Applied Catalysis B: Environmental 57 (2005) 125–137

www.elsevier.com/locate/apcatb

Novel Zn–Ti-based mixed metal oxides for low-temperature

adsorption of H2S from industrial gas streams
K. Polychronopouloua, J.L.G. Fierrob, A.M. Efstathioua,*
a
Department of Chemistry, University of Cyprus, P.O. Box 20537, CY 1678 Nicosia, Cyprus
b
Instituto de Catálisis y Petroleoquimica, CSIC, C/Marie 2, Cantoblanco, 28049 Madrid, Spain
Received 30 August 2004; received in revised form 28 October 2004; accepted 29 October 2004
Available online 8 December 2004

Abstract

The efficiency of various Zn–Ti-based mixed metal oxides prepared by the sol–gel method towards H2S adsorption from a gas mixture
containing 0.06 vol.% H2S, 25 vol.% H2, 7.5 vol.% CO2 and 1 vol.% H2O was studied in the 25–100 8C range. The effects of the chemical
nature of a third metal additive (M = Mn, Cu, Mo) and its at.% composition in the M–Zn–Ti–O solid on the H2S adsorption and regeneration
performance of the latter were studied. The nominal chemical composition (metal at.%) of the solid adsorbent was found to have an important
effect on the number, chemical composition and particle morphology of the crystal phases formed. It was found that the mixed metal oxides
with compositions 20Zn–80Ti–O and 40Zn–60Ti–O present higher maximum H2S uptakes than ZnO and TiO2 solids also prepared by the
sol–gel method. In addition, the Zn–Ti–O mixed metal oxides showed higher H2S uptakes after regeneration with 20% O2/He in the 500–
750 8C range compared to the ZnO and TiO2 solids. It was found that the10Mn–45Zn–45Ti–O solid results in higher H2S uptakes than a
commercial Ni-based H2S adsorbent in the 25–50 8C range. The effectiveness of the regeneration procedure of the 10Mn–45Zn–45Ti–O solid
following sulfidation was found to be in the 45–170% range depending on the sulfidation temperature and regeneration conditions applied.
The solid with composition 10Cu–45Zn–45Ti–O calcined at 200 8C (after synthesis) exhibited three times higher H2S uptakes at 25 8C than a
commercial Ni-based adsorbent, result not obtained at higher calcination temperatures.
# 2004 Elsevier B.V. All rights reserved.

Keywords: H2S adsorption; Zn–Ti-based mixed metal oxides; Regenerable H2S adsorbents; Transient adsorption; H2-TPR

1. Introduction literature for the development of low-temperature H2S

Hydrogen sulfide and other sulfur-containing compounds
can be present in natural gas and other industrially important
hydrocarbon feedstocks [1,2]. These impurities need to be
removed to less than few ppmv since they are extremely
toxic and odorous and poison many transition metal-based
catalysts, such as supported Ni used in steam reforming of
hydrocarbon reactions [2]. Furthermore, hydrogen sulfide in
excess of 3 ppmv causes pipeline corrosion and limits plant
lifetime [1].
The removal of H2S at high temperatures (ca. 350 8C) has
been extensively studied but little work has appeared in the
* Corresponding author. Tel.: +357 2 2892776; fax: +357 2 2892801.
E-mail address: efstath@ucy.ac.cy (A.M. Efstathiou).
adsorbents [1]. Westmoreland and Harrison [3] have shown
that sulfidation of the oxides of Fe, Mn, Zn, Ca, V, Cu, Co
and W is thermodynamically feasible at temperatures above
300 8C. A kinetic study of the reaction of H2S with MnO,
CuO, ZnO, V2O3 in the 300–800 8C range has shown that
this is first order with respect to H2S [4]. Ahmed et al. [5]
have found that zinc ferrites exhibit high reactivity towards
H2S in the 600–650 8C range. These adsorbents have also
shown good regeneration performance in oxidant atmo-
spheres but progressive decay of their sulfidation activity,
loss of adsorption efficiency and degradation of their
mechanical properties, especially when used in fluidized-
bed reactor applications, in multi-cycle tests.
The first hydrogen sulfide adsorbents used at low
temperatures can be traced back to the purification of coal

