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2222 PDF
Abstract
Textile industrial wastewaters are one of the important sources of environmental contaminants because they produce
large quantities of highly colored effluents. In recent years, use of advanced oxidation processes (AOPs) by
producing highly active and reactive components such as hydroxyl radicals have been proposed. Among AOPs
Photocatalysis has been used to oxidize persistent organic compounds that cannot be oxidized completely in the
biological treatment plants.
In this study, an oxygenated system of UV/ZnO was applied for degradation of C.I. reactive orange 16 dye as an
organic pollutant in textile effluents. The synthetic effluent was prepared by addition of sodium carbonate salt and
sodium sulfate salt to the dye solution. It was conducted to simulate the real wastewater conditions. During 90
minutes of the reaction time, pertinent operational parameters were investigated and optimized, such as temperature,
pH, initial dye concentration and catalyst dose. Response surface methodology as a statistically based experimental
design was applied to optimize process effective parameters. A thin gap annular photoreactor based on well mixing
and sufficient photon adsorption was designed and applied for experiments. This photoreactor provides larger
surface area exposed to UV light and solution layer renewal on UV source surface, resulting in higher photocatalytic
degradation. Experimental results revealed that at optimum conditions, maximum degradation higher than 97
percent was achieved in UV/ZnO systems.
Keywords: Textile wastewater treatment, Advanced oxidation processes, photocatalytic degradation, Zinc oxide,
Optimization of parameters, Response surface methodology
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1. Introduction
Textile wastewater is an active research area because of releasing colored organic compounds which cause
significant problems for human health and aquatic life[1]. The environmental problems related to industrial
wastewaters have become severe problem because of toxicity of their effluents. So developing new methodologies
for efficient treatment of effluents is necessary [2]. Textile industries are major consumers of water and
consequently one of the largest groups of industries causing intense water pollution [3]. The dyes usually have a
synthetic origin and a complex aromatic molecular structure which make them more stable and difficult to
degradation [1]. Azo dyes are an interesting class of colorants that are widely used in textile, food, cosmetics and
paper industries. They are known with N N in their structure [3]. They may cause allergic dermatitis, skin
irritation, carcinogenic and mutagenic to living organisms. Also, releasing dyes to the environment causes
disturbance to the ecological system of receiving waters. Therefore, industrial effluents containing dyes need to be
treated before discharging to the environment. Different chemical, physical and biological techniques have been
expanded to remove dyes from wastewater, such as membrane separation, flocculation-coagulation, adsorption and
ozonation. These traditional treatment methods are generally ineffective for complete color removal. The alternative
to conventional methods are advanced oxidation processes (AOPs) which are based on the generation of reactive
species such as hydroxyl radicals which oxidize organic materials quickly and non-selectively. Among AOPs,
photocatalysis is an attractive method for degradation of organic pollutants specially the dyes. Photocatalytic
processes can be carried out under atmospheric pressure and ambient conditions so they have received attention in
environmental issues [4,5]. Many catalysts have been used for degradation of a wide variety of contaminants.
Among them, ZnO appears a promising photocatalyst [6].
Photocatalytic process starts when a semiconductor absorbs a photon of light more energetic than its band gap. TiO 2
and ZnO have wide band gaps of 3.2 and 3.37 eV, respectively. In this condition, an electron is excited from the
valence band (VB) to the conduction band (CB) of the semiconductor and a hole-electron pair is being formed
(Figure1) . In aqueous phase the holes and hydroxyl groups can produce the hydroxyl radical (.OH) which is a
strong oxidizing agent [7].
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Figure 1: Photocatalysis mechanism
As international environmental standards are becoming more stringent, technological systems for the removal of
organic pollutants, such as dyes have been recently developed. Process optimization is a topic of central importance
in industrial processes. Conventional methods for optimization involve changing an independent variable at a time,
while the other variables remain fixed. However, statistical method offers several advantages over the conventional
method; it is rapid and reliable,helps to understand the interactions among the parameters at various amounts, and
reduces the total number of experiments. These improvements result in saving time, chemicals and man power[8,9].
In this research, the operating parameters were optimized using a response surface methodological approach.
2. Experimental
2.1. Chemicals
Reactive orange 16 was obtained from Sigma-Aldrich with 50% purity and was used without further purification. Its
chemical structure is depicted in figure 2. The photocatalyst ZnO was purchased from TECNAN (99.98% purity),
has a particle size of 29 nm and surface area of 41 m²/g. X-ray diffraction analysis of ZnO is exhibited in figure 3.
Deionized water was used for preparation of various solutions. pH of the solutions was adjusted with 0.1 M HCl and
0.1 M NaOH obtained from Merck. Sodium sulfate and Sodium carbonate were achieved from Merck.
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Figure 3: XRD of ZnO nanoparticles
2.2. Apparatus
The reactions were carried out in a thin gap annular photoreactor made of plexiglass with a heat exchanger placed in
the reactor to adjust and control the temperature of the solution. The light source was a 15 W low pressure mercury
vapor UV-C lamp (Phillips), inserted into the center of the reactor. A water bath (fater electronic) was applied to
adjust the temperature of circulating water to the heat exchanger and a peristaltic pump was used to circulate water.
In all experiments, an aeration pump (Hailea, ACO-5503 , China) was used to maintain catalyst particles suspended
and increase photo-degradation efficiency. The photoreactor and its attachments are presented in figure 4. A Hettich
EBA 20 centrifuge with the maximum speed of 6000 rpm was used for the complete separation of the
semiconductor particles from the sample solution. Absorption analysis was recorded by a UV-visible
spectrophotometer (Camspec M501).
