Research Journal of Chemical and Environmental Sciences

RJCES
Res J. Chem. Environ. Sci. Vol 5 [1] February 2017: 31-39
Online ISSN 2321-1040
CODEN: RJCEA2 [USA]
©Academy for Environment and Life Sciences, INDIA
Website: www.aelsindia.com/rjces.htm

ORIGINAL ARTICLE

Photo Catalytic Oxidation: A Novel Route For Removing Pollutant

Present In The Seafood Industry Effluent
R.Sorna Prema1*, S. Kandasamy 2
1, 2 Department of Food Technology
Kongu Engineering College, Perundurai, Erode-638 052, Tamil Nadu, India
* Corres. Author: [email protected]

ABSTRACT
The photo catalytic oxidation of sea food industry waste water was studied using batch photo catalytic UV reactor. In the
current research work, green synthesized Zinc Oxide (ZnO) nano catalyst with the average catalyst size 60 nm used as a
photo catalyst which produces the hydroxyl radical when it exposed to UV radiation. The main objective of this study was
to optimize the process variables such as radiation time, pH and dosage of catalyst on BOD, COD removal by three factors
three level Box-Behnken design (BBD). The experimental result was analyzed by Pareto Analysis of Variance (ANOVA)
and 3D plots to predict the effects of individual variables and their interaction effects. The optimal condition was found
at pH 4, catalyst dosage 55 mg/100ml, radiation time 60 min under this condition 90.92 % of BOD removal and 92.75 %
of COD removal was obtained with 0.9 desirability value.
Key words: ZnO nano catalyst, sea food industry, photo catalytic oxidation, Box-Behnken design (BBD)

Received 20.01.2017 Accepted 03.02.2017 © 2017 AELS, INDIA

INTRODUCTION
Water is an important commodity in the world for drinking, sanitation, agriculture and industrial
activities although it was present only 75% on the earth surface. Rapid globalization, industrialization
and population growth generates huge amount of waste water that will create a negative impact on the
ecological system. A few decades before there is no stringent law and regulation for disposing of
industrial and municipal effluent but now adays many new regulations were framed to implement zero
discharge concept. Therefore effluent treatment is an important element in for different industries, of
which sea food industry generates huge quantity of waste water originated from the unit operations
scalding, washing, evisceration, cooking, thawing and freezing which is rich in organic pollutants because
of presence of blood, dissolved protein and phosphorous so that it requires great concern to prevent the
threatening of environment [1]. Numerous effluent treatment methods such as coagulation, filtration,
sedimentation, membrane processing, ozonation, flocculation and biological method are followed to treat
the various industrial effluents [2-4]. Among those methods photo catalytic oxidation method has
received much attention for industrial wastewater treatment due to its eco friendliness and superior
removal of organic pollutants without any sludge formation. In photo catalytic oxidation process electron
and hole pairs was produced when the UV energy was incident on the catalyst surface that generates the
hydroxyl radical which can oxidize the organic pollutants present in the waste water [5-9].
Recently nano catalyst synthesis has been focused by many researchers to develop the nano photo
catalyst with better size and surface morphology [10]. There are several physical and chemical methods
such as solgel technique [11] , inert gas condensation technique [12] , plasma based synthesized method
[13] spray pyrolysis method [14] , precipitation method [15] and hydro thermal synthesis [16] have been
reported for zinc oxide nano catalyst synthesis. Currently plant mediated green synthesis of different
nano particles from various plants such as Cassia alata, Camellia sinensis, Mangifera indica, Azadirachta
indica, Syzygium cumini and Ocimum basilicum have been reported [17]. Hence the present study uses the
sesbania grandiflora leaf extract as a reducing agents to synthesis the zinc oxide nano catalyst because
sesbania grandiflora leaf contains good source of phytochemicals such as phenolic acids, poly phenol and
flavanoids that capable to reduce the precursor effectively [18].
An extensive literature review shown that no research report is available for treating of sea food industry
waste water by photo catalytic oxidation using zinc oxide nano catalyst hence the presence study deals

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 Prema and Kandasamy

about the utilization of the prepared zinc oxide nano catalyst synthesized by sesbania grandiflora leaf
extract to treat the sea food industry waste water and optimize the photo oxidation process variables
such as dosage of catalyst, pH and radiation time on the reduction of BOD and COD level.