0926-3373/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2004.10.017
126 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137
gas using hydrated iron oxides [6,7]. One disadvantage of
using such solid adsorbents is that their regeneration with air
is rapid, exothermic and potentially hazardous in the
presence of a combustible gas. On the other hand, it was
reported [8,9] that zinc sulfide is much less susceptible in air
than iron sulfide. The presence of water is a crucial
parameter that affects the adsorbing ability of a solid
towards H2S. Kinetic studies of the reaction of ZnO with
H2S at ambient temperatures have shown that water has an
autocatalytic effect on the reaction rate [10]. In order to
improve the ZnO performance in multicycle adsorption tests
of H2S, addition of some inorganic oxides has also been
proposed [11]. The addition of TiO2 was found to increase
the stability of ZnO through the formation of other mixed
metal oxides, such as Zn2TiO4, a spinel structure-like
compound [11].
As previously mentioned, little research work has been
published in H2S adsorption on solid surfaces at low
temperatures. Carnes and Klabunde [12] have studied
nanocrystalline metal oxides prepared by sol–gel methods.
At low temperatures (25–100 8C), the activity order was
ZnO > CaO > Al2O3
MgO. Davidson et al. [13] have
reported on the adsorption of H2S on ZnO in the 25–45 8C
range, where about 40% conversion of H2S was observed.
Sasaoka et al. [14] have also studied the adsorption of H2S
on ZnO in the presence also of CO, CO2 and H2O. They
have found that CO inhibits sulfidation reaction due to its
competitive adsorption for the same active sites, while H2O
inhibits the reaction due to promotion of the reaction with
ZnS to form H2S and ZnO. Baird et al. [15] have found that
the mineral feroxyhite is an efficient adsorbent of H2S at
room temperature due to its high surface area and the
presence of the redox couple of Fe3+/Fe2+. In another
study, Baird et al. [2] have found that reaction of H2S with
ZnO doped with first-row transition metals was restricted
to about 0.6 surface monolayers. The main role of the
transition metal oxide is to increase the total surface area
available for reaction with H2S. Baird et al. [16] have also
studied Co–Zn–Al–O mixed metal oxides as adsorbents of
H2S at 28 8C. A comparison of the H2S uptakes with those
of Co–Zn–O suggested that the presence of aluminum ions
in the mixed oxide gave rise to an increased surface area
but not of H2S uptake. Other H2S adsorbent materials
investigated are the activated carbons [17,18]. It is well
known that besides the high surface area of these materials,
the surface chemistry of carbons plays an important role in
the adsorption of gases of basic nature due to their acidic
properties.
Based on the various studies reported in the literature, an
ideal metal oxide adsorbent of H2S present in an industrial
gas-stream must have the following properties: (i) good
capability of regenerating the metal sulfide formed into the
initial metal oxide, (ii) durable in highly reducing gas
atmospheres and adsorption temperatures, (iii) highly
reactive towards H2S, (iv) suitable pellet morphology and
porosity to promote diffusion ability and increasing
reactivity, and (v) able to minimize undesired reactions
under reducing gas and regeneration conditions [19].
The present work concerns the development of novel Zn–
Ti-based mixed metal oxides prepared by the sol–gel method
and tested for the first time towards low-temperature
adsorption of H2S from a gas mixture containing also H2,
CO2 and H2O. The effects of the following fundamental
parameters on the H2S adsorption performance of various
mixed metal oxides prepared by the sol–gel method have
been studied: (a) metal oxide composition, (b) temperature
of adsorption, (c) temperature of adsorbent regeneration in
20% O2/He, (d) time of regeneration in 20% O2/He, and (e)
presence of water in the feed stream. Hydrogen sulfide
adsorption studies on a commercial Ni-based catalyst were
also conducted for a critical comparison. The present work
was motivated by a European research project [20] where the
water effluent stream of a bioreactor used to reduce toxic
Cr6+ into Cr3+ by the use of sulfate metal reducing bacteria
(SMRB) had to be cleaned from the non-desirable H2S gas.
2. Experimental
2.1. Synthesis of adsorbent solid materials
The Zn–Ti–O mixed metal oxides were prepared by the
sol–gel method [21] using (CH3COO)2Zn and Ti(i-OPr)4
(Aldrich) as precursors of Zn and Ti, respectively.
Appropriate amounts of each reagent were used so as to
obtain a Zn/(Zn + Ti) metal atom ratio of 0.0, 0.2, 0.4, 0.5
and 1.0 in the final product. The synthesis procedure was as
follows. Appropriate amounts of (CH3COO)2Zn and
titanium isopropoxide were dissolved in H2O and propa-
nol-2, respectively. The zinc acetate solution pH was
adjusted to the value of 8.8 by dropwise addition of ammonia
solution (25%, v/v). The solution of titanium isopropoxide
was added to that of zinc acetate and the resulting solution
was kept at 60 8C under continuous stirring until a gel was
obtained.
The M–Zn–Ti–O (M = Mn, Cu, Mo) mixed metal oxides
were also prepared by the sol–gel method using
(CH3COO)2Mn, Cu(NO3)2, MoOCl2, (CH3COO)2Zn and
Ti(i-OPr)4 (Aldrich) as precursors of Mn, Cu, Mo, Zn and Ti,
respectively. The exact amount of each reagent was
calculated so as to obtain a M/(M + Zn + Ti) metal atom
ratio of 0.1, 0.4 and 0.8 in the final product. The synthesis
procedure was as follows. An appropriate amount of
(CH3COO)2Zn was dissolved in H2O and the solution pH
was adjusted to the value of 8.4 by dropwise addition of
ammonia solution (25%, v/v). After pre-hydrolysis of the
zinc acetate solution had taken place, the solutions of
manganese acetate (copper nitrate or molybdenum oxy-
chloride) and titanium isopropoxide were added. The solid
samples after synthesis and drying (overnight at 120 8C)
were first calcined in air at 200 8C for 2 h and then at 500 8C
for 4 h before storage and further use. A reference to an H2S
 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137
solid adsorbent in the rest of the text will be according to the
following example. A 10Mn–45Zn–45Ti–O solid sample
will be referred to a mixed metal oxide having a metal atom
composition of 10% Mn, 45% Zn and 45% Ti.
2.2. Characterization of adsorbent solid materials
2.2.1. Surface area measurements
The specific surface area (m2/g) of all solid adsorbents
was checked by N2 adsorption at 77 K (BET method) using a
multipoint Micromeritics 2100E system. Before any
measurements were taken, the samples were outgassed at
400 8C under vacuum (P  1.3  103 mbar). The specific
surface area of the best adsorbents in terms of H2S uptake
(mmol/g) was measured following adsorption from a H2S/
H2/CO2/He gas mixture and regeneration of the sulfided
adsorbent in 20% O2/He.
2.2.2. XRD analyses
The crystal structures of the sol–gel prepared solids were
checked by XRD measurements (SIEMENS Diffract 500
system, Cu Ka radiation (l = 1.5418 Å)). The crystal
structures of the best adsorbents were also determined after
sulfidation (use of H2S/H2/CO2/He gas mixture) and
regeneration in 20% O2/He gas mixture.
2.2.3. Scanning electron microscopy (SEM) studies
The particle size and morphology of the solids (fresh,
after sulfidation, and also after regeneration) were examined
through a JEOL JSM 5200 scanning electron microscope
(25 kV). Powdered specimens were spread on the SEM slabs
and sputtered with gold.
2.2.4. H2 temperature-programmed reduction studies
H2 temperature-programmed reduction (TPR) experi-
ments were conducted by passing a 2% H2/He gas mixture at
a flow of 50 N mL/min over 0.2 g of the precalcined (20%
O2/He, 500 8C, 2 h) adsorbent solid and using a linear
temperature-ramp of 30 8C/min. The H2 concentration
(mol%) as a function of temperature was monitored using
an on line mass spectrometer (Omnistar, Balzers). The mass
numbers (m/z) 2, 18 and 32 were used for H2, H2O and O2,
respectively. Based on a material balance, the rate of
hydrogen consumption (mmol/g min) versus temperature
was estimated.
2.2.5. Temperature-programmed desorption studies
Temperature-programmed desorption (TPD) of NH3 and
CO2 experiments were conducted in order to measure the
surface acidity and basicity of the H2S solid adsorbents,
respectively. The amount of sample used was 200 mg, the
heating rate was 30 8C/min, and the He gas flow rate was
30 N mL/min. The mass numbers (m/z) 15, 30 and 44 were
used for NH3, NO and N2O (NH3-TPDs), while the (m/z) 28
and 44 were used for CO and CO2, respectively (CO2-
TPDs). Ammonia and carbon dioxide chemisorption was
127
conducted at room temperature over the series of: (a) Zn–Ti–
O, (b) Mn–Zn–Ti–O, (c) Cu–Zn–Ti–O and (d) Mo–Zn–Ti–O
mixed metal oxides. Before NH3 and CO2 chemisorption,
the sample was pretreated in 20% O2/He gas mixture at
500 8C for 2 h. NH3-TPD and CO2-TPD experiments were
also conducted following H2S adsorption and regeneration
of the sulfided adsorbent in order to study the effects of
sulfidation and regeneration procedures on the acid–base
surface properties of the solid.
2.2.6. X-ray photoelectron spectroscopy studies
The surface chemical composition (at.%) of certain H2S
solid adsorbents was studied by X-ray photoelectron
spectroscopy (XPS). The sample in powder form was
pressed firmly into a carved stainless-steel holder and then
introduced into the ultra high vacuum (UHV) chamber.
The UHV system (base pressure < 1  107 Pa) consisted
of a fast entry assembly, preparation and analyses
chambers. The UHV system was equipped with a
hemispherical analyzer (SPECS LH-10) and a twin-anode
X-ray gun. High-resolution spectra were recorded in the
constant pass energy mode at 20 eV. Under these
conditions, the Au 4f7/2 line was recorded with 1.25 eV
FWHM at a binding energy of 83.9 eV. The spectrometer
energy scale was calibrated using Ag 3d5/2 and Au 4f7/2
photoelectron lines at 368.1 and 83.9 eV, respectively. The
ECLIPSE software package was used for data acquisition
and analysis. Peak intensities were estimated by calculat-
ing the integral of each peak after smoothing and
subtraction of Shirley-type background. Atomic surface
concentrations were estimated from the areas of the peaks,
corrected using the corresponding sensitivity factors [22].
Charge referencing was carried out against adventitious
carbon (C 1s at 284.9 eV).
2.2.7. Transient adsorption studies
The gas flow-system used for conducting transient
experiments (e.g., adsorption of H2S, NH3- and CO2-TPDs)
consisted of a flow measuring and control system (MKS
Instruments, Model 247C), mixing chambers and a quartz
fixed-bed microreactor (2 ml nominal volume). The gas
flow-system, the microreactor and the analysis system have
been described elsewhere [23]. The H2S adsorption capacity
of the solids was determined by transient isothermal
adsorption experiments using a 0.06% H2S/25% H2/7.5%
CO2/He gas mixture at temperatures in the 25–100 8C range.
Before adsorption was taken place, the fresh catalyst sample
was pretreated in 20% O2/He at 500 8C for 2 h and then
purged in He gas at 500 8C to insure a ‘‘surface-free’’ from
adsorbed water and carbon dioxide present in ambient air.
The reactor was then cooled in He to the adsorption
temperature.
The amount of solid adsorbent used was 5 mg diluted in
45 mg of SiO2, while the total flow rate was 30 N mL/min.
Chemical analysis of the gas effluent stream of reactor
during transients was done with an on line quadrupole mass
128 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137

spectrometer (Omnistar, Balzers) equipped with a fast

response inlet capillary/leak valve (SVI 050, Balzers) and
data acquisition systems. The mass numbers (m/z) 34, 64,
44, 18 and 32 were used for H2S, SO2, CO2, H2O and O2
during H2S transient adsorption experiments. Before any
measurements were taken, the materials were pretreated in
20% O2/He at 500 8C for 2 h.

