Chinese Chemical Letters 24 (2013) 167169

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Chinese Chemical Letters

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Original article

Novel ZnOAl2O3 composite particles as sorbent for low temperature H2S removal
Hamid Tajizadegan a,*, Mehdi Rashidzadeh b, Majid Jafari a, Reza Ebrahimi-Kahrizsangi a
a
b

Department of Materials Engineering, Najafabad Branch, Islamic Azad University, P.O. Box 517, Isfahan, Iran
Catalysis & Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-137, Tehran, Iran

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 28 September 2012
Received in revised form 13 December 2012
Accepted 24 December 2012
Available online 4 February 2013

ZnOAl2O3 composite particles composed of ZnO nanosheets (thickness of 4080 nm) on alumina
particles were prepared by heterogeneous precipitation method using bayerite seed particles. The asprepared composite particles were characterized in terms of crystal structure, morphology, surface area
and pore volume. The composite particles were used as sorbent for H2S adsorption at low temperature,
and were compared with pure ZnO sorbent. The composite sorbent showed a greater sulfur adsorption
capacity (0.052 g/g) than pure form of ZnO (0.028 g/g). This signicant improvement was mainly
attributed to higher surface area, more pore volume and unique morphology in nanoscale, which were
also obtained by low cost presented method in this work for synthesis of ZnO sorbent supported on
alumina particles.
2013 Hamid Tajizadegan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights
reserved.

Keywords:
ZnO
H2S
Composite
Surface area

1. Introduction
Presently, many industrial processes generate signicant
quantities of hydrogen sulde (H2S). Due to the fact that it is
extremely toxic, hazardous and corrosive, H2S gas must be
removed completely [1]. ZnO has a high equilibrium constant in
reaction with H2S gas, even in low temperatures (below 300 8C)
[1,2]. Despite thermodynamic conditions, occurrence of this
reaction can be limited by kinetic conditions, especially in low
temperatures [1,3]. This reaction takes place between the gas
phase and surfaces of the solid phase; and hence, external mass
transfer and internal mass transfer (diffusion) play key roles in the
adsorption process [4]. In this regard, many scientists have
attempted to modify the ZnO sorbents in different ways, such as
using: (i) nano-sized ZnO with the aim of reducing the diffusion
distance (internal mass transfer) [5], (ii) high surface area ZnO in
order to provide more active sites on the ZnO sorbents [6], (iii)
porous morphology of nano-ZnO for reducing the external mass
transfer resistance of H2S [7,8], (iv) catalyst support for introducing
higher surface area, more pore volume and more catalytic sites of
ZnO nanoparticles, such as mesoporous silica [9]. In spite of good
performance of ZnO sorbents supported on mesoporous silica, they
can hardly transfer into the industrial scale due to the high
production cost [911]. For this reason, activated alumina is used
extensively as support in a large industrial scale [1214].

* Corresponding author.
E-mail address: Hamid_tjz@yahoo.com (H. Tajizadegan).

Therefore, in the present study, considerable efforts have

been devoted to designing a one-step, effective approach with
low cost of materials in order to prepare ZnO sorbents with
nano-size, higher surface area and a unique morphology. In this
regard, attempts were rst made to support ZnO sorbents on
alumina particles via heterogeneous precipitation on bayerite
(Al(OH)3) particles and also by using urea as a homogeneous
hydrolysis agent. Finally, compared to pure ZnO sorbent, the
adsorption performance of new composite sorbent was evaluated. It should be mentioned that, this is a new method in the
eld of synthesis and improving ZnO sorbents supported on
alumina for H2S adsorption at low temperature.
2. Experimental
ZnOAl2O3 sorbent with ZnO content of 80 wt% was prepared
via heterogeneous precipitation using bayerite particles as seed.
First, 0.3 mol/L zinc acetate dehydrate (Zn(CH3COO)22H2O, Merck,
99.5%) solution was mixed with urea (NH2CONH2, Merck, 98%) by
mole ratio of 1:6, respectively. Then, bayerite powder (Al(OH)3,
Ardakan Industrial Ceramics Co., 98% purity, mean particle size
4 mm) was added to the previous solution. After that, the solution
was placed in an oil bath and reuxed under magnetic stirring at
90 8C for 4 h. By heating the solution, urea hydrolysis led to
precipitation of zinc carbonate hydroxide (Zn5(CO3)2(OH)6) on
bayerite seed particles (Eqs. (1) and (2)). After being reuxed, the
obtained precipitate was ltered and washed with distilled water
several times. Synthesis of high purity ZnO sorbent was similarly
followed without the addition of bayerite powder. All samples

