Fuel 157 (2015) 183190

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Selective removal of H2S from biogas using a regenerable

hybrid TiO2/zeolite composite
Chunguang Liu a,,1, Rui Zhang a, Song Wei a, Jing Wang a, Yang Liu a, Man Li b, Rutao Liu a,,1
a
b

School of Environmental Science and Engineering, Shandong University, Jinan 250100, China
Nuclear and Radiation Safety Monitoring Center in Shandong Province, Jinan 250013, China

g r a p h i c a l a b s t r a c t
To remove selectively H2S and reduce SO2 emission, a regenerable hybrid TiO2/zeolite composite was developed with double advantages of zeolite adsorption and TiO2 photocatalysis.
To verify the performance of the hybrid TiO2/zeolite composite in biogas purication, research about the effect of moisture and CO2 in biogas on H2S
removal was carried out.
Meanwhile, a research on the regeneration of TiO2/zeolite by basic washing and calcination is also conducted.

a r t i c l e

i n f o

Article history:
Received 29 March 2015
Received in revised form 27 April 2015
Accepted 1 May 2015
Available online 9 May 2015
Keywords:
H2S removal
TiO2 photocatalysis
Biogas purication
Zeolite

a b s t r a c t
It is difcult to selectively remove H2S and simultaneously avoid SO2 emission in biogas purication process with a low-cost and efcient method. In this study, an efcient hybrid adsorbent/photocatalytic
composite (TiO2/zeolite) was synthesized for the H2S removal and SO2 capture by coating TiO2 on the surface of cheap natural zeolite with an ultrasonic-calcination way. The TiO2/zeolite showed the highest H2S
removal capacity and lowest SO2 emission, compared with the single zeolite adsorption and TiO2 photocatalysis. H2S removal capacity and SO2 capture capacity of TiO2/zeolite were affected little by the high
level of CO2 in biogas, and were favored with the presence of moisture in the biogas. Moreover, the regeneration of the TiO2/zeolite could be easily achieved by a weakly basic washing and calcination. The results
indicated that the TiO2/zeolite was economically promising, sustainable and nontoxic material for the
direct elimination of H2S from biogas.
2015 Elsevier Ltd. All rights reserved.

Corresponding authors. Tel./fax: +86 053188364868.

1

E-mail addresses: chunguangliu2013@sdu.edu.cn (C. Liu), rutaoliu@sdu.edu.cn (R. Liu).

These authors contributed equally to this work.

http://dx.doi.org/10.1016/j.fuel.2015.05.003
0016-2361/ 2015 Elsevier Ltd. All rights reserved.

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C. Liu et al. / Fuel 157 (2015) 183190