3. Results and discussion

Fig. 1. XRD patterns of 10Mn–45Zn–45Ti–O solid. (a) Fresh (calcined in
20% O2/He, 500 8C, 4 h); (b) after sulfidation (H2S/H2/CO2/He, 100 8C,
3.1. Catalyst characterization
0.5 h); (c) after sulfidation followed by regeneration (20% O2/He, 750 8C,
10 h). XRD peaks: (1) ZnO, (2) ZnTiO3, (3) ZnMnO3, (4) ZnS, (5) MnS and
(6) ZnxMn1xS.
3.1.1. BET surface area measurements
The BET areas of the mixed metal oxides of the Zn–Ti–O
series (fresh solids) investigated were found to be in the 100– results to be presented next which point out the change in
140 m2/g range with the highest value of 137 m2/g exhibited crystal size and morphology of the adsorbent occurred after
by the solid with 40 at.% Zn content (Table 1). The BET area sulfidation and regeneration procedures were applied. The
of the latter solid, which exhibited the largest H2S uptake, surface area of the Cu–Zn–Ti–O series of fresh solids was
was reduced to 67 m2/g following sulfidation at 100 8C (see found to decrease with increasing Cu-content in the final
Table 1). After regeneration with 20% O2/He at 750 8C for mixed metal oxide system (Table 1) in agreement with XRD
10 h a severe reduction in its specific surface area (3 m2/g) results to be presented next. The same behavior was obtained
was noticed. Sasaoka et al. [24] have reported the synthesis with the Mo–Zn–Ti–O series of solids (Table 1).
of a 50 mol% ZnO–50 mol% TiO2 solid with BET area of
5.3 m2/g, much lower than the value of 113 m2/g obtained 3.1.2. XRD studies
for the present 50Zn–50Ti–O solid of similar composition. Fig. 1 shows the XRD patterns of the 10Mn–45Zn–45Ti–
The surface area of the Mn–Zn–Ti–O series of solids was O solid as prepared (Fig. 1a, see Section 2.1), after used in
found to decrease with increasing Mn-content (see Table 1), H2S adsorption studies (Fig. 1b), and after used in H2S
while the BET area of the fresh 10Mn–45Zn–45Ti–O solid adsorption studies followed by regeneration in a 20% O2/He
(103 m2/g) was reduced to 34 m2/g following sulfidation at gas mixture at 750 8C for 10 h (Fig. 1c). The main crystalline
100 8C for 0.5 h. After regeneration with 20% O2/He at phases detected in the fresh solid according to ASTM data
750 8C for 10 h a further decrease was noticed (22 m2/g, were ZnO (1) and ZnTiO3 (2), while ZnMnO3 (3) appeared
Table 1). These BET results are in harmony with SEM as a minor phase. The main crystalline phases of the fresh
40Mn–30Zn–30Ti–O solid (not shown) were ZnO, MnO2,
Mn2O3 and ZnTiO3, while those of 80Mn–10Zn–10Ti–O
Table 1 solid (not shown) were Mn2O3, MnO2, TiO2 and ZnTiO3
BET surface areas (m2/g) of various mixed metal oxides obtained after
(Table 2).
different gas treatments
Mixed metal oxide BET (m2/g)
Fresha Usedb Regeneratedc Table 2
20Zn–80Ti–O 98 XRD crystalline phases of various H2S solid adsorbents prepared by the sol–
40Zn–60Ti–O 137 67 3 gel method
50Zn–50Ti–O 113 Solid adsorbenta Crystalline phases
10Mn–45Zn–45Ti–O 103 34 22 40Zn–60Ti–O ZnTiO3
40Mn–30Zn–30Ti–O 74 50Zn–50Ti–O ZnTiO3, Zn2TiO4
80Mn–10Zn–10Ti–O 20 40Mo–30Zn–30Ti–O MoO3, MoO2, TiMoO5, TiO2, ZnO,
ZnTiO3 (major); ZnMoO4 ZnMo8O10 (minor)
10Cu–45Zn–45Ti–O 165
10Cu–45Zn–45Ti–O No crystallinity was observed
40Cu–30Zn–30Ti–O 61
40Cu–30Zn–30Ti–O No crystallinity was observed
80Cu–10Zn–10Ti–O 9
80Cu–10Zn–10Ti–O CuO, Cu2O (major); ZnTiO3 (minor)
10Mo–45Zn–45Ti–O 60 10Mn–45Zn–45Ti–O ZnO, ZnTiO3 (major); ZnMnO3 (minor)
40Mo–30Zn–30Ti–O 9 40Mn–30Zn–30Ti–O ZnO, MnO2, Mn2O3, ZnTiO3
a
After calcinations in 20% O2/He gas mixture at 500 8C for 4 h. (major); ZnMnO3 (minor)
b
After sulfidation (0.06% H2S/25% H2/7.5% CO2/He) at 100 8C for 80Mn–10Zn–10Ti–O TiO2, ZnTiO3, MnO2, Mn2O3 (major);
0.5 h. ZnMnO3, ZnO (minor)
c a
After sulfidation (0.06% H2S/25% H2/7.5% CO2/He) at 100 8C for The solids were calcined in 20% O2/He at 500oC for 4 h before XRD
0.5 h followed by regeneration with 20% O2/He at 750 8C for 10 h. measurements were taken.
 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137 129

After exposed to the H2S/H2/CO2/He gas mixture at

100 8C for 0.5 h, the 10 Mn–45Zn–45Ti–O solid exhibited
some diffraction peaks that were not observed in the
fresh solid (compare Fig. 1a and b). For example, the new
peaks appeared at 2u = 26.48, 48.98 and 55.58 correspond to
ZnS (4), while the peaks at 26.48 and 48.98 correspond also
to MnS (5). The XRD peak at 35.58 obtained in the fresh
solid disappeared after sulfidation, result that suggests that
some structural changes in crystal phases occurred. Minor
phases of ZnMnO3 (3) and ZnxMn1xS (6) were also
observed (Fig. 1b).
The solid after sulfidation followed by regeneration in
20% O2/He at 750 8C for 10 h presented broad diffraction
peaks of very low intensity (Fig. 1c). The latter may indicate
that the solid was transformed into an amorphous material.
From the results of Fig. 1 it is clear that structural changes
had been occurred in the initial oxide lattices of ZnO and
ZnTiO3 after H2S adsorption, and a mixture of metal oxides
and metal sulfides is obtained following the applied H2S
adsorption conditions. The crystalline phases detected in all
fresh solid adsorbents prepared by the sol–gel method and
tested for their H2S adsorption performance are listed in
Table 2.

