Experimental studies on photocatalytic degradation of dye in simulated

textile wastewater using Zinc oxide nanoparticles

M. Dehabadi
MSc. Student, Department of Chemical & Petroleum Engineering, Sharif University of Technology, Azadi Ave.,
Tehran, Iran
H.R. Kariminia*
Assistant Professor, Department of Chemical & Petroleum Engineering, Sharif University of Technology, Azadi
Ave., Tehran, Iran
M. Vosoughi
Professor, Department of Chemical & Petroleum Engineering, Sharif University of Technology, Azadi Ave.,
Tehran, Iran
kariminia@sharif.ir

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.

Figure 2: Reactive orange 16 molecular structure

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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).

Figure 4: set-up configuration

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

Where C0= initial concentration of dye solution

C = concentration of dye solution after photo irradiation

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.

Table 1: actual level of variables

Parameter Variable Low level Center point High level

Temperature A 40 55 70
pH B 5 8.5 12
Initial dye concentration C 24 60 96
Catalyst loading D 200 1350 2500

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).

2.4. Response Surface Method

Response surface methodology is a combination of mathematical and statistical techniques used for developing,
improving and optimizing the processes. It is used to evaluate the relative significance of several affecting factors,
even in the presence of complex interactions. RSM typically contains three steps: (1) design and experiments; (2)
response surface modeling through regression; and (3) optimization [10]. Box-Behnken design was used to design
the experiments.
Empirical models describing the experimental results were developed using data collected from the designed
experiments and were generated using the least squares method. Model parameters were estimated using a second
order model of the form (Eq.(10))

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.

3. Results and discussion

3.1. Optimization of effective parameters by Box-Behnken design
The statistical software package, Design Expert 8.0.5 (stat-Ease, Inc., Minneapolis, MN, USA) was used for the
regression analysis of the experimental data and to plot the response contours and surface graphs.
p-values were applied to check the significance of each of coefficients. According to the p-values of the model terms
(data not shown) independent variables A(temperature), C(initial dye concentration) and D(catalyst loading),
interaction variable AC (temperature initial dye concentration) and quadratic variable B 2 (pH) are common
significant terms in the model. These terms have high effect in obtaining the optimized condition in which dye
removal efficiency is as high as possible.
The analysis of variance for the p-values of the temperature, initial pH of the solution, initial dye concentration and
catalyst loading were 0.017, 0.46, <0.0001 and <0.0001, respectively. The p-value smaller than 0.05 indicates that
the model term is significant[11]. The initial dye concentration and catalyst loading with the lowest probability value
were determined to be the most effective factors. Also, p-value for the model was <0.0001 which indicates that the
model was statistically significant with the confidence of 99.99%.

Table 2: Experimental design and results of the central composite design

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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

*: X%= degradation percent

3.2. Fitted regression model as related to the dye degradation

The overall second order polynomial equation for dye degradation can be written as follows:

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).

Figure 5: Predicted vs. actual plot for dye degradation efficiency

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 %.

3.3. Response surface plotting

To achieve a graphical interpretation of the interactions, two-dimensional contour plots and three-dimensional
surface plots are recommended [13]. Interaction terms with p-values<0.05, AC was selected for the axes of the
response surface plots.
Figure 6 shows a three-dimensional surface plot of the empirical model for dye degradation as a function of four
factors. As depicted in this figure, at the highest temperature and catalyst loading, the lowest initial dye
concentration and specific pH the highest dye degradation efficiency was achieved.

3.4. Validation of the model

According to numerical optimization by Design Expert 8.0.5, the maximum predicted dye degradation efficiency
was 99.80% (Table 3). The optimal conditions with the aim of maximizing the dye removal efficiency are as
follows: temperature at 62.09°C, pH of 7.78 , initial dye concentration of 27.08 ppm and catalyst loading of 2349
ppm . these values are all in agreement with the results obtained from the three-dimensional surface plots. To
validate this prediction, an actual experiment at optimal conditions was carried out twice and the average efficiency

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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.

Table 3: optimum process and validation experiment result

Response (%) Target Correlation Confirmation Confidence(%)
predicted(%) experiment(%)
Dye removal Maximize 99.80 97.64 97.84

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 Figure 6: contour and surface plots of dye degradation efficiency

3.5. Effect of individual parameters

To gain a better understanding of the individual effect of four mentioned parameters, one-dimensional plots are
recommended.

3.5.1. Effect of catalyst loading

Figure 7 shows the effect of catalyst loading on the degradation of the dye. It can be seen that by increasing catalyst
dosage the higher dye removal efficiency is achieved. Increasing the catalyst dosage, provides more active surface
area and causes an enhancement in dye degradation. But using more catalyst dose is not economically suitable.
Therefore, in adjusting catalyst concentration many limitations should be considered.

figure 7: effect of catalyst loading

3.5.2. Effect of initial dye concentration

The study of the initial dye concentration is an important issue due to the application point of view. The degradation
of reactive orange 16 was studied by varying its initial concentration from 24 to 96 ppm at pH of 8.5, 55°C and 1350
ppm catalyst. Result shown in figure 8 reveals that destruction decreases by increasing the initial dye concentration.
As the concentration of dye increases, the path length of photon entering the solution and the number of photon
absorption decreases. The same behavior has been observed by S. K. Kansal et. al. during the destruction of reactive
black 5 and reactive orange 4 [14].

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 figure 8: effect of initial dye concentration

3.5.3. Effect of initial pH

Textile wastewaters are discharged at different range of pH values. It is important to study the role of pH on photo-
degradation of dyes. The interpretation of this effect on destruction process is a complicated task because surface
properties of semiconductor and dye type affect on the pH influence on degradation efficiency. Figure 9 exhibits the
degradation efficiency of reactive orange 16 as a function of pH for ZnO nanophotocatalyst.
The maximum degradation was observed at pH of 7.78 and under acidic and basic media the degradation decreases.
The zero charge point of ZnO is at pH 9. Firstly, ZnO surface is negatively charged under basic condition and
reactive orange 16 is an anionic dye, thus, there would be a columbic repulsion between dye and catalyst. Thus, dye
adsorption of catalyst reduces and results in reduction of degradation efficiency at high pH values. Secondly, it
should be noted that ZnO dissolves in acidic solutions therefore the active sites of the catalyst decreases and causes
in reduction of dye destruction.

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 figure 9: effect of pH

3.5.4. Effect of temperature

It has been reported that the optimum temperature for photocatalysis is between 20 to 80 °C [15]. Figure 10 shows
the effect of temperature (40 to 70°C) on degradation efficiency of reactive orange 16. The curve exhibits that by
increasing temperature from 40 to 70°C photodegradation increases. The results show that low increase in
temperature helps the reaction to complete more efficiently.

figure 10: effect of temperature

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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