing 0.025% SO2 in air (SV = 8000 h1). The adsorption
capacity was determined by gas chromatography (GC) with a sulfur
chemiluminescent detector. The SO2 capture occurred through the
oxidation of SO2 to SO3 by Mn4+ followed by SO3 reaction with Mn2+
to form MnSO4. This sulfate can be recycled for another synthesis of
cryptomelane with only a little decrease of the adsorption capacity.
The high adsorption capacity obtained may be partially explained by
the low space velocity of 8000 h 1; therefore, the performance of
such sorbent may signicantly decay in the presence of higher space
velocity gures (e.g. SV in the range of 25,000 to 35,000 h1 are
expected in gas turbine applications). Sinha et al. [76] developed
mesoporous -MnO2 modied with gold nanoparticles (3 wt.%) and
reported an adsorption capacity of 700 mg/g at ambient temperature
for a gas feed containing 0.2% SO2, 20% O2 in N2 (adsorption capacity de-
termined by GC using a sulfur chemiluminescent detector). No data
were given about the FR and the SV. La-doped ceria was found to be a
highly active catalyst for the SO2 reduction by CH4 at temperatures
above 550 C [77].
Table 1 summarizes the main studies dealing with the use of sin-
gle oxides for DeSOx.
3. Mixed oxides
3.1. The CuO/-Al2O3 system
CuO/-Al2O3 systems represent interesting SOx sorbent candi-
dates for industrial applications. In contrast to the single-use oxides
employed in traditional FGD processes, they offer several advantages
such a high thermal stability of the support (800900 C), reasonably
high specic area data (ranging from 150 to 300 m 2/g) and a relative-
ly low temperature (450500 C) required for copper desulfation.
CuO/-Al2O3 adsorbents are generally regenerated under a reductive
ow of H2, CH4 or NH3 and the desorbed SO2 is converted into sulfuric
acid by further oxidation or into elemental sulfur via the Claus pro-
cess. The following main reactions are generally accepted for the cap-
ture (11) and for the regeneration process under H2 or CH4 (12, 13):
CuO SO2 1=2 O2 CuSO4 11
CuSO4 2H2 Cu SO2 2H2 O 12
CuSO4 1=2 CH4 Cu SO2 1=2 CO2 H2 O: 13
In contrast to traditional FGD process using lime or limestone, the
technology based on CuO/-Al2O3 exhibits sober operational costs
since it does not entail any waste liquid nor cumbersome by-products.
The preparation of CuO/-Al2O3 materials for desulfurization is
performed by (i) wet impregnation of the support using an aqueous so-
lution of copper sulfate or nitrate followed by (ii) drying and calcination
leading to the production of CuO particles. In the industry, -Al2O3 is a

Table 1
Main studies dealing with the use of single oxides for DeSOx.

Nature SBET Cads FR Gas composition (vol.%) T (C) Ref

(m2/g) (mg/g) (ml/min)
SO2 O2 Balance

CaO a 310330 90 0.2 5 N2 300 [41]

CaO 31134b 590900b 60 0.3 0 He 800 [38]
348c 250 0.3 0 N2 300 [42]
TiO2 118124 34.539.5 2.5 0 N2 120 [70]
120 36 100 0 0 RTd [68]
MgO 270 140
Al2O3 240 7778.5
3 wt.% Na/Al2O3 235 107110
CeO2 115 57
1 wt.% Pt/CeO2 1827e 3500 0.1 7 Ar 250400 [72]
KxMn8O16 74 ~700f 0.25 0 air 325 [74]
3 wt.% Au/-MnO2 700 2 20 N2 25 [76]
NOx trap 53 30 0.02 7 N2 300 [73]
a
Not reported.
b
Related to the nature of the precursor limestones, SBET determined from CO2 chemisorption method at 300 C (details reported in [37]).
c
SBET determined from CO2 chemisorption method at 300 C (details reported in [37]).
d
Room temperature.
e
SV of 34,400 h1.
f
SV of 8000 h1.
 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100 85

widely used product namely in catalysis, gas separation, liquid ltration
or as coating material [7880]. Aluminum oxyhydroxide known as
boehmite (-AlOOH) is the traditional starting material to produce
-Al2O3 alumina supports. The synthesis of boehmite can be accom-
plished via three main routes: (1) hydrolysis of an aluminum alkoxide
under reux or by hydrothermal treatment at low temperatures
(b 100 C) [8183]; (2) precipitation of inorganic salts in an aqueous
medium under ambient conditions [8487] or (3) hydrothermal syn-
thesis at elevated temperatures (>100 C) [8891]. The calcination of
boehmite at 450500 C yields -Al2O3.
It is noteworthy that not only copper but also -Al2O3 acts as ac-
tive SO2 trappers. The studies relating to the use of such -Al2O3 ma-
terials impregnated with CuO or other oxides are summarized in
Table 2.
The mechanism of SO2 adsorption on -Al2O3 materials has been
the subject of numerous studies using namely infrared (IR) spectros-
copy and X-ray diffraction (XRD) techniques, in an attempt to shed
light on the main sulfate species formed [9299]. Karge and Dalla
Lana [92] studied the interaction of SO2 with the surface of a commer-
cial -Al2O3 (SBET = 100 m 2/g) by IR spectroscopy. After the adsorp-
tion/desorption runs, they observed characteristic IR bands that were
assigned to SO2 molecules both chemically adsorbed on basic sites
and physically adsorbed on acid sites. Working also on a commercial
-Al2O3, Datta et al. [93] identied by IR spectroscopy that the most
strongly adsorbed species were supercial sulte ions. These species
were formed after an initial adsorption on basic sites consisting in ex-
posed oxygen atoms followed by a cleavage of an Al\O bond. After
saturation of the basic sites, SO2 molecules were further physically
adsorbed on \OH sites. Pollack et al. [94] examined by XRD and elec-
tron diffraction some fresh, adsorbed and regenerated CuO/-Al2O3
sorbents (containing 7.2 wt.% Cu). They showed that copper com-
pounds are not crystalline or that the CuO units are very small and
that copper atoms are surrounded by 2.42.7 oxygen atoms in aver-
age. Waqif et al. [95] identied three types of sulfate species on
Al2O3 i.e.: supercial species; species in interaction with Cu 2+ and
species in interaction with both Cu 2+ and Al 3+. They found that the
ones linked to Al sites were more difcult to reduce than those linked
to Cu sites. Centi et al. [96] observed that copper acts as a promoter
for the oxidation of SO2 to SO3 that immediately reacts with -Al2O3
at around 300 C to essentially form supercial sulfates without any
deep bulk sulfation effect. In this process, SO3 molecules once chem-
ically adsorbed immediately react with neighboring Al atoms to
form aluminum sulfates species and to a less extent with Cu
atoms to form copper sulfates. The same authors used a kinetic
model to describe the adsorption process of SO2 on -Al2O3, the re-
sults of which are in good agreement with previous spectroscopic ex-
periments [97]. The inuence of temperature and the CuO loading of a
commercial -Al2O3 sorbent was studied by Yoo et al. [98]. The au-
thors identied three different types of sulfation reactions: (i) a su-
percial sulfation which occurred for a CuO loading between 2 and
11 wt.% at a temperature ranging from 250 to 350 C; (ii) a slightly
deep sulfation for a CuO loading below 4 wt.% at 350600 C and
(iii) a bulk sulfation for a CuO loading above 6 wt.% at 450600 C.
As shown by XRD, bulk sulfation leads to the formation of aluminum
sulfates according to the reaction: Al2O3 + 3SO3 Al2(SO4)3, which
requires a relatively high desulfation temperature (700 C in N2). Yu
et al. found that the monolayer coverage of CuO supported on a
-Al2O3 (SBET = 278 m 2/g) represents 0.275 g CuO per g of -Al2O3
and that, below this value, CuO is found in a highly dispersed state
[99].

Table 2
Main studies devoted to the use of CuO/-Al2O3 systems for DeSOx.

Nature SBET Cads FR Gas composition (vol.%) T (C) Ref

(m2/g) (mg/g) (ml/min)
SO2 O2 Balance

-Al2O3 100 ~30 a 100 0 0 100 [100]