3.1.3. SEM–EDX studies

Fig. 2 presents SEM micrographs of the 10Mn–45Zn–
45Ti–O solid after calcined at 500 8C (Fig. 2a, Section 2.1),
and after sulfidation (H2S/H2/CO2/He, 100 8C, 0.5 h) (Fig.
2b) and regeneration in 20% O2/He at 750 8C for 10 h (Fig.
2c). The fresh solid calcined at 500 8C consists of large
particles (Fig. 2a). However, after exposed to the H2S/H2/
CO2/He adsorption gas mixture the morphology of the
particles drastically changed (compare Fig. 2a and b), where
part of the solid shows rod-like shape with triangular cross-
section. After sulfidation and regeneration, the morphology
of the solid particles was changed again (Fig. 2c). However,
in this case a rather uniform particle size distribution and
morphology are obtained. As previously mentioned, a very
important experimental parameter that affects the morphol-
ogy and size distribution of solid particles is the synthesis
route (e.g., sol–gel versus precipitation) and the experi-
mental parameters used (e.g., pH and temperature). Fig. 2. SEM photographs of the 10Mn–45Zn–45Ti–O solid. (a) Fresh
In the case of 40Cu–30Zn–30Ti–O and 40Mo–30Zn– (calcined in 20% O2/He, 500 8C, 4 h); (b) after sulfidation (H2S/H2/CO2/
30Ti–O solid adsorbents, the nature of the third metal He, 100 8C, 0.5 h); (c) after sulfidation followed by regeneration (20% O2/
He, 750 8C, 10 h).
additive (Cu or Mo) used in the sol–gel synthesis of M–Zn–
Ti–O mixed metal oxides largely affected the morphology
and particle size of the final solid. In particular, the particle ducted on the 40Mo–30Zn–30Ti–O solid in different
morphology of the 40Cu–30Zn–30Ti–O solid was nearly domains showed composition homogeneity throughout
spherical, while that of 40Mo–30Zn–30Ti–O was nearly these domains.
rod-like. Novochinskii et al. [25] have reported that in the
case of flat or flake crystal morphologies, the external mass 3.1.4. XPS studies
transfer limitations during adsorption are much smaller than XPS measurements were performed on the Mn–Zn–Ti–O
those encountered with cubes or prisms. Therefore, the series of solids in order to study the effects of sulfidation and
method used to prepare a given solid adsorbent is of great regeneration procedures on the chemical composition of the
importance since it can lead to a structure that facilitates gas solid surface and the oxidation state of its metal elements.
diffusion and gas–solid interactions. EDX analyses con- The surface at.% composition of the adsorbent solids after
130 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137

Table 3
Surface at.% concentrations in the Mn–Zn–Ti–O series of solids (fresh, after sulfidation and after regeneration) derived from XPS analyses
Sample Mn Ti Zn Mn/(Mn + Zn + Ti) S
a b b b
10Mn–45Zn–45Ti, fresh 11.6 45 43.4 0.12 –
10Mn–45Zn–45Ti, after sulfidationc 5.24, 26.6b 9.65, 49.0b 4.78, 24.4b 0.26 1.99
10Mn–45Zn–45Ti, after regenerationd 2.52, 12.3b 12.99, 63.4b 4.98, 24.3b 0.12 1.08
40Mn–30Zn–30Ti–O, fresha 42.2 33.9 23.9 0.42
80Mn–10Zn–10Ti–O, fresha 86.8 5.7 7.5 0.87
a
After calcination in 20% O2/He at 500 8C for 4 h.
b
Values correspond to metal at.% surface composition (e.g., Mn/(Mn + Zn + Ti)).
c
After sulfidation (0.06% H2S/25% H2/7.5% CO2/He) at 100 8C for 0.5 h.
d
After sulfidation (0.06% H2S/25% H2/7.5% CO2/He) followed by regeneration with 20% O2/He at 750 8C for 10 h.

exposed to different gas atmospheres is reported in Table 3. 3.1.5. H2-TPR studies

In the case of 10Mn–45Zn–45Ti–O solid, there is an Fig. 4a presents hydrogen temperature-programmed
increase of Mn surface concentration by 130%, a minor reduction (H2-TPR) profiles in terms of rate of H2
increase of Ti surface concentration, and a decrease of consumption (mmol H2/g min) versus temperature obtained
Zn surface concentration by 44% after the solid was exposed over the 40Mn–30Zn–30Ti–O and 80Mn–10Zn–10Ti–O
to the H2S/H2/CO2/He gas mixture. These results indicate solids. The former solid shows a TPR trace characterized by
that there is a preferential migration of Mn to the surface a broad peak in the 150–800 8C range. As the amount of Mn
during sulfidation. It is interested to note that the Mn/
(Mn + Zn + Ti) ratio appears to be the same in both the fresh
and regenerated solids (Table 3). It appears that the
treatment of fresh 10Mn–45Zn–45Ti–O solid with the given
H2S-containing gas mixture causes a severe inhomogeneity
between the metal composition of the surface and the
bulk. This inhomogeneity is partly inversed after rege-
neration of the solid with 20% O2/He at 750 8C for 10 h
(Table 3). From the present XPS results it is deduced that the
chemical composition of the surface is not much different
from that in the bulk for the fresh Mn–Zn–Ti–O series of
solids (Table 3).
Fig. 3 presents XP spectra of Mn 2p (a), Zn 2p3/2 (b) and
Ti 2p (c) core electron levels obtained on the 40Mn–30Zn–
30Ti–O solid. The existence of two peaks after deconvolu-
tion of the Mn 2p3/2 XP peak (Fig. 3a) with binding energies
at 641.9 and 643.3 eV is a proof for the existence of two Mn
species of a different oxidation state. These are Mn3+ and
Mn4+ in octahedral environment according to Oku et al. [26]
and Di Castro and Polzonetti [27]. The XPS results for the
Mn species are in good agreement with the XRD results that
indicate the presence of MnO2, Mn2O3 and ZnMnO3 crystal
phases (Table 2). Fig. 3b presents XP spectra of Zn 2p3/2 core
electron levels obtained on the 40Mn–30Zn–30Ti–O solid.
The Zn 2p3/2 peak appears as a single one at 1021.5 eV,
which is assigned to Zn2+ cation. The Ti 2p3/2 peak appeared
as a single one at 1021.2, 1021.3 and 1021.4 eV for the
10Mn–45Zn–45Ti–O, 40Mn–30Zn–30Ti–O (Fig. 3c) and
80Mn–10Zn–10Ti–O solids, respectively, and is assigned to
Ti4+. The O 1s peak (not shown) split into two peaks, one at
529.9 eV assigned to O2 ions in metal oxides and another
one at 531.1 eV assigned to –OH groups (fresh Mn–Zn–Ti–
O series of solids). In the case of sulfidation and regeneration
of the 10Mn–45Zn–45Ti–O solid, only a single O 1s peak Fig. 3. X-ray photoelectron spectra of (a) Mn (2p), (b) Zn (2p3/2) and (c) Ti
was clearly observed, mostly arising from the oxygen (2p) core electron levels obtained on the fresh 40Mn–30Zn–30Ti–O mixed
bonded with sulfur. metal oxide prepared by the sol–gel method.
 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137 131

