ISSN 1001-0742

Journal of Enuironmentol Sciences Vol. 18, No. 6, pp. 1189- 1192,2006 CN 11--2629/X
~~ ~~ ~~

Article ID: 1001-0742(2006)06-1189-04 CLC number:X505 Document code: A

Preparation and characterization of Fe203-Ce02-TiO&A1203

catalyst for degradation dye wastewater
LIU Yan, SUN De-zhi', CHENG Lin, LI Yan-ping
(School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China. E-mail: sdzlab@l26.com)

Abstract: In order to develop a catalyst with high activity for catalytic wet oxidation (CWO) process at room temperature and
atmospheric pressure, FezO3-CeO2-TiO~-y-AIzO3 catalyst was prepared by consecutive impregnation method and the prepared
parameters were optimized. The structure of the catalyst was characterized by BET, XRF, SEM and XF'S technologies, and the actual
wastewater was used to investigate the catalytic activity of FezO3-CeO2-TiO&AlZO3in CWO process. The experimental results
showed that the prepared catalyst exhibited good catalytic activity when the doping amount of Ti was 1.O wt% (the weight ratio of Ti
to carriers), and the middle product, CeOZ-TiO&Al2O3, was calcined in 450'C for 2 h. The CWO experiment for treating actual dye
wastewater indicated that the COD, color and TOC of actual wastewater were decreased by 62.23%, 50.12% and 41.26% in 3 h,
respectively, and the ratio of BODJCOD was increased from 0.19 to 0.30.
Keywords: catalytic wet oxidation (CWO); Fez03-Ce0z-TiOz/-y-A1zOp catalyst; dye wastewater treatment

degradation of pollutants. Additionally, TiO, also can

Introduction
The treatment of organic wastewater is one of the
most urgent subjects in pollution control because of
the high concentration and refractory degradation
(Golka et d.,2004). In recent years, catalytic wet
oxidation (CWO), by adding catalysts and oxidants to
improve the oxidation rate, has been considered as a
promising treatment method to destroy organic
pollutants in wastewaters (Gomes et d.,2000; Cao et
d.,2003; Hung et al., 2003). However, this process is
usually carried out at high temperature and pressure,
thus, leading to high equipment and operation costs,
which limits a wide application of CWO. More and
more attention has been focused on developing new
processes to improve the efficiency of CWO, such as
the preparation of new type heterogeneous catalysts
with high catalytic activity, making the CWO
combined with biological methods to treat wastewater.
Usually, in a combined CWO-biological treatment
system, CWO is used as pre-treatment process to
improve the biodegradation of wastewater, and then
followed by biological method, to lower the treatment
cost and improve the treatment efficiency. Currently,
the oxidants used in CWO are air (or 03, H202,O3and
so on.
The key in CWO process is the preparation of
heterogeneous catalysts with high activity and stability
(Gould et $., 2001; Neamtu et a!., 2004). In our
previous study (Liu and Sun, 2006), Fe203-Ce02/y-
A1203catalyst was prepared and its catalytic activity
was evaluated by using an azo dye, methyl orange, as
model pollutant in CWO at room condition. The
results show the activity of the catalyst is not satisfac-
tory. Titanium dioxide has received a lot of attention
as a promising material for photocatalysis and
be used as carrier of catalyst in CWO process because
of high specific surface areas (Maugans and Akger-
man, 2003; Bang et al., 2003). Based on the so many
advantages of Ti02, Ti was chosen as assistant
component of catalyst in this study. Fe203-Ce02-
Ti02/y-A1203was prepared by consecutive impreg-
nation method and the prepared parameters were
optimized. BET, XRF, SEM and X P S technologies
were employed to characterize the structure of
Fe203-Ce02-Ti02/y-A1203, and the catalytic activity of
the catalyst was also investigated in CWO process for
treating actual dye wastewater.
1 Experimental
1.1 Catalyst preparation
Fe203-Ce02-Ti02/y-A1203 catalyst was prepared by
consecutive impregnation method. A precursor of
tetrabutyl titanate was added dropwise to 50 ml
absolute ethanol contained with 0.5 wt% Ce under
vigorous stirring, then small amount of distilled water
and nitric acid was added to the mixed solution drop
by drop. The volume ratio of tetrabutyl titanate and
distilled water is 4 :1. Twenty grams y-A1203carrier
was added into the above mixed solution for 12 h after
the solution was stirred for 1 h under room
temperature, then the sample was dried at 809: for 10
h followed by dried at 1 10T for 2 h. The dried
samples were calcined in an oven for some hours, so
that the intermediate Ce02-Ti02/y-A1203 was obtained.
Secondly, Fe was loaded on Ce02-Ti02/y-A1203by
impregnation of Ce02-TiOz/y-A1203with 100 ml
aqueous solution containing 0.1 m o m Fe(NO& for 12
h under room condition, after the same drylng process,
the dried samples were calcined at 350C for 3 h, thus
the Fe203-Ce02-Ti02/y-A1203 catalyst was obtained.

