Applied Physics Frontier

February 2013, Volume 1, Issue 1, PP.9-15

Synthesis of Special Morphology ZnO Materials

and the Performance for Reaction Adsorption
Desulfurization of Thiophene
Jingcheng Zhang 1#, Jun Nan 1, Zhangyong Liu2, Haibin Yu 1, Shan Geng 1, Yulin Shi 1, Xiaolong Qu1,
Chenguang Liu3, Hongguang Liu 1
1. CNOOC Tianjin Chemical Research & Design Institute, Tianjin, 300131, China
2. Shandong Zhonghai chemical industry Co. Ltd, China
3. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao, 266555, China
#
Email: zjc8226@yahoo.com.cn

Abstract
Special morphology ZnO materials with smaller crystallite size were synthesized by hydrothermal homogeneous precipitation
method, and the corresponding Ni/ZnO adsorbents were prepared by incipient impregnation method. The materials obtained were
characterized by FE-SEM and XRD methods. The structure and the morphology of the porous materials were characterized by
XRD, SEM, N2 adsorption-desorption and TEM. Reactive adsorption desulfurization (RADS) of model gasoline using thiophene
as model sulfur-containing compounds over Ni/ZnO adsorbent was carried out in a fixed bed reactor in the presence of hydrogen.
The results showed that both the crystalline size and BET surface areas of special morphology ZnO were better than that of
commercial ZnO materials. Meanwile, the activity evaluations indicated that the Ni/ZnO adsorbents prepared with special
morphology ZnO exhibited good activity of removing thiophene. The sulfur adsorption capacity was maximized depending on
surface morphology and particle size of ZnO particles.
Keywords: Special Morphology ZnO; Surface Morphology; Crystalline Size; Hydrothermal Homogeneous Precipitation
Method; Reactive Adsorption; Thiophene

1 INTRODUCTION
Sulfur removal from refinery streams is becoming more challenging due to stringent environmental and new
government sulfur regulations. During combustion sulfur compounds in the fuel are converted to sulfur oxide (SOx),
the main reason for acid rain [1]. Several techniques have been utilized to desulfurize refinery fuels since 1950s.
Among all these technologies, reactive adsorption is a desulfurization technique that can be applied to remove very
low concentrations of sulfur from fuels, which has been implemented in S-Zorb desulfurization technology used on
industrial scale [2, 3]. This approach brings together advantages of catalytic and adsorption technologies. It is able to
remove rather stable compounds like thiophene and in the same time to achieve very low S concentration. The
method is demonstrated to possess some valuable features like low hydrogen consumption and absence of olefin
hydrogenation saturation reactions provoking decrease in octane number [4].
A literature survey reveals that Ni/ZnO is the most widely applied metal oxide to remove sulfur species because of
its high-sulfur binding capacity and favorable thermodynamics at moderate temperature. Tawara et al. reported that a
13% Ni/ZnO catalyst was certified as an adsorptive HDS catalyst for the kerosene-fed FC, which would keep less
than 0.03 wt ppm of the average sulfur for 1 year [5]. The ConocoPhillips’s S-Zorb process is the first real
commercial process of importance based on reactive adsorption. And also there are several S-Zorb gasoline units in
the ConocoPhillips’s refineries. The process is carried out under the following operating conditions: the temperature
of 370℃-410℃, the pressureof 0.7-2.8 Mpa and LHSV of 4-10h-1. However, during the adsorption reaction, only a
thin layer of ZnO can be accessed and the inner part of it is unavailable to the reactants unless the thickness of the
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adsorbent is extremely thin. To maximize the utilization and efficiency of the adsorbents, it may be a significant job
to explore new synthetic routes to the ZnO materials with favorable physical properties.
In the present work, we investigated the surface morphology and size influences of ZnO particle on the interaction of
thiophene and Ni/ZnO. ZnO were prepared in two ways. One was purchased from Sinopharm Chemical Reagent Co.,
Ltd, and the other was synthesized by hydrothermal homogeneous precipitation method. Surface morphology and
size influences of ZnO particles on the interaction of thiophene and Ni/ZnO were evaluated in a fixed bed reactor.

2 EXPERIMENTAL
2.1 Chemicals
Zn(NO3)2·6H2O, Ni(NO3)2·6H2O, urea, PEG-6000 and ZnO of analytical reagent grade was purchased from
Sinopharm Chemical Reagent Co., Ltd. Diatomite of chemical pure grade was purchased from Jilin Changbai
Diatamite Co., Ltd. All chemicals were used as received.