1. Introduction
Biogas can be used as a natural gas substitute in households and
industry or be served as a renewable and sustainable energy source
for producing heat and power in internal combustion engines [1].
However, some impurities, e. g. hydrogen sulde (H2S) must be
removed before utilization to guarantee better performance and
to avoid environmental pollution of toxic gas emissions during biogas production, upgrading and utilization processes [2]. The content of H2S in biogas spans from 1030 to 5002000 ppm, which
is typically limited to a few ppm in the natural gas grids to avoid
facility corrosion, unnecessary production of byproducts, and possible public exposure and complaints [3,4]. Conventional H2S
removal methods include adsorption desulfurization, e. g. metal
oxides [5,6] and zeolite [7], biological desulfurization [8,9] and
chemical scrubbing [10]. Each method not only possesses its
advantages but also some disadvantages for H2S removal from biogas. For example, biological desulfurization could efciently
remove H2S, but was time-consuming and inefcient with high
H2S concentration compared to other methods [8]. Metal oxides
could adsorb H2S but with high temperature [11] and the regeneration was difcult [5].
TiO2 photocatalysis as an advanced oxidation process could be
an alternative way to remove H2S due to the chemical stability,
low toxicity, renewability, high efciency, low cost and with moderate reaction conditions [12,13]. However, some problems should
be concerned. One is the deactivation of TiO2 which could be
ascribe to the deposition of sulfur or sulfate on TiO2 surface covering the active sites during H2S photocatalytic oxidation process
[14]. Another one is the formation and emission of some toxic or
ecologically harmful components, e. g. SO2, in the H2S photocatalytic oxidation process [15]. The third one is that the research is
insufcient on the supporting materials of TiO2 with efcient
removal of H2S and avoiding or retarding emission of SO2 [16].
On the other hand, a promising technology for H2S removal from
biogas should be efcient and selective for H2S removal at moderate process conditions using cheap and ecologically harmless
reagents. Meanwhile, consumption of the reagents was not too
much or could be regenerated in a simple and low-cost way.
Moreover, non-desirable products should be avoided or retarded
during H2S removal and the construction should be designed in a
simple and easy way [1]. Based on this, it is necessary to develop
an efcient hybrid adsorbent/photocatalysis composite to avoid
or retard the deactivation of TiO2 and the formation of
non-desirable products. Zeolite could be an attractive TiO2 supporting material due to its superior porous structure, high special
surface and low cost [17,18]. On the other hand, zeolite could
improve TiO2 activity for H2S removal by prolonging the lifetime
of the photogenerated electrons and holes [19,20] and capture
SO2 to reducing its emission [21]. Therefore, an efcient hybrid
TiO2/zeolite composite would be developed by combining the
advantages of zeolite and TiO2.
Furthermore, the biogas from anaerobic digester reactor contained high concentration CO2 which is similar with H2S in many
of their physical and chemical properties. Therefore, CO2 and H2S
removal in biogas by adsorption are simultaneous and competitive,
resulting in excessive amount of absorption medium being used for
CO2 adsorption [4,22]. Thus, it is necessary to improve the selectivity for H2S removal from biogas containing high concentration CO2,
but little research work has been conducted about the effect of CO2
on H2S removal by TiO2 photocatalysis. On the other hand, the
moisture content of the biogas before and after dehydration is different. The moisture content in biogas not only inuences the
adsorption capacity of zeolite [23], but also affects the

photocatalytic efciency of TiO2 and the relative mechanisms of

H2S removal by TiO2 photocatalysis [15,24]. Many research studies
have investigated the improvement and inhibition of moisture on
the photocatalytic degradation of organic pollutants in gas streams
using TiO2 nano-particles or thin lms [25], while it is insufcient
to understand the effect of moisture on H2S removal and SO2 capture by TiO2-based photocatalyst.
The objective of this paper is to evaluate a hybrid TiO2/zeolite
composite for its desulfurization performance and clarify the
effects of moisture and CO2 in biogas on H2S removal by
TiO2/zeolite. The mechanisms of H2S removal by TiO2/zeolite photocatalysis in dry and moist condition were also studied. Finally, a
research on the regeneration of TiO2/zeolite by basic washing and
calcination was conducted.
2. Material and methods
2.1. Preparation of zeolite, TiO2, and TiO2/zeolite granules
Zeolite powder (N. F. K. Natural Zeolite Powder NO.70, GihHwa
Enterprise Co., Ltd, Japan) with a grain size of less than 100 lm was
made into paste by adding NaOH aqueous solution (pH = 10). The
paste was manually granulated to rounded granules (1.01.5 mm
in diameter). TiO2 powder was added into TiO2 slurry (Ishihara
Sangyo Kaisha, Ltd. Japan) to form paste and then granulated into
1.31.5 mm granules. The obtained two granules were then dried
at 105 C for more than 12 h and sintered in a mufe furnace. A series of sintered experiments (at 300 C, 400 C, 500 C for 1.0 h,
2.0 h, 3.0 h, respectively) were carried out to determine the optimum conditions (data not shown). The results showed that the
optimal condition was sintering for 2 h at 400 C to obtain maximum removal capacity and better mechanical properties. Finally,
the two kinds of granules were cooled to room temperature and
sieved to a diameter of 1.01.3 mm and 1.31.5 mm, respectively.
These zeolite and TiO2 granules with 1.31.5 mm diameter were
labeled as granular zeolite and granular TiO2, respectively. The
small granular zeolites with 1.01.3 mm diameter were impregnated with the excess of TiO2 slurry for 30 min under strong stirrings at room temperature, followed by ultra-sonication.
Ultra-sonication was performed on the TiO2 slurry using a probe
type sonicator (0.7 cm diameter Ti Horn, 140 W, 23 kHz) for
10 min to improve the surface area and the dispersion of TiO2.
The mixture of zeolite and TiO2 were placed in an oven at 60 C
for 2 h followed by the ltration and drying of TiO2/zeolite at
105 C for 24 h in an oven and further calcined at 400 C in a furnace for 2 h. Finally, the granules were cooled at room temperature
and labeled as TiO2/zeolite granules. TiO2/zeolite granules with different TiO2 content (3 wt%, 5 wt%, 8 wt%) were obtained by repeating the above operation.
2.2. Characterisation of TiO2/zeolite
X-ray powder diffraction (XRD, Bruker D5005 diffractometer,
Cu Ka radiation, scan range 2h between 10 and 90, 40 kV, 30 mA)
was used to identify the crystalline phases present in
TiO2/zeolite. Field emission scanning electron microscopy
(FE-SEM, Hitachi S-4700, secondary electron imaging mode, accelerating voltage 2 kV, beam current 10 mA, working distance 3 mm)
was used to observe the morphologies of zeolite deposited with
TiO2. A BrunauerEmmettTeller (BET) specic surface analysis
device (Coulter SA3100, US) was used to determine the specic
surface area and pore volume distributions of the zeolite, TiO2
and TiO2/zeolite.