Foundation item: The National Basic Research Program (973) of China (No. 2004CB418505) and the Foundation for Excellent Youth of Heilongjiang
Province; *Correspondingauthor
1190
1.2 Characterization of the catalyst sample
The surface area, total pore volume and average
pore size of samples were analyzed by using the BET
nitrogen adsorption method in surface area and pore
size analyzer (Autosorb-1, Quantachrome Com.,
USA).
The elementary compositions of samples were
determined by a model AXIOS pw4400 XRF
analyzer. Rh Ka was used as X-ray source, which
operated at 4 kW.
The surface morphology of the samples was
investigated by means of a Hitachi S-4700 SEM
analyzer.
XPS spectra were recorded using a model
PHI5700 analyzer (Perkin Elmer Co., USA). A Al Ka
(hu =1486.60 ev) was used as X-ray source. The
source was operated at 250 W and 12.5 kV. Kinetic
energies of photoelectrons were measured using a
hemispherical electrostatic analyzer working in the
constant pass energy mode. The C 1s peak fiom the
adventitious carbon-based contaminant, with the bind
energy of 284.62 eV, is used as the reference for
calibration.
1.3 Operation of CWO process
The catalytic activity of FezO3-CeO2-TiOJy-Al2O3
was investigated in CWO process. Methyl orange
synthetic wastewater was used as model pollutant in
the experiment of optimizing the preparation
condition of the catalyst. The concentration of dye is
500 mgL and H202was used as oxidation agent in this
process. CWO process was carried out in a cylindrical
reactor of 200 ml with constant temperature
waterbath. The reaction was conducted at atmospheric
pressure and 25C.3 g catalysts and 33 mg HzOZwere
added to 100 ml of an aqueous dye wastewater.
Actual dye wastewater was collected fiom the
textile industry in Harbin City, China. The main dye in
the wastewater is an azo dye, Reactive Black 5. The
initial concentrations of COD and BOD, of actual
wastewater were 9 15.2 and 171.6 mgL, respectively,
pH is 7-8. Air was used as oxidation agent in CWO
process for treating actual dye wastewater. The
reaction was carried out in a cylindrical reactor of 200
ml with bubbled air at 50C and normal pressure. 3 g
catalysts were added to 100 ml ,of dye wastewater and
$ 100
0 80
'E
8 60
40
+-0.50 wt%
-s- 0.75 wt%
1.00 wt%
1
-A-
b t 1.25 wt%
0:s 1:O If5 2fO 215 310 3!5
Reaction time, h
Fig.1 Effect of Ti doping amount (a), calcinations taperahue (b) and calcinations time (c) on decolorization efficiency, respectively
LIU Yan et al. Vol. 18
the air flow rate was 400 ml/min.
Liquid samples were taken out immediately at
regular intervals to analyze absorbance, COD and total
organic carbon (TOC). The visible light absorbance at
the characteristic wavelength of dye wastewater, 465
nm for the synthetic one and 600 nm for the actual
one, was measured by a spectrophotometer (model
721). TOC measurement was carried out with a
Shimadzu TOC analyzer model TOC-Vm. The COD
and BODSwere measured according to the standard
methods of China (State Environmental Protection
Administration of China, 2002). For evaluating the
catalytic activity of catalysts, color, COD and TOC
removal efficiencies were calculated as follows:
X=- co-ct x 100%
co
where Coand C,are the initial absorbance value and
final absorbance value of dye, or the initial and final
COD, or the initial and final TOC, respectively.
2 Results and discussion
2.1 Optimization of preparation condition
The effects of Ti doping amount, calcination
temperature and time of CeO2-TiO2/y-Al2O3on
catalytic activity were evaluated by the decolorization
efficiency of methyl orange synthetic wastewater in
detail, and the preparation parameters were optimized.
2.1.1 Effect of Ti doping amount
The decolorization efficiency of dye wastewater is
summarized in Fig. 1a. When the doping amount of Ti
was 0.5 wt%, 0.75 wt%, 1.0 wt% and 1.25 wt% ,
respectively. The results show that increasing the
doping amount of Ti enhanced the catalytic activity of
Fez03-Ce0z-Ti02/y-A1203, whereas, when the doping
amount of Ti was higher than 1.0 wt%, the catalytic
activity could not be improved any more. So, the best
doping amount of Ti is 1.0 wt%.
2.1.2 Effect of calcination temperature of Ce02-
TiO#y-A1203
Fig. 1b shows the decolorization efficiency of dye
wastewater when Ce02-TiOdy-A1203was calcined for
the same time at 400, 450, 500 and 550C ,