CuO/-Al2O3 14.2 0.2 0 Air 256 [101]
(6 wt.% Cu)
CuO/-Al2O3 112 65 0.8 2.9 He 300 [95]
(4.9 wt.% CuO)
b e
CuO/-Al2O3 117 38 250 0.2 3 Air 350 [105]
(4.3 wt.% CuO) 36c
CuO/-Al2O3 113 48b
(7 wt.% CuO) 61d
CuO/-Al2O3 244 1793 8.9 0.2 0 Air 500300 [107]
(9 wt.% CuO)
CuO/-Al2O3 171 40 3800 0.1 0 Air 450 [108]
(6 wt.% CuO)
CuO/-Al2O3 166 115 460 0.15 5.6 Ar 400 [110]
(8 wt.% Cu)f
CuO/-Al2O3 68 200 0.32g 3 He 350 [102]
(25 wt.% CuO)
Na--Al2O3 150 83 150 0.11 0 N2 30 [111]
(5.5 wt.% Na)h
i
Na--Al2O3 72 51.5 6.4 Ar 115 [113]
LiClCuO/-Al2O3 148 460 900 1.5 0 Air 500 [112]
(8 wt.% CuO and 5 wt.% LiCl)
LiClCuO/-Al2O3 600
(8 wt.% CuO, 6.5 wt.% LiCl)
NaMnCaO/-Al2O3 100 1520 200 0.005 12 He 250 [134]
(5.5 wt.% Ca, 9.2% Na, 2.8% Mn) 2080j
a
Not reported.
b
Adsorption capacity after 2 adsorption-regeneration cycles.
c
Adsorption capacity after 750 adsorptionregeneration cycles.
d
Adsorption capacity after 100 adsorptionregeneration cycles.
e
Gaseous melange containing also 10% H2O, 0.1% NH3 and 10% CO2.
f
After one sulfationregeneration cycle, Cads ~70 mg/g (gaseous melange containing 3% H2O).
g
Gaseous melange containing also 800 ppm NO, [NH3/NO] = 1.
h
After 3 sulfationregeneration cycles, Cads ~ 45 mg/g.
i
Molar composition. Gaseous melange containing also 22.4% mol NO.
j
Adsorption capacity obtained in the presence of 10% H2O.
86 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100
A drawback of -Al2O3 support is the modest porosity which is only
textural due to the agglomeration of -Al2O3 particles. Thus, adsorption
capacities found in the literature for CuO/-Al2O3 are generally lower
than those of porous silica-based materials or activated carbon bers
(ACFs) containing metal oxides as set out below. For instance, according
to Dalla Lana et al. [100], a commercial -Al2O3 reference (origin: Cabot
Corporation, SBET = 100 m2/g), has an adsorption capacity of ca.
30 mg/g at 100 C in the presence of a pure SO2 gas. Uysal et al. [101]
reported an adsorption capacity of 14.2 mg/g for a CuO/-Al2O3
(6 wt.% Cu) at 256 C for a gas stream containing 0.2% SO2 in air. Waqif
et al. [95] studied by TGA the adsorption properties of CuO/-Al2O3
(SBET = 112 m2/g, 4.9 wt.% CuO) at 300 C for a gas containing 0.8%
SO2, 2.9% O2, 96% He. The adsorption capacity was found to increase as
a function of the temperature (from 250 to 350 C) and with the oxygen
content (from 10 to 2900 ppm) of the gaseous stream. At 350 C, an ad-
sorption capacity around 65 mg/g was obtained. Regeneration was
performed under a stream of 2% in H2 at 420 C. The adsorption capaci-
ties obtained after regeneration were slightly lower indicating that some
sulfate species were difcult to remove. Similar observations were fur-
ther made by Centi et al. [96]. These authors developed a CuO/-Al2O3
material, in the form of pellets, containing 2575 wt.% Al, via a sol gel
method to obtain highly dispersed CuO particles and studied by TGA
their DeSOx and DeNOx performances at 350 C. To that end they in-
volved NH3 as a reducing agent, using a gas composition of 0.32% SO2,
800 ppm NO, [NH3/NO] = 1, 3% O2, and balance: helium (FR =
200 ml/min) [102]. A SO2 adsorption capacity of 68 mg/g was obtained
for the fresh sorbent, which decreased to 42 mg/g after four adsorp-
tionregeneration cycles. The decrease of the adsorption capacity was
explained by the presence of CuO particles in the outer shell of the
pellets.
Another parameter that inuences adsorption capacity is the Cu
loading. Jia et al. [103] observed that the adsorption capacity of
-Al2O3 pellets at 400 C is strongly related to the Cu content (gas-
eous composition of 0.3% SO2, 5% O2, in argon). A maximal adsorption
capacity was reached for a Cu loading of 8%. Further increase of the Cu
loading between 8 and 14% led to a decrease of the specic surface
area and adsorption capacity due to the apparition of agglomerated
CuO particles at the -Al2O3 surface. Flores et al. [104] developed
CuO supported on alumina, zirconia and titania and performed TGA
SO2 adsorption tests in a gas stream of 0.36% SO2 in N2, at a tempera-
ture ranging from 100 to 400 C. The best removal activity was
obtained at 400 C with the CuO loadings of 6.9 and 14.3 wt.% CuO.
The behavior of sorbents after repeated regeneration treatments
was particularly investigated by Macken et al. [105]. They studied the
adsorption capacity at 350 C of fresh and aged CuO/-Al2O3 materials
containing 4.3 and 7 wt.% CuO, respectively. The gas composition was
0.2% SO2, 3% O2, 0.1% NO, 0.1% NH3, 10% CO2 in air (FR = 250 ml/min)
and the regeneration was performed under a ow of 10% CH4 at
500 C. After two adsorptionregeneration cycles, the capacity of the
4.3 wt.% CuO/-Al2O3 sample (SBET = 117 m2/g) was 36 mg/g and
stayed remarkably constant over 750 cycles (Cads = 38 mg/g). For the
7 wt.% CuO/-Al2O3 (SBET = 113 m2/g), the adsorption capacity was
slightly higher with 48 mg/g after 2 adsorptionregeneration cycles;
moreover, an increase of the adsorption capacity was observed after
100 cycles (Cads = 61 mg/g) which was attributed to an improved dis-
persion of CuO particles in the -Al2O3 support. Thus, in these mild re-
generation conditions, CuO/-Al2O3 materials offer very interesting
performances within industrial desulfurization applications.
As mentioned in several studies, increasing the porosity of the
-Al2O3 support strongly affects the adsorption capacity. As the phase
transition of -AlOOH into -Al2O3 is known to be topotactic, the con-
trol of morphological features of the primary boehmite particles is a
key parameter to obtain alumina with high specic areas. Wang and
Lin [106,107] prepared nanostructured mesoporous CuO/-Al2O3 sor-
bents (SBET = 244 m 2/g, 9 wt.% CuO) by the sol gel method and studied
the impact of the temperature on the adsorption capacity with a gas
composition of 0.2% SO2 in air (FR = 8.9 ml/min). A decrease of the ad-
sorption capacity as a function of the temperature was observed; data
were: 93, 69, 36 and 17 mg/g at 300, 400, 450 and 500 C, respectively.
This was assigned to a decrease of the number of active sites. Xiang et al.
[108] also showed that the adsorption capacity was related to the tex-
tural characteristics of the -Al2O3 support. Their CuO/-Al2O3 samples
prepared by the wet impregnation method (SBET = 171 m 2/g, 6 wt.%
CuO) had an adsorption capacity of around 40 mg/g for a gas containing
0.1% SO2 in air (FR = 3800 ml/min) at 450 C and remained constant
during 4 sulfationregeneration cycles; the regeneration was
performed under a ow of CH4 in N2. Moreover, no pore sintering oc-
curred and the CuO particles remained in a highly dispersed state on
the -Al2O3 support. Centi et al. [109] also showed that the SO2 removal
capacity of CuO/-Al2O3 materials containing 4.2 wt.% of CuO was relat-
ed to the pore volume and in particular to the mesoporous characteris-
tics of the support. Xie et al. [110] obtained an adsorption capacity of
115 mg/g for a CuO/-Al2O3 with an adsorbent having the following
characteristics: SBET = 166 m 2/g, 8 wt.% Cu. The test was performed
at 400 C using a gas composition of 0.15% SO2, 5.6% O2, and 3% H2O in
argon (FR = 460 ml/min). The regeneration was carried out using a
stream of 5% NH3 in argon, at around 400 C. After one cycle of
sulfationregeneration, the adsorption capacity decreased down to
around 70 mg/g but stayed practically constant after three more cycles.
A few studies mention the signicant role played by some addi-
tives such as alkaline ions which improve the adsorption process of
SO2 on -Al2O3 or CuO/-Al2O3 materials. For instance, Mitchell et
al. [111] prepared sodium-doped alumina materials procured from
Goodfellow (SBET = 150 m 2/g) loaded with 1.1, 3.3 and 5.5 wt.% Na,
respectively, and studied their adsorption capacities by TGA at 30 C
for a gas containing 0.11% SO2 in N2 (FR = 150 ml/min). The regener-
ation of the sorbents was carried out by increasing the temperature
from 25 to 700 C (15 C/min) under a ow of N2. At the lower sodi-
um content (1.1 wt.%), the adsorption capacity slightly decreased
from 32 to 26 mg/g after 3 cycles. The best performance was obtained
for the 5.5 wt.% Na/-Al2O3 with an adsorption capacity around
83 mg/g which is four times that of the sodium-free -Al2O3. Howev-
er, the adsorption capacity tends to decrease more signicantly as the
number of cycles increases (Cads = 45 mg/g after 3 cycles). From
these results and based on of IR studies, the authors found that at
low coverage levels, the sodium acts as a promoter for the formation
of sulfate and sulte species which become chemically adsorbed as
aluminum salts; very low amounts of sodium sulfate species were
also observed. However, at higher loadings, one sees the predominant
formation of sodium sulfate that is not regenerable. As shown by Yoo
et al. [98], the addition of 5 wt.% NaCl leads to a bulk sulfation reac-
tion starting at a lower temperature (by 50 C) and for a Cu loading
(by 2 wt.%), as compared with the sodium-free system. Jeong et al.
[112] prepared a series of 8 wt.% CuO/-Al2O3 sorbents containing al-
kaline additives (LiCl, LiBr, NaCl, LiF, KCl or NaF) and studied by TGA
the adsorption of SO2 at 500 C. The SO2 adsorption tests was made
using 1.5% SO2 in air (FR = 900 ml/min); the capacity was measured
after 150 min; the regeneration steps were performed under a ow of
5% H2 in N2. They found that the adsorption capacity was strongly en-
hanced by the presence of alkaline salts especially when LiCl was
added. Based on their XRD studies, they concluded that alkaline addi-
tives promote the formation of Al2(SO4)3. No characteristic peaks of
CuO or LiCl were observed due to a high dispersed state of the corre-
sponding particles. For the CuO/-Al2O3 sorbent containing 5 wt.%
LiCl, the adsorption capacity was as high as 460 mg/g, a value 3
times higher than the additive-free sorbent. For a still higher LiCl con-
tent (6.5 wt.%), the adsorption capacity climbed to around 600 mg/g.
Although some losses of adsorption capacity after regeneration were
observed, the performance was superior than those of the alkaline-
free sorbents. Furthermore, the presence of alkaline additive was
found to decrease the decomposition temperature of the sulfates
formed which is interesting for the regeneration step. Wilde and
 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100
Marin [113] studied the simultaneous removal of SO2 and NOx on a
Na/-Al2O3 (Na content not mentioned). An adsorption capacity of
72 mg/g was obtained at 115 C for a gas containing 2.3 mol% SO2,
0.2875 mol% NO, 1.0 mol% O2 in argon. The effect of Na2O additions
to an Al2O3-coated honeycomb cordierite-supported CuO was studied
by Liu et al. [114]. Adsorption tests were performed at 400 C using a
gas containing 0.2% SO2, 500 ppm NO, 5.5% O2, 2.5% H2O and 500 ppm
NH3 (balance: argon) at 440 ml/min (SV = 2800 h 1). The best per-
formance was again obtained for the higher sodium loaded adsorbent
(2 wt.% Na). XRD examination after sulfation showed that SO2 mole-
cules were chemically adsorbed on -Al2O3 as CuSO4, NaCu2(SO4)2-
OHH2O and Na2SO4 species. The regeneration of the sorbent that
was performed at 400 C, under a ow of 5% NH3 in argon (1.5 h),
led to the decomposition of CuSO4 [115]. However, the mixed
NaCu2(SO4)2OHH2O salt was not fully reduced, thus decreasing sig-
nicantly the SO2 removal.
Another potential advantage of the CuO/-Al2O3 materials is that,
after the sulfation reaction has been completed and provided some
active sites remain, they can remove NOx from ue gases via the se-
lective catalytic reduction (SCR) method, leading to an economically
attractive process [102,105,109,116126]. In this process, CuO and
CuSO4 were found to catalyze the reduction of NOx into N2 with
NH3 as reducing agent with an efciency of more than 90%, according
to the following reactions (14, 15):
4NO 4NH3 O2 4N2 6H2 O 14
2NO2 4NH3 O2 3N2 6H2 O: 15
3.2. Use of others oxides/metals in association with -Al2O3
In the patent literature, some alumina materials coated with me-
tallic catalysts (platinum, cerium, thorium, vanadium, etc.) both in
free and in combined forms (Pt-CeO2/Al2O3, MgOCeO2/Al2O3, K
ThO2/Al2O3, etc.) were developed to remove SOx in uid catalytic
cracking units [127130]. These studies clearly show that the metallic
catalyst promotes the oxidation of SO2 to SO3 which gets further
chemically adsorbed on the support. Svoboda et al. [131] developed
CaO/-Al2O3 materials for FGD operating within the temperature
range of 120240 C. They found that the main factors that strongly
inuence the rate of desulfurization and the attainable conversion
are the pore size distribution, the phase composition and the content
of weakly bound CaO to -Al2O3. Other authors, who also studied
CaO/-Al2O3 sorbents for the capture of SO2 showed that their attri-
tion resistance was much higher than that of limestone [132].
The trapping of SOx before the NOx-storage/reduction (NSR) pro-
cess attracted also a high interest in the past few years. The NSR tech-
nology is a promising process which consists of trapping NOx during
the lean cycling mode (oxygen excess) of the engine in the form of ni-
trites/nitrates on a catalyst. The material of the catalyst is generally
made of three major components including a highly refractory sup-
port (-Al2O3), a NOx storage component (basic oxide) and an oxida-
tion promoter (Pt, Rh, Pd, etc.). However, the NSR catalysts were
strongly deactivated by SO2 molecules that block the NOx sorption
sites. Hence, a solution to prevent sulfur poisoning is to develop SOx
storage materials that adsorb SO2 of the exhaust gas before passing
on the NSR catalysts. Under lean operating conditions, SO2 is oxidized
in SO3 and chemically adsorbed on the SOx trap. In that case, a high
thermal stability of the corresponding sulfates is required to avoid