MATERIALS AND METHODS

Raw materials
Sesbania grandiflora was procured from local market near Perundurai, Tamil Nadu, India and it was
utilized for the synthesis of nano catalyst. The wastewater was collected from an industry located at
Thoothukudi, Tamil Nadu, India and stored at 4 ºC for further experimental analysis. All the chemicals
used in this study were obtained from Sigma chemical, Chennai. The initial characteristics of effluent used
in the present study are given in the Table 1.
Table 1: Characteristics of sea food industry effluent
Characteristic Value
COD 912ppm
BOD 625ppm
Total suspended solids 7892.22ppm
Turbidity 859 NTU
Total Dissolved Solids 2057 ppm
pH 6.56
Preparation of nano catalyst
Fresh leaves with uniform size and without any blemishes were manually separated from the stem of the
plant and washed in running tap water in order to remove the impurities present on the surface. 5 grams
of leaves were taken in a beaker, add 100 ml of distilled water and kept it in a hot plate at the
temperature of 60 ºC until the color of the water was turned to green. Then the extract was filtered using
filter paper (What man No-1), 50 ml of the filtered leaf extracts were taken in a glass beaker, add 5 g of
zinc nitrate precursor on the extract, the mixture was kept it on a hot plate at the temperature of 60 ºC
and heating was carried out until the formation of yellow color paste. After cooling the yellow paste, the
paste was collected in a ceramic crucible and placed in a muffle furnace at 500 ºC until the paste was
turned in to powdered form. Then the powder was scrapped carefully from the crucible and packed in a
hermetically sealed container for further experimental analysis.
Experimental setup and procedure
Photo catalytic reactor was designed and fabricated to treat the sea food industry waste water was shown
in the fig 1. The reactor consists of UV lamp ( = 288) which act as a light source for photo catalytic
reaction. The reactor contains sample inlet and out let to pour the effluent inside the rector. The UV light
source was surrounded with the quartz tube in which cold water was circulated to maintain the
temperature of the reactor. At the bottom of the reactor magnetic stirring system was located in order to
prevent the settling of nano catalyst while processing and also at the top reactor the lamp was connected
to the power supply.
A known quantity of effluent was taken in a beaker and pH was adjusted using 0.1N HCL and NaOH then
nano catalyst was added as per the Table 3 . This mixture was poured in to the reactor via the sample
inlet after a particular time the effluent was taken from the reactor through sample out let and filtered to
separate the nano catalyst from the effluent. After that the treated effluent water was undergone the
experimental work for as per the method described by the American Public Health Association (APHA) to
determine the BOD and COD removal. Removal efficiency of BOD and COD was calculated by the following
equation [19,20].
Cᵢ − Cᵨ
RE(%) = ∗ 100
Cᵢ
where Cᵢ, Cᵨ were the initial and final concentration of COD and BOD respectively

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Fig. 1. Schematic diagram of photo catalytic oxidation unit

Experimental design
Response Surface Methodology (RSM) was a statistical technique employed for multiple regression
analysis. It was also be an effective tool to optimize and design under RSM was adopted in this present
study for optimization of process variables such as radiation time, catalyst dosage and pH. Each
independent variable was coded as -1, 0 and +1 which correspond to lower level, middle level and higher
level respectively [21]. Coding of variables were done based on following equation,

Xᵢ − Xᵨ
xᵢ =
∆Xᵢ
where xᵢ is the dimension less variable of an independent variable, Xᵢ is the real value of an independent
variable and Xᵨ is the real value of an independent variable at center point. ∆Xi is step change of the real
value of the variable ‘i’ corresponding to a variation of a unit for the dimensionless value of the variable ‘i’.
Ranges of independent variables and their levels are shown in the Table 2.