C. Liu et al. / Fuel 157 (2015) 183190

2.3. Experimental setup and procedure

Three biogas purication columns (setup in parallel) were made
using clear glass tubes. Each laboratory column was 8 mm in interior diameter and 420 mm in height. The columns were lled with
zeolite, TiO2 and TiO2/zeolite to a height of 400 mm, labeled as
reactor A, reactor B and reactor C, respectively. The material was
held in place within the columns by a nylon wire that allowed
for gas ow without media loss. A UV-light (Philips, 40 W) was
set up in the center of the columns to supply irradiation
(3 mW cm2, 365 nm), and a compound parabolic concentrator
was installed to supply irradiation in the back of the columns.
The UV-light was managed by a timer, and then was used to control photocatalytic reaction in the columns. A schematic diagram of
the system is shown in Fig. 1.
Simulated biogas (SB1) (35% CO2, 65% CH4, dry), SB2 (35% CO2,
65% CH4 with 40% moisture), SB3 (35% N2, 65% CH4, dry) and SB4
(35% N2, 65% CH4 with 40% moisture) containing 0.1%
(1000 ppm) H2S were passed through the column lled with zeolite or TiO2 or TiO2/zeolite at a ow rate 0.02 L/min. The ow rate
of the simulated biogas was controlled using ow meters
(LZB-4DKF, Changzhou, China). The concentrations of H2S and
SO2 in the outlet gas were monitored with a Draeger (Pac III) electrochemical sensor. The test was stopped at the H2S breakthrough
concentration of 100 ppm. The removal capacities of each material
were calculated from the H2S concentration in the inlet gas, ow
rate, breakthrough point, and mass of material. The pH information
about the acidity and basicity of the material was determined by
immersing 0.2 g material powder into 8 mL distilled water and
stirring for 5 h to reach equilibrium, nally measuring the pH of
the water. For each sample, the test was repeated for three times
at 25 C.
2.4. Regeneration and reuse of TiO2/zeolite
To investigate the ability of regeneration and the reuse of
TiO2/zeolite granules and the availability of the regeneration

185

method, the regeneration of photocatalysts were carried out by

washing the used photocatalysts under mechanical stirring
(DF-101S, Zhengzhou, China) in deionized water or a 0.01 M
NaOH solution (10 mL/g) at 60 C for 5 h. After washing, the samples were driedat 110 C for 12 h in a drying oven (DHG-9053A,
Shanghai, China) or calcined at 400 C for 2 h in a mufe
(Y-CSQL-2.5-10, Changsha, China) after drying at 110 C for 12 h,
then cooled backup.