the release of SO2 during the regeneration process of the NOx cata-
lysts. Calcium, magnesium or barium oxides, transformed into sul-
fates, proved interesting trapping agents for such a purpose.
Different SOx trap materials based on mesoporous -Al2O3 supports
modied with storage components (Ca or Ba) and oxidation catalysts
(Pt, Cu or Mn) were developed and studied by Schreier et al. [133].
87
The adsorption tests were performed over a temperature range of
50600 C and repeated four times, using a gas composition of
50 ppm SO2, 6% O2, and 5% CO2 in He. The best SOx trap material
was found to be the Ca- or Ba-modied alumina associated with Mn
as an oxidation component, which is able to adsorb 17% of its weight
as sulfate. Additional modication with 10 wt.% Na increased the SO2
uptake to about 22%. The efciency of the SOx traps was found to de-
crease over the temperature cycles due to increasing occupation of
the active adsorption sites. The same team developed another high
capacity sorbent based on a mesoporous CaO/Al2O3 material doped
with Na and Mn [134]. An adsorption capacity around 1520 mg/g
was obtained at 250 C for a gas containing 50 ppm SO2, 12% O2 in
He (FR = 200 ml/min). The presence of 10% H2O in the gas composi-
tion was found to increase signicantly the adsorption capacity up to
around 2080 mg/g. A low SO2 concentration and a moderate temper-
ature favored such high performances. The presence of water en-
hanced the transport rates of sulfates from the surface to the bulk.
The mechanism of the SOx storage on a CuO/-Al2O3 impregnated
with barium was studied in details by this group [135,136].
3.3. Spinels and mixed oxides derived from hydrotalcites
An important part (7%) of SOx emissions stem from uid catalytic
cracking (FCC) units used in the petroleum industry. For the reasons
explained below, the desulfurization methods applied to FCC plants
involved the use of spinels. An FCC unit is a renery installation de-
voted to the conversion of high-molecular weight hydrocarbon frac-
tions into valuable fuels such as gasoline or diesel. Since the 1960s,
main catalysts employed in FCC units are based on microporous ma-
terials such as Y or ZSM-5 zeolites which dramatically improved the
gasoline selectivity, the octane number and the yield of olens
[137]. Operating conditions in an FCC reactor are typically a tempera-
ture range of 500550 C and a pressure of around 1.7 bar. The
amount of SOx emitted from an FCC unit is closely related to the quan-
tity of sulfur present in the feed, the coke content and the conversion
yield. As it was showed by Byrne et al. [138], 4555% of the feed sulfur
is converted to H2S in the FCC reactor, 3545% remains in the liquid
products and about 510% lead to the formation of carbonaceous ma-
terial (coke) that deposit on the catalyst. During the oxidative regen-
eration of the catalyst at a temperature of 700800 C, the sulfur
compounds present in the coke are burned off leading to SOx emis-
sions (around 90% SO2 and 10% SO3). Thus, a possible route to de-
crease the SOx emissions from FCC units is to adsorb them during
the regeneration process. However, several requirements are needed
for trapping SOx in FCC units: (1) high thermal stability of the adsor-
bent under FCC conditions, (2) capacity to oxidize SO2 to SO3,
(3) chemical adsorption of SO3 in the form of stable metal sulfates,
(4) regeneration of the adsorbent under a reductive ow of H2 to re-
lease sulfur as H2S in the FCC riser [139] and (5) absence of negative
impact on the conversion and selectivity of FCC products.
For this purpose, materials having an intermediate basicity such as
MgAl2O4 spinels were rst investigated to trap SOx under conditions
similar to those of FCC units [140144]. The spinel structure is based
on a cubic close-packed array of oxide ions with a unit cell containing
32 oxygen atoms (8MgAl2O4). Alkaline earth metal ions, such as calcium
or barium can replace all or a part of the magnesium ions. Similarly, tri-
valent metal ions, such as iron, chromium or cobalt can replace a portion
of the aluminum ions. Few studies report the development of
earth-alkaline and rare earth metal containing spinels for the desulfuri-
zation of industrial gases [145147]. Bhattacharyya [148] added small
amounts of kaolin clays to the spinels to improve their surface area and
attrition resistance during the removal process of SOx and NOx in FCC
units. The incorporation of iron in mixed solid solution spinels was
found to catalyze the oxidation of SO2 to SO3 and to decrease signicantly
the sulfate reduction temperature during the regeneration process [149].
Lithium doped magnesium aluminate spinels were developed by Wang
88 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100
[150] for SOx removal. Spinels containing rare metals such as lanthanum,
cerium or praseodymium were developed by Bertolacini et al. [151] to
remove sulfur oxides from FCC units. However, the major drawback of
spinels MgAl2O4 is their rich aluminum content leading to the formation
of bulk like sulfates during the sulfation which are hardly reducible thus
decreasing the amount of SOx captured after several cycles.
In contrast, mixed oxides derived from hydrotalcites appeared as
promising materials for trapping SOx under FCC conditions and exhib-
it higher adsorption capacities than spinels. Thus, they attracted
growing interest in industry [152158]. Hydrotalcite-like materials
(HT) are layered double hydroxides with a structure closely related
to brucite (Mg(OH)2) with divalent cations M 2+ located in octahedral
sites and replaced by trivalent cations M 3+ through isomorphic sub-
stitution leading to positively charged M 2+M 3+ layers [159161].
This positive charge is counterbalanced by anions located in the
interlayer along with water molecules. A wide range of HT materials
can be prepared and are represented by the following generic formula:
2+ 3+ x+
[M(1 x)Mx (OH)2] [An]x/nmH2O where M2+ and M3+ represent
any divalent and trivalent cations and A n any anions. Hydrotalcites
materials are traditionally prepared by co-precipitation methods using
the corresponding metals salts; they are thermally stable up to about
400 C and transforms into mixed oxides for higher temperatures. Sev-
eral studies were devoted to the use of mixed oxides derived from
hydrotalcites to decrease the emission of many contaminants such as
CO2 [162,163] or NOx [164166]. Therefore, it seemed logical to study
mixed oxides derived from hydrotalcites, having a wide range of chem-
ical compositions, for the removal of SOx from FCC units. Corma et al.
[167] developed a ternary CuMgAl mixed oxide derived from a
hydrotalcite to study the simultaneous removal of SOx and NOx under
FCC conditions. The molar composition of the mixed oxide obtained
after calcination of the hydrotalcite at 750 C in air for 3 h was 7MgO:
Al2O3:CuO. The test of simultaneous removal of SOx and NOx was
performed at 750 C under oxidative conditions using a gas feed of
450 ppm NO, 540 ppm SO2 and variable amounts of O2 and N2 as gas
balance (FR = 1600 ml/min). Reductive conditions were also used
with 450 ppm C3H8 added to the gas composition. The authors observed
that, for an oxygen concentration ranging from 0 to 1.5%, the mixed
oxide can remove simultaneously SO2 (under oxidative or reductive
conditions) and NO (only under reductive conditions). The SO2 removal
of several ternary CuMgAl and CoMgAl mixed oxides derived from HTs
was studied by Palomares et al. [168]. CuMgAl and CoMgAl HTs were
prepared by the co-precipitation method using a solution of the appro-
priate metal nitrates (or acetate in the case of Co). The role of cerium as
an oxidation promoter was also studied as it was added in CuMgAl and
CoMgAl sorbents. The calcination was performed at 750 C in air for 3 h
to produce the corresponding mixed oxides. The gas composition was
0.14% SO2, 3% O2, and N2 balance (FR = 700 ml/min) and the SO2 re-
moval was studied at 750 C. In fact, it was shown that, to get an optimal
removal of SO2 by the CoMgAl mixed oxide, it is necessary to have an
oxidation promoter such as CeO2 to oxidize SO2 to SO3 which is further
adsorbed as magnesium and aluminum sulfates. Ce-doped mixed ox-
ides show higher SO2 removal efciency than the Ce-non containing
ones and can be fully regenerated under a reductive ow of H2
(530 C, FR = 700 ml/min) during 2 h. It is known that cerium is a
choice metal to develop adsorbents having a high potential for SOx re-
moval in FCC units [169]. Cant et al. [170] studied the effect of the
chemical composition and the cerium incorporation method of several
mixed oxides derived from HT on the SOx removal. HTs were synthe-
sized via the classical co-precipitation method using the corresponding
nitrate salts and were further calcined at 500 C during 18 h. The SO2
adsorption test was carried out by TGA at 650 C for a gas composition
containing 1% SO2 in air (FR = 20 ml/min). Regeneration was
performed under a ow of H2 (20 ml/min) at 550 or 650 C depending
on the samples. Very high adsorption capacities were obtained for the
MgAl and MgAlFe mixed oxides with values of 1150 and 1080 mg/g, re-
spectively. However, due to the formation of very stable MgSO4 species,
MgAl mixed oxides need to be regenerated at higher temperature (62%
of the sample regenerated at 650 C, 100% at 700 C) in contrast to
MgAlFe sample where the isomorphic incorporation of iron increased
its reduction capability (94% at 550 C and 100% at 650 C). Cerium
containing samples, obtained by impregnation on the calcined
hydrotalcite with a cerium nitrate solution or by in situ incorporation,
showed similar adsorption capacities with values of 1110 and
1090 mg/g. The presence of cerium signicantly improved the satura-
tion time of the different samples because CeO2 promotes the oxidation
of SO2 to SO3. This is an important factor since, in FCC units, the resi-
dence time of the catalyst is very short (515 min). These mixed oxides
can be fully regenerated and showed similar adsorption capacities after
a second SO2 adsorption test. They have higher adsorption capacities
than a commercial adsorbent made up of 61 wt.% MgO, 18% Al2O3,
16% CeO2, and 4.5% V2O5 (600 and 690 mg/g after one and two cycles).
Polato et al. [171] reported an adsorption capacity of 715 mg/g for a
mixed oxide derived from a HT with a Mg/Al molar ratio of 1 and a
CeO2 content of 21 wt.%. The adsorption test was performed at 700 C
using a gas composition of 0.15% SO2, 1.5% O2, and balance He (FR =
175 ml/min). The mixed oxide having both the periclase and spinel-
phase, the authors observed that the sulfates formed from the
spinel-phase were more easily reduced than those of the periclase-
phase. By using ternary CuMgAl mixed oxides derived from HTs as SOx
traps, Centi and Perathoner [172] performed catalytic tests with a gas
mixture containing 0.1% SO2 in air. This catalytic test was performed
using TGA at 200 C on a gas mixture containing 0.1% SO2 in air. An ad-
sorption capacity of around 80 mg/g was obtained at 200 C for the
mixed oxide with a Cu/Mg/Al molar ratio of 1:1:2 and a specic surface
area of 80 m2/g (nearly three times higher than that of 1:2:1 mixed
oxide). At 500 C, the SO2 adsorption capacities of both the 1:1:2 and
1:2:1 mixed oxides improved signicantly with values around 450
and 940 mg/g. However, after hydrothermal treatment at 600 C during
6 h under a ow containing 11% CO2, 5% O2, and 57 H2O in N2, which
reproduces FCC conditions, a sudden decrease of the adsorption capac-
ity was observed with a value around 35 mg/g obtained at 200 C for
the 1:1:2 mixed oxide. Ternary mixed oxides showed improved perfor-
mances with respect to the binary samples (containing only Cu and Al)
that had been previously prepared by Centi and Perathoner [173],
thus underlining the important role of Mg to get high SO2 uptake and
hydrothermal stability. Various mixed oxides derived from MgAl-
hydrotalctite compounds and containing Fe, Cu, Co and Cr were pre-
pared and tested against SO2 adsorption by Polato et al. [174]. The ad-
sorption test was performed at 720 C using a gas containing 0.16%
SO2, 1.6% O2 and balance He (FR = 175 ml/min). Cu and Co containing
mixed oxides were found to be the most efcient for SOx removal with
adsorption capacities of 956 and 811 mg/g, respectively. Samples were
partially regenerated under a ow of 30% H2 in He (74 and 79% for the
CuMgAl and CoMgAl mixed oxides respectively). Cheng et al. [175] syn-
thesized several MgAlFe mixed oxides derived from hydrotalcite mate-
rials and impregnated them with copper to study their SO2 adsorption
capacity. Copper oxide can be a good oxidation promoter in replace-
ment of cerium oxide. The SO2 adsorption test was performed at
700 C for a gas composition containing 2% SO2, 8% O2, and balance N2
(FR = 50 ml/min) by TGA. Regeneration was performed under a ow
of 33% H2 in N2 (FR = 50 ml/min) at 600 C during 40 min. An adsorp-
tion capacity of 1600 mg/g was obtained for the Cu/MgAlFe mixed
oxide containing 1 wt.% of copper, which could be fully regenerated
under H2. Furthermore, the catalyst reached its saturation in 6 min
which is favorable for FCC applications. The 8.0 wt.% Ce/MgAlFe
presented a slightly lower adsorption capacity of 1460 mg/g and a sim-
ilar saturation time. Cheng et al. [176] also studied the crystalline struc-
ture and the SO2 adsorption capacity of several MgAlFeCu mixed oxides
with different Mg/Al atomic ratios derived from hydrotalcites. XRD ex-
periments showed that the mixed oxides, having a Mg/Al atomic ratio
ranging from 3 to 10, exhibit the characteristic Mg(Al)O periclase type
phase. An increase of the SO2 adsorption capacity was observed when
 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100 89