Table 2: Ranges of independent variables and their levels

Variables Factors Levels
(X)
-1 0 1
Dosage of catalyst (mg/100ml) A 10 55 100

Radiation time (min) B 30 60 90

pH C 2 4 6
Statistical analysis
Design Expert 8.0.7.1 (star ease Inc.,USA) software package used for statistical analysis. Analysis of
variance (ANOVA) was performed to identify the significance of factors, responses and their interaction in
addition to that probability value (p value) and lack of fit indicates the level of significance quantitatively.
Moreover R2, adjusted R2 and predicted R2 were used to check the adequacy of various models (linear,
quadratic, cubic and 2FI). Optimum conditions for removal of COD and BOD depends on dosage of
catalyst, radiation time and pH and it was obtained from derringer’s methodology. Actual and predicted
values were compared in order to find the effective model.

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Table 3: BBD design matrix along with observed responses

Dosage of catalyst Radiation time BOD COD
Run pH
(mg/100ml) (min) removal (%) removal (%)
1 100 60 2 77.5 78.9
2 10 60 6 71.5 74.3
3 55 60 4 90.4 92.7
4 55 90 2 70.7 72.1
5 55 60 4 90.3 92.3
6 10 30 4 72.7 74.3
7 55 90 6 79.6 81.7
8 100 30 4 82.5 83
9 100 90 4 77 79
10 55 60 4 90.5 92.2
11 10 60 2 69.3 71.4
12 100 60 6 80.8 82.3
13 10 90 4 71.2 73.2
14 55 60 4 90.9 92.5
15 55 60 4 90.8 92.4
16 55 30 6 65.3 68.9
17 55 30 2 73.6 75.7

RESULTS AND DISCUSSION

Nano catalyst characterization
Synthesized nano catalyst was proved by X-Ray
X Ray diffraction (XRD) and Scanning Electron Microscope, it
was shown in the figure 2&3 respectively. From the figure 2 , the peaks were identified at 31.77º, 34.44º,
36.28º, 47.60º, 56.52º, 62.88º and 67.96º. These
These peaks were well agreement with the literature report
[22, 23] and also well consistent with the JCPDS File Card No. 01-075-0576
01 0576 thus shown the synthesized
nano catalyst was identical to hexagonal phase with Wurtzite structure of zinc oxide [24]. The aveaverage
particle size was found to be 60mm by using Debye-Scherrer
Debye formula [25].
SEM analysis was carried out to find the surface morphology of zinc oxide nano catalyst using JSM
JSM-6360
scanning electron microscope at different magnification levels and results were shown in the figure 3.The
micrographs (fig.3) was shown that the occurrence of network formation and agglomeration moreover,
the synthesized zinc oxide nano catalyst had a spherical in shape with rough surface

Fig. 2. XRD pattern of ZnO nano particles

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Fig. 3. SEM image of ZnO nano particles

Photo catalytic oxidation studies

Effect of process variables on treatment efficiency
Effect of pH
pH was a significant factor that offer a greater influence on photo catalytic oxidation process, in this
present study pH of the effluent was varied in the range of 2.0- 6.0 to investigate its effects on photo
catalytic degradation of pollutant present in the sea food industry waste water. From the results (Fig
4&5) found that the photo catalytic efficiency was increased when increasing pH 2-4, this is because of
the formation of per hydroxyl radical and hydroxide ions under acidic conditions which could effectively
take part in the degradation of pollutant present in the sea food industry effluent [10]. pH also alters the
surface properties of the molecules , at pH 4allows the strong adsorption of water and hydroxyl radical,
effluent and ZnO catalyst resulting higher BOD and COD removal was obtained [26].
Effect of catalyst dosage
Optimum level of catalyst dosage is an important parameter to be examined in order to avoid the
ineffective usage of ZnO nano catalyst. For this study, the catalyst dosage was varied from 10 to 100mg
for 100ml of sea food industry waste water when the amount of catalyst dosage increased the photo
catalytic degradation of pollutant was increased slightly up to 55mg , after that drastically decreasing of
removal efficiency was obtained. However this might be due to the particle agglomeration and turbidity
formation which causes inaccessible active site for adsorbing radiation resulting minimum level of free
radical generation [5, 7].
Effect of irradiation time
Irradiation time plays a key role on photo oxidation process for BOD and COD removal, it was studied at a
range of 30-90 min and its influence was shown in the Fig 2&3 From the results it was observed that at
initially the pollutant removal efficiency was low because at the initial period was required to initiate the
equilibrium adsorption of radiation on the catalyst surface [27] when increasing the time up to 60 min
the removal efficiency was maximum because the hydroxyl radical level increased which had a capability
to oxidize the organic matter present in the sea food industry waste water. Thereafter there was drastic
decreasing the removal efficiencies that can be found by the fact at longer time produces more radical but
these radicals were unstable in nature which leads to decrease the photo catalytic degradation process.