1001-8417/$ see front matter 2013 Hamid Tajizadegan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
http://dx.doi.org/10.1016/j.cclet.2013.01.027

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H. Tajizadegan et al. / Chinese Chemical Letters 24 (2013) 167169

were dried at 40 8C for 24 h and then were calcined at 400 8C for 3 h

at a heating rate of 10 8C/min. Also, high purity Al2O3 sample was
synthesized by calcination of bayerite powder at 400 8C for 3 h
without any pre-treatment.
CONH2 2 H2 O ! 2NH4 HCO3  OH

(1)

5Zn2 2CO3 2 6OH ! Zn5 CO3 2 OH6

(2)

The crystal structure of sorbents was characterized by X-ray

diffraction (XRD, Philips, operated at 40 kV and 30 mA) using CuKa radiation. Fourier transform infrared (FTIR) spectrum was
performed using FT-IR-6300/JASCO in the wave number of 400
4000 cm1. The morphology and the size distribution of sorbents
were studied by eld-emission scanning electron microscope (FESEM, Hitachi S-4160). The BrunauerEmmettTeller (BET) specic
surface area (m2/g) and pore volume (Vt) of sorbents were
measured using N2 adsorption isotherms at 77 K (Micromeritics
ASAP-2010).
The H2S adsorption experiment was carried out at 150 8C and
1 atm. The adsorption test was performed in a U-type stainless
steel reactor (inside diameter of 6 mm) placed in an electric
furnace. 4.5 cm3 of sorbent particles (obtained by pressing,
crushing and then sieving to 0.51.41 mm particles) was loaded
in the middle of reactor and xed from both sides by glass wool. A
gas ow rate of 150 mL/min (composition: 1.02% H2S; balanced
with N2) was fed in the reactor. The H2S outlet gas from the reactor
was detected with a chemical detector. The experiments were
terminated when the outlet H2S concentration exceeded 5 ppm
(the minimum detector sensitivity) and the time of experiment
was dened as H2S breakthrough time. The sulfur capacity for the
prepared ZnO was also calculated from the H2S breakthrough time.
3. Results and discussion
The X-ray diffraction patterns of as-prepared samples are
presented in Fig. 1. The peaks corresponding to g-Al2O3 (JCPDS 100425 [14]) and wurtzite-type ZnO (JCPDS 36-1451) can be clearly
observed in XRD patterns of pure Al2O3 and ZnO samples,
respectively. The XRD pattern of ZnOAl2O3 composite sample
indicates sharp peaks of wurtzite-type ZnO. In addition, wide and
weak g-Al2O3 peaks cannot be detected easily in the composite
sample due to lower portion of this phase in X-ray diffraction, and
also intense ZnO peaks.
In order to conrm the XRD result, the ZnOAl2O3 composite
sample was analyzed with FTIR spectrometer at room temperature
(Fig. 2). The broad band centered at 3447 cm1 is due to OH
stretching vibration, and other bands at 1371, 1500 and 1630 cm1
are due to the CO, C5
5O and CO2 groups. As seen, the FTIR
spectrum shows an absorption peak at around 497 cm1 which is

Fig. 1. The XRD pattern of as-prepared samples: (a) pure Al2O3; (b) ZnOAl2O3
composite particles; and (c) pure ZnO.