increasing the Mg/Al atomic ratio up to 6. For Mg/Al = 6, the SO2 ad- Table 3
sorption capacity culminated at 1620 mg/g and remained constant Main studies devoted to the use of mixed oxides for DeSOx.

after 8 cycles (similar experimental conditions than those reported in Nature SBET Cads FR Gas composition T (C) Ref
[175]). This atomic ratio corresponds to an optimal Mg(Al)O structure (m2/g) (mg/g) (ml/min) (vol.%)
combined with a maximum specic surface of 196 m2/g. Further in- SO2 O2 Balance
crease of the magnesium content results in a decrease of the SO2 adsorp-
MgAl 204 1150 20 1 0 Air 650 [170]
tion capacity due to a decrease of the specic surface area of the mixed a [179]
oxide. For instance, for Mg/Al = 10, the SO2 adsorption capacity and the MgFe 75 1010 1 0 Air 650 [179]
surface area were 1260 mg/g and 129 m 2/g, respectively. Ce/MgAl 153 715 175 0.15 1.5 He 700 [171]
Lee et al. [177] studied the effect of Ti on the sulfur removal ef- CuMgAlb 80 80 0.1 0 Air 200 [172]
450 500
ciency of a CeFeMg mixed oxide at 700 C (0.5% SO2, 5.2% O2, N2). CuMgAlc 111 940
The CeFeMgTi compound showed a sulfur removal efciency of CuMgAl 114 956 175 0.16 1.6 He 720 [174]
86.4%, which is signicantly higher than the other mixed oxide com- MgFeAl 74 1080 20 1 0 Air 650 [170]
binations: CeFeMg, CeFeMgZr and CeFeMgAl (69.4, 38.1, and 58.5%, 169 1070 [179]
MgZnAl 193 870 1 0 Air 650 [179]
respectively). The sulfur removal capacity stayed constant for over 8
CoMgAl 179 811 175 0.16 1.6 He 720 [174]
sulfationregeneration cycles; the regenerations were performed Ce/MgAlFed 144 1110 20 1 0 Air 650 [170]
under a reductive ow of 50% H2 in N2. The authors also found that Ce/MgAlFee 109 1090
the sulfur removal efciency could be improved by using TiO2 parti- 1% Cu/MgAlFe 154 1600 50 2 8 N2 700 [175]
cles obtained via the sol gel method during the synthesis of the 8% Ce/MgAlFe 1460
CuMgAlFef 196 1620 50 2 8 N2 700 [176]
CeFeMgTi HT [178]. As it was mentioned by Cant et al. [179], the
a
SO2 adsorption capacity of mixed oxides is strongly dependent to Not reported.
b
Cu/Mg/Al molar ratio of 1:1:2.
the chemical composition of the precursor HTs. Several mixed oxides c
Cu/Mg/Al molar ratio of 1:2:1.
obtained from binary and ternary HTs containing copper, nickel, zinc, d
Impregnation of the calcined hydrotalcite with a cerium nitrate solution.
iron, magnesium and/or aluminum were studied for SOx adsorption. e
In situ incorporation of cerium during the synthesis of the HT.
The SOx adsorption test was performed by TGA using a ow of 1% f
Mg/Al atomic ratio of 6.
SO2 in air at 650 C. The best results were obtained for MgAl, MgFe,
MgFeAl and MgZnAl with adsorption capacities of 1150, 1010, 1070 were investigated for the removal of SOx from FCC units and residue
and 870 mg/g, respectively. The reduction temperature under a ow uid catalytic cracking units (RFCC) by Jae et al. [182]. The test was
of H2 is also strongly inuenced by the nature of the transition performed at 700 C for a gas composition of 0.5% SO2, 5.2% O2, and
metal. For instance, due to the formation of stable metal sulfates, N2 balance (FR of 50 ml/min and SV of 5000 h 1). The oxidative
MgZnAl and MgNiAl required a higher reduction temperature of power of these promoters was found to increase in the following
650 C; MgCuAl required 700 C. After a second adsorption cycle, order: Fe b Co b Ce. The MgO sorbent simultaneously promoted
MgAl, MgFe, MgNiAl and MgFeAl showed similar adsorption capaci- with 15 wt.% Ce and 5 wt.% Fe exhibited a high adsorption capacity
ties than those obtained in the rst cycle. However, a signicant de- (440 mg S/g) and excellent regeneration performance under a reduc-
crease of the adsorption capacity was observed with NiAl, ZnAl and tive ow of 50% H2 in N2 at 530 C.
MgZnAl and was explained by the formation of stable metal suldes
during the regeneration process. Unfortunately, it is not possible to 4. Oxides supported on carbonaceous materials
compare the results of these authors with those of Cheng et al.
[176] since the adsorbents are not really the same. Oxides supported on carbonaceous materials involve activated
These results show in overall that mixed oxides derived from carbons (ACs) and ACFs as supports. ACs are generally obtained by
hydrotalcite-like materials boast very high SO2 uptake efciencies in pyrolysis and activation of coal, lignite or biomass products. During
comparison with spinels or traditional commercial catalysts and the pyrolysis stage, hydrogen and oxygen are eliminated and the re-
have a strong potential application in FCC units (Table 3). However, sult is an increase of the carbon content of the support. Then, an acti-
it is noteworthy that their DeSOx efciency decreases under condi- vation is performed in an inert gas ow at high temperatures
tions similar to those in FCC units, namely in the presence of H2O whereby enhancing the porosity of the carbon support.
and CO2 [172]. Because of their low cost, ACs have been widely used for SO2 re-
moval [183195]. A number of studies report the introduction of
3.4. Other mixed oxides heteroelements such as copper, iron, vanadium, potassium or calcium
in ACs [196212].
Kikuyama et al. [180] studied the adsorption and desorption of SO2 Alvarez-Merino et al. [196] studied the adsorption of SO2 by ACs
on mixed oxides MZr (M = Cr, Mn, Fe, Co, Ni, Cu) with M/Zr = 1, containing alkaline-oxides at 25 and 300 C. The ACs were prepared
which were prepared via the ammonia co-precipitation method from a bituminous coal which was demineralized with HCl or HF,
from a solution of the corresponding nitrate mixtures. The adsorption washed with distilled water, pyrolyzed in N2 at 1000 C and activated
test was performed at 200 C using a gas composition of 0.1% SO2, 10% in a CO2 ow at 900 C for 18 (31 wt.% burn-off) or 45 h (72 wt.%
O2, and balance He (FR = 60 ml/min). The SO2 desorption was burn-off). The gas composition was 2% SO2 in air (FR = 60 ml/min)
performed by temperature programmed desorption (TPD) under a re- and the adsorption test was carried out by TGA. Before the adsorption
ductive ow of 5% H2 in He to 950 C at a rate of 5 C/min. The best of SO2, the ACs previously impregnated with nitrate salts were heated
performance was obtained in the presence of manganese and copper at 600 C in N2 whereby according to the authors the corre-
with an adsorption capacity of respectively 74 and 47 mg/g. However, sponding oxide was formed via the following reaction (16):
the major drawback is the weak regeneration ability of these oxides
as, except in the presence of manganese (56.9%) and in a less degree 2MNO3 2CM2 O CO2 CO 2NO with M Na; K; Rb: 16
of iron (42.5%), the other oxides exhibit very low regeneration rate
(35.5%). A XPS investigation study performed on CeZr mixed ox- At 25 C, the adsorption capacities of the ACs containing alkaline-
ides by Romano and Schulz [181] showed that the SO2 molecules oxides (burn-off of 31 or 72%) are lower than the adsorption capacities
were chemically adsorbed in the form of sulfate and sulte species. of the ACs free of alkaline-oxides. According to the authors, the adsorp-
Regenerable MgO-based sorbents promoted with Ce, Co, Fe and Cu tion capacity at 25 C is mainly governed by the microporosity of the
90 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100
sample. The specic surface (obtained by benzene adsorption at 30 C)
is higher for the ACs free of alkaline-oxides (634 m2/g for a burn-off of
31% and 1644 m2/g for a burn-off of 72%) than the ACs loaded with
alkaline-oxides (433 SBET 577 m2/g for a burn-off of 31% and
980 SBET 1413 m2/g for a burn-off of 72%). At 300 C, the adsorp-
tion capacities of the ACs containing alkaline-oxides were lower than
those observed at 25 C. For instance, adsorption capacities of 176,
206 and 219 mg/g in the presence of Na (6.6 wt.%), K (6.2 wt.%) and
Rb (6.4 wt.%) were observed at 25 C for a burn-off of 31%. At 300 C,
all the adsorption capacities are lower with values of 140, 116 and
110 mg/g in the presence of Na, K and Rb. The same trend was observed
for a higher degree of activation (burn-off of 72%). However, at 300 C,
these values remain higher than the corresponding ACs free of any alka-
line oxide (56 or 48 mg/g for a burn-off of 31 and 72%, respectively).
After adsorption, ACs were not fully regenerated under a ow of N2 by
heating up to 600 C and their adsorption capacities decreased
(Cads = 70, 51 and 63 mg/g for the regenerated ACs containing Na, K
and Rb, respectively), reportedly due to the deposition of sulfur on the
surface of the ACs.
Same trends were observed by GuO et al. [197] for ACs prepared
from oil-palm shells pre-treated with potassium hydroxide. They
studied their performances from 25 to 100 C by TGA with a gas
feed containing 0.2% SO2 in N2. The adsorption capacity was found
to decrease as a function of the temperature; from 76 mg/g at 25 C
down to 8 mg/g at 100 C for an AC containing 10 wt.% KOH charac-
terized by a specic area of 1408 m 2/g. Some other AC materials,
containing in particular iron were studied. For instance, Davini et al.
[198] worked on ACs having different acidic and basic surface proper-
ties and containing up to 1.3 wt.% Fe. Their adsorption tests were
performed at 100 C using a gas composition of 0.1% SO2, 5% O2 and
10% H2O in N2 (FR = 50 ml/min). The best performances were
obtained with ACs displaying basic properties at their surface. For in-
stance, the AC containing 1.3 wt.% Fe (SBET = 920 m 2/g) and having
the most basic character boasted an adsorption capacity of 125 mg/
g. For an AC containing 3.5 wt.% Fe (SBET = 831 m 2/g), Ma et al.
[199] obtained an adsorption capacity of 35 mg/g at 200 C (gas com-
position: 0.12% SO2, 5% H2O, 6% O2 in argon). Adsorption of SO2 on the
Fe sites resulted in the formation of Fe2(SO4)3 along with H2SO4 on
the surface of AC. During the regeneration process that consisted in
heating the sample from room temperature to 200 C under a ow
of Ar (400 ml/min), CO and CO2 were detected according to the fol-
lowing reactions (17, 18):
Fe2 SO4 3 3CFe2 O3 3CO 3SO2 17
H2 SO4 CCO SO2 H2 O: 18
The Fe/AC sample can be regenerated by a ow of 5% NH3 in Ar at
350 C for 90 min but 20% of the activity was lost. Other oxides sup-
ported on AC materials were also studied. Carabineiro et al. [200] im-
pregnated an AC (SBET = 1077 m 2/g) with several metals including:
Ba, Co, Fe, Cu, Mg, Mn, Ni, Pb and V. The best performance was
exhibited by the 4% Cu4% V/AC sample (SBET = 691 m 2/g) with an
adsorption capacity of 140 mg/g at 20 C (gas: 0.47% SO2 in argon,
FR = 100 ml/min). No further testing was performed at higher tem-
perature. The authors carried out a TDP study, in which the samples
were heated from room temperature to 1100 C at a rate of 5 C/min
under a ow of 350 ml/min He, and identied the evolution of CO
and CO2. Wey et al. [201] showed that additions of CuO and CeO2 im-
prove the SO2 adsorption performance. Tseng et al. [202] developed
oxides supported on ACs, using namely CuO, Fe2O3 and V2O5 and
showed that these materials exhibit a better SO2 removal performance
than the traditional CuO/Al2O3 materials. The same team prepared
sorbents containing from 3 to 10 wt.% Cu on activated coal and tested
them at 250 C using the following gas feed: 400 ppm SO2 and 7.68%
O2 in N2 (SV = 63,840 h 1) [203]. The SO2 adsorption capacity was
found to increase as a function of the copper content. For the sample
containing 10 wt.% Cu (SBET = 843 m 2/g), an adsorption capacity of
ca. 42 mg/g was obtained. The adsorbent was regenerated by heating
from 250 to 475 C in an N2 stream. However, after 10 adsorption
regeneration cycles, the SO2 uptake dropped by about 16%. During
the regeneration, decomposition of surface oxygen species occurred,
leading to the formation of CO2 and CO and the latter was able to act
as a reducing gas during the regeneration step. Tseng et al. [204] also
showed that the performance of CuO/ACs was greatly inuenced by
an acid pre-treatment of the ACs with HCl or HNO3, which enhanced
the catalyst dispersion and activity. The authors studied the inuence
of other parameters such as metal loading and support particle size
[205]. For instance, at 250 C, the adsorption capacity of an AC
containing 5 wt.% Cu and pre-treated with HCl (SBET = 938 m 2/g,
particles ranging from 250 to 300 m) was 31 mg/g (gas composition:
200 ppm SO2 in N2, FR = 700 ml/min). Increasing the copper content
up to 10 wt.% (SBET = 844 m 2/g) led to an increase of the adsorption
capacity (Cads = 59 mg/g). ACs with smaller particle sizes (from 125
to 180 m) showed improved performances for the samples loaded
with 5 wt.% (Cads = 57 mg/g) and 10 wt.% Cu (Cads = 116 mg/g).
Similar results were obtained by Zhu et al. [206] who found an adsorp-
tion capacity of 55 mg/g at 120 C for an AC containing 6.5 wt.% KOH
(SBET = 578 m 2/g). The gas composition was 0.06% SO2, 0.015% CO,
13% CO2, 9.8% O2 and N2 (SV = 2000 h 1). Fortier et al. [207] studied
the adsorption capacity of ACs as a function of the K2CO3 loading (gas
composition of 0.1% SO2 in air, FR = 200 ml/min). The impregnation
of the ACs by K2CO3 was performed by the soaking and incipient
wetness methods with a loading ranging from 1.7 to 22 wt.%. For the
ACs prepared by the soaking method (SBET = 900 m 2/g, Cads =
106 mg/g), the authors observed that the adsorption capacity linearly
increased in function of the K2CO3 content up to 12 wt.%. For a K2CO3
content higher than 12 wt.%, the adsorption capacity was found to de-
crease mainly due to pores becoming blocked by aggregates of K2CO3.
For the ACs prepared by the incipient wetness method, the adsorption
capacities were much higher. For instance, for an AC loaded with
22 wt.% K2CO3 (SBET = 835 m 2/g), the adsorption capacity reached
147 mg/g. Xiao et al. [208] developed some V2O5/AC for the removal
of SO2 at 200 C and studied the role of lattice oxygen. They found
that the adsorption process occurred via the formation of a VOSO4-like
intermediate due to the presence of lattice oxygen in V2O5. As it was
shown by GuO et al. [209], such V2O5/AC systems were also found to
be active for the simultaneous removal of SO2 and NO at 200 C.
Commercial synthetic ACs containing CaO were studied by TGA at
300 C (gas feed: 0.3% SO2 in He, FR = 60 ml/min) by Macas-Prez
et al. [210,211]. The surface oxygen content of the AC was found to
mainly control both the overall calcium loading and the calcium con-
tent at the surface of the CaO/AC samples. An adsorption capacity of
123 mg/g was obtained for the higher calcium loading (12.2 wt.%
Ca, SBET = 1708 m 2/g). A loss of activity of around 20% was observed
after the regeneration during which the sample was heated up to
880 C under a ow of N2. It is worth mentioning that about 5% of
the AC support is systematically consumed during each regeneration
cycle. Other works carried out by the same team allowed to comple-
ment the previous results. These authors prepared CaO/carbon
samples with Ca contents ranging from 1.5 to 8 wt.% and studied
the adsorption of SO2 at 300 C (gas ow: 0.3% SO2 in He, FR =
60 ml/min) [212]. An increase of the adsorption capacity was ob-
served as a function of the Ca loading (19 mg/g for 1.5 wt.% Ca and
91 mg/g for 8 wt.%). The regeneration is possible by thermal treat-
ment but the degree of regeneration is strongly related to the calcium
loading; high calcium loadings leading to sintering problems.
ACF materials offer several advantages in contrast to traditional
ACs such as higher specic areas (13002000 m 2/g) and larger pore
volumes (0.52.5 cm 3/g). They are generally obtained by pyrolysis
and activation of precursor polymers such as polyacrylamide or
polyacronitrile. Thus, ACFs exhibit in general higher SO2 uptake than
 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100 91