3. Results and discussion

3.1. Characteristics of TiO2/zeolite
The XRD pattern of TiO2/zeolite is also shown in Fig. 2a. The
results showed that TiO2 was coated successfully onto the zeolite.
It can be seen that the main peak positions of natural zeolite are
unchanged, and TiO2 exists in the form of anatase. The results also
reveal the structure of natural zeolite and TiO2 that exhibits good
thermal stabilization after 400 C calcination. Fig. 2b and c shows
the SEM images of zeolite and TiO2/zeolite. From the SEM images,
it is evident that TiO2 coating resulted in a rougher surface morphology of the zeolite and the TiO2 particles are relatively
non-uniform, either as nanoparticles or clusters attaching to the
zeolite surface. Most parts of TiO2 are distributed on the surface
of natural zeolite while a small fraction of TiO2 encapsulated into
the cavities of natural zeolite. Table 1 shows the average pore volume and specic surface area of the raw zeolite and TiO2/zeolite
calcined at 400 C. As can be seen in Table 1, average pore volume
and specic surface area of TiO2/zeolite become slightly smaller
than that of raw zeolite. This can be ascribed to the supporting of
TiO2 nanoparticles on/in the surface/pores of zeolite. The nanoparticles block the pores of the zeolite and decrease the average pore
volume and specic surface area of the samples. Although the average pore volume and specic surface area of TiO2/zeolite decrease,
they are still much larger than that of TiO2. Compared to BET and
meso/macropore surface area, micropore surface area of
TiO2/zeolite only slightly decrease, which could be owing to the
new micropore formation with TiO2 partly blocked meso/macropore during the process of origin micropore disappearance with TiO2
completely blocking. On the other hand, the surface area and pore
volume of TiO2/zeolite after ultrasonic treatment become larger
than that without treatment. The TiO2/zeolite after ultrasonic
treatment was used for further investigation.

3.2. Effect of TiO2 content on TiO2/zeolite photocatalytic activity

Fig. 1. Schematic diagram of experimental setup for H2S removal.

Fig. 3a and b presents the concentration variation of H2S and

SO2 during the photocatalytic process with time for different
TiO2/zeolite prepared with various amounts of TiO2. H2S removal
capacity using TiO2, 3% TiO2/zeolite, 5% TiO2/zeolite and 8%
TiO2/zeolite were 0.06 mmol/g, 0.10 mmol/g, 0.13 mmol/g and
0.15 mmol/g after 300 min treatment in moisture condition,
respectively; and the breakthrough points are at 140, 210, 270
and 300 min. This result indicates that small amount of TiO2 loading on the zeolite can enhance the photocatalytic performance
remarkably. However, when the amount of TiO2 increase from 5%
to 8%, H2S removal capacity of the TiO2/zeolite slightly increases
but SO2 emission obviously increases to 13 ml (shown in Fig. 3b).
This result demonstrates that an initial increase in the amount of
TiO2 will increase H2S removal and was optimized at 5%, whereas
a continuous increase in the amount of TiO2 will slightly increase
H2S removal but obviously increase the production of SO2.
Therefore, the 5% TiO2/zeolite was chosen for further investigation
and labeled as 5-TiO2/zeolite.

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C. Liu et al. / Fuel 157 (2015) 183190

Fig. 2. Characteristics of 5-TiO2/zeolite.

