Received: 7 March 2019 Revised: 23 April 2019 Accepted: 23 May 2019

DOI: 10.1002/cjce.23609

ARTICLE

A new sol-gel route alumina for selective oxidation

of H2S to sulphur

H. Mehmet Tasdemir | Yavuz Yagizatli | Sena Yasyerli | Nail Yasyerli | Gulsen Dogu

Department of Chemical Engineering, Gazi

University, Ankara, Turkey
Correspondence
Sena Yasyerli, Department of Chemical
Engineering, Gazi University, 06570,
Ankara, Turkey.
Email: syasyerli@gazi.edu.tr
Funding information
Türkiye Bilimsel ve Teknolojik Araştirma
Kurumu, Grant/Award Number: 114M185
Abstract
In this study, a new synthesis method was developed for the production of modi-
fied sol-gel alumina (SG-M) for the selective oxidation of H2S to elemental sul-
phur. The catalytic activity of this modified alumina without any active metal
incorporation was then compared with the activity of commercial alumina (alu-
mina-com) for H2S selective oxidation. The N2 adsorption-desorption isotherm
showed that the SG-M alumina synthesized in this work has a mesoporous struc-
ture with well-defined hysteresis loops. Both alumina materials showed a γ-Al2O3
crystalline phase with an amorphous structure in their crystal structure. The surface
acidity of the alumina materials was determined using pyridine-adsorbed FTIR ana-
lyses, and both alumina showed Lewis acid sites on their surfaces. The catalytic
activity tests were performed at 250
C using a feed ratio of O2/H2S:0.5. The com-
plete conversion of H2S over SG-M was achieved during 400 minutes of reaction
time. However, the commercial alumina lost its activity at earlier reaction times.
Lewis acid sites and surface hydroxyl groups caused the alumina to be active in
H2S selective catalytic oxidation, and the formation of Al-S bonds, observed when
the H2S conversion fell, caused a decrease in the catalytic activity of the alumina
materials. A high sulphur yield (≥95%) was obtained over SG-M, even though
there was no active metal incorporation and even in the presence of excess oxygen.
Considering the catalytic activities, the new sol-gel alumina synthesized in this
work is superior to commercial alumina. It was concluded that, as a catalyst with-
out any active metal, SG-M is a promising catalyst in H2S selective oxidation to
sulphur.

KEYWORDS
alumina, FTIR, H2S selective oxidation, sol-gel

1 | INTRODUCTION structure while the others are called transitional alumina.[1,2]

Alumina (Al2O3) is a commonly used support material for cata-
lytic reactions due to its thermal and mechanical stability. It
can be produced from bayerite (Al[OH]3) or boehmite
(AlOOH) by thermal dehydration. Different forms of alumina,
such as γ, δ, θ, and α, can be obtained by changing the calcina-
tion temperature. α -Al2O3 has a crystallographically ordered
γ-Al2O3, with a high surface area, mesoporous structure, and
surface acid/base characteristics, is widely used as a support
and/or a catalyst in oxidation reactions.[3–7]
H2S a significant poisonous pollutant that originates from
coal gasification systems and petroleum refineries, and it is
released into the atmosphere in significant amounts. H2S can
be converted to elemental sulphur, which is an important