1-Photoreactor
2- UV-lamp
3- Heating coil
4- Air bubbles
5- Sparger
6- Peristaltic pump
7- Water bath
8- Aeration pump
2.3. Procedure
The effect of temperature, initial pH of the solution, photocatalysts concentration and initial concentration of the
pollutant were investigated during 90 minutes of the reaction time. These parameters have been changed from 40°C
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to 70°C, 5 to 12, 200 to 2500 ppm and 24 to 96 ppm, respectively. The ranges of parameters were determined by
preliminary experiments based on the literature review. In all cases 750 mL of dye solution containing appropriate
quantity of the ZnO and 5000 ppm of Na2SO4 and 400 ppm of Na2CO3 was applied to simulate the real textile
wastewater. At the end of the reaction time 5 mL of sample was withdrawn and semiconductor particles were
removed by centrifugation. The degradation process of the dye was determined by measuring the solution absorption
at 486 nm. The percentage of decolorization was calculated as follows:
C0 C
% Decolorization 100 (Eq. 9)
C0
In this study, response surface methodology (RSM) was applied to assess the individual and interactive effects of the
four main independent parameters in the photocatalytic process. The effect of variables on dye removal efficiency
was studied using Box-Behnken design (BBD). The experimental variables with the name and actual level are
shown in table 1.
Then, the experimental design and statistical analyses of the data were performed using the Design Expert 8.0.5
(Stat-Ease, Inc., Minneapolis, MN, USA).
k k 2
Y 0 i x i ii x i ij x i x j (Eq.10)
i 1 i 1 i j
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Where Y is the expected value of the response variable, 0 , i , ii and are the model parameters, x i and x j are
ij
the factors and k is the number of factors being studied. Y represents the dye degradation percentage.
In this study with four parameters, 29 batch tests were performed to satisfy a BBD design. The design matrix and the
corresponding results of BBD experiments to determine the effects of the four independent variables are shown in
table 2. As shown in the table, each of the significant variables was assessed at three levels.
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Standard No. Run A B C D X% *
1 25 40 5 60 1350 63.08
2 7 70 5 60 1350 59.78
3 10 40 12 60 1350 56.97
4 14 70 12 60 1350 64
5 1 55 8.5 24 200 79.88
6 13 55 8.5 96 200 38.38
7 19 55 8.5 24 2500 97.36
8 4 55 8.5 96 2500 58.77
9 17 40 8.5 60 200 58.7
10 16 70 8.5 60 200 65.92
11 5 40 8.5 60 2500 60.37
12 28 70 8.5 60 2500 80.89
13 15 55 5 24 1350 91.43
14 18 55 12 24 1350 86.79
15 27 55 5 96 1350 38.58
16 6 55 12 96 1350 42.9
17 22 40 8.5 24 1350 91.99
18 12 70 8.5 24 1350 95.55
19 9 40 8.5 96 1350 35.74
20 11 70 8.5 96 1350 63.14
21 8 55 5 60 200 49.13
22 24 55 12 60 200 33.33
23 3 55 5 60 2500 77.24
24 26 55 12 60 2500 77.43
25 29 55 8.5 60 1350 65.9
26 21 55 8.5 60 1350 65.12
27 2 55 8.5 60 1350 73.46
28 23 55 8.5 60 1350 61.18
29 20 55 8.5 60 1350 79.21
3
Degradation 130.69302 0.99373 Temperature 4.89701 pH 1.52077 dye.concentration 9.86077 10 Catalyst 0.049190
4 4
Temperature pH 0.011037 Temperature dye.concentration 1.92754 10 Temperature Catalyst 9.93168 10 pH
2 3 2
Catalyst 0.55103 pH 2.49314 10 (dye.concentration)
(Eq.11)
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The actual and predicted degradation percent is shown in figure 5. Actual values are the measured response data for
a particular run, and the predicted values are evaluated using the approximating functions generated for the model
(Eq.(11)) [11]. The adjacency of the points to the 45 line shows that the model is appropriate for predicting the
response (figure 5).
The quality of fit of the second order polynomial model equation ((Eq.11))was expressed by the coefficient of
determination (R2) [12]. The coefficient of determination (R2) of the model was 0.9064 which indicates that the
model ((Eq.11)) was suitable for adequate representation of the real relationships among the variables. According to
the R-squared value, which is close to 1.0, the regression line is fitted with the experimental points. It indicates that
the model is useful to predict the results at specific points with an accuracy of 90.64 %.
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is presented in table 3. as shown in table 3 actual efficiency from fitted model is 97.64 % and is in close agreement
with the predicted experiment at a 97.84 % confidence.
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Figure 6: contour and surface plots of dye degradation efficiency
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figure 8: effect of initial dye concentration
11
figure 9: effect of pH
4. Conclusion
Once more time, heterogeneous photocatalysis proves to be an efficient method for wastewater treatments because
complete mineralization of reactive orange 16 was achieved. Four variables (temperature, pH, initial dye
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concentration and catalyst loading) were optimized for degradation of reactive orange 16 from textile wastewater.
The optimal values gained by BBD experiments for dye degradation efficiency. Analysis of variance showed a high
coefficient of determination (R2=0.9064) and satisfactory prediction. The optimum conditions were found to be
initial dye concentration of 27.08 ppm, initial pH of the solution of 7.78, catalyst loading of 2349 ppm and
temperature of the solution at 62.09 °C. Under optimal values of process parameters, the maximum dye removal
percentage from predicted model was 99.80%. This value was in perfect agreement with the actual experimental
value which was 97.64%. The high correlation of the model with the experimental results indicates that this
analytical procedure could be a general method to describe other similar ZnO photocatalytic system and to predict
its behavior. This should be of great importance for the optimization of the experimental conditions for
technological applications such as scale up of photocatalytic reactors.
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