ISSN 0126-2807

Abdulhamid Hamza, Haji A. Mohammed and Saidu M. Waziri, 2013. Removal off Chromium Ions from Tannery
Effluent Using ZnO--ZnFe2O4 Composite Photocatalyst onn Activated Carbon Support.
Support
V o l u m e 8 , N u m b e r 3 : 2 25 - 2 3 0 , S e p t e m b er , 2 0 13
© T2013 Department of Environmental Engineering
Sepuluh Nopember Institute of Technology, Surabaya
& Indonesian Society of Sanitary and Environmental Engineers, Jakarta
International peer-reviewed
reviewed journal Open Access http://www.trisanita.org/jases
This research paper is licensed under the Creative Commons Attribution 3.0 Unported License,
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REMOVAL OF CHROMIUM IONS FROM TANNERY EFFLUENT USING ZnO-

ZnO
ZnFe2O4 COMPOSITE PHOTOCATALYST ON ACTIVATED CARBON SUPPORT
ABDULHAMID HAMZA1*, HAJI A. MOHAMMED1,2 and SAIDU M. WAZIRI1
1Department of Chemical Engineering, Ahmadu Bello University, Zaria, Nigeria.
2Nigerian Institute of Leather and Science Technology, Zaria, Nigeria.
Nigeria
*Corresponding Author: Phone: +234
+234-07035374494; Email: abbamid@gmail.com

Received: 4th April 2013; Revised: 13th August 2013; Accepted: 19th August 2013

Abstract: ZnO-ZnFe2O4 composite photocatalyst on activated carbon support has been

synthesized and applied for the removal of chromium ions from a raw tannery effluent.
Only 13% of the chromium ions in the raw effluent were removed via adsorption on the
surface of the ZnO-ZnFeZnFe2O4 composite photocatalyst in the dark for 120min.
Photocatalysis with ZnO--ZnFe2O4 composite achieves 85% removal of total chromium
in 30min and 91% in 120
120min.. The photocatalytic removal of the chromium ions nicely
Hinshelwood kinetic model (R2=0.999). The chromium adsorption
fitted the Langmuir–Hinshelwood
was found to be the rate controlling step of the photocatalytic process.

Keywords: Activated
ctivated carbon, chromium, photocatalyst, tannery, Zno-ZnFe2O4

INTRODUCTION

Chromium salts are used in the tanyard of most tanneries to form a protective layer that
prevents penetration of water inside the leather pores in order to avoid putrefaction. Usually, the
leather takes up about 60–80% 80% of the chromium; the remaining chromium is often discharged into
the environment [1]. Effluents emanating from the tanyard are generall
generallyy characterized by high
chromium content and low pH. Chromium in tannery effluents occurs in trivalent (Cr3+) and
hexavalent (Cr6+) forms. The toxicity of chromium compounds is strongly dependent on the
oxidation state. It has been reported that Cr6+ may cause lung cancer. Cr3+ compounds are
neither irritating nor corrosive under normal conditions [2]. However, people who are allergic to
chromium may have asthma attacks after breathing high levels of Cr3+ [3].. Prolong contact with
Cr3+ may also cause itching and redness of skin. Both Cr6+ and Cr3+ have high chronic toxicity [4].
Removal of chromium from tannery effluents is achieved by the application of various
processes such as sedimentation, adsorption, ion exchange, chemical precipitation, biological
biologic
treatment, filtration, etc [2, 5].. Most of the conventional methods for treating industrial effluents
are characterized by high operating costs and often generate secondary pollutants into the
environment [6]. Some of the methods concentrate the polluta
pollutants
nts present in water by transferring
them to other phases. It is often very difficult and costly to treat the generated sludge. Biological
treatment of effluents is time consuming and is often characterized by low reduction efficiency.
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 Abdulhamid Hamza, Haji A. Mohammed and Saidu M. Waziri, 2013. Removal of Chromium Ions from Tannery
Effluent Using ZnO-ZnFe2O4 Composite Photocatalyst on Activated Carbon Support.