traditional ACs [213222]. However, only few studies report the use
of ACFs impregnated with metal oxides for the removal of SO2.
Hong et al. [223] prepared ACFs impregnated with a number of metals
including Ni, Pd, Co, V and Cr and showed improved DeSOx perfor-
mances as compared to those exempt of metal. Gaur et al. [224] im-
pregnated ACFs with transition metals such as Cu, Ni, Co and Cr in
an attempt to achieve the catalytic oxidation of SO2 into H2SO4. The
best performance was obtained with an ACF sample containing
5 wt.% CuO (SBET = 1300 m 2/g) that yielded a conversion rate of
around 95%.
The main results of the oxides supported on carbonaceous mate-
rials are summarized in Table 4.
5. Oxides supported on microporous and mesoporous
silica-based materials
Porous silica-based oxides, especially zeolites and mesoporous orga-
nized silica are promising materials for SO2 adsorption since they exhib-
it interesting properties such as high specic surface area and pore
volume, thermal stability, chemical stability versus SOx, ability to un-
dergo multiple regenerations and incorporate heteroelements for
chemisorption. Among these materials, the zeolites that are character-
ized by a microporous structure with cavities ranging in diameter
from 3 to 13 , have been the most studied desulfurization supports.
Zeolites are crystalline tectoaluminosilicates, the structure of which is
formed by TO4 tetrahedra (T = Al, Si), each apical oxygen atom being
shared between two adjacent tetrahedral [225]. Synthetic zeolites are
generally obtained under hydrothermal conditions in uoride or hy-
droxide media in the presence of inorganic precursors at various tem-
peratures over durations ranging from a few hours to several days;
this primary treatment is followed by post-synthesis treatments includ-
ing washing, drying and calcination. Moreover, complex organic tem-
plates, such as alkylammonium based molecules, can be used to
obtain zeolites with tuned properties. These microporous materials
were also found to exist in natural form (clinoptilolite, mordenite,
chabazite, etc.). Numerous applications in industrial areas such as gas
separation and petrochemical-based catalysis are known [226,227].
Therefore, many studies were devoted to the adsorption of SO2 by zeo-
litic materials. The structure type, the Si/Al molar ratio, the adsorption
temperature, the gas mixture composition (in particularly the SO2 con-
centration) and the presence of water in the gas mixture are among the
most studied parameters. Few parameters are known to have a negative
effect on the SO2 adsorption such as the increase of the temperature or
the presence of water in the gas composition.
The impact of temperature on the SO2 adsorption capacity of zeolites
was mentioned numerous times in the literature [228231]. For in-
stance, Chriswell and Gjerde [228] rst studied the adsorption capacity
of a commercial silicalite-1 zeolite from Union Carbide using a synthetic
stack gas containing 0.05% SO2, 9.4% O2 and 10.3% CO2 in N2 (FR =
150 ml/min). The adsorption capacities were determined from the
breakthrough curves using an UVvis spectrophotometer as detector.
The framework of silicalite-1 consisting of intersected channels with
ten-membered rings and a cross section of 5.5 in diameter is suitable
to adsorb SO2 molecules having a diameter of around 3.7 . Increasing
the temperature from 0 to 150 C led to a decrease of the adsorption ca-
pacity from 30 to 5 mg/g. A similar trend was reported by Gollakota and
Chriswell [229] for the same silicalite-1 when the temperature was in-
creased up to 800 C. For a gas composition of 0.2% SO2, 10.1% O2,
10.3% CO2 in N2 (FR = 150 ml/min, UVvis spectrophotometry detec-
tion), the authors observed a decrease of the SO2 adsorption capacity
from 38 mg/g at 25 C to 8 mg/g at 800 C. Ling and Deng [230] further
studied the inuence of the temperature (from 25 to 100 C) and the
SO2 partial pressure (from 0.5 to 5% SO2 in air, FR = 230 ml/min and
using an electronic microbalance) on the SO2 adsorption capacity of
two commercial hydrophobic zeolites, i.e. DAY (Degussa, SBET =
710 m2/g) which is a dealuminated Y zeolite and silicalite-1 (Union
Carbide, SBET = 420 m 2/g). The specic area which is signicantly
higher for the DAY zeolite, seems not to be a key parameter since
silicalite-1 shows a higher adsorption capacity at 25 C: for a gas
containing 4% of SO2 in air, the adsorption capacity was 16 and
109 mg/g for the DAY zeolite and the silicalite-1, respectively. This phe-
nomenon was attributed to a stronger afnity of the SO2 molecules to-
wards the adsorption sites of the silicalite-1 structure. The authors
reported also a strong decrease of the adsorption capacity with values
lower than 16 and 5 mg/g for silicalite-1 and DAY zeolite, respectively,
when the temperature was increased from 25 to 100 C. Higher values
of adsorption capacity (170 mg/g) were reported by Marcu and
Sndulescu [231] for a Y zeolite (SBET = 387 m2/g) at 25 C for a gas