Can J Chem Eng. 2019;1–13. wileyonlinelibrary.com/journal/cjce © 2019 Canadian Society for Chemical Engineering 1
2 TASDEMIR ET AL.
raw material for the chemical industry, using the well-known
Claus process. In the Claus process, 90-96% H2S conversion
can be obtained in two catalytic reactors.[8] Due to increased
environmental sensitivity, restrictions concerning the emis-
sion of gasses containing sulphur compounds have been
introduced. Therefore, the permissible level of sulphur emis-
sion cannot be reached using the Claus process.
The Claus process has been modified to the SuperClaus
process through the addition of a new H2S selective catalytic
oxidation reactor at the end of the process. Thus, 99% H2S
conversion can be achieved by the addition of this unit for
the selective catalytic oxidation reaction of H2S (Reac-
tion (R1))[9]:
H2 S + 1=2O2 ! ð1=nÞ Sn + H2 O ðR1Þ
However, the complete oxidation of H2S (Reaction (R2))
and sulphur oxidation (Reaction (R3)) reactions may also
take place, and SO2 formation can occur. The formation of
SO2 reduces the sulphur yield during catalytic
oxidation[10,11]:
H2 S + 3=2O2 ! SO2 + H2 O ðR2Þ
1=nSn + O2 ! SO2 ðR3Þ
The development of an active, selective, and stable cata-
lyst is the key for obtaining a high conversion of H2S with a
high sulphur yield. In the literature, active metals and/or
active metal incorporated supports were mostly used for
selective oxidation reactions. Among those, titanium,[12–15]
vanadium,[16–18] and iron-based metal oxide catalysts are
very common.[19–23] In some studies supported catalysts that
use Al2O3, SBA-15, clays (such as layered double hydrox-
ides and laponite), and SiC as the catalyst support materials
were tested in H2S oxidation.[23–28] In the literature, it has
been emphasized that the sufficient distribution of active
metals within the catalyst support is particularly important
for improving catalytic activity.[27,29]
V2O5-supported Fe-pillared (V/Fe-PILC) and alumina
pillared (V/Al-PILC) clays were investigated as catalysts for
H2S selective oxidation. The results showed that the addition
of vanadia onto the Fe-PILC and Al-PILC increased the cat-
alytic performance.[29,30] In the study conducted by
Davydov et al,[4] H2S oxidation by oxygen and SO2 was
investigated over a wide range of groups I-VIII metal oxides
such as MgO, Al2O3, ZrO2, CuO, and Mn2O3. They reported
that V2O5 was the most active catalyst and alumina was
among the lowest catalytic activity in H2S selective oxida-
tion among the 21 metal oxides studied.[4]
The catalytic activity of γ-Al2O3, (γ + χ) -Al2O3, and
α-Al2O3, which were synthesized by the hydrocarbon-
ammonia molding method, in H2S oxidation was provided
by Yashnik et al.[31] It was reported that ~40% H2S conver-
sion was obtained with γ-Al2O3 at 250
C. They suggested
that H2S was adsorbed on weak Lewis acid sites.
The study by Shen et al[32] synthesized γ-Al2O3 and
tested in H2S selective oxidation. A maximum sulphur yield
of 93% was obtained at 240
C. It was also reported that sur-
face acidity had a significant influence on catalytic activity.
In the selective oxidation of H2S, many active metals,
mainly vanadium, iron, and titanium, were used. Alumina is
usually used as a support material in this reaction, and there
are a few articles in which alumina is used as a direct cata-
lyst. Conflicting results were reported in the literature for the
catalytic performance of alumina in the selective oxidation
of H2S. The novelty of this study is to determine the cata-
lytic performance of pure alumina prepared using a novel
synthesis method.
The catalytic properties of alumina synthesized by a new
sol-gel route was investigated in the selective oxidation of
H2S and the results were compared with the corresponding
results obtained with commercial alumina. The catalytic per-
formance of these materials (without any active metal incor-
poration) was tested in the selective oxidation of H2S to
elemental sulphur at 250
C with different feed gas composi-
tions (O2/H2S: 0.5-2.0).
2 | EXPERIMENTAL
2.1 | Catalyst preparation and
characterization
In this work, the catalytic activity of two different alumina
materials was investigated in the selective oxidation of H2S
to elemental sulphur. One of these materials was commercial
alumina (alumina-com, Merck), while the other (SG-M) was
synthesized by a new sol-gel route called SG-modified. In
the modified sol-gel procedure, aluminum tri-seconder
butoxide (C12H27AlO3, 0.97 g/g, Merck), was used as the
aluminum source. Since ethylene diamine degrades in an
oxygen-containing atmosphere through the photochemical-
oxidative reaction with the produced hydroxyl radicals, a
glove-box, which provides an oxygen-free environment, was
used in this synthesis method.[33] All of the steps, except the
drying and calcination steps, were carried out in a glove box
filled with N2 at 25
C. First, the solution was formed by
mixing aluminum tri-seconder butoxide and ethyl
acetoacetate. Then, ethylene diamine-water (0.67 L/L) and
ethanol-water (0.87 L/L) solutions were added into the initial
solution, sequentially. After the formation of the gel, it was
aged for 1 week in the glove-box. Sol and gel formation
were observed. These materials were then dried at 100
C
overnight and calcined at 600
C for 24 hours.[10]
TASDEMIR ET AL.
N2 adsorption-desorption (Quantachrome Autosorb1),
XRD (Riguka D/MAX 2200), TGA-DTA (Setaram; experi-
mental conditions: 50 mL/min flow rate and 10
C/min
heating rate), TPR (Quantachrome Chembet 3000, experi-
mental conditions: 5% H2-95% N2 gas mixture and 10
C/min
heating rate), FTIR (Perkin Elmer Spectrum One), and XPS
(SPECS) were used for the characterization of the samples
prepared. The acidity of the materials was also determined
using pyridine adsorbed FTIR analyses. The experimental
details were given in our previous publications.[10,12]
2.2 | Catalytic tests
Catalytic activity tests were performed in a fixed bed quartz
reactor. A FTIR spectrophotometer (Perkin Elmer Spectrum
One) was used to analyze the reactor exit stream. The pro-
duced sulphur was collected in a sulphur condenser that was
placed between the reactor and the FTIR. The temperature
of this line was maintained at ~200
C in order to prevent
sulphur condensation. To prevent the condensation of the
water, the temperature between the sulphur condenser and
FTIR was maintained at ~100
C. In all of the experiments
the flow rate of the gas mixture was 100 cm3/min (measured
at 25
C). Different gas compositions (O2 /H2S: 0.5, 1.0, and
2.0) were used. A constant H2S concentration (0.01 L/L)
and 0.2 g of catalyst were used in all of the reaction tests.
Catalysts with an average diameter of 0.75 mm were used.
GHSV was 30 000 h−1 for the reaction test system. The
catalytic activity tests were performed at 250
C. The details
of the catalytic tests were given in our previous work.[10,12]
Equations (1) and (2) were used to determine the H2S con-
version and sulphur selectivity:
ðH 2 SÞin− ðH 2 SÞout
H 2 S Conversion ð%Þ = *100 ð1Þ
ðH 2 SÞin
ðH 2 SÞin− ðH 2 SÞout − ðSO2 Þout
S Selectivity ð%Þ = *100
ðH 2 SÞin − ðH 2 SÞout
ð2Þ
3 | RESULTS AND DISCUSSION
3.1 | Characterization of fresh materials
Some of the physical and structural properties of the synthe-
sized and commercial alumina materials are presented in
Table 1. Alumina that was prepared by the new sol-gel route
(SG-M) possessed a surface area approximately two times
higher (300 m2/g) than the surface of the commercial
3
alumina (139 m2/g). The pore diameter of the commercial
alumina was also smaller than the pore diameter of the alu-
mina synthesized in this study. The crystallite sizes of the
alumina materials were evaluated using the Scherrer equa-
tion.[34] The crystallite size of the commercial alumina was
larger than that of the SG-M. The nitrogen adsorption-
desorption isotherms and pore size distributions of alumina
materials are given in Figure 1.
The SG-M exhibited a type IV isotherm. This type of iso-
therm indicates that the SG-M consists of a mesoporous
structure. The isotherm with parallel adsorption and desorp-
tion branches showed a H1-type adsorption hysteresis, rep-
resenting a uniform pore size distribution. The presence of a
mesopore structure was also observed in the isotherm of the
commercial alumina. However, its hysteresis behaviour was
different than that of the synthesized SG-M alumina mate-
rial. This behaviour was similar to the H3-type hysteresis
loop, indicating narrow slit-shaped pores.[35,36] Catalysts
with mesoporous structures have become important in the
selective oxidation of H2S since sulphur deposition on the
structure of catalysts with small pore diameters cause cata-
lytic activity loss.[12] N2 adsorption-desorption isotherm ana-
lyses showed that the alumina material prepared by the
modified sol-gel route had a high surface area and more uni-
form pore size distribution compared to the commercial
alumina.
The low and high angle XRD patterns of the SG-M and
alumina-com are given in Figure 2. Both the SG-M and
alumina-com showed γ-Al2O3 crystalline phase (2θ:
66.76100, 45.7980, and 37.6065) in addition to amorphous
structures in the XRD patterns. No reflection peaks were
detected in the low angle XRD pattern of the commercial
alumina. Reflection peaks obtained in low angle region the
XRD pattern of the SG-M showed the formation of an
ordered mesoporous structure,[37] and this supported the
results obtained from the N2 adsorption-desorption analyses.
In order to observe the thermal stability of the SG-M alu-
mina prepared by the new sol-gel route, a TG/DT analysis of
the uncalcined sample was performed in air with a heating
rate of 10
C/min. The TGA/DTA profile is given in
Figure 3. Two small endothermic peaks were observed at
~95
C and 120
C in the DTA profiles of the uncalcined SG-M
sample. These peaks correspond to the removal of adsorbed
TABLE 1 Physical properties of alumina materials
BET Average
surface pore Pore
area diameter volume Crystallite
Catalyst (m2/g) (nm) (cc/g) size (nm)
SG-M 300 8.2 0.74 3.3
alumina-com 139 4.7 0.29 5.4
4 TASDEMIR ET AL.