These limitations have triggered the search for more effective alternative materials and methods
for treating tannery effluents. Heterogeneous photocatalysis is one of the recently developed
methods for wastewater treatment which has the potential of destroying various hazardous
pollutants including metals ions [6-8]. Photocatalysis is based on the reactive properties of
electron–hole pairs generated in semiconducting photocatalysts, such as TiO2, ZnO, Fe2O3, ZnS,
etc, under illumination by ultraviolet or visible light that has energy greater than the
semiconductor bandgap [6].
TiO2 and ZnO have been widely used for photocatalytic applications, but their wide band gap
of about 3.2 eV make them effective under ultraviolet light irradiation only. This limits their
practical application because it is expensive to generate artificial ultraviolet light. Less than 5% of
solar irradiation is in the ultraviolet region [9]. Zinc ferrite (ZnFe2O4) is a well known visible light
active photocatalyst with a narrow band gap of about 1.9 eV [9, 10]. One major problem with
photocatalysts that have narrow band gap is the fast electron/hole recombination which reduces
their activity [9]. This problem can be solved by coupling two or more photocatalysts with different
band gaps. Recently, ZnFe2O4 has been coupled with various high band gap semiconductors in
order to extend their photocatalytic activities. Shao et al. synthesized ZnO-ZnFe2O4 composite
photocatalyst by coating ZnO on the surface of ZnFe2O4 particles [10]. The composite was found
to be very active for photocatalytic degradation of methylene blue dye. Yuan and Zang
synthesized and investigated the photocatalytic activity of ZnFe2O4-TiO2 nanocomposite and
found that the ZnFe2O4-TiO2 nanocomposite is more effective than pure TiO2 in the degradation
of phenol [11]. The efficiency of photocatalytic processes can be enhanced by supporting the
photocatalyst particles on an inert support such as clays and activated carbons [12, 13]. Activated
carbon has a large surface area and a high adsorption capacity for various polar and non polar
compounds. The objectives of this work were to synthesize ZnO-ZnFe2O4 composite
photocatalyst on activated carbon support via co-precipitation route and evaluate the potential of
the synthesized photocatalyst for the removal of chromium ions from a raw tanyard effluent.

MATERIALS AND METHODS

ZnO-ZnFe2O4 composite on activated carbon support was prepared by co-precipitation of

222mmol of Zn(NO3)2.6H2O and 17mmol of Fe (NO3)3.9H2O with 613mmol of aqueous solution of
NH4OH in the presence of 20g of activated carbon at 50◦C and a pH of 8. The formed precipitate
was aged for 24 h. The solid product was filtered and washed with deionized water, dried at 120
◦C in an oven overnight, and then calcined in a furnace at 1000◦C for 8 hours to yield ZnO-

ZnFe2O4 composite on activated carbon support. All reagents used were of analytical grade.
X-ray diffraction (XRD) pattern of the synthesized ZnO-ZnFe2O4 composite on activated
carbon support was recorded using a powder X-ray diffractometer (Shimadzu, model 6000)
employing Cu Kα radiation (λ=0.154nm). The chemical composition of the synthesized composite
was determined using energy dispersive X-ray florescence (EDXRF) spectrometer (Panalytical,
Minipal 4). The specific surface area of the photocatalyst was obtained using a modified BET
method which is based on the adsorption of water molecules on the surface of solid samples [14].
The effluent used was obtained from the tanyard of the Nigerian Institute of Leather and
Science Technology (NILEST), Zaria, Kaduna state, Nigeria. The effluent was filtered to remove
suspended solids. 100ml of the effluent was mixed with a fixed amount of the ZnO-ZnFe2O4
composite photocatalyst in a 200ml beaker, and then placed on a hot plate and magnetically
stirred for two hours in the dark in order to establish adsorption-desorption equilibrium of the
components of the tannery on the photocatalyst. Thereafter, the mixture was exposed to visible

226
Journal of Applied Sciences in Environmental Sanitation, 8 (3): 215-230.
 Abdulhamid Hamza, Haji A. Mohammed and Saidu M. Waziri, 2013. Removal of Chromium Ions from Tannery
Effluent Using ZnO-ZnFe2O4 Composite Photocatalyst on Activated Carbon Support.

light irradiation provided by a 500W halogen lamp under continuous stirring at room temperature
(25±2°C). Periodically, samples were taken for analysis after separating the photocatalyst
particles. The total chromium content of the raw and treated samples of the effluent was
determined using flame atomic absorption spectrometer (Shimadzu, model AA6800). Previous
works on the adsorption and photocatalytic removal of both Cr3+ and Cr6+ ions from model
chromium salt solutions using various adsorbents and photocatalysts concluded that the removal
efficiency is highest in acidic medium with pH of 2.5 – 4.0 [1, 2, 4, 8]. Therefore, all experiments
were performed at the pH of 3.0 which is pH of the raw tanyard effluent.