solid and each redox cycle appears to have influenced the

strength of the M–O–M0 bonds of the various metal oxide
lattices.
In the case of 40M–30Zn–30Ti–O (M = Mn, Mo and Cu)
solids, the third metal was found to play an important role in
the redox behavior of the solid. The Mn-containing solid
appeared to be largely reducible in the wide temperature
range of 150–800 8C, indicating the existence of various
kinds of reducible oxygen species in the surface and the bulk
of the solid, in agreement with the XRD results (Table 2).
According to TPR experiments conducted on the 50Zn–
50Ti–O, MnO2 and Mn2O3 solids (not presented here), the
Mn-containing crystal phases were the main source of the
easily reducible oxygen species present in the 40Mn–30Zn–
30Ti–O solid. In the case of 40Cu–30Zn–30Ti–O solid, the
H2-TPR trace (not shown) was also characterized by a broad
peak (150–780 8C, 2960 mmol H2/g). Given that CuIIO is
reduced to CuIO at T > 190 8C [28], and reduction of 50Zn–
50Ti–O occurs in the 225–700 8C range resulting in a small
number of reducible oxygen species (87.8 mmol H2/g), it is
concluded that most of the oxygen reduced in the 200–
700 8C range should be assigned to that present in the CuO
and Cu2O phases of the 40Cu–30Zn–30Ti–O solid.
Fig. 4. (a) Hydrogen temperature-programmed reduction (H2-TPR) profiles The H2-TPR trace of 40Mo–30Zn–30Ti–O solid has
in terms of hydrogen consumption rate (mmol H2/g min) vs. temperature presented two peaks. The first one appeared in the 30–
obtained over the fresh 40Mn–30Zn–30Ti–O and 80Mn–10Zn–10Ti–O
solids. (b) H2-TPR profiles obtained on 40Mn–30Zn–30Ti–O solid
150 8C range and the second broad one in the 300–800 8C
during three consecutive oxidation/reduction cycles: 20% O2/He (500 8C, range. The latter peak reflects the reduction of Mo6+ to Mo4+
2 h) ! 2% H2/He (TPR), repeat cycle. FH2 =He = 50 N mL/min; b = 30 8C/ and Mo4+ to Mo0 [29]. The broadness of the peak can be
min; W = 0.2 g. explained by the fact that there are two main solid phases
containing Mo6+ according to the present XRD results
in the solid increases, the H2-TPR trace is shifted towards (Table 2) in which Mo6+ is in different coordination
higher temperatures. This means that introduction of further environments with oxygen. The low-temperature TPR peak
Mn ions (Mn3+/Mn4+) in the oxide lattice of Mn–Zn–Ti–O was assigned to the reduction of ZnTiO3. It can be concluded
decreases the reducibility of its lattice oxygen, thus that insertion of Mn or Cu in the Zn–Ti–O oxide matrix
promoting the M–O–M0 bond strength. By integrating
the H2-TPR traces the amount of hydrogen consumed and
the equivalent amount of reducible lattice oxygen species Table 4
Amounts of H2 consumed (mmol/g) during TPR experiments
can be estimated. This is found to be 4400, 6050 and
3030 mmol H2/g for the 10Mn–45Zn–45Ti–O (not shown), Fresh solid adsorbenta Amount of H2 DTb/TMc (8C)
(103 mmol/g)
40Mn–30Zn–30Ti–O and 80Mn–10Zn–10Ti–O solids,
respectively. These results are in good agreement with the 20Zn–80Ti–O 0.1 150–800/285, 570
40Zn–60Ti–O 0.47 300–800/625
results of Alonso et al. [28] obtained over Mn–Cu–O oxides. 50Zn–50Ti–O 0.088 150–800/625
The redox behavior of the 40Mn–30Zn–30Ti–O solid in
10Cu–45Zn–45Ti–O 1.14 150–650/275, 470
three consecutive runs of the TPR experiment is presented in
40Cu–30Zn–30Ti–O 2.96 150–780/400
Fig. 4b. After calcination in 20% O2/He at 500 8C for 2 h, a 80Cu–10Zn–10Ti–O 6.7 150–800/275
H2-TPR run was followed. This is termed a redox cycle. In
40Mo–30Zn–30Ti–O 2.95 30–800/80, 520
Fig. 4b it is shown that the TPR trace exhibits much lower
reduction rates in the 200–500 8C range during the second 10Mn–45Zn–45Ti–O 4.4 75–800/530
40Mn–30Zn–30Ti–O 6.05 75–800/525
redox cycle compared to the first one. On the other hand,
80Mn–10Zn–10Ti–O 3.03 150–800/775
comparing the second and third redox cycles it is seen that
the TPR trace of the third redox cycle exhibits higher MnOx 3.7 150–800/525
TiO2 0.2 400–750/660
reduction rates in the 400–775 8C range. The amount of CuO 8.6 400–700/500
hydrogen consumed is found to be 6050, 1780 and a
Prepared by the sol–gel method (see Section 2.1).
2250 mmol H2/g for the three consecutive redox cycles, b
Temperature range in which a measurable H2 reduction rate was
respectively. These results are related to the fact that during obtained.
c
consecutive redox cycles structural changes occur in the Temperature at which maximum reduction rate was observed.
132 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137

indicate that the surface acid character of the sol–gel prepared

Fig. 5. Dependence of surface acidity (mmol/g) of Mn–Zn–Ti–O solid on
Mn composition (at.%) as a function of gas treatment: fresh, after sulfidation
(H2S/H2/CO2/He, 25 8C, 0.5 h), and after sulfidation followed by regenera-
tion (20% O2/He, 500 8C, 4 h).
results in an increase of the amount of easily reducible
oxygen species (reduced at T < 400 8C).
According to similar H2-TPR experiments conducted
over ZnO and TiO2 single metal oxides also prepared by the
sol–gel method, ZnO was found to be non-reducible in the
25–800 8C range, while TiO2 was found to be reducible in
the 400–750 8C range (TM = 660 8C). The amounts of H2
consumed during all H2-TPR experiments performed are
summarized in Table 4 along with the reduction temperature
range (DT) and the temperature (TM) at which maximum
reduction rate was observed.
3.1.6. Surface acidity and basicity studies—correlation
with H2S adsorptive capacity
Fig. 5 presents comparative results of acidity measure-
ments (NH3-TPD) performed on the Mn–Zn–Ti–O series of
solids as fresh, after exposed to the adsorption mixture of
H2S/H2/CO2/He at 25 8C for 0.5 h, and after regeneration in
20% O2/He at 500 8C for 4 h. The surface acidity seems to
increase in the 10–40 at.% Mn range, while it decreases in the
40–80 at.% Mn range. After sulfidation the acidity drops
significantly, while after regeneration it is even lower than that
obtained after sulfidation. On the other hand, the dependence
of acidity on Mn concentration remains the same as for the
fresh Mn–Zn–Ti–O solids. The amounts of NH3 (acidity,
mmol/g) and CO2 (basicity, mmol/g) obtained (Table 5)
mixed metal oxides (fresh) is predominant compared to their
surface basic character. The general trend is a severe decrease
of surface acidity after sulfidation and regeneration. On the
other hand, the surface basicity drops after sulfidation
followed by regeneration for the 40Mn–30Zn–30Ti–O and
80Mn–10Zn–10Ti–O solids, while it increases by a factor of
10 and 19 after sulfidation and regeneration for the 10Mn–
45Zn–45Ti–O solid. The severe decrease of acidity and
basicity after sulfidation and regeneration was also noticed in
the 40Zn–60Ti–O solid (Table 5).
The results presented in Fig. 5 and Table 5 can be explained
based on the findings of Ziolek et al. [30] who have studied the
change of surface acidity upon H2S adsorption on MgO, ZrO2,
Al2O3, TiO2 and CeO2 metal oxides. They have reported that
three possible H2S adsorption steps can be considered. First,
exchange of the oxygen of metal oxide for sulfur, second,
dissociation of H2S into HS and H+, the latter found as –OH
species, and third, coordinatively bonded H2S. Also, Travert
et al. [31] have studied the adsorption of H2S on SiO2, Al2O3,
TiO2 and ZrO2 by means of IR spectroscopy using CO as a
probe molecule. They have reported that the decrease of
Lewis acidity was due to the occupation of acidic sites by
adsorbed hydrogen sulfide and the products of its dissociation.
An increase in the number of Brönsted acid sites as well as
modification of their strength was also observed.
As shown in Fig. 5, the fresh solid with 80 at.% Mn
content exhibits the lowest concentration of acid sites after
sulfidation and the lowest maximum H2S uptake (see
Section 3.2), while according to the TPR results (see Section
3.1.5) it shows the strongest M–O–M0 bonds. These results
can be explained by considering that the pathway of
exchange of oxygen for sulfur and/or dissociation of H2S
reported by Ziolek et al. [30] is not the main one for the
80Mn–10Zn–10Ti–O solid during H2S adsorption. It is
suggested that an associative coordination of H2S on Lewis
acid sites is favored instead. The acidity after sulfidation of
the 80Mn–10Zn–10Ti–O solid is found to be 2.5 times lower
compared to the fresh sample, and 2.9 and 3.2 times lower
compared to the fresh 10Mn–45Zn–45Ti–O and 40Mn–