water and alcohol.[38] The small narrow endothermic peaks at involving the elimination of OH groups through the occurrence
~245
C and 450
C showed the removal of structural water of the following reactions[38,39]:
from the uncalcined SG-M. This can be expressed as the
decomposition of pseudo-boehmite to produce γ-Al2O3, AlOðOHÞ:nH2 O ! AlOðOHÞ + nH2 O ðR4Þ

600 (A) 2 AlOðOHÞ ! γ − Al2 O3 + H2 O ðR5Þ

Adsorption Desorption

500
The exothermic peak at ~370
C was ascribed to the
Adsorbed Volume (cm3/g)

SG-M
removal of the residual organic group.[40] A 68% weight loss
400
was determined in the TG analysis of the uncalcined SG-M
300
between 25
C-1000
C and no weight loss was observed
after 600
C, at which point the SG-M was calcined. Organic
200 chemicals were used in the modified sol-gel method, there-
fore, the high amount of weight loss in the SG-M sample
100 alumina-com
was expected. The TG/DT analysis of the uncalcined SG-M
alumina indicated that a calcination temperature of 600
C
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 was appropriate for the formation of γ-Al2O3 crystallites
(P/P0) Relative Pressure
with a high surface area.[39]
(B) It has been reported that the surface acid/base properties
Alumina-com SG-M
of materials are important in determining catalytic perfor-
mances for the catalytic selective oxidation reactions.[12,27]
FT-IR studies of the pyridine adsorbed SG-M and alumina-
com were performed to investigate the acid/base properties
dV/dlog (d)

of the alumina in the band range of 1390 cm−1-1690 cm−1.