Table 4
Main studies devoted to the use of oxides supported on carbonaceous materials.

Nature SBET Cads FR Gas composition (vol.%) T (C) Ref

(m2/g) (mg/g) (ml/min)
SO2 O2 H2O Balance

1.3% Fe/AC 920 125 50 0.1 5 10 N2 100 [198]

3.5% Fe/AC 831 35 a 0.12 6 5 Ar 200 [199]
10% Cu/AC 843 42 0.04 7.7 0 N2 250 [203]
5% Cu/ACb 938 31 700 0.02 0 0 N2 250 [205]
10% Cu/ACb 844 59
5% Cu/ACc 57
10% Cu/ACc 116
4% Cu4% V/AC 691 140 100 0.47 0 0 Ar 20 [200]
CaO/AC 1708 123 60 0.3 0 0 He 300 [210]
(12.2 wt.% Ca)
CaO/AC 91 60 0.3 0 0 He 300 [212]
(8 wt.% Ca)
10% KOH/AC 1408 8 0.2 0 0 N2 100 [197]
10% KOH/AC 76 25
d
6.5% KOH/AC 578 55 0.06 9.8 0 N2 120 [206]
6.4% Rb/AC 110 60 2 0 0 N2 300 [196]
6.2% K/AC 116
6.6% Na/AC 140
12% K2CO3/AC 900 106 200 0.1 0 0 Air [207]
22% K2CO3/AC 835 147
a
Not reported.
b
Pre-treated with HCl, particle size ranging from 250 to 297 m.
c
Pre-treated with HCl, particle size ranging from 125 top 177 m.
d
Gas composition containing also 0.015% CO, 13% CO2.
92 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100
composition of 1.85% SO2 in N2 (FR = 135 ml/min). The adsorption ca-
pacity was determined by iodometric titration. The regeneration of the
zeolite was made by increasing the temperature up to 400 C in N2. In-
terestingly, the adsorption capacity remained constant after 20 regener-
ation cycles. However, increasing the temperature from 25 to 200 C
resulted in a strong decrease of the adsorption capacity down to
10 mg/g. In all these cases related to silica-rich zeolites, the essential ad-
sorption process is the physical adsorption which explains the relatively
low values of adsorption capacity and their strong dependence on
temperature.
Recently, Zhi et al. [232] studied the adsorption of SO2 at 25 C on a
mesoporous SBA-15 material with surface modied by triethanolamine
(TEA). The SO2 adsorption experiment was carried out using a simulated
ues gas containing 0.13% SO2, 11% CO2 in N2 (FR = 312 ml/min, IR an-
alyzer). An SO2 adsorption capacity of 177 mg/g was obtained at 25 C.
Increasing the temperature at 80 C resulted in a decrease of the adsorp-
tion capacity (124 mg/g). A slight decrease of the adsorption capacity
was observed (168 mg/g) after regeneration of the sorbent (performed
under N2 at 120 C during 30 min, FR = 100 ml/min). However, this
adsorption capacity was constant after 6 adsorptionregeneration
cycles.
Other works on zeolites, report the formation of sulte or sulfate in
the presence of compensation cations or with Al in the framework. In
these conditions, a loss of crystallinity of material and difculties for
regeneration can be expected. For instance, Gupta et al. [233] showed
that the adsorption capacity of a commercial zeolite 5A was related to
the temperature as a maximum breakthrough time was observed at
70 C (1.0% SO2 adsorbed in 30 min) and not at room temperature.
Sakurai et al. [234] studied the amount of sulfate formation on the
surface of two faujasite zeolites with different sodium contents, i.e.,
NaY (SBET = 700 m 2/g, 12.4 wt.% Na2O) and the decationed HY
(SBET = 570 m 2/g, 4.3 wt.% Na2O), exposed to a gas stream of SO2 in
air (from 8.6 to 20 l/l) for a temperature ranging from 25 to 75 C.
An increase of the sodium content enhanced the chemical adsorption
of SO2 molecules thus giving rise to higher amounts of sulfate formed
in the case of NaY zeolite. The authors observed also that the amount
of sulfate formation increases when the temperature, the specic sur-
face area and the relative humidity in the air are high. Studies
performed by IR and UV spectroscopy showed that, in the presence
of water, the SO2 molecules were chemically adsorbed in the form of
hydrogen sulte ions HSO3 onto the NaY zeolites [235,236].
However, an overview of some studies showed that the presence
of water in the gas composition has a negative impact on the SO2 ad-
sorption capacity of microporous materials [237241]. As it was men-
tioned by Stenger et al. [237] the SO2 adsorption capacity at 100 C of
several mordenite samples was strongly decreased by the presence of
water in the gas composition. Tantet et al. [238] showed that the
presence of water in the gas mixture led to as strong decrease of
the adsorption capacity over a wide range of commercial MFI and
MOR zeolites exhibiting different Si/Al molar ratios (5.5175). The
adsorption capacity measured at 50 C for a gas composition of 0.2%
SO2 in N2 (FR = 2000 ml/min, IR SO2 analyser) was strongly related
to the Si/Al molar ratio of the zeolite. For the MFI zeolites, the adsorp-
tion capacities were: 13, 31, 42 and 96 mg/g for respectively Si/Al
molar ratios of 175, 75, 21.5 and 13. The same trend was observed
for MOR zeolites, with adsorption capacities of 25, 62 and 171 mg/g
for Si/Al molar ratios of 17.5, 10 and 5.5. A lower degree of hydropho-
bicity (rich Al content in the structure) and the presence of Na pro-
moted chemical adsorption in addition to physical adsorption, thus
led to high adsorbed quantities of SO2. However, in the presence of
3.2% H2O, a sudden shrinkage of the SO2 adsorption capacities of
both the MFI and MOR zeolites was observed with values lower
than 10 mg/g. In this case, a competition between SO2 and H2O mol-
ecules occurred to reach the adsorption sites of the zeolite structure
thus reducing the adsorption capacity of SO2. Similar conclusions
were further obtained by Ei and co-workers [239,240] using the
same commercial hydrophilic zeolites. The same team studied the in-
uence of water on the adsorption capacities of MFI (Si/Al = 13) and
MOR (Si/Al = 10) zeolites in the presence of CO2 [241]. The ternary
gas mixture used was 0.18% of SO2, 03.5% H2O and 9% CO2 in N2
(IR SO2 analyser). Without water, the adsorption capacities measured
at 50 C were 52 and 27 mg/g for the MFI and MOR zeolites, respec-
tively. Adsorption capacities lower than 5 mg/g were obtained at
50 C for the two zeolites in the presence of water.
In the absence of water, the inuence of the Si/Al molar ratio on the
adsorption capacity was also shown by Garcia-Martinez et al. [242] for
two NaY zeolite samples. The NaY zeolites were rst dehydrated at
400 C and then cooled at 30 C and exposed to a gas stream of 0.22%
of SO2 in He (FR = 90 ml/min). The amount of adsorbed SO2 was calcu-
lated by TGA methods. The authors obtained an adsorption capacity of
267 mg/g for the NaY (Si/Al = 9.6) zeolite and showed that, after
10 min in He at 150 C, all the adsorbed SO2 molecules were completely
removed thus conrming that the dehydrated NaY (Si/Al = 9.6) zeo-
lite only physisorbs SO2. On the other hand, decreasing the Si/Al molar
ratio of the NaY zeolite (Si/Al = 5) result in an adsorption capacity
slightly higher with 276 mg/g but only 84% of SO2 was removed after
heat treatment at 150 C in He showing that SO2 molecules were also
chemisorbed.
It is surprising to see that for the NaY zeolite (Si/Al = 9.6) no
chemical adsorption occurs whereas for MOR and MFI-type zeolites
with similar Si/Al ratios (Si/Al = 10) chemical adsorption is observed
(ref [238]). These studies show that the balance between physical and
chemical adsorption is governed by several parameters including the
Si/Al molar ratio, the nature of the counter-ion and the structure of
the zeolite.
A less expensive way to synthesize zeolite consists in the alkaline
attack of coal y ash, having a high content of silica and alumina, by
using concentrated ( 1 M) aqueous solutions of KOH or NaOH,
followed by hydrothermal treatment. However, one drawback fre-
quently reported is the presence of major impurities in the nal zeo-
litic product. Thus, the SO2 adsorption capacities of zeolites
synthesized from y ash are generally lower than those of pure zeo-
lites. Srinivasan et Grutzeck [243] obtained a mixture of analcime
and sodalite after a hydrothermal treatment of 7 days at 150 C of a
y ash (from the United States) previously attacked by 3 M NaOH.
A low adsorption capacity ranging from 6 to 7 mg/g was obtained
for this mixture of analcime and sodalite at 25 C with a gas composi-
tion of 0.20% SO2, 10% O2 and 10% CO2 in N2 (FR = 600 ml/min, UV
vis spectrophotometer). Impure zeolites with major phases such as
Na-chabazite, Na-P1 (gismondine) or KM (phillipsite) were obtained
by Querol et al. [244] by hydrothermal treatment of y ash (from
Spanish) previously attacked by NaOH or KOH. A high purity 4A-X ze-
olite mixture (60:40%) was also obtained by hydrothermal treatment
of high silica solutions extracted from the y ash and attacked by
NaOH 2 M. For such a zeolite mixture (4A-X), a high adsorption ca-
pacity of 297 mg/g was obtained at 25 C (the gas composition tested
was 0.3% SO2 in He and the adsorption capacity was determined by
TGA analysis). The authors explain this high value, which is three
times higher than that of Na-chabazite (99 mg/g), by the presence
of large pore openings mainly in the structure of X zeolite (7 ) and
in a lower proportion in 4A zeolite (4 ) in comparison to those of
Na-chabazite (3.8 ). Adsorption capacities of other zeolites are not
very high and range from 20 to 33 mg/g for Na-P1 and KM zeolites,
respectively.
Besides, few studies were performed by Wei et al. [245247] about