Table 5
NH3 and CO2 uptakes measured during TPD experiments on Zn–Ti–O-based mixed metal oxides prepared by the sol–gel method
Solid composition Uptake NH3/CO2 Uptake NH3/CO2 Uptake NH3/CO2
(mmol/g), fresha (mmol/g), after sulfidationb (mmol/g), after regenerationc
10Mn–45Zn–45Ti–O 267/6.3 91/61.3 49/122
40Mn–30Zn–30Ti–O 322/11 100/5 73/4
80Mn–10Zn–10Ti–O 154/21 62/13 65/5.9
20Zn–80Ti–O 62.6/43.3
40Zn–60Ti–O 174/78 129/20 94/9
50Zn–50Ti–O 48.3/35.6
40Cu–30Zn–30Ti–O 11.1/13.1
80Cu–10Zn–10Ti–O 21.7/9.9
a
After calcination at 500 8C in 20% O2/He for 4 h.
b
After had being exposed to the 0.06% H2S/25% H2/7.5% CO2/He gas mixture at 25 8C for 0.5 h.
c
After had been exposed to the 0.06% H2S/25% H2/7.5% CO2/He gas mixture at 25 8C for 0.5 h followed by regeneration in 20% O2/He at 500 8C for 4 h.
 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137
Fig. 6. Transient isothermal H2S gas phase response curves obtained after
the switch He ! 0.06% H2S/25% H2/7.5% CO2/He (t) at 25 8C was made
over the fresh 10Mn–45Zn–45Ti–O and a Ni-based commercial H2S
adsorbents. The response curve of H2S obtained with empty reactor (blank)
is also noted (solid line).
30Zn–30Ti–O solids, respectively. This behavior might be
indicative of a different sulfidation mechanism on each of
these mixed metal oxides. As Mn content increases, the Mn–
O–Mn bond strength in the MnO2 and Mn2O3 phases present
in 40Mn–30Zn–30Ti–O and 80Mn–10Zn–10Ti–O solids
but not in the 10Mn–45Zn–45Ti–O solid increases, and as a
result of this sulfidation becomes more kinetically con-
trolled. The 10Mn–45Zn–45Ti–O solid seems to largely
favor H2S adsorption through an exchange of oxygen
for sulfur and H2S dissociation into HS and H+, in
accordance to the increase of its basicity after sulfidation
(6.3 mmol CO2/g versus 61.3 mmol CO2/g). These pathways
of H2S adsorption are also supported by the TPR results that
show a large number of easily reducible oxygen species for
the 10Mn–45Zn–45Ti–O solid (Table 4).
3.2. Mn–Zn–Ti–O H2S solid adsorbents
3.2.1. Transient H2S adsorption studies
Fig. 6 presents transient isothermal H2S response curves
obtained after the switch He ! H2S/H2/CO2/He (t) was
made over the 10Mn–45Zn–45Ti–O solid and a commercial
Ni-based (Kataleuna GmbH Catalysts, KL6512A) H2S
adsorbent. A blank experiment was also conducted
following the same experimental procedure but using an
empty reactor (solid line, Fig. 6). The area difference
between the H2S response curve shown by the solid line and
that obtained with the adsorbent is proportional to the
amount of H2S adsorbed and/or reacted with the adsorbent
material. It is found that the sol–gel prepared 10Mn–45Zn–
45Ti–O solid adsorbs at 25 8C higher amounts of H2S
than the commercial solid (1.21 mmol H2S/g versus
0.75 mmol H2S/g). These amounts correspond to the point
where no consumption of H2S was observed (the outlet
concentration of H2S was the same as the feed concentration,
600 ppm). Also, it is concluded from the results of Fig. 6 that
the transient adsorption/reaction kinetics of H2S on the given
solids are much different in the early period (first 10 min) of
the transient.
133
Fig. 7. H2S uptake (mmol/g) and percentage of regeneration of 10Mn–
45Zn–45Ti–O solid adsorbent as a function of adsorption temperature in the
25–100 8C range. Results are shown for the fresh solid and after its
sulfidation followed by regeneration (500 8C, 4 h). Adsorption gas mixture
used: 0.06% H2S/25% H2/7.5% CO2/He; F = 30 N mL/min.
3.2.2. Effect of adsorption temperature on the H2S uptake
Fig. 7 presents results of H2S uptake as a function of
adsorption temperature in the 25–100 8C range over the
10Mn–45Zn–45Ti–O solid. The H2S uptakes were calculated
in a similar way according to the transient experiments
presented in Fig. 6. For the fresh sample, there is a small
increase of H2S uptake in the 25–75 8C range and a sudden
large increase at 100 8C (by a factor of 3.8 compared to the
adsorption at 25 8C). On the other hand, a different behavior is
obtained on the regenerated solid (20% O2/He at 500 8C for
4 h). The highest uptake now occurs at 50 8C, which is higher
than that obtained on the fresh solid. On the other hand, at 25,
75 and 100 8C the H2S uptake of regenerated sample is lower
than that obtained on the fresh solid. The percentage
regeneration of the adsorbent as a function of adsorption
temperature is also presented in Fig. 7. The lowest percentage
regeneration is obtained at 100 8C. This is likely due to the
fact that at this temperature sulfidation proceeded to a larger
extent into the bulk of the solid, and as a result of this the
regeneration conditions applied seem not to be so efficient.
The lower H2S adsorption capacity of the solid after
regeneration is due to the presence of remaining sulfides (S2)
and sulfates (SO42) in the bulk of the solid, the formation of
which is favored in the presence of Mn [19]. It has been
reported [19] that calcination in air of manganese sulfates at
high temperatures (T > 750 8C) leads to a larger degree of
manganese oxides formation. We have also performed
regeneration of the 10Mn–45Zn–45Ti–O solid at 500 8C
for 10 h and the H2S uptake was found to be slightly
higher (0.93 mmol H2S/g versus 0.85 mmol H2S/g). The
value of 0.85 mmol H2S/g refers to regeneration at 500 8C
for 4 h. A regeneration procedure at a high temperature (ca.
T  750 8C) is likely to cause sintering of the adsorbent solid
which then would result in a significant decrease of its
adsorption capacity. In fact, after regeneration of the 10Mn–
45Zn–45Ti–O solid at 750 8C for 4 h, the decrease of H2S
uptake was significant (0.37 mmol H2S/g versus 0.85 mmol
H2S/g). The regeneration conditions discussed above had
similar effects on the other Mn–Zn–Ti–O series of solids.
The formation of MnS after adsorption of H2S at 100 8C
on 10Mn–45Zn–45Ti–O solid was probed by XRD (Fig. 1),
134 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137
while that of MnSO4 by XPS. The S 2p XP peak appeared at
169.4 and 169.1 eV for the sulfated and regenerated
samples, respectively, and these values correspond to
sulfates according to the literature [28]. Based on the
surface atomic concentration values of sulfur (Table 3), only
55% of sulfur in the surface and sub-surface region of the
solid had been removed during regeneration. Since the
escape depth of photoelectrons in the solid analyzed by the
XPS is confined to a depth of 3–4 nm, only the upmost layers
of the solid particles are concerned. However, the percentage
of sulfur removal from the bulk of the solid is not excluded to
be similar or even higher to that of the surface of the solid.
The latter is supported by the fact that similar percentages of
H2S uptake reduction (due to the sulfur left in the solid after
regeneration, Fig. 7), and higher than 100% regeneration
values (in terms of the H2S uptake obtained compared to the
fresh solid, Fig. 7) were observed when adsorption of H2S
was performed at 50 8C.
3.2.3. Comparison of H2S uptakes of the sol–gel prepared
solids with a commercial Ni-based solid adsorbent
Fig. 8 compares the maximum H2S uptakes obtained on the
10Mn–45Zn–45Ti–O and commercial Ni-based H2S adsor-
bents as a function of adsorption temperature. For the lowest
temperature of 25 8C, the sol–gel prepared solid shows a
larger by 60% H2S uptake than the commercial one
(1.21 mmol/g versus 0.75 mmol/g) but a similar uptake at
50 8C. However, at 75 and 100 8C the commercial adsorbent
exhibits H2S uptakes larger by a factor of 5.1 and 3.2,
respectively. It appears that sulfidation of NiO to form NiS is
facilitated at T > 50 8C compared to ZnO, ZnTiO3 and
ZnMnO3 present in the 10Mn–45Zn–45Ti–O solid. In fact,
the thermodynamic constant of sulfidation of NiO to form NiS
is higher than that of ZnO to form ZnS (log Kf = 135.5 versus
34.7 at 25 8C). At temperatures lower than 50 8C, it appears
that the kinetics of sulfidation of the bulk of NiO is not favored
to the extent observed in the case of ZnO and ZnTiO3 solids.