FT-IR spectra of both fresh alumina materials are given in
Figure 4. The peaks observed at 1445 cm−1 and 1595 cm−1
showed that the pyridine bonded on the Lewis acid sites for
the synthesized and commercial alumina. Absorption peaks
of the Bronsted acid sites, namely at 1540 cm−1 and
1 10 100 1640 cm−1, were not observed.[41,42] The FT-IR spectrum of
D (nm) the pyridine adsorbed SG-M and alumina-com showed that
FIGURE 1 A, Nitrogen adsorption-desorption isotherms; and B, both alumina had nearly the same Lewis acid sites on their
pore size distributions of alumina materials surfaces. The redox properties of the alumina materials were

FIGURE 2 XRD patterns of

alumina: A, low angle; and B, high angle
TASDEMIR ET AL. 5

investigated by TPR analyses. Figure 5 shows the TPR pro- 100% to ~62% within this reaction time period. Therefore,
files of the SG-M and alumina-com. catalytic activity test with alumina-com was not continued
As can be seen from Figure 5, small reduction peaks after 150 minutes due to the loss of its activity. In the case
were observed in the TPR profiles of the alumina materials. of SG-M, the activity test was continued to determine the
The TPR profiles showed that both alumina materials have stability. The SG-M catalyst, which was synthesized by the
weak redox properties. However, in the case of SG-M, a new sol-gel route and possessed an ordered mesoporous
reduction peak occurred at a somewhat lower temperature, structure, showed the complete conversion of H2S, and no
between 250
C-350
C, than that of the commercial alumina. deactivation was observed over a longer reaction period
In the literature, it was mentioned that alumina has a ten- (~400 minutes) with this catalyst. It is interesting to observe
dency to retain the structural oxygen.[39] that the deactivation process resulted a sharp decrease in
activity rather than a gradual decrease in the H2S conversion
3.2 | Catalytic activity tests of fresh catalysts for both alumina catalysts. This showed that the break-
through due to deactivation is significantly sharp. In general,
Catalytic activity tests of the SG-M and alumina-com in the fast deactivation processes cause sharp breakthrough curves.
selective oxidation of H2S to elemental sulphur were per- These results indicate that H2S conversion mainly takes
formed at 250
C with a stoichiometric feed ratio of O2/ place in a rather narrow reaction zone that moves along the
H2S. Conversions of H2S with respect to reaction time over reactor. The new SG-M catalyst synthesized in this work has
the commercial and synthesized alumina are presented in a higher surface area (more than twice) than the commercial
Figure 6. A significant activity loss was observed within the alumina. The SG-M catalyst with the high surface area
first 50 minutes of the reaction period in the test of commer-
cial alumina, and the conversion of H2S decreased from

80 0

70
H y d r o g e n Co n s u m p t i o n

-10
60
-20
50
Weight Loss (%)

exo DTA TGA SG-M

Heat Flow (mV)

-30
40
endo
30 -40

20
-50
10
alumina -com
-60
0
-70
-10
150 200 250 300 350 400 450 500 550 600 650 700 750 800
-20 -80 Temperature (°C)
0 100 200 300 400 500 600 700 800 900 1000
Temperature (°C)
FIGURE 5 Hydrogen TPR profile of: A, alumina-com; and B
FIGURE 3 TGA/DTA profiles of uncalcined SG-M alumina SG-M

alumina-com

Lewis
Lewis 1595
1445
Transmittance

SG-M

FIGURE 4 FTIR spectra of pyridine- 1390 1440 1490 1540 1590 1640 1690

adsorbed alumina materials Wavenumber (cm-1)

6 TASDEMIR ET AL.

alumina-com F I G U R E 6 H2S conversion values obtained

SG-M with alumina at different times on stream tests.
100

90
(250
C; 1% H2S-0.5% O2 + He)

80
H2S Co n v er s i o n (%)

70

60

50

40

30

20

10

0
0 100 200 300 400 500 600
Time (min)

provides the sharper deactivation process at a much longer

reaction time. The surface area of the SG-M changed from
300 m2/g to 278 m2/g after the reaction. The surface area of
the fresh alumina-com was 139 m2/g, and after the reaction
this value was 128 m2/g. These results showed that there
was a slight change in the catalysts surface areas after the
reaction. Considering the average pore diameters and pore
volumes of the catalysts, it was found that the commercial
alumina had a lower pore volume and a narrower pore diam-
eter (Table 1). Due to its smaller pore sizes, the pores are
plugged more easily, and this may have caused rapid deacti-
vation. A similar result was obtained in our previous
study.[12]
After the 150 minutes reaction tests, colour changes in
F I G U R E 7 H2S conversion and sulphur selectivity values
the used catalysts were observed. The colour of the alumina- obtained with alumina at 150 minutes (250
C; 1% H2S-0.5% O2 + He)
com changed from white to light-yellow, indicating the
deposition of the elemental sulphur. No colour change was
observed for the SG-M catalysts after the same reaction
period. H2S conversion and the sulphur selectivity of the and the sulphur deposited on the catalyst determined by
synthesized and commercial alumina were obtained at the EDS and XPS. There were no other sulphur-containing com-
150th minute and are compared in Figure 7. The alumina- pounds detected throughout the experiments. The calcula-
com showed 100% sulphur selectivity at that reaction time. tions showed that 93% of the inlet sulphur appeared at the
A small amount of SO2 formation was observed in the reac- outlet. Therefore, the mass balance holds within a 7%
tion test of the SG-M catalyst during a reaction period of accuracy.
150 minutes. The selectivity value obtained with the SG-M In order to explain the catalytic activity test results of alu-
catalyst was slightly lower (97%) than the corresponding mina materials in the selective oxidation of H2S, characteri-
value obtained with the alumina-com (Figure 7). A higher zation studies of the used alumina were also performed and
sulphur yield was obtained with SG-M (97%) than the compared with the corresponding characterization results of
alumina-com (62%) at 250
C. The high selectivity values fresh alumina. The XRD patterns of used SG-M and
showed that all of the alumina materials could prevent the alumina-com catalysts after activity tests at different reaction
complete oxidation of H2S (H2S + 3/2O2 ! SO2 + H2O) times are presented in Figure 8. The γ-Al2O3 crystalline
and/or sulphur oxidation to SO2 (1/nSn + O2 ! SO2) during phase with the amorphous structure was maintained after
the selective oxidation of H2S. 150 minutes, and after 630 minutes of reaction tests and
The sulphur mass balance was performed by considering there was no characteristic sulphur peak (eg, d: 3.85100,
the inlet and outlet amounts of sulphur. The sulphur at the 3.2180, 3.4440) in the XRD patterns of all of the used alu-
outlet was determined by considering the sulphur collected mina. These results indicated that the sulphur either had
in the condenser, the sulphur leaving in the form of SO2, small particles, was in the amorphous form, or there was
TASDEMIR ET AL. 7