2.2 Preparation of Ni/ZnO adsorbents

Special morphology ZnO materials were synthesized by hydrothermal homogeneous precipitation method. The
preparation process was as follows: appropriate amount of Zn(NO3)2·6H2O was dissolved in deionized water to
obtain 1.0 M, and (NH2)2CO was added into the solution with a molar Zn:(NH2)2CO ratio of 1:3, a certain amount of
PEG-6000 was then mixed to the aqueous solution. A given volume (85 ml) of the stock solution was poured into a
Teflon bottle (100 ml) held in a stainless-steel autoclave. After the autoclave was sealed tightly, it was placed in a
temperature-controlled electric oven, heated at 120°C for 12h. The precipitate was then filtered, washed thoroughly
with water and alchol, and finally dired in air at 100°C overnight.
ZnO Precursors and Silica Sol used as inorganic binder was grinding for 30 min, and then extruded in 3.0 mm
diameter, heated at 120 °C for 12h. Finally, the mixture was calcined in air at 400°C for 2h.
The Ni/ZnO was prepared by using incipient impregnation method [6], Ni(NO3)2·6H2O was used as Ni precursor.
The solid were dried in an oven at 120 °C for 12h, and then calcined in air at 500°C for 4h. The adsorbent thus
obtained was labeled as ADS-1.
ADS-2 was prepared in the same way, except using commercial ZnO as ZnO precursor.

2.3 Characterization
The BET surface area of the catalysts was determined by nitrogen adsorption-desorption isotherm at 77K in an
ASAP2010 adsorption apparatus. The X-ray powder Diffraction (XRD) determinations were carried out in a
Panalytical X' Pert Pro MPD diffractometer, equipped with a curved graphite monochromator, using Cu-Kα radiation
(λ = 1.5406 Å) operating at 45 kV and 40 mA at a scanning rate of 5 min−1. Scanning electron micrographs were
obtained using Hitachi S-2380N scanning electron microscope.
The BET surface area of the adsorbents was measured by nitrogen sorption at -196 ℃ with a TriStar-3000 gas
absorption analyzer (Micromeritics Instrument Co.). The samples were degassed at 300℃ for 3h prior to the
measurement. X-ray diffraction (XRD) was measured by a Rigaku D/max 2500v/pc X-ray diffractometer (Cu Kα,
λ=0.154 06 nm, 40 kV, 40mA) in the step scanning mode (6o/min) with a 2θ range from 10o to 80o. The crystal
phase compositions of the adsorbents were identified by machting with the ICDD/JCPDS database. The average
crystallite size of various species was calculated by the Scherrer formula. The superficial shape and distributions was
analysed through Hitachi S-2380N scanning electron microscope.

2.4 Desulfurization experiments

The desulfurization experiments were carried out in a fixed bed reactor, using a mixture of cyclohexane and
thiophene as model compounds and approximately 10ml of adsorbent was used per run. Reaction temperature T =
280 C, space velocity = 2.0h-1, H2/Oil rate = 200:1. Prior to the activity test, the adsorbent was reduced in

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hydrogen flow at 450 °C for 4h (1.0 MPa, 50 ml/min).The reduced samples were used in the study. The products
were analyzed, quantitatively using a Agilent 6890N (with FID detector) and qualitatively using a Finnigan
SSQ710 GC-MS.

3 RESULT AND DISCUSSION

3.1 XRD characterization of ZnO and NiO/ZnO materials
Fig. 1a shows the X-ray diffraction pattern of the as-synthesized ZnO precursor and ZnO materials. The results
showed that the hydrozincite precursor (Zn4(CO3)2(OH)6，JCPDS 00-011-0287) was obtained in the hydrothermal
homogeneous precipitation process. The sharp diffraction peaks corresponding to zinc oxide (100), (002) and (101)
(JCPDF 01-087-0510) exhibit the as-synthesized zinc oxide has good crystallinity. The intensity of peaks is lower
than that of purchased commercial ZnO materials (see Fig. 1b), which means that the crystallite size is smaller. The
average crystallite size of the two ZnO materials analyzed using Scherrer equation, 29.5 nm for special morphology
ZnO and more than 100 nm for commercial ZnO, respectively.