However, it should be noted that the commercial Ni–NiO/
SiO2 catalyst is not regenerable, as opposed to the present
developed 10Mn–45Zn–45Ti–O solid adsorbent.
Fig. 8. H2S uptake (mmol/g) as a function of adsorption temperature in
the 25–100 8C range obtained on the 10Mn–45Zn–45Ti–O and Ni-based
commercial solid adsorbents. Adsorption gas mixture used: 0.06% H2S/
25% H2/7.5% CO2/He; F = 30 N mL/min.
3.3. Zn–Ti–O, Cu–Zn–Ti–O and Mo–Zn–Ti–O H2S solid
adsorbents
Fig. 9a presents results of H2S uptake as a function of Zn
content (at.%) for the solids with composition x% Zn–
(100  x)% Ti–O obtained at 25 8C. A significant improve-
ment in H2S uptake is achieved in the case of 20Zn–80Ti–O
and 40Zn–60Ti–O mixed metal oxides compared to the
single oxide of zinc. The 40Zn–60Ti–O solid with the
highest BET area (fresh) presented the highest H2S
adsorption capacity at 25 8C. The ZnO exhibited improve-
ment of its H2S uptake after regeneration at 750 8C for 4 h
(Fig. 9a) in good agreement with the results of Pineda et al.
[32]. This improvement is due to structural and textural
changes occurred in ZnO as a consequence of the successive
treatments in 20% O2/He. On the contrary, the Zn–Ti–O
solids loose to a significant extent their H2S adsorption
ability after the same regeneration conditions were applied
(Fig. 9a). One of the reasons is likely the fact that the
regeneration conditions were not sufficient for the removal
to a significant extent of sulfates/sulfides that had been
formed. It is important to note that the Zn–Ti–O solids
prepared by the sol–gel method in the present work exhibit
better performance towards H2S uptake than the commercial
zinc titanate adsorbent (UCI-4169) used in the 350–550 8C
range [19]. The latter solid presented an adsorption capacity
of 0.31 mmol H2S/g at 350 8C. In another study, Novo-
chinskii et al. [25] reported H2S removal of 2.81 g S/100 g of
Fig. 9. (a) H2S uptake (mmol/g) as a function of Zn content (at.%) in the
Zn–Ti–O series of solids and of regeneration conditions applied. Adsorption
conditions: 0.06% H2S/25% H2/7.5% CO2/He, 25 8C, F = 30 N mL/min.
Regeneration conditions: 20% O2/He at either 500 8C/4 h or 750 8C/10 h.
(b) H2S uptake (mmol/g) as a function of Cu content (at.%) in the Cu–Zn–
Ti–O series of solids. Adsorption conditions: 0.06% H2S/25% H2/7.5%
CO2/He, 25 8C, F = 30 N mL/min. Regeneration conditions: 20% O2/He at
either 500 8C for 4 h or 750 8C for 4 h.
 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137
ZnO or 0.878 mmol H2S/g of ZnO at 300 8C from a gas-
stream containing 0.0008% H2S/34.4% H2/20% H2O in N2.
Fig. 9b shows results of H2S uptake as a function of Cu
content (at.%) obtained over the fresh Cu–Zn–Ti–O series of
solids and after regenerated in 20% O2/He for 4 h at 500 or
750 8C. The following remarks are appropriate. The fresh
samples with compositions 10Cu–45Zn–45Ti–O and 40Cu–
30Zn–30Ti–O exhibit significantly larger H2S uptakes than
the sample with composition 80Cu–10Zn–10Ti–O. It is
known that solids with high Cu-content exhibit low reactivity
towards H2S due to copper migration to the surface [28].
According to the XPS results obtained over the 10Cu–45Zn–
45Ti–O solid, the latter presented 6.74% Cu, 35.2% Zn and
58.0% Ti on the surface. The XP spectrum (not presented
here) of this adsorbent gave a Cu 2p3/2 peak at 932.7 eV.
The Cu species associated with this binding energy is Cu+.
The shake-up satellite observed at 950 eV indicates that Cu2+
was present along with Cu+. The fresh 10Cu–45Zn–45Ti–O
solid exhibits higher H2S uptake (2 mmol H2S/g versus
0.8 mmol H2S/g), higher BET area (164.8 m2/g versus
20.3 m2/g) but lower amount of reducible oxygen species
(1142 mmol O/g versus 3030 mmol O/g) compared to the
80Mn–10Zn–10Ti–O solid. These results indicate that the
mechanism of propagation of sulfidation over these solids
must be different. For example, the mechanism of surface
reconstruction [1] is favored over solids with high BET
surface areas, while the mechanism of O2 exchange for
S2 that is favored over solids with weak M–O bonds seems
not to be favored over the present solids.
After regeneration in 20% O2/He at 500 8C for 4 h, the
solids present lower uptakes except that of 80Cu–10Zn–
10Ti–O that exhibits a slightly higher uptake (Fig. 9b). The
latter solid due to its high Cu-content is expected to exhibit a
reduced stability of the copper sulfate formed compared to
the other two Cu-based adsorbents, a fact that was reported
to be an advantage of Cu-based adsorbents used in SO2
removal [33]. In fact, regeneration at 750 8C for 4 h leads to
a significant reduction of H2S uptake in the solids containing
10 and 40 at.% Cu but not in the solid containing 80 at.% Cu
(Fig. 9b).
The Mo–Zn–Ti–O series of solids, fresh and after
regenerated in 20% O2/He for 4 h either at 500 or 750 8C
have been also tested for their adsorption capacity towards
H2S. The following remarks are noted. The fresh 10Mo–
45Zn–45Ti–O (60 m2/g) presented higher H2S uptakes than
of 40Mo–30Zn–30Ti–O solid (9 m2/g). According to the
XPS studies performed on the 10Mo–45Zn–45Ti–O solid,
Mo atoms were found in mixed valence states (Mo6+ and
Mo5+) with Mo6+ in higher surface concentrations. The
mixed valence states of Mo lead to an unsaturated co-
ordinatively environment that favors H2S adsorption [2].
The solid after sulfidation and regeneration at 500 8C for 4 h
resulted in a state that a drastic increase of its H2S adsorption
capacity was observed compared to the fresh solid. The same
result was seen also in the 40Mo–30Zn–30Ti–O solid. This
increase of H2S uptake is due to structural changes occurred
135
Fig. 10. Specific surface area (BET, m2/g) and H2S uptake (mmol/g) as a
function of Zn content (at.%) in the fresh Zn–Ti–O series of solids. Adsorption
conditions: 0.06% H2S/25% H2/7.5% CO2/He, 25 8C, F = 30 N mL/min.
in the solid at 500 8C as also found by Pineda et al. [32].
After regeneration in 20% O2/He at 750 8C for 4 h, the
10Mo–45Zn–45Ti–O exhibits lower H2S uptakes than the
fresh solid, a result opposite to that found in the 40Mo–
30Zn–30Ti–O solid.
3.4. Correlation of BET with H2S adsorptive capacity
According to the literature [19], a key parameter in
achieving acceptable H2S adsorption values at T < 100 8C is
that of specific surface area of the adsorbent. The latter
provides immediate availability of sites for adsorption (first
step of the sulfidation process). Fig. 10 shows results of BET
and H2S uptake as a function of at.% Zn for the Zn–Ti–O
series of solids. The increase of BET area with increasing Zn
content (up to 40 at.%) is accompanied by an increase of the
H2S uptake. On the other hand, in the 40–100 at.% Zn range
the trends of H2S uptake and BET as a function of Zn content
in the solid are completely different. These results strongly
support the view that the interaction of H2S with these solids is
not confined to the surface. A solid-state diffusion of HS and
S2 species towards the bulk of the solid particles to
eventually form metal sulfide compounds could be proposed
[1]. The initial step of H2S adsorption, dissociation into HS
and H+, is followed by diffusion of HS and S2 species into
the oxide lattice and migration of lattice oxygen to the surface
of the solid to form H2O [1]. However, bulk diffusion of
anions is unlikely at low temperatures and surface reconstruc-
tion was proposed instead [1,34]. Such a mechanism is
expected to depend on BET area, as previously mentioned,
and the details of surface morphology.
The depth of sulphidation reaction can be calculated
assuming a stoichiometry of one molecule of H2S for one
Zn2+O2 surface ion pair (the case of ZnO). It is found that
the ZnO surface contains about 1  1019 Zn2+O2 ion pairs
per square meter. Thus, the average depth of the reaction in
terms of surface monolayers can be calculated according to
the following relationship (1):
number of surface monolayers
molecules of H2 S adsorbed per m2
¼ (1)
number of Zn2þ O2 ion pairs per m2
136 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137