Fig. 2. FTIR spectrum of ZnOAl2O3 composite particles.

the characteristic absorption peak of ZnO bond of ZnO [15]. Also,

the two broad absorption bands at around 610 cm1 and 747 cm1
were due to AlO stretching vibrations [15]. The FTIR results
suggested that ZnOAl2O3 composite was formed after 3 h
calcination at 400 8C as estimated in X-ray pattern.
Considering different morphologies of ZnO [7,16], the morphology of ZnOAl2O3 composite sorbent together with pure ZnO
sorbent was investigated by FE-SEM analysis (Fig. 3). The pure ZnO
sorbent is composed of agglomerated ZnO nanoparticles with
spherical shape and a size distribution of 4060 nm. But after the
combination of ZnO sorbent and Al2O3 support, spherical
morphology of ZnO particles changed to a at morphology by
forming ZnO nanosheets. The FE-SEM micrograph of 80ZA sample
is shown in Fig. 3b. The obtained micrograph indicated that the
80ZA sample consists of a porous structure of ZnO nanosheets that
are intercrossed with each other to cover alumina particles. Every
nanosheet has a thickness of about 4080 nm. Novochinskii et al.
[8] found that ZnO sorbents with at morphology have better
performances than agglomerated ZnO sorbents. Also, Rashidi et al.
[7] have interpreted the effect of morphology on adsorption
process by this fact that external mass transfer resistant of H2S gas
through the texture of sorbents is higher in the case of spherical
morphology. The FE-SEM observations are in complete agreement
with those obtained by Novochinskii et al. [8] and Rashidi et al. [7].
Therefore, in comparison with pure ZnO, the ZnOAl2O3 composite
sorbent showed a great stability against agglomeration and a
superior morphology in nanoscale, which can enhance the contact
area between H2S gas and solid active sites.
The BET surface area and total pore volume of as-prepared
samples are listed in Table 1. Pure ZnO sorbent has the lowest
surface area and total pore volume; and in contrast, pure Al2O3
support has the highest surface area and total pore volume. It is
obvious that by combining Al2O3 support and ZnO sorbent, the BET
surface area and total pore volume of composite sorbent can
sharply increase in comparison to pure sorbent. Therefore, the
textural properties of ZnO sorbent supported on alumina particles
is greater than the pure ZnO sorbent, which can mainly be related
to unique morphology of ZnO component obtained by the
incorporation of high surface area alumina particles. This result
suggests that using the ZnOAl2O3 composite sorbent can show a
better performance in H2S adsorption due to its higher surface area
and higher pore volume [4,6,9].
In order to evaluate the sulfur adsorption capacity of ZnOAl2O3
composite sorbent in comparison to pure ZnO sorbent at low
temperature of 150 8C, H2S adsorption test was carried out on both
samples (Table 2). It was concluded that composite sorbent has a
considerably higher sulfur capacity and higher breakthrough time
than pure ZnO sorbent. Therefore, it was conrmed that ZnO
sorbent supported on alumina particles by heterogeneous
precipitation method in this study was effective at low temperature H2S removal.

H. Tajizadegan et al. / Chinese Chemical Letters 24 (2013) 167169

169

Fig. 3. The FE-SEM micrographs of pure ZnO sorbent (a) and ZnOAl2O3 composite sorbent (b).

Table 1
BET surface area (SBET) and total pore volume (Vt) of as-prepared samples.
Sample

ZnO ratio (wt%)

SBET (m2/g)

Vt (cm3/g)

Al2O3
ZnO
ZnOAl2O3

0
100
80

341
16
96

0.36
0.13
0.29

Table 2
Sulfur adsorption capacity of sorbents.
Run

Sorbent

Breakthrough
time (min)

Breakthrough
capacity
(g of S/g of sorbent)

1
2

ZnO
ZnOAl2O3

76
140

0.028
0.052

4. Conclusion
Based on these results, ZnOAl2O3 composite sorbent prepared
by heterogeneous precipitation method using bayerite seed
particles has a great sulfur adsorption capacity with respect to
the pure form of ZnO. This fact is mainly attributed to the novel
composite sorbent with a higher surface area, unique morphology in
nanoscale (ZnO nanosheet array), higher stability against agglomeration and more micro and meso-pores volume. As a result, due to
the low cost and great efciency of the new sorbent, it is necessary to
optimize the amount of sulfur adsorption in a thorough research
work, which is to be conducted in our future work.
References
[1] D. Stirling, The Sulfur Problem: Cleaning up Industrial Feedstocks, The Royal
Society of Chemistry, Cambridge, 2000.