101 Zn4(CO3)2(OH)6
a ZnO
Intensity/(a.u.)

100

002

as-synthesized ZnO

10 20 30 40 50 60 70 80
o
2 Theta/( )

101

100
Intensity/ (a.u.)

002
110
103 112
102
201

commercial ZnO 200 004

as-synthesized ZnO

10 20 30 40 50 60 70
o
2 Theta/( )

FIG. 1 X-RAY DIFFRACTION PATTERNS OF ZNO SYNTHESIZED BY HYDROTHERMAL HOMOGENEOUS

PRECIPITATION METHOD (FIG. 1A) AND COMMERCIAL ZNO PURCHASED FROM SINOPHARM CHEMICAL
REAGENT CO., LTD(FIG. 1B)
In the present work, a simple urea aqueous solution process at low temperature (120 oC) was employed for the
preparation of zinc hydroxide carbonate from zinc nitrate in the presence of PEG-6000. The surface area, pore
volume and average pore diameter of the two ZnO samples was aslo summarized in Table 1, obtained by nitrogen
adsorption at 77K in an ASAP2010 adsorption apparatus. ZnO samples with the surface area of 44.2m2/g were
obtained. It is obvious that both the surface area and pore volume of ZnO materials As-synthesized are larger than
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those of commercial ZnO materials, which may derives from the great difference in surface morphology (see Fig. 2).
The micrograph in Fig. 2a and Fig. 2b shows that ZnO materials synthesized are porous spherical particles in the
shape of chrysanthemums with an average size of 10 μm, and the flower-like particles consist of nanosized sheets,
while the commercial ZnO materials, see Fig. 2c and Fig. 2d, shows the shape of agglomerated large particles.
Bitenc et al. reported a similar experimental result that porous and a surface area of 16m2/g were obtained in the
presence of poly-vinyl pyrrolidone (PVP-K30) [7]. After heat treatment, ZnO particles preserved the size and shape
of the hydrozincite precursor.

TABLE 1 BET SURFACE AREA, BJH DESORPTION PORE VOLUME AND AVERAGE PORE DIAMETER OF ZNO
MATTERIALS

Specific surface Average pore diameter

Sample 2
BJH Desorption pore volume (cm3/g)
area（m /g） (nm)

Commercial ZnO 3.1 0.012 25.1

Special morphology ZnO 44.2 0.17 12.6

a b

c d

FIG. 2 SEM IMAGES OF SPECIAL MORPHOLOGY ZNO AS-SYNTHESIZED (A AND B) AND COMMERCIAL ZNO
MATERIALS (C AND D)

3.2 Thiophene reactive adsorption on Ni/ZnO

The desulfurization activities of Ni/ZnO adsorbents are shown in Figure 3. The sulfur content of the feedstock in test
is 308.5 μg/g, according to the analysis results of the Agilent 6890 Gas Chromatograph. The sulfur compound is
removed completely by both ADS-1 and ADS-2 until the eluted volume is 80.1 ml/g and 62.9ml/g, respectively. The
breakthrough of sulfur compound (10μg/g) is 183 ml/g and 92.8 ml/g, respectively. It is quite obvious that the ADS-

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1 adsorbent has the higher activity and stability of removing thiophene. During the period of the breakthrough
evaluation experiment, the volume of model gasoline fuel treated of the ADS-1 adsorbent maintains at twice as much
as that of the ADS-2 adsorbent. Moreover, the desulfurization rate drops slowly with the increase of treatment
capacity in the whole stage. The results of activity evaluation are related with the textural structures of ZnO materials
to some extent. The larger surface area and the smaller crystalline sizes of ZnO are, the higher desulfurization
activity of the corresponding Ni/ZnO adsorbent is (see Table 2).

ZnO (hexagonal )
Intensity/(a. u.) NiO (cubic)

ADS-2

ADS-1

10 20 30 40 50 60 70
o
2 Theta/( )

FIG. 3 X-RAY DIFFRACTION PATTERNS OF NIO/ZNO ADSORBENTS, ADS-1 AND ADS-2

TABLE 2 BET SURFACE AREA, BJH DESORPTION PORE VOLUME AND AVERAGE PORE DIAMETER OF
NIO/ZNO ADSORBENTS

Specific surface area

Sample BJH Desorption pore volume (cm3/g) Average pore diameter (nm)
（m2/g）

ADS-1 23.3 0.07 5.8

ADS-2 2.5 0.01 19.5

The XRD patterns of ADS-1 before and after reaction with thiophene are shown in Fig. 4. The XRD diffractogram of
the fresh adsorbent displays reflection characteristics of ZnO phase and NiO phase. In the range of 2θ=30-40o, the
strong diffraction peaks belong to ZnO. Comparing the XRD diffractogram of regenerated adsorbent with the fresh
one, we can conclude that they are very similar, and we can assume that they have the same crystallite size and
structure. It clearly indicates that all of NiO peaks have disappeared while the diffraction peaks of metallic nickel
appear. This result clearly indicates that all the NiO phase have been transformed to Ni0 phase. The additional peak
(at 2θ = 28.59) can belong to ZnS (JCPDF 03-065-0309), which strongly suggest that the interaction of thiophene
and Ni/ZnO adsorbent should be reactive adsorption. The results are in good agreement with the observation of
Tawara et al [5]. Ni reacts with sulfur under H2 to form NiS which then passes the sulfur to ZnO to form ZnS and
regenerate Ni. Bezverkhyy et al. used thermal gravimetric analysis to study kinetics of thiophene adsorption on
Ni/ZnO and Ni/SiO2. The interaction proceeds in at least three steps: the first one, fast sulfur chemisorptions, is
followed by a nucleation-controlled sulfidation of ZnO surface. This means that bulk sulfidation of Ni particles does
not occur and sulfur species, formed through thiophene decomposition, react preferably with ZnO. The XRD
analysis of the deactivated adsorbents in Fig. 4 indicates that the diffraction peaks of ZnS appear. The results
revealed that the decomposition of thiophene on Ni/ZnO might occur and S was trapped in the adsorbent. Because of
the nucleation-controlled sulfidation on ZnO surface [8-9], larger surface area and smaller crystal particles of ZnO
can supply with lower diffusion resistance, and thus to maximize the utilization and efficiency of the adsorbents.