the simultaneous removal of SO2 and NOx in reductive or oxidative con-
ditions by a microwave treatment of some zeolites. A microwave reac-
tor with a mixture of ammonium bicarbonate and zeolite was used to
improve signicantly the desulfurization and denitrication reac-
tions [245]. For a microwave power ranging from 211 to 280 W, the
best purifying efciency for SO2 and NOx, was 99.1 and 86.5%, respec-
tively. The mechanism was described as the microwave-induced
 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100
catalytic reaction between SO2, NOx and a reductive agent i.e. the am-
monium bicarbonate; the zeolite being the catalyst and microwave ad-
sorbent. The reduction of SO2 and NOx by ammonium bicarbonate leads
to the production of native S, N2 and H2O, respectively. The same study
was further performed using a Fe/Ca-5A zeolites [246]. Simultaneous
removal of SO2 and NOx by microwave over zeolite could also be
performed using an oxidative agent such as potassium permanganate
[247]. For a microwave power of 280 W, purication efciency of 95%
for SO2 and 98.2% for NOx were obtained. The oxidation of SO2 and
NOx by potassium permanganate gives rise to the production of sulfates
and nitrates. However, despite the high potential of this technique,
such an application may be difcult to develop at an industrial scale. Be-
sides, Pantazis et al. [248] elaborated copper and cerium-containing
mesoporous silica for the simultaneous reduction of SO2 and NO by
CO leading to elemental sulfur and N2, respectively.
Another cheaper desulfurization route is through the use of natural
porous materials, such as natural zeolites and clay minerals. For
instance, Allen et al. [249] studied SO2 adsorption on a natural
clinoptilolite (Si/Al = 4.7) from Bulgaria after acid modication. The
gas mixture contained 0.7% SO2 in dry air and the adsorption test was
carried out in a xed bed reactor at 25 C. The acid treatment,
performed with HCl or NH4Cl solutions of various concentrations, led
to a strong release of Ca2+ and Na + cations and to a dealumination by
24% of the zeolite, likely to increase the pore volume. After such an
acid modication, a slight increase of the adsorption capacity was
observed.
Several studies reported also the use of natural or synthetic clay
minerals to adsorb SO2 [250256]. Venaruzzo et al. [250] used natural
bentonites from Argentina to study the SO2 adsorption at 25 C. The
bentonite clays were previously activated by acid treatment to remove
the interlayer (Ca +, Na+, K +) and octahedral cations (Mg2+, Fe2+/3+
and Al3+) thus generating an accessible porosity. SO2 adsorption capac-
ities ranging from 40 to 79 mg/g were obtained at 25 C (with pure gas-
eous SO2 using a standard volumetric apparatus) depending on the
nature of the bentonite and the acid treatment. Volzone and Ortiga
[251] studied both the adsorption capacity and the regeneration of a
montmorillonite containing cristobalite as a minor impurity. An adsorp-
tion capacity of around 30 mg/g was found at 25 C (with same ex-
perimental conditions as in Ref [250]). The regeneration of the
montmorillonite was made under boiling water at 100 C during 2 h.
The authors observed that the regeneration process leads to a release
of interlayer cations thus increasing the specic surface area from
73 m 2/g (montmorillonite not regenerated) to 138 m2/g (montmoril-
lonite regenerated 7 times). The increase of the specic surface area
after 7 regeneration cycles slightly increased the adsorption capacity
from 30 to 40 mg/g. Panasyugin et al. [252] modied natural montmo-
rillonites from Georgia using polyhydroxo complexes of several metals
including Fe, Al, Ni or Zr and studied the adsorption capacity at 20 C
using pure SO2. The higher adsorption capacity (88 mg/g) was obtained
for the montmorillonite modied with Fe and Al (SBET = 250 m 2/g).
Pinnavaia et al. [253,254] reported the use of smectite clay minerals
for SOx removal while Albers et al. [255] described a novel process for
SO2 sorption using chlorite-like phyllosilicate materials. An addition of
a NiO-containing montmorillonite to hard coal (ratio 1:500) was
found to reduce signicantly the SO2 emission in the combustion pro-
cess (performed at 900 C) by around 75% [256].
These studies denitely highlight the fact that porous silica mate-
rials such as zeolites mesoporous compounds or clay minerals are in-
teresting materials when used at low temperatures for SO2
capture which mainly proceeds via physical adsorption. However,
most of the ue gases in industry are treated at high temperatures
mainly between 300 and 500 C and the use of only physical sorbents
are not suitable. Therefore, a number of studies mention the incorpo-
ration of heteroelements in porous silica materials to chemically ad-
sorb SO2 mostly as metal sulfates. For instance, Sub and Niiyama
[257] prepared Cu/Y-type zeolites starting from a commercial Y-type
93
zeolite (Si/Al = 2.8) by both ion-exchange and impregnation
methods, using aqueous copper nitrate solutions at different concen-
trations. The Cu/Y zeolites were further calcined at 500 C during 5 h
to form CuO/Y zeolites containing 3, 6, 11 and 33 wt.% copper. The
gas was 0.34% SO2 in air (FR = 250 ml/min), the temperature
450 C and the adsorption capacity was monitored by an IR SO2
analyser. The CuO/Y zeolite adsorbed SO2 as copper sulfate and the
sorbent loaded with 33% wt. in copper showed the best performance
with an adsorption capacity of 165 mg/g. Furthermore, the sorbent
could be fully regenerated by using a reductive ow of 5% H2 in N2 at
450 C and the adsorption capacity maintained constant up to 15 re-
generation cycles. Dathe et al. [258] studied the SO2 adsorption capac-
ity at 200 C (gas feed composition of 0.005% SO2, 5% O2 in He, FR =
200 ml/min, uorescence detector) of various metals (Cu, Fe, Ba,
Mg and Al) impregnated on zeolites such as ITQ-2, MCM-36 and
MCM-22 and compared them to commercial metal oxide supports.
In general, the adsorption capacities of the MCM-36 zeolites
(SBET = 350750 m 2/g) are higher than non-modied zeolites but
they stay lower than those of commercial metal oxide supports. Natu-
ral clinoptilolites from Bulgaria, chemically modied with several
metal salt solutions via the ion-exchange method, were prepared by
Ivanova and Koumanova [259] to study SO2 adsorption at 25 C only.
Modied clinoptilolites containing transition metal ions such as Cu +,
Co 2+, Cd 2+ or Mn 2+ showed the highest adsorption capacities with
values ranging from 71 to 85 mg/g (gas composition of 0.65% SO2 in
a model gasdry air mixture, FR = 2750 ml/min; the adsorption ca-
pacity was determined by iodometric titration). After heating to
360 C at a rate of 5 C/min under dry air, most of the sorbents (espe-
cially the modied clinoptilolites containing transition metal ions)
were not fully regenerated except when the added metal was Co 2+.
However, no adsorption tests at higher temperatures were performed.
Modied clinoptilolites containing alkaline and alkaline earth metals
showed good regeneration capability (with amounts of undesorbed
SO2 lower than 3%). Teraoka et al. [260] used a conventional volumet-
ric apparatus to study the adsorption of pure SO2 at 25 C on Y-type
zeolites containing alkaline (Li +, K +) and alkaline earth metals
(Mg 2+, Ca 2+, Sr 2+, Ba 2+). The various samples were prepared
by the ion-exchange method performed on a commercial NaY
(Si/Al = 5.1) zeolite at 75 C for 24 h in aqueous acetates (K, Mg) or
nitrates (other cations) solutions. Under these experimental condi-
tions, Y-type zeolites containing alkaline metals showed the best ad-
sorption capacities with values of 365, 373 and 387 mg/g for K +, Li +
and Na +, respectively. It should also be noted that Y-type zeolites
adsorbed more SO2 (387 mg/g) than MFI (198 mg/g) and mordenite
(204 mg/g) indicating that the pore volume is an important parame-
ter for the adsorption capacity.
Recently, a MCM-41 mesoporous sorbent containing copper oxide,
cerium oxide and LiCl was investigated by our group [261] for the ad-
sorption of SO2 at 400 C. The gas mixture used was 0.025% of SO2,
10% O2 in N2 (FR = 14.7 ml/min, UV analyzer). The modied
MCM-41 sorbent (7.2 wt.% Cu, 5.2% Ce and 0.8% Li) was found to
have a high adsorption capacity of 130 mg SO2/g at 400 C. The com-
bination of a SOx trap (copper oxide), an oxidation promoter (cerium
oxide) and lithium chloride to assist the sulfation reaction was found
to be necessary to reach a high SOx removal activity.
Table 5 summarizes the results along with the characteristics (na-
ture of the adsorbent, SO2 adsorption capacity) and experimental
conditions (FR, gas composition and temperature) of the main studies
reported in the literature devoted to the use of porous silica-based
materials for SO2 removal.
6. Regeneration by thermal decomposition of the metal sulfates
Once the sulfation reaction has taken place, the metal sulfates
formed on the support must be decomposed for another adsorption
cycle. This reaction can be performed by heating under a reductive
94 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100

Table 5
Main studies devoted to the use of porous silica-based materials for DeSOx.