FIGURE 8 XRD patterns of fresh and used SG-M

alumina catalysts γ γ
γ
used (630 min)
γ γ γ

used (150 min)

γ γ γ

Intensity
fresh

alumina-com
γ
γ
γ
γ γ
used (150 min)
γ
γ
γ
fresh

0 10 20 30 40 50 60 70 80 90
2θ

only a small amount of sulphur and was not detectable by

the XRD analyses. S 2p3/2

Intensity
In order to determine the presence of sulphur on the SG-
M catalyst, XPS analyses were performed at reaction times
Al 2s
of 150 minutes and 630 minutes. The XPS analyses of fresh 180 170 160
Binding Energy (eV) Al 2p
and used catalysts are shown in Figure 9. The XPS peak
observed at binding energy values of 119 eV
(1 eV = 1.602*1019 J) and 74 eV corresponds to Al 2 sec-
S 2p3/2
onds and Al 2p of Al2O3 in fresh SG-M. After selective oxi- Used (630 min)
dation runs for 150 minutes and 630 minutes, the SG-M still (c)
Al 2s
possessed the same XPS peaks, indicating the Al3+ state in
Intensity

Al 2p
the catalyst. There was no peak corresponding to sulphur
compounds in the XPS spectrum of the SG-M catalyst pre-
pared by the modified sol-gel method after 150 minutes of Used (150 min)
reaction time. A complete conversion of H2S and very high (b)
Al 2s
sulphur selectivity were obtained at the same reaction
Al 2p
period. At a reaction time longer than 630 minutes, a small
peak assigned to s 2p3/2 of aluminum sulphate (Al2[SO4]3))
including Al-O-S = O bonds in its crystal structure was
observed at a binding energy of 169 eV in the XPS spectrum
of SG-M catalyst.[10,43] The S/Al ratio of SG-M catalyst was Fresh
(a)
determined to be 0.011 at the end of the stability test (after
630 minutes of reaction time). Although 100% sulphur selec-
180 160 140 120 100 80 60
tivity was obtained with SG-M, the H2S conversion Binding Energy (eV)
decreased to 59% after 630 minutes of reaction time.
FTIR analyses were carried out to clarify the effect of the FIGURE 9 XPS analyses of: A, fresh; and used B, 150 minutes;
surface properties of SG-M on the selective catalytic oxida- and C, 630 minutes SG-M alumina catalyst
tion reaction. The XRD analyses indicated that SG-M was in
the γ-Al2O3 crystalline phase with an amorphous structure. and used modified sol-gel alumina (SG-M) in a band range
γ-Al2O3 is a well-known aluminum oxide form called transi- of 3200-3800 cm−1 that originated from the OH stretching
tional alumina. In the literature, it was reported that transi- are presented in Figure 10. The spectra of the fresh SG-M
tional alumina possess well-defined hydroxyl bands and that showed the presence of different types of surface hydroxyl
the acid-base properties of alumina can be attributed to the groups on the surface. The peak at 3768 cm−1 is due to I6
presence of these hydroxyl bands.[44,45] The surface OH group, and bands at 3611 cm−1 and 3630 cm−1 indicate
hydroxyl group in the presence of alumina has a significant type III OH groups.[46] The type II66 OH group, which indi-
effect on the catalytic activity. The FTIR spectra of the fresh cates the OH band bound to the octahedrally coordinated
8 TASDEMIR ET AL.
3450
3611 3450
3611
Absorbance
3750 3730
3903
3764
3853
3611
3750 3630
3730
3764
3853
3903
3950 3750 3550 3350
Wavenumber (cm-1)
F I G U R E 1 0 FTIR of: A, fresh; and used SG-M alumina (B,
150 minutes; and C, 630 minutes)
two Al3+ ions, is located at 3730 cm−1. The peak at
3750 cm−1 belongs to the type II surface hydroxyl groups
on γ-Al2O3.[10] In the spectra of SG-M before and after reac-
tion, the large band centered at 3450 cm−1 was due to the
presence of adsorbed water on the surface.[47] The intensity
of the peak centered at 3450 cm−1 was observed to increase
in the after-reaction samples of the SG-M catalyst. This may
be due to the adsorption of the water,[48] which is also a
reaction product (Reaction (R1)).
In the literature, similar FTIR spectra indicating vibra-
tions of different types of hydroxyl groups on alumina were
reported in many studies.[44,46,49,50] After 150 minutes of
reaction, the FTIR spectrum of SG-M showed that the inten-
sity of the peaks at 3610, 3630, 3730, and 3764 cm−1
decreased. The peaks corresponding to the surface hydroxyl
groups disappeared in the spectrum of the used SG-M after
630 minutes of reaction. Liu and Truitt[46] emphasized the
relationship between the surface OH groups and the Lewis
acid sites for the reactivity and they reported that the surface
hydroxyls and Lewis acid sites were adjacent to each other.
In the study by Lo et al[45] regarding H2S adsorption on the
γ-Al2O3 surfaces, it was reported that H2S was not physi-
cally adsorbed on the hydroxyl group. H2S adsorption on the
γ-Al2O3 surfaces only involves coordination to surface Al
sites. In the same study, it was mentioned that there are two
different types of adsorption on alumina: one is the irrevers-
ible adsorption on a Lewis acid site; and the other is the
reversible adsorption on a Lewis basic site through a hydro-
gen band.[45] In the work of Ryczkowski,[44] it was men-
tioned that reaction intermediates and products were
1595
(c) 1445
used (630 min)
Transmittance
(b)
used (150 min)
(a)
Fresh
3150
1390 1440 1490 1540 1590 1640 1690
Wavenumber (cm-1)
F I G U R E 1 1 FTIR spectra of pyridine adsorbed SG-M before
and after reaction period
adsorbed on Lewis acidic centers of catalysts such as Fe2O3/
γ-Al2O3, γ-Al2O3. Reshetenko et al,[51] using FTIR analyses,
suggested that H2S adsorbed on Al2O3 interacts with the sur-
face oxygen to form the oxygen-sulphur compounds which
then transform into elementary sulphur. As seen from previ-
ous studies, the presence of hydroxyl groups and the Lewis
acidity of alumina are important in catalytic application and
H2S adsorption. Studies emphasizing the importance of the
acidity of the catalyst in H2S selective oxidation are pres-
ented in the literature.[12,13,27] Zhang et al[27] reported that
H2S is adsorbed on the acidic sites of the catalyst and these
acidic sites improve the catalytic activity. They also indi-