Table 1
Surface area and pore volume of zeolite, TiO2 and TiO2/zeolite before and after the desulphurization.
Sample

Meso/macropore BET
surface area (m2/g)

Micropore BET surface

area (m2/g)

Meso/macropore
volume (cm3/g)

Micropore
volume (cm3/g)

Fresh

Zeolite
TiO2
Zeolite/TiO2
Ultrasonic-zeolite/TiO2

52.18 0.03
8.45 0.03
20.35 0.03
28.32 0.03

64.64 0.03
32.22 0.03
62.27 0.03
65.10 0.03

0.582 0.003
0.112 0.003
0.281 0.003
0.301 0.003

0.301 0.003
0.061 0.003
0.162 0.003
0.291 0.03

Used

TiO2
Zeolite/TiO2
Ultrasonic-zeolite/TiO2

3.66 0.03
9.33 0.03
10.25 0.03

6.23 0.03
12.22 0.03
13.22 0.03

0.062 0.003
0.085 0.003
0.101 0.003

0.01 0.003
0.022 0.03
0.032 0.03

3.3. Performance of 5-TiO2/zeolite

3.3.1. Water effect on H2S removal

It is very important to completely remove sulfur-containing
compounds for avoiding second pollution during the combustion
of biogas. Thus, the monitoring of H2S removal and SO2 emission
was conducted simultaneously in this research. The results were
presented in Fig. 4. In dry conditions, reactor A exhibited a good
H2S removal capacity (0.05 mmol/g) before the appearance of
H2S breakthrough point, and no SO2 was detected, which indicated
that no H2S was oxidized into SO2 on the surface of zeolite. For
reactor B, although H2S removal capacity (0.06 mmol/g) was higher
than that of reactor A, another pollutant SO2 was produced. About
16 ppm SO2 was measured in the only TiO2 contained reactor B,
and the lower adsorption capacity of TiO2 could be the main reason
for the emission of SO2. In reactor C, 5-TiO2/zeolite showed the best
H2S removal efciency compared to reactor A and B with the
capacity of 0.10 mmol/g. Less SO2 (8 ml) was detected and SO2
emission point (180 min) was earlier than the appearance of H2S
breakthrough point of 200 min (shown in Fig. 4c). This indicates
that although strong oxidation occurred on the surface of

5-TiO2/zeolite along with the production of SO2, a large part of

SO2 was absorbed by 5-TiO2/zeolite due to its higher adsorption
capacity.
When zeolite, TiO2 and 5-TiO2/zeolite were exposed to moist
biogas respectively, H2S removal capacity decreased markedly in
zeolite contained reactor A of 0.03 mmol/g, little increased in only
TiO2 contained reactor B of 0.07 mmol/g, and increase clearly of
0.13 mmol/g in 5-TiO2/zeolite contained reactor C (shown in
Fig. 4b), which indicated that the moist condition inhibited H2S
removal with zeolite adsorption [7] but enhanced H2S removal
due to TiO2 photocatalysis [15,24]. Relative mechanism would be
stated in the following part. On the other hand, less SO2 of 13 ml
and 4 ml emission was detected and the start time of emission
SO2 lagged about 30 min in TiO2 and 5-TiO2/zeolite contained reactors B and C, respectively, compared to that in dry condition
(shown in Fig. 4d). The reason could be that SO2 or its oxide SO3
2
reacted with water to produce SO2
3 or SO4 resulting in the reduction of SO2 emissions. This indicates that the moisture in biogas
could inhibit SO2 emission produced from H2S oxidation by TiO2
[26]. 5-TiO2/zeolite enhanced H2S removal and SO2 capture as
the result of proton abstraction in basic Lewis sites of TiO2 intensied with its combination with the basic zeolite [16].

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C. Liu et al. / Fuel 157 (2015) 183190

control

100

120

3 wt%
5 wt%

80

8 wt%

60
40
20

80
60
40
20
0

50

100

150

200

250

300

50

100

150

200

250

300

Time (mins)

Time (min)

Fig. 5. Effect of CO2 on H2S removal in reactors A, B and C.

16
control

14

3 wt%

12

5 wt%

10

8 wt%

8
6
4
2
0
0

60

120

180

240

300

Time (min)
Fig. 3. Effect of TiO2 content on photocatalytic activity of 5-TiO2/zeolite.