[2] C. Li, Z.S. Yu, S.M. Fang, et al., Fabrication and gas sensing property of honeycomblike ZnO, Chin. Chem. Lett. 19 (2008) 599603.
[3] J. Skrzypski, I. Bezverkhyy, O. Heintz, J.P. Bellat, Low temperature H2S
removal with metal-doped nanostructure ZnO sorbents: study of the origin of
enhanced reactivity in Cu-containing materials, Ind. Eng. Chem. Res. 50 (2011)
57145722.
[4] I. Rosso, C. Galletti, M. Bizzi, G. Saracco, V. Specchia, Zinc oxide sorbents for the
removal of hydrogen sulde from syngas, Ind. Eng. Chem. Res. 42 (2003) 1688
1697.
[5] Y.J. Lee, N.K. Park, G.B. Han, et al., The preparation and desulfurization of nano-size
ZnO by a matrix-assisted method for the removal of low concentration of sulfur
compounds, Curr. Appl. Phys. 8 (2008) 746751.
[6] T.J. Lee, I.H. Cho, N.K. Park, Desulfurization using ZnO nanostructure prepared by
matrix assisted method, Korean J. Chem. Eng. 26 (2009) 582586.
[7] R. Habibia, A.M. Rashidib, J.T. Daryana, A.M. Ali Zadeh, Study of the rod-like and
spherical nano-ZnO morphology on H2S removal from natural gas, Appl. Surf. Sci.
257 (2010) 434439.
[8] I.I. Novochinskii, C.H. Song, X. Ma, et al., Low temperature H2S removal from
steam-containing gas mixtures with ZnO for fuel cell application: 1. ZnO particles
and extrudates, Energy Fuels 18 (2004) 576583.
[9] G. Liua, Z.H. Huanga, F. Kang, Preparation of ZnO/SiO2 gel composites and their
performance of H2S removal at room temperature, J. Hazard. Mater. 215216
(2012) 166172.
[10] X. Wang, T. Sun, J. Yang, L. Zhao, J. Jia, Low-temperature H2S removal from gas
streams with SBA-15 supported ZnO nanoparticles, Chem. Eng. J. 142 (2008)
4855.
[11] L. Chen, J. Shen, Effect of resorcinol formaldehyde resin gel on the preparation of
Co/SiO2 catalysts for FischerTropsch synthesis, Chin. J. Catal. 33 (2012)
621628.
[12] Qiherima, H. Li, H. Yuan, Y. Zhang, G. Xu, Effect of alumina support on the
formation of the active phase of selective hydrodesulfurization catalysts Co
Mo/Al2O3, Chin. J. Catal. 32 (2011) 240249.
[13] Qiherima, H. Yuan, H.F. Li, Y.H. Zhang, G.T. Xu, Investigation on the active phase of
Co/Mo catalyst for selective HDS by low temperature in situ FT-IR, Chin. Chem.
Lett. 22 (2011) 366369.
[14] K. Wefers, C. Misra, Oxides and Hydroxides of Aluminum, Alcoa Research
Laboratories, Pennsylvania, 1987.
[15] C. Xu, J. Sun, B. Zhao, Q. Liu, On the study of KF/Zn(Al)O catalyst for biodiesel
production from vegetable oil, Appl. Catal. B 99 (2010) 111117.
[16] M. Mozibur Rahman, M.K.R. Khan, M. Raqul Islam, et al., Effect of Al doping on
structural, electrical, optical and photoluminescence properties of nano-structural ZnO thin lms, J. Mater. Sci. Technol. 28 (2012) 329335.