cated that OH groups on the catalyst surface specifically
increase the Lewis acidity. In particular, strong Lewis acid
sites interact with OH groups (type I6) with a 3764 cm−1
band because this provides an interaction between the
adsorbed molecules and the alumina surface.
FTIR analyses of pyridine-adsorbed on used SG-M alumina
were also carried out to identify the change in surface Lewis acid-
ity after the reactions. As mentioned before, the SG-M catalyst
had Lewis acid sites (1445 cm−1 and 1595 cm−1 in Figure 4) on
its surface. As seen in Figure 11, it was observed that the intensity
of the peaks corresponding to the Lewis acid sites decreased sig-
nificantly after a reaction period of 630 minutes. This observation
was consistent with the decrease in the surface hydroxyl groups
of SG-M. It was concluded that the bond between the sulphur
and alumina caused a decrease in the surface hydroxyl groups
and initiated a loss in catalyst activity.
FTIR analyses were performed using alumina-com and
SG-M catalysts after selective oxidation runs for reaction
TASDEMIR ET AL.
periods of 150 minutes and 630 minutes in order to investi-
gate the deposited sulphur on the alumina surface. The FTIR
spectra of the synthesized and commercial alumina are given
in Figure 12. Two broad peaks between 1200-1300 cm−1
and 1000-1150 cm−1 were observed in the FTIR spectrum
of the alumina-com (Figure 12A). The maximum absorbance
of the peaks at 1257 cm−1 and 1230 cm−1 were observed
within a range of 1200-1300 cm−1. The peak at 1230 cm−1
is attributed to S = O stretching vibrations due to the sulphur
that is bound with oxygen. Sulphites with a strong S = O
vibration appear from 1240-1180 cm−1.[52] Also, the other
broad peak observed at 1000-1150 cm−1 provides the
highest absorbance value at two wavelengths, namely, 1053
and 1068 cm−1. In the literature it was reported that sulphur
compounds with an S = O double bond and two Al-S single
bonds of sulphur/oxygen functional groups in sulphoxide
provided S = O stretching vibration within the range of
1030-1070 cm−1 absorbance band.[52,53] Thus, the broad
peaks within the range of 1000-1150 cm−1 were due to the
sulphoxide structure containing an S = O double bond and
two Al-S bonds. The peak located at 1257 cm−1 indicates the
chemisorption of sulphur on alumina.[54] Therefore, the FTIR
analyses of the used alumina-com showed that a significant
amount of deposited sulphur was bound to Al. As a result of
the FTIR analyses of alumina-com, the formation of com-
pounds with sulphur/oxygen functional groups, which were
bound with alumina, can be determined to be the cause of the
decrease in the activity of the catalyst early in the
reaction time.
In the FTIR spectrum of the used SG-M, after
150 minutes of reaction time (Figure 12B), two broad peaks
centered at 1145 and 1325 cm−1 were observed. S = O
SG-M 1135
1175
1100
1325 1235
1360 1145
(c)
1235
Absorbance
1325
(b)
1068
alumina -com
(a)
1257 1230
1400 1300 1200 1100
Wavenumber (cm -1)
FIGURE 12 FTIR spectra of used alumina-com and SG-M in
the sulphur region
9
stretching in the sulphone functional group was reported to
be observed between 1165-1135 cm−1 (symmetric SO2
stretching) and 1340 cm−1-1310 cm−1 (asymmetric SO2
stretching), respectively.[52] The functional groups that con-
tained a sulphur atom with two S = O bonds, shortened as
SO2, were called sulphones. Also, Şentürk et al[54] reported
that peaks at 1140 cm−1 and between 1320-1326 cm−1 were
related to the sulphur that was bound to oxygen in the alu-
mina structure. Additionally, small peaks at ~960 cm−1,
1000 cm−1, and 1235 cm−1 were observed in the spectrum
of SG-M. The small peak at 1235 cm−1 shows the formation
of a small amount of the sulphite functional group
(1240 cm−1-1180 cm−1). Other peaks at ~960 cm−1 and
1000 cm−1 indicated the presence of the sulphur to oxygen
bond. The FTIR spectra of the used SG-M after 150 minutes
of reaction time indicated that the sulphur was significantly
bound with the oxygen.
The FTIR spectrum of SG-M after 630 minutes of reac-
tion time is given in Figure 12C. The peak centered at
~1325 cm−1 shows that sulphone functional groups are still
present despite the continuation of the reaction period. The
peak at 1235 cm−1 related to the sulphur bound to oxygen
became slightly more pronounced. The formation of new
peaks at ~1059 cm−1 and 1135 cm−1 wavelengths were
detected. These peaks showed the beginning of the forma-
tion of the Al-S bond as the sulphoxide functional group.
Also, the peak at ~1175 cm−1 corresponding to Al2(SO4)3
was observed. The small shoulders at 1100 cm−1 and
1360 cm−1 were detected after a 630 minute run using SG-
M alumina, and these peaks belong to the surface sulphates
on alumina. This phenomenon confirmed that the amount of
sulphur bound to Al increased as the reaction time prog-
ressed. After a 630 minute run, the FTIR spectra of SG-M
indicated that most of the sulphur was bound to oxygen
while some of it was bound to Al, causing a decrease in the
630 min catalytic activity of the synthesized alumina. In the FTIR
998
spectra of the used SG-M for all of the reaction periods,
1059 1030
915 there was no peak corresponding to chemisorbed sulphur on
Al as there had been in the case of alumina-com. Therefore,
1000
960
the complete conversion at 150 minutes obtained with the
150 min SG-M catalyst decreased as the S-Al bond formation started.
In the literature, infrared bands of S-H stretching were
1053
reported at wavenumbers of 2590 cm−1-2560 cm−1. In our
FTIR spectra of all of the used alumina catalysts, the forma-
150 min
tion of S-H stretching was not observed. Wavenumbers of
SOx species observed in the FTIR spectra of the alumina are
summarized in Table 2.
1000 900
The catalytic activity of SG-M, which was highly active
and stable in the selective oxidation reaction of H2S, has
also been investigated with different O2/ H2S ratios at
250
C for 150 minutes of reaction time. The H2S
10 TASDEMIR ET AL.