Porous solids SBET Cads FR Gas composition (vol.%) T (C) Ref

(zeolite structure type) (m2/g) (mg/g) (ml/min)
SO2 O2 CO2 Balance

Silicalite-1 530 150 0.05 9.4 10.3 N2 0150 [228]

(MFI) 838 150 0.19 10.1 10.3 N2 25800 [229]
420 10916 100 0.4 0 0 Air 25100 [230]
DAY (FAU) 710 165
Y (FAU) 387 170 135 1.85 0 0 N2 25 [231]
NaY (Si/Al = 9.6) 267 90 0.22 0 0 He 30 [242]
(FAU) (Si/Al = 5) 276
Y (K+, Li+ or Na+) 365387 a 100 0 0 0 25 [260]
(FAU)
CuO/Y (33 wt.% Cu) 160 250 0.34 0 0 Air 450 [257]
(FAU)
Modied clinoptiloliteb 7185 2750 0.65 0 0 Air 25 [259]
(HEU)
Analcime + sodalitec 67 600 0.2 10 10 N2 25 [243]
(ANA) + (SOD)
4A + Xc 297 3060 0.3 0 0 N2 25 [244]
(LTA) + (FAU)
Na-chabazitec (CHA) 99
Mordenite (MOR) 28164d 150 0.2 0 0 N2 50 [240]
(5.5 Si/Al 17.5)
ZSM-5 (MFI) 3080d
(13 Si/Al 75)
Mordenite (MOR) 27 0.18 0 9 N2 50 [241]
(Si/Al = 10)
ZSM-5 (MFI) 52
(Si/Al = 13)
ZSM-5 (MFI) 1393d 2000 0.2 0 0 N2 50 [238]
(13 Si/Al 175)
Mordenite (MOR) 25171d
(5.5 Si/Al 17.5)
Montmorillonite 73 30e 100 0 0 0 25 [251]
FeAl/montmorillonite 250 88 100 0 0 0 20 [252]
Bentonite 264f 4079 100 0 0 0 25 [250]
TEA/SBA-15g 118 177 312 0.13 0 13.4 N2 25 [232]
Li-doped/MCM-41h 453 130 14.7 0.025 10 0 N2 400 [261]
a
Not reported.
b
Modied clinoptilolites containing transition metal ions such as Cu+, Co2+, Cd2+ or Mn2+.
c
Zeolites obtained by alkaline attack of coal y ash.
d
In the presence of 3.2% H2O in the gas composition, Cads b 10 mg/g.
e
After 7 regenerations, Cads = 40 mg/g and SBET = 138 m2/g.
f
SBET = 264 m2/g for the best sample (Cads = 79 mg/g).
g
SBA-15 with surface modied by TEA (80% TEA loading ratio).
h
Sorbent containing CuO, CeO2 and LiCl (7.2 wt.% Cu, 5.2% Ce and 0.8% Li).

gas ow (CH4, H2 or NH3). However, undesired reactions often oc-
curred such as: over-reduction (for instance formation of Cu2O in
the case of CuO/-Al2O3 sorbent); formation of native S or toxic
H2S. Thus, a more common approach consists in a thermal regenera-
tion under air or N2 which is also a less expensive route. Numerous
works were devoted to study the decomposition of metal sulfates
under air or N2. Most of these studies were carried out by TGA and
DTA. The thermodynamic properties, kinetics parameters and decom-
position temperatures of several metal groups, including transition
metals (Cu, Zn, Fe, Ti, Co, Zr), rare earth metals (Ce, La) and others
(Sn, Al) were investigated. The thermal stability of the sulfate anion
was found to strongly depend on the nature of the metal cation
[262]. The stability also decreased with the polarizing power of cat-
ion. Counter-ions with large sizes and high charges facilitate the de-
composition. The general literature available shows different initial
thermal temperature decomposition of metal sulfates under air or
N2. In most cases, the decomposition products are the metal oxide
and SO3. For a given metal sulfate, various decomposition data are
often reported and, for some metals, literature may differ as to the ex-
istence or not of intermediate oxysulfates species.
Table 6 summarizes the main thermal decomposition data of sev-
eral metal sulfates interest in desulfurization (decomposition in air or
in N2). Among the metals investigated, copper, magnesium, alumi-
num and cerium oxides were particularly studied due to their
favorable reactivity of their oxides towards SOx. Mu and Perlmutter
[263] showed that the thermal decomposition of CuSO4 under N2
started at around 572 C leads to the formation of an oxysulfate
CuO.CuSO4 as an intermediate compound and ended slightly above
700 C with CuO as the end product. Other authors did not mention
this intermediate product and considered only the decomposition of
CuSO4 into CuO. According to Wendlandt et al. [264], a loss of water
between 100 and 300 C was observed for CuSO45H2O followed by
the decomposition of CuSO4 around 500 C. Tagawa [265] studied
the decomposition of copper sulfate under both N2 and air ow. By
decreasing the rate of heating (from 5 C/min to 2 C/min), the initial
decomposition temperature was found to decrease by around 20 C
(561 to 538 C and 605 to 586 C under N2 and air, respectively).
Siriwardane et al. [266] showed that the decomposition of CuSO4 oc-
curred between 600 and 840 C via the formation of an oxysulfate.
Stern [262] showed that the decomposition of hydrated MgSO4
occurred at between 1000 and 1200 C. However, an initial decompo-
sition temperature of 780 C was given by Mu and Perlmutter [263]
and the corresponding oxide MgO was detected around 980 C.
Regarding the decomposition of the hydrated aluminum sulfate
(Al2(SO4)316H2O), Gruver [267] showed that the dehydration oc-
curred between 100 and 350 C followed by the formation of the cor-
responding oxide Al2O3 at 850 C. Based on the work by Wendlandt
et al. [264], the loss of water occurred between 200 and 500 C and
 Y. Mathieu et al. / Fuel Processing Technology 114 (2013) 81100 95

Table 6 the relatively cheap starting materials, its widespread manufacturing

Initial and nal decomposition temperatures of several metal sulfates. process and its popular use in chemical engineering. The main draw-
Name Dehydration Anhydrous sulfate decomposition Ref back of this kind of support lies in its moderate specic area proper-
ties, in the range of 100350 m 2/g, which is only of the textural
T (C) Initial T (C) Final T (C)
type, as compared with those offered by alternative other supports
N2 air N2 air
such as the porosity offered by silica materials or ACFs (up to
Al2(SO4)316H2O 25 to 350 580 a 805 [263] 1000 m 2/g).
500 524 [265]
As far as AC materials are concerned, they boast low cost provided
750 900 [267]
CaSO42H2O 100 to 300 >1100 >1320 [267]
they originate from natural sources (coal). However, after the incor-
1240 1450 [268] poration of the active metal oxides, they lose a large fraction of
Ce2(SO4)3 / 650 666 [265] their porosity, thus leading generally to middle adsorption capacity
750 830 [269] performances. Another important drawback of AC supports is the
Ce(SO4)24H2O 75 to 500 600 860b [270]
consumption of carbon by oxidation at high temperature, which
25 to 322 379 383c [265]
322 360 390c [269] leads to limited sorbent life after repeated adsorptionregeneration
CuSO45H2O 35 to 230 572 678d [263] cycles. ACFs are interesting supports since they boast high specic
561 605 [265] surface areas (13002000 m 2/g) at the expenses of cost since they
600 840 [266] are obtained by pyrolysis and high temperature activation of expen-
CuSO4 / 625 800e [271]
Fe2(SO4)3xH2O 25 to 260 494 635 [263]
sive precursor polymers (polyacrylamide, polyacronitrile, etc.). Fur-
485 545 [265] thermore, they face the similar regeneration limitations as ACs.
550 650 [272] Mixed oxides derived from clay-like materials such as hydrotalcites
500 600 [266] are reported to exhibit high adsorption capacities and as excellent, high
MgSO47H2O 25 to 290 780 980 [263]
temperature DeSOx materials in FCC units. However, their efciency for
>1000 b1300 [267]
803 849 [265] FGD at 300400 C is not well established. Moreover, only a limited
1130 [273] number of studies have been performed under conditions similar to
MnSO4 / 693 717 [265] those of FCC units namely to evaluate the impact of CO2 or H2O on the
NiSO46H2O 50 to 450 675 [271] DeSOx performance.
700 950 [266]
SnSO4 / 290 620 [263]
In this context, micro- and mesoporous silica based materials are
Ti(SO4)2xH2O 25 to 260 540 580 [274] among the most promising supports as they exhibit a large specic sur-
a face (7001200 m 2/g) and a high thermal stability (7001200 C). An-
Not reported.
b
Oxysulfate between 400 and 946 C. other strong advantage is that the silica support is completely inert
c
Ce2(SO4)3 intermediary decomposition. towards SOx in contrast to single oxides or mixed oxides where bulk
d
Oxysulfate decomposition between 660 and 704 C. sulfations can occur. The incorporation of heterolements in these mate-
e
Oxysulfate decomposition. rials is particularly easy and can be performed via ion exchange, in situ
incorporation or wet impregnation. Their costs are generally lower than
those of ACFs.
the decomposition of the anhydrous sulfate started at around 700 C Mesoporous materials with pores in the range of 2030 (for
and ended at 900 C with the formation of Al2O3. Mu and Perlmutter MCM-48), 2545 (for MCM-41) or 70100 (SBA-15) have been stud-
[263] gave 580 C and 805 C as the initial/nal decomposition tem- ied for the removal of H2S but have not been well investigated as alter-
perature of this anhydrous sulfate. Some metal sulfates, such as: native metal oxide supports for the removal of SOx [275277]. A
Fe2(SO4)3xH2O, SnSO4 and Ti(SO4)2xH2O, were found to decom- number studies mention a signicant improvement of the catalytic
pose at relatively low temperature under air or N2; however, the per- performance of these materials when metal oxide nanoparticles are
formances of their respective oxides in SOx removal was not clearly conned inside the porosity. Thus, the incorporation of metal
established. Another aspect of interest is the effect of some third com- oxide nanoparticles in the pores of zeolites or mesoporous materials
pounds on the decomposition of metal sulfates, which was studied by looks to offer promising prospects for the enhancement of DeSOx
Mu and Perlmutter [263]. Carbon and NaCl were found to decrease by performances.
20 to 220 C the decomposition temperatures, depending on the
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