respectively. The catalytic activity of Fe203-Ce02-
Ti02/y-A1203was declined when the calcinations
-
450C
-c
- 500C
+ 550C
- , , I l l ,
Readon time, h Reaction time, h
No.6 Preparation and characterizationof Fe2O3-CeOrTi0&Al2O3 catalyst for degradation dye wastewater
temperature exceeded 450T. This decline probably
occurred because the metal oxides on the support
could form larger crystals at calcinations temperature
above 450C, additionally, the agglomeration of metal
oxides can be formed on the support, which resulting
in a decrease of specific surface area and the amount
of active sites, therefore a decline in activity for CWO
of dye. So, the optimal calcinations temperature of
Ce02-Ti02/y-A1203 is fixed at 450C.
2.1.3 Effect of calcinations time of Ce02-TiOdy-
A1203
The effect of calcinations time of Ce02-
TiO2/y-AI2O3on the catalytic activity of Fe203-
CeO2-TiOdy-Al2O3was investigated (Fig.1c). When
CeO2-TiO2/y-AI2O3 was calcined for 2 h, the catalytic
activity of obtained catalyst was slightly higher than
that of catalyst calcined for 1 h. When calcination time
exceeded 2 h, the activity of the catalyst was
decreased greatly, this was probably caused by the
agglomeration of metal oxides on the supports which
resulted in a decrease in the surface area and amounts
of active sites. So, the optimal calcinations time of
CeO2-TiO4y-Al2O3 is 2 h.
Based on the above results, the Ti doping amount
(a)
Fig.2 SEM image of y-A1203carrier (a) and Fez03-Ce02-TiO~y-A1z00,
2.2.4 Results of XPS measurements
Fe and Ti, without Ce, were found from the survey
XPS pattern of Fe203-Ce02-Ti02/y-A1203 catalyst. Ti
and Ce were loaded on the surface of support
synchronously according to the preparation procedure
of Fe203-Ce02-Ti02/y-A1203, and according to the
results of XRF, the content of Ce was higher than that
of Ti in the catalyst, which indicates that Ce can not
be seen because it was covered by Fe,03 rather than its
lower content. As has been known, XPS only can be
used to analyze the surface of catalyst with a limited
depth (5-10 nm), so Ce could not be detected on the
surface of Fe2O3-CeO2-TiO2/y-AI2O3.
Fe 2p and Ti 2p XPS patterns of Fe203-Ce02-Ti02/
y-A1203are shown in Fig.3, respectively. The Fe 2p3/2
peak was found at 710.87 eV, which ascribable to
Fe203 (Tan et d.,1990). According to the X P S
handbook (Wagner et d.,1979), the Ti 2p3/2 peak of
1191
was fixed at 1.O wt%, the calcinations temperature and
time are 400C and 2 h, respectively, for preparing
Fe203-Ce02-Ti0&A1203catalyst.
2.2 Characterization of Fe203-CeOrTiOdy-Alz03
catalyst
2.2.1 Analysis of BET results
A high specific area is good for the catalytic
activity of catalysts. The specific surface area, total
pore volume and average pore size of the investigated
catalysts measured using the BET nitrogen adsorption
method show that the catalyst has a specific surface
area of 2 13.1 m2/g,and total pore volume and average
pore size of 0.4863 mYg and 9.127 nm.
2.2.2 Analysis of XRF results
The component contents of Fe203-Ce02-Ti02/y-
A1203 catalyst were analyzed by XRF technology.
According to the results, the contents of FeyCe and Ti
in the catalyst were 2.137% , 0.285% and 0.168% ,
respectively.
2.2.3 SEM images
Compared with Fig.2(a), it can be seen from Fig.2
(b) that the Fe203particles are equally dispersed on the
surface of Fe203-Ce02-Ti02/y-A1203 catalyst, and the
crystal size is very uniform as shown in SEM images.
@I
catalyst (b)
Ti02 should be at 458.8 eV, but for Fig.3bYthe Ti
2p3/2 peak is found at 458.0 eV, so, it is confirmed
that Ti does not exist in the from of TiO, only.
To investigate the existence state of Ce in
Fe2O3-CeOrTiO2/y-Al2O3 catalyst, X P S was employed
to analysis the surface of intermediate Ce02-Ti02/y-
A1203. Fig.3~represents the Ce 3d X P S pattern of
Ce02-Ti02/y-A1203.In F i g . 3 ~Ce ~ 3d5/2 peak can be
observed at binding energy of 886.75 eV, which can
be ascribed that Ce in CeO2-TiO2/y-AI2O3 was exist as
the compound oxides form, Ce02and Ti& (Dauscher
et al., 1990).
2.3 Practical application of Fe203-Ce02-TiOdy -
A1203catalyst
In order to investigate the applicability of
Fe203-Ce02-Ti02/y-A1203,actual wastewater was
subjected to CWO process. It can be seen from the
Fig.4 that the COD, color and TOC of actual
1192 LIU Yan et d. Vol. I8
850 1550
1400 - ~