In the case of ZnO, the extent (depth) of sulfidation reaction

at 25 8C was found to be 8.1 equiv. surface monolayers. This
result confirms that bulk sulfidation does occur in the solid
crystals of ZnO and also in other similar in structure solids,
where significantly higher H2S uptakes than those on ZnO
have been obtained.
Scheme 1 illustrates the sulfidation process of a given
metal oxide after interaction with gaseous H2S. The initial
step 1 presents the approach of gaseous H2S to the surface
adsorption site of the metal oxide. Step 2 shows the result of
chemisorption of H2S onto the surface, the formation of a
chemical bonding with a metal cation (Lewis acid site). Step
3 shows the interaction (transition state) of one atom of
hydrogen (belonging to H2S) with the surface oxygen atom.
Step 4 presents the evolution of water with the subsequent
formation of an oxygen vacant site. Finally, step 5 shows the
incorporation of sulfur in the previously formed oxygen
vacant site to form a surface metal sulfide.
3.5. Effect of calcination temperature on the H2S uptake
The H2S uptake obtained on the 10Cu–45Zn–45Ti–O
solid (fresh) at 25 8C following calcination in 20% O2/He at
200 8C for 2 h was compared to that obtained on the Ni-
based commercial adsorbent. It was found that the former
solid presents seven times higher H2S uptake than the
commercial one. The temperature of calcination for this sol–
gel prepared mixed metal oxide seems to be a crucial
parameter for the examined sulfidation process. According
to the XPS data obtained (not shown), this solid presented
the highest amount of surface carbon (29.9 at.%) compared
to other mixed metal oxides calcined at 500 8C. The
decomposition temperature of the metal precursors used
appears, therefore, to be an important parameter for the final
H2S adsorption properties of Cu–Zn–Ti–O solids.
3.6. Effect of H2O in the feed stream on the adsorption
of H2S
Fig. 11 compares the effect of H2O at the level of 1 vol.%
present in the adsorption gas mixture on the H2S uptake of
Fig. 11. Effect of 1 vol.% H2O present in the adsorption gas mixture on the
H2S uptake (mmol/g) in the 25–100 8C range for the 10Mn–45Zn–45Ti–O
solid adsorbent. Adsorption conditions: 0.06% H2S/25% H2/7.5% CO2/He;
F = 30 N mL/min.
10Mn–45Zn–45Ti–O solid as a function of adsorption
temperature. In the absence of water, the H2S uptake
increases with adsorption temperature in the 25–100 8C
range. On the other hand, the presence of 1 vol.% H2O in the
feed leads to a significantly higher H2S uptake at 25 8C and
to a lesser extent at 75 8C. The simplest reaction scheme
consistent with these observations is the following (the case
of a MIIO metal oxide):
H2 S þ MO , MS þ H2 O (2)
H2 O þ MO , MðOHÞ2 (3)
H2 S þ MðOHÞ2 , MS þ 2H2 O (4)
According to reactions (2)–(4), the presence of water can
cause hydroxylation of the oxidic surface and the bulk of the
oxide (sub-surface region). The hydroxylated surface results
to higher rates of H2S adsorption and surface diffusion of the
derived species in the case of ZnO [35]. It was also reported
[13] that a water promoted cation diffusion mechanism
operates in the case of interaction of H2S (0.05–0.8% in
N2) with ZnO at 45 8C, which facilitate the formation of
ZnS. At the temperature of 100 8C, it is likely that the
formation of a metal hydroxide shell to a greater extent
compared to the case of 25 8C limits the diffusion of

Scheme 1. Mechanistic steps of sulfidation of a metal oxide surface after interaction with gaseous H2S.
 K. Polychronopoulou et al. / Applied Catalysis B: Environmental 57 (2005) 125–137
HS and S2 into the bulk of unreacted metal oxide, thus
reducing the final H2S uptake obtained.
4. Conclusions
The following conclusions can be derived from the results
of the present work:
The nature of a third metal additive (M = Mn, Cu or Mo)
in the sol–gel synthesis of M–Zn–Ti–O mixed metal
oxides largely determines the morphology and particle
size of the final solid. The particle morphology of the
40Cu–30Zn–30Ti–O solid was found to be nearly
spherical, while that of 40Mo–30Zn–30Ti–O nearly
rod-like. The morphology of the 10Mn–45Zn–45Ti–O
solid drastically changes after sulfidation followed by
regeneration at 750 8C for 10 h.
The use of Mn, Cu or Mo in the Zn–Ti–O matrix leads to
the formation of a solid with an enhanced number of
easily reducible oxygen species. This leads to the
improvement of H2S uptake for the regenerated solid
compared to the Zn–Ti–O one.
The lower H2S uptake on the 10Mn–45Zn–45Ti–O solid
after regeneration compared to the fresh one, is partly due
to the presence of remaining sulfates (SO42) and sulfides
(S2) in the lattice, the formation of which is favored in
the presence of Mn. The lowest percentage regeneration
(37%) is obtained after the fresh solid was exposed to the
H2S adsorption mixture at 100 8C, while the highest one
(170%) at 50 8C.
For the lowest adsorption temperature of 25 8C, the sol–
gel prepared 10Mn–45Zn–45Ti–O solid shows a sig-
nificantly larger H2S uptake than a commercial Ni-based
adsorbent, and a similar one at 50 8C. However, at 75 and
100 8C the commercial adsorbent exhibits H2S uptakes
larger by a factor of 5.1 and 3.2, respectively.
The fresh 10Cu–45Zn–45Ti–O solid prepared by the sol–
gel method and calcined at 200 8C exhibits a significantly
larger H2S uptake at 25 8C compared to a Ni-based
commercial adsorbent.
The presence of 1 vol.% H2O in the feed stream of 0.06%
H2S/25% H2/7.5% CO2/He enhances significantly the
H2S uptake on the 10Mn–45Zn–45Ti–O solid at 25 8C.
Acknowledgements
We acknowledge the financial support by the European
Union (Fifth FP) through the EVK1-CT-1999-00033
research project, and the Research Committee of the
University of Cyprus. The research group of Professor
P.G. Koutsoukos at the Chemical Engineering Department
of the University of Patras (Greece) is also acknowledged for
performing the SEM measurements.
137
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