TABLE 2 Wavenumbers detected in FTIR spectra of alumina after the selective oxidation reaction runs

SG-M
alumina-com
Compounds 150 min 150 min 630 min
−1
… 1000 and 960 cm 998 and 915 cm−1

(960-1000 cm−1; ~910 cm−1)[54]

1257 cm−1 … …

(1255 cm−1)[54]
… 1325 and 1145 cm−1 1325 cm−1

(1140 cm−1;1326-1320 cm−1)[54]

1068 and 1053 cm−1 … 1059 and 1135 cm−1

(1050-1065 cm−1; 1135 cm−1)[54]

1230 cm−1 1235 cm−1 1235 cm−1

(1240–1180 cm−1)[52]
Al2(SO4)3 … … 1175 cm−1
(1170 cm−1)[54]
Surface sulphates on Al2O3 … … 1100 and 1360 cm−1
(1100; 1368 cm−1)[54]

conversion and sulphur selectivity results are presented in

Figure 13.
As can be seen from Figure 13, the complete conversion
of H2S was obtained with different gas compositions. Possi-
ble side reactions (H2S + 3/2O2 ! SO2 + H2O and
1/nSn + O2 ! SO2) were successfully prevented even in the
presence of excess oxygen in the feed stream. A high sul-
phur yield was obtained with this new sol-gel route alumina
catalyst at 250
C. A comparison of performance of the syn-
thesized alumina catalyst in the present study with the results
reported in some of the recent publications in H2S selective
oxidation reaction is given in Table 3.
Alumina has the potential to be a support material in
many catalytic processes, particularly in oxidation reac- F I G U R E 1 3 H2S conversion and sulphur selectivity values
tions. In this work, alumina was synthesized by a new obtained with SG-M with different O2/ H2S ratios for 150 minutes of
sol-gel route and used directly as a catalyst without any reaction time (T = 250
C)
TASDEMIR ET AL. 11