800 I500
I200 -

,I;:
750 1450
1400
1000

Id
d
800
-
600 -
-

a
a 550
500
1!if
1200
450
400 I I 1 I I I

wastewater were decreased by 62.23%, 50.12% and biodegradability of wastewater improved. As a

41.26% in 3 h, respectively, and as an important
environmental parameter, BODJCOD was increased
fiom 0.19 to 0.30. Fez0~-Ce02-Ti0z/y-A1zO~ shows an
excellent catalytic activity in the oxidation of non-
biodegradation dye wastewater, and can efficiently
improve the biodegradability of wastewater. So, CWO
can be used as pretreatment process combined with
traditional biological methods for treating dye
wastewater without high operating cost and disposal
problems.
loo 7 0.4
- 0.3
- 0.2 %
8 of low molecular weight carboxylic acids using a carbon
- 0.1
-+COD -A- TOC
0 Hung C M, Lou J C, Lin C H, 2003. Removal of ammonia solutions
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Reaction time, h
Fig.4 Degradation efficiency for treating actual wastewater by using Liu Y, Sun D Z, 2006. Study on Characterizationand catalytic activity
Fe203-Ce0,-TiOdy-A120,catalyst
3 Conclusions
Fe203-Ce02-Ti02/y-A1203 catalyst was prepared
by consecutive impregnation method and the
preparation parameters were optimized. The catalyst
showed the best activity when the doping amount of
Ti is 1.0 wt% (the amount ratio of Ti to carriers) and
the calcinations temperature of intermediate CeOz-
Ti02/y-A1203 was at 450T for 2 h.
The characterizations of Fez03-Ce02-TiOz/~-A1203
by BET, XRF, SEM and X P S indicated that the metal
oxides was dispersed equably on the surface of
catalyst, and the content of Fe, Ce and Ti in the
catalyst was 2.137% , 0.285% and 0.168% ,
respectively. Fe was located on the surface of catalyst
as Fe203,and Ce and Ti existed as compound oxides
form, Ce02and TiO,.
Fez03-Ce02-Ti02/y-A1z03 shows viable applica-
bility in treating actual wastewater, and can make the
promising technology, CWO process can be operated
as pretreatment process combined with biological
methods for treating aqueous solutions containing
non-biodegradable organics.
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(Received for review April 25,2006. Accepted July 3 I, 2006)