RESULTS AND DISCUSSION

According to the XRF data, the synthesized ZnO-ZnFe2O4 composite photocatalyst is

composed of Zn – 89.9 %, Fe – 6.7 %, and traces of other elements such as Si, Ni, Ag, Yb, P,
Ca, etc. As presented in Fig. 1, the diffractrogram of the ZnO-ZnFe2O4 composite photocatalyst
on activated carbon support is dominated by the characteristic peaks of hexagonal wurtzite
structure of ZnO (31.7°, 34.4°, 36.2°, 47.5° and 69.1°) and minor peaks due to the cubic spinel
structure of ZnFe2O4 (30.0°, 35.3°, 43.2° and 53.7°). The XRD pattern is characterized by sharp
peaks, indicative of high crystallinity of ZnO and ZnFe2O4. The diffractrogram does not feature
any peak that can be attributed to activated carbon due to its amorphous nature. The XRD and
XRF data agree well with the ZnO:ZnFe2O4 molar ratio of 13:1 obtained from the stoichiometry of
the chemical reactions involved during the synthesis. The crystallite size of the composite
photocatalyst was estimated using the Debye–Scherrer equation:
kλ
τ= (1)
βcosθ
where τ is the particle size, λ is the wavelength of the X-ray radiation (0.1542 nm), k is the shape
factor (0.94 was selected for k), β is the line width at half maximum height and θ is the angular
position of the peak maximum (diffracting angle). The calculated crystallite size of the composite
photocatalyst is 49.1nm. The surface area of the composite photocatalyst is 362m2/g which is
substantially smaller than the surface area of the commercial activated carbon (735m2/g) used
because of agglomeration of ZnO:ZnFe2O4 particles on the surface of the activated carbon.
Intensity, arbitrary units.

5 15 25 35 45 55 65 75
2θ, degrees

Fig. 1: XRD pattern of the synthesized ZnO-ZnFe2O4 composite photocatalyst ZnO-ZnFe2O4

composite/activated carbon

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Journal of Applied Sciences in Environmental Sanitation, 8 (3): 215-230.
 Abdulhamid Hamza, Haji A. Mohammed and Saidu M. Waziri, 2013. Removal of Chromium Ions from Tannery
Effluent Using ZnO-ZnFe2O4 Composite Photocatalyst on Activated Carbon Support.

The initial concentration of chromium ions in the raw effluent was 3900mg/L. Results of
control experiments show that 13% of the chromium in the raw effluent was removed via
adsorption on the surface of the ZnO-ZnFe2O4 composite photocatalyst in the dark for two hours.
Chromium removal was not observed after irradiation of the effluent for two hours in the absence
of the photocatalyst.
The photocatalytic efficiency of chromium removal (PE) was calculated using Eq. (2):
(C − C t ) × 100%
PE = 0 (2)
C0
where C0 and Ct are the initial concentration of chromium and the concentration of chromium after
irradiation for a period of time (t), respectively. The effect of photocatalyst dosage on the
photocatalytic efficiency of chromium removal of chromium is presented in Fig. 2. The percentage
removal of chromium increased from 47% to 91% when the photocatalyst dosage was increased
from 0.5 to 1g/L. The increase in the photocatalyst dosage led to an increase in the active surface
area of the photocatalyst which results in enhanced chromium removal [12]. However, further
increase of the photocatalyst dosage resulted in the decrease in the percentage removal of
chromium. This observation can be attributed to the increased turbidity of the suspension, which
reduces light penetration and inhibits the photocatalytic process. Similar observations were made
by other researchers [7, 12].
Efficiency of chromium removal, %