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 350
Initial 308.5 ppmw level
300
ADS-2
ADS-1

Outlet Sulfur conc. (ppmw)

250

200

150

100

50
10 ppmw level

0 50 100 150 200 250 300

Volume of model gasoline fuel treated

(ml/g of adsorbent)

FIG. 3 BREAKTHROUGH CURVES OF NI/ZNO ADSORBENTS

ZnO (hexagonal )
ZnS (wurtzite 2H)
NiO (cubic)
Ni (cubic)
*
Intensity/(a. u.)

ADS-1 after reaction

* *

ADS-1 before reaction

10 20 30 40 50 60 70
o
2 Theta/( )

FIG. 4 X-RAY DIFFRACTION PATTERNS OF ADS-1 BEFORE AND AFTER REACTION WITH THIOPHENE

4 CONCLUSIONS
Special morphology ZnO materials with favorable porous spherical structure and crystalline size were synthesized
successfully by hydrothermal homogeneous precipitation method. The Ni/ZnO adsorbent using ZnO with larger
surface area and smaller crystal gains as active component shows higher desulfurization activity and stability. During
the adsorption process of thiophene on Ni/ZnO adsorbent, S is trapped by ZnO and converts into ZnS. ZnO with
special morphology porous spherical structure has good activity of taking up the S, which may be the main reason
for the activity difference of the Ni/ZnO adsorbent.

REFERENCES
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2003, 86(1-4): 211-263
[2] Babich I. V., Moulijn J. A.. Science and technology of novel processes for deep desulfurization of oil refinery streams: a review.
Fuel, 2003, 82(2): 607-631

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[3] Ito E., Van Veen J. A. R.. On novel processes for removing sulphur from refinery streams. Catal. Today, 2006, 116(4)：446–460
[4] Igor Bezverkhyy, Andrey Ryzhikov, Geoffroy Gadacz, Jean-Pierre Bellat. Kinetics of thiophene reactive adsorption on Ni/SiO2 and
Ni/ZnO. Catal. Today. 2008. 130(1): 199-205
[5] Tawara, K., Nishimura, T., Iwanami, H., et al. New hydrodesulfurization catalyst for petroleum-fed fuel cell vehicles and
cogenerations. Ind. Eng. Chem. Res. 2001, 40: 2367-2370
[6] Yang J., Shi Q., Li B.. Properties of Ni Supported on ZnO-based Mixed Oxides for Hydrodesulfurization of Thiophene. J.
Nanchang Univ. (Natur. Sci.), 2008, 33(1): 42-45
[7] Bitenc M., Marinšek, M and Crnjak Orel, Z. (2008) Preparation and characterization of zinc hydroxide carbonate and porous zinc
oxide particles. J. European Ceramic Soc. 28: 2915-2921
[8] Fan J., Wang G., Sun Y., et al. Research on Reactive Adsorption Desulfurization over of Ni/ZnO-SiO2-Al2O3 Adsorbent in a Fixed-
Fluidized Bed Reactor. Ind. Eng. Chem. Res. 2010, 49, 8450-8460
[9] Andrey Ryzhikov, Igor Bezverkhyy, Jean-Pierre Bellat. Reactive adsorption of thiophene on Ni/ZnO: Role of hydrogen
pretreatment and nature of the rate determining step. Appl. Catal. B: Environ., 2008, 84: 766-772

AUTHORS
1 2
Jingcheng Zhang (1982- ), corresponding Jun Nan (1971- ), Male, Zhuang Nationality, PH. D., Senior
author, Male, Han Nationality, PH. D., Engineer, Research Interests: catalytic material and
Engineer, Research Interests: preparation petrochemical. Email: nj9858@sina.com
and application of advanced functional
materials. Email: zjc8226@yahoo.com.cn

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