3.3.2. CO2 effect on H2S removal

It is essential to explore the effect of CO2 on H2S removal by
5-TiO2/zeolite due to its acidity and higher content in biogas.
120

Reactor A

Reactor B

Reactor C

100

b
H2S concentration (ppm)

H2S concentration (ppm)

Fig. 5 shows the effects of CO2 on H2S removal under moisture conditions. It is clear that competition occurred between CO2 and H2S
leading to the reduction of H2S removal capacity in reactor A, in
which zeolite adsorption dominated H2S removal; but little effect
was observed in reactor B and C, where TiO2 photocatalytic governed H2S removal, especially in moist condition. Belmabkhout
et al. also proposed that zeolite posed higher CO2 selectivity [27].
In initial phase, zeolite and 5-TiO2/zeolite exhibited good performance on H2S removal, but zeolite was saturated quickly due to
abundant adsorption of CO2, resulting in reduction of H2S removal
capacity. Wang et al. [22] showed that H2S removal by zeolite
decreased as the result of the presence of adsorption competition
between CO2 and H2S. However, CO2 affected little on H2S removal
capacity of reactor B, in which the main H2S removal pathway was
TiO2 photocatalysis rather than zeolite adsorption. Moreover, weak
acid and lower adsorption capacity of TiO2 determined that
adsorption was not the main way for H2S removal in only TiO2 contained reactor [14]. In 5-TiO2/zeolite contained reactor C, the

80
60
40
20
0

Reactor A

120
100
80
60
40
20

50

100

150

200

250

300

50

Time (mins)

SO2 concentration (ppm)

Reactor B

Reactor C

0
0

20
Reactor A

Reactor B

Reactor C

15

100

150

200

250

300

Time (mins)

10

SO2 concentration (ppm)

SO2 concentration (ppm)

Reactor C
contained CO2
Reactor C

100

(b)

Reactor B
contained CO2
Reactor B

Reactor A
contained CO2
Reactor A

120

H2S concentration (ppm)

H2S concentration (ppm)

(a)

16

Reactor A

14

Reactor C

Reactor B

12
10
8
6
4
2
0

60

120

180

Time (mins)

240

300

60

120

180

240

Time (mins)

Fig. 4. H2S removal and SO2emissionin reactors A, B and C in dry (a and c) and moist (b and d) condition.

300

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C. Liu et al. / Fuel 157 (2015) 183190

presence of aboundant CO2 lowered H2S removal in some degree

by means of adsorption, but it affected little on H2S removal capacity in the whole process. Two facts could give an explanation. On
one hand, continuous oxidation of H2S on the surface of
5-TiO2/zeolite made the 5-TiO2/zeolite unsaturation on H2S, which
could enhance continuous adsorption of 5-TiO2/zeolite on H2S. On
the other hand, the presence of moisture in biogas could impede
CO2 adsorption [17] but improve H2S removal by photocatalysis
and the mechanisms would be stated in the following part.

oxidation of OH surface groups on TiO2 by the holes [28]. The production of S, and SO2 could be indirectly certicated by the decrease
in pore volumes and pH, shown in Tables 1 and 2, respectively. They
could be described as the following Eqs. 36.

OH 2h !  OH

3.3.3. pH changes of 5-TiO2/zeolite after treatment

pH values were determined by immersing the materials into
deionized water (3 ml/g) for 5 min and then checked by pH test
strips before adsorption and photocatalysis with results shown in
Table 2. It is found that the origin pH values of materials in reactors
A, B and C are 10, 6.3 and 10, respectively. The alkalinity of materials in reactors A and C is concerned with their preparation. After
treatment, the pH values of materials in reactors A, B and C
exposed to dry and moist biogas dropped to 8.1, 6.1, 6.8 and 8.3,
5.9, 5.9, respectively. The pH decrease of zeolite in reactor A could
be due to H2S and CO2 adsorption during treatment processes.
However, the decrease of TiO2 and 5-TiO2/zeolite in reactors B
and C was not only ascribed to H2S and CO2 adsorption, but also
to the formation of stronger acid, e. g. H2SO3, generating from
H2S oxidization with TiO2 photocatalysis [14]. It is worth mentioning that the pH value of the materials exposed to moist biogas
dropped more in reactor C but dropped less in reactor A compared
to that exposure to dry biogas. For reactor A, the reason could be
that moisture was unfavorable for H2S removal by zeolite adsorption [7]. For reactor C, when the 5-TiO2/zeolite was directly
exposed to moist biogas, a water lm was formed on the surface
of the 5-TiO2/zeolite. The lm presented in the small pores of
5-TiO2/zeolite favored to the solubility and dissociation of H2S.
H2S could be oxidized into SO2, then further oxidized to SO3, and
after its reaction with water, H2SO4 is formed resulting in the
decrease of pH values [8,24].