TABLE 3 Comparison of the performance of the synthesized SG-M catalyst with studies in the literature

Researcher Catalyst Reaction condition Sulphur yield (%)

Eslek and Yasyerli [19]
2Fe-2Ce T: 250
C 98
O2/ H2S: 0.5
GHSV: 21 000 h−1
Tasdemir et al[12] Ti-Fe T: 250
C 98
O2/ H2S: 0.5
GHSV: 30 000 h−1
Bineesh et al[30] 7 wt% V/Fe-PILC T: 260
C 95
O2/ H2S: 0.5
GHSV: 10 000 h−1
Zhang et al[27] 7 wt%Fe/Al-Lap T: 180
C 95
O2/ H2S: 0.5
GHSV: 7000 h−1
Palma and Barba[16] 20 wt% V2O5/CeO2 T: 250
C 83
O2/ H2S: 0.5
GHSV: 180 000 h−1
Chun et al[13] TiO2 T: 275
C 93
O2/ H2S: 0.5
30 wt% TiO2/SiO2 GHSV: 3000 h−1 93
Li et al [20]
FeSbO4 (Fe/Sb:3/2) T: 260
C 100
FeSbO4 (Fe/Sb:3/4) O2/ H2S: 5 76
[55]

Tasdemir et al CeO2 T: 250 C 68
O2/ H2S: 0.5
GHSV: 30 000 h−1
Shen et al[32] γ-Al2O3 T: 240
C 93
O2/ H2S: 0.5
Yashnik et al[31] γ-Al2O3 T: 250
C 40
O2/ H2S: 0.5
GHSV: 6000 h−1
Uhm et al[56] 10 wt% Cr/SiO2 T: 250
C 56
O2/ H2S: 0.5
GHSV: 3000 h−1
This study γ-Al2O3 T: 250
C 97
O2/ H2S: 0.5
GHSV: 30 000 h−1

active metal incorporation in the H 2S selective oxidation.
Most of the catalysts in other studies were synthesized
through the use of metals, which are active for the H 2S
selective oxidation reaction. When the activities of cata-
lysts were compared, it was determined that the activity
achieved in this study, which only uses alumina, was at
least as high as the activity of other catalysts. SG-M pro-
vided complete H 2S conversion for ~400 minutes. This
result showed that SG-M exhibited successful stability.
An alumina that has uniform pore size distribution with
Lewis acid sites was developed by a new sol-gel route.
High catalytic activity was obtained in H2S selective oxi-
dation with this catalyst. It was determined that the meso-
porous SG-M alumina catalyst that was synthesized by
the new sol-gel route is a significant addition to the litera-
ture on this subject.
4 | CONCLUSION
In this study the catalytic activities of modified sol-gel syn-
thesized alumina (SG-M) and commercial alumina were
investigated for the selective oxidation of H2S to elemental
sulphur. Both SG-M and alumina-com have γ-Al2O3 a crys-
talline phase with an amorphous structure. While the mate-
rial synthesized using the new sol-gel route (SG-M) has a
high surface area and a uniform pore distribution, it has been
observed that commercial alumina has narrow slit-shaped
12
pores in its structure. Lewis acid sites were detected on both
the catalyst surfaces. The complete conversion of H2S and
high sulphur selectivity over SG-M alumina was obtained,
while the alumina-com lost its catalytic activity at earlier
reaction times at 250
C with a feed containing a stoichio-
metric ratio of H2S to O2. FTIR analyses showed that the
SG-M alumina had different types of surface hydroxyl
groups, which were responsible for the catalytic activity, and
FTIR analyses of the used SG-M and alumina-com provided
important clues about the differences in the catalytic activity
in the selective oxidation of H2S. After 150 minutes of reac-
tion time, the FTIR analyses of the spent alumina-com
showed that the largest fraction of deposited sulphur was
bound to Al in the form of sulphoxide and sulphite. This
could have initiated the activity loss at early reaction times.
In the same reaction period, sulphur was bound to oxygen,
as sulphone on the surface of SG-M, and the deactivation of
the catalyst was not observed. The formation of bonds
between sulphur and aluminum was thought to cause a
decrease in the H2S conversion over SG-M alumina in the
stability test. High sulphur selectivity was obtained with SG-
M in the presence of excess oxygen in the feed stream. In
conclusion, as a catalyst without any active metal, SG-M
synthesized by the new sol-gel route and with a uniform
mesopore structure showed high catalytic activity in H2S
selective oxidation and, therefore, is a promising catalyst for
this reaction.
ACKNOWLEDGEMENTS
The Türkiye Bilimsel ve Teknolojik Araştirma Kurumu
(TUBITAK, Grant 114 M185) and the contributions of Pro-
fessor Timur Dogu of Orta Dogu Teknik Üniversitesi are
gratefully acknowledged.
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How to cite this article: Tasdemir HM, Yagizatli Y,
Yasyerli S, Yasyerli N, Dogu G. A new sol-gel route
alumina for selective oxidation of H2S to sulphur.
Can J Chem Eng. 2019;1–13. https://doi.org/10.1002/
cjce.23609