100
80
60
40
20
0
0 0.5 1 1.5 2 2.5
Catalyst dosage, gL-1
Fig. 2: Effect of catalyst dosage on the photocatalytic efficiency of chromium ions removal using
ZnO-ZnFe2O4 composite/activated carbon
Efficiency of chromium removal, %

100
80
60
40
20
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130
Time, mins
Fig. 3: Effect of irradiation time the photocatalytic efficiency of chromium ions removal using ZnO-
ZnFe2O4 composite/activated carbon

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Journal of Applied Sciences in Environmental Sanitation, 8 (3): 215-230.
 Abdulhamid Hamza, Haji A. Mohammed and Saidu M. Waziri, 2013. Removal of Chromium Ions from Tannery
Effluent Using ZnO-ZnFe2O4 Composite Photocatalyst on Activated Carbon Support.

Fig. 3 shows the effect of contact time on the percentage removal of chromium. Removal of
chromium was very fast in the first 30mins of irradiation; the percentage removal of chromium
reaches 85% within 30mins. Thereafter, the process becomes slower most likely due to the
formation of some products of the photocatalytic reaction that may alter cause of the chromium
removal. It should be noted that real tanyard wastewater contains a wide variety of organic and
inorganic compounds, many of which can undergo photocatalytic reaction under the experimental
conditions employed. Indeed, substantial decrease of chemical oxygen demand (COD) is
sometimes observed during photocatalytic treatment of industrial effluents [15]. The percentage
removal increases from 85% to 91% when the irradiation time was increased from 30mins to
120mins.
The kinetics of heterogeneous photocatalytic processes is often described by the Langmuir–
Hinshelwood kinetic model [12, 16].
dC k r K e C
r=- =
dt 1 + K e C
(3)
where r is the reaction rate, C is the concentration of chromium ions. kr and Ke are the apparent
reaction rate constant and the apparent equilibrium of adsorption constant, respectively. By
replacing r with the initial reaction rate r0 and C with the initial concentration of chromium ions in
the raw effluents, C0, Eq. (3) can be written in the following linearized form:
1 1 1
= +
r0 k r K e C 0 k r
(4)
In order to determine the values of kr and Ke using the initial rate method, a series of
experiments were carried out with varying initial concentration of chromium ions. The initial
concentration of chromium was varied by diluting the tanyard wastewater. Fig. 4 shows the plot of
(1/r0) against (1/C0) with very high correlation coefficient (R2=0.999).The calculated values of kr
and Ke were 71.429mgL−1min−1 and 0.007Lmg−1, respectively. The chromium adsorption is the
controlling step of the photocatalytic process because the value of kr is substantially higher than
that of Ke. A similar rate controlling step was concluded for the photocatalytic degradation of
methyl orange over α-Fe2O3-supported HY photocatalyst [12].

1.1

0.9 y = 2.022x + 0.014

1/r0 R² = 0.999
0.8

0.7

0.6
0.25 0.3 0.35 0.4 0.45 0.5 0.55
1/C0
Fig. 4: Langmuir–Hinshelwood kinetics plot for photocatalytic removal of chromium ions using
ZnO-ZnFe2O4 composite/activated carbon
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Journal of Applied Sciences in Environmental Sanitation, 8 (3): 215-230.
 Abdulhamid Hamza, Haji A. Mohammed and Saidu M. Waziri, 2013. Removal of Chromium Ions from Tannery
Effluent Using ZnO-ZnFe2O4 Composite Photocatalyst on Activated Carbon Support.

CONCLUSIONS

Only 13% of the chromium ions in the raw effluent were removed via adsorption on the
surface of the ZnO-ZnFe2O4 composite photocatalyst in the dark for 120mins. Photocatalysis with
ZnO-ZnFe2O4 composite photocatalyst achieves 85% removal of chromium in 30mins and 91% in
120mins. The photocatalytic removal of the chromium ions nicely fitted the Langmuir–
Hinshelwood kinetic model. The calculated values of the apparent reaction rate constant (kr) and
apparent equilibrium of adsorption constant (Ke) were 71.429mgL−1min−1 and 0.007Lmg−1,
respectively. The chromium adsorption is the controlling step of the photocatalytic process.

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