H2 Sads 4 OH ! SO2;ads 2H 2H2 Oads

3.4. Mechanism of H2S removal by 5-TiO2/zeolite

Although H2S removal pathways include adsorption and photocatalysis in 5-TiO2/zeolite contained reactor C, the key point of this
research is not adsorption but photocatalysis. Hypothetical photocatalytic reaction pathways in dry and moist conditions could be
described as the following Eqs. 113. In both condition, reactions
originated the excitation of TiO2 by UV-light to produce holes/electrons and transformation of H2S from gaseous state to adsorbed
state, described as Eqs. (1) and (2).

H2 Sads 2h ! Sads H2

Sads O2 ! SO2;ads

Under moist condition, after the adsorption of H2S, H2Sads could

be directly oxidized by holes or hydrolyzed to form HS
ads (Eq. (7)),
and then Sads could be produced from the oxidation of H2Sads and
HS
ads by holes (Eqs. (3) and (8)), similarly to the proposition of
Rasmussen et al. [26].

H2 Sads H2 O ! HSads H3 O

HSads h ! Sads H

7
8

SO2,ads could be produced not only from the oxidation of S by O2

(Eq. (4)) or OH hydroxyl radicals (Eq. (9)), but also from the oxida
tion of HS
ads by OH hydroxyl radicals (Eq. (6)) formed by the oxidation of either H2Oads or of OH surface groups on TiO2 by the holes
(Eq. (5)), and the HS derived from the reaction of H2S with H2O
(Eq. (7)).

4 OH Sads ! SO2;ads 2H2 O

SO2
4

The possible formation of

originated from the oxidation of
SO2 by O2 to form SO3, which is further rapidly hydrated into sulfuric acid due to its very hygroscopic nature, then sulfuric acid
reacted with hydroxyl ion on the surface of 5-TiO2/zeolite to form
SO2
4 , according to Eqs. 1012, which could explain the sulfate formation on the surface of 5-TiO2/zeolite and the non-detection of
SO3 in the gas phase. This was not only indirectly certicated by
the decrease in pore volumes and pH, shown in Tables 1 and 2,
respectively, but also was consistent with the proposition mentioned by Alonso-Tellez et al. [29].

2SO2;ads O2;ads ! 2SO3;ads

10

SO3;ads H2 Oads ! H2 SO4;ads

11

H2 SO4;ads 2OHads ! SO2

4 ads 2H2 Oads

12


Another pathway of SO2
4 formation was the reaction between HSads
and OH, Eqs. (13),

TiO2 hv h e

HSads 8 OH ! SO2
4 ads H 4H2 O

H2 Sgas ! H2 Sads

This process would be directly in competition with the formation of

SO2,ads produced by the reaction between Sads and OH (Eq. (5)),
which could be indirectly certicated by the decrease in SO2 production compared to that in dry condition, shown in Fig. 4c and d.

Under dry condition, H2Sads could be directly oxidized into sulfur by

holes, then sulfur could be partly oxidized by O2 into SO2, similarly
to the proposition of Portela et al. [15]. Another possibility, a thimbleful of H2S could be oxidized by hydroxyl radicals formed by the

Table 2
pH values changes of materials in reactors A, B and C before and after
desulphurization.

Dry biogas
Moist biogas

Origin pH
After treatment
After treatment

Reactor A

Reactor B

Reactor C

10
8.1
8.3

6.3
6.1
5.9

10
6.8
5.9

13

3.5. Regeneration of 5-TiO2/zeolite by washing or calcination

The regeneration of 5-TiO2/zeolite is a crucial factor in practical
application for H2S removal by adsorption and photocatalytic oxidation. The results are presented in Fig. 6. It can be seen that the
regenerated 5-TiO2/zeolite showed a good adsorption and photocatalysis capacity as the fresh one, which indicates that the
5-TiO2/zeolite is stable and efcient for H2S removal.
Furthermore, weakly basic washing and calcination were effective
method for the regeneration of 5-TiO2/zeolite. One point should be
noted that water as the regenerant only led to partial regeneration

C. Liu et al. / Fuel 157 (2015) 183190

Acknowledgments

100

Removal rate (%)

189

This study has been supported by The Fundamental Research

Funds of Shandong University (2014BT013) and (2015JC030)
and China Postdoctoral Science Foundation funded project
(2014M560555).

90
80
NaOH/400

70

NaOH
H2O/400

60

References

H2O

50
0

Time (h)
Fig. 6. Regeneration of 5-TiO2/zeolite by washing or calcination.

of the activity of the 5-TiO2/zeolite, although calcination was favorable to the regeneration efciency. Indeed, the 5-TiO2/zeolite
regenerated with water or followed with calcination at 400 C
resulted in a H2S removal rate of 72% and 82%, respectively, after
a reaction of 5 h, while the fresh photocatalyst still displayed a
conversion of 98%. By contrast, whatever the calcination, basic
washing with a 0.01 M NaOH aqueous solution was more efcient
to recover the 5-TiO2/zeolite, and the regeneration rate of 87%
without calcination and 93% with calcination, respectively. The
slight decrease compared to the fresh photocatalyst of 98% could
be ascribed to the loss of TiO2 during the successive washing, drying and calcination steps. The improvement of H2S removal after
basic washing treatment could be attributed to the isoelectrical
point change of TiO2 [16], fresh at 6.3. After adsorption, the surface
of 5-TiO2/zeolite was positively charged as TiOH2+ due to the
adsorption of acid gas (H2S, SO2, CO2), which was unfavorable for
the regeneration of the activity of 5-TiO2/zeolite as the result of
the deposition of sulfate anions on the surface of 5-TiO2/zeolite.
On the contrary, the negatively charged 5-TiO2/zeolite surface
was not only conducive to the resorption of acid gas but also in
favor of sulfate anions removal [29]. The efciency of the regenerative calcination treatment on 5-TiO2/zeolite could be explained in
consideration of the mechanisms and physical origin for the
observed increase in H2S removal. After calcination, the dispersion
of TiO2 on zeolite could be enhanced, and that the surface area and
volume of 5-TiO2/zeolite with site-blocking effect due to sulfur or
sulfate deposition could be improved [30,31].

4. Conclusions
The performance of the 5-TiO2/zeolite used in this research in
the process of hydrogen sulde removal from biogas was affected
little by the high level of CO2 in biogas, and favored with the presence of moisture in the biogas, especially in photocatalytic stages.
5-TiO2/zeolite showed the highest H2S removal capacity
(0.13 mmol/g) compared with the zeolite (0.05 mmol/g) and TiO2
(0.07 mmol/g), and the lowest SO2 emission compared with TiO2
in moist condition. Water present in the biogas reacted with holes
forming OH and with H2S forming HS, which contributed to H2S
removal by 5-TiO2/zeolite photocatalysis. Simultaneously, the
combination between TiO2 and zeolite could avoid TiO2 deactivation which stemmed the reaction between water and
CO2/SO2/SO3 forming carbonic/sulfurous/sulfuric acid on the surface of 5-TiO2/zeolite. Basic washing and calcination could regenerate the activity of the 5-TiO2/zeolite. Therefore, the 5-TiO2/zeolite
could be as a promising photocatalyst for the desulfurization of
biogas.

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