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Fig .4. Effect of process variables on BOD removal

Fig. 5. Effect of process variables on COD removal

Development of mathematical model

Fitting of data to the various models such as linear, quadratic, cubic and interactive was performed to
obtain the regression equation. The model summary was depicted in the Table 4. The outcome of the
model summary indicated that quadratic model was suggested
suggested and cubic model was not suggested for the
experiment due to insufficient points to correlate the coefficient of the mathematical model. F
F-value is the

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 Prema and Kandasamy

ratio of regression mean square and the real error mean which indicates the influence of each contro
controlled
factor on the tested model. ANOVA results in the Table 4 shows that F value for BOD removal and COD
removal was high in the quadratic model which implies the model was highly significant and also the
probability value of quadratic model was lower than
than cubic model so that quadratic model had been
recommended for the effluent treatment process.

Table 4 : Model summary statistics for BOD and COD removal

Source SD R² Adjusted R² Predicted R² Press p F Remark
value value
Model summary statistics for BOD removal
Linear 9.41 0.1143 -0.0901
- -0.3466 1750.01 0.6512 0.56
2F₁ 10.2 0.2001 -0.2779
- -1.0007 2600.15 0.7851 0.36
Quadratic 2.03 0.9779 0.9495 0.6494 455.58 <0.0001 141.53 Suggested
Cubic 0.26 0.9998 0.9992 0.0012 82.14 Aliased
Model summary statistics for COD removal
Linear 8.94 0.1074 -0.0986
- -0.3272 1543.92 0.6750 0.52
2F₁ 9.84 0.1671 -0.3327
- -1.0294 2360.86 0.8674 0.24
Quadratic 1.98 0.9765 0.9462 0.6255 435.71 <0.0001 245.20 Suggested
Cubic 0.19 0.9999 0.9995 0.0420 80.28 Aliased

Adequacy of developed model

Adequacy of developed model was investigated using ANOVA. ANOVA fitted quadratic model of photo
catalytic oxidation were shown in the Table 5. The higher F value and lower p value (0.0001) denoted that
the model was significant and the model equation can effectively
effectively used to illustrate the photo catalytic
treatment process under wide range of operating conditions. The p value lower than 0.05 for the model
and coefficients indicates it significance. Actual and Predicted values of the responses were illustrate
illustrated in
the fig. 6. in which pointes in the figure was closed to the center points that indicated that the model was
well fitted.

Fig.6. Actual and Predicted values of the responses

Fitting of second order polynomial equation

Empirical relationship between the input variables and their interaction on the responses were expressed
in terms of second order polynomial equation. The equation with coded variables as follows,
(%)
= 92.42 + 375 + 0.51 + 1.14 − 0.73 + 0.12 + 4.10 − 6.46 − 8.58
− 9.23 ^2
(%)
= 90.58 + 4.14
14 + 0.11 + 1.2 − 1.0 + 0.27 + 5.17 − 5.69 − 9.04
− 10.12 ^2

Optimization of photo catalytic oxidation process parameter

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Optimization was performed on the basis of derringer’s desirability function to find out the optimal
conditions for COD removal and BOD removal. The results shown that the optimum conditions were
catalyst dosage of 55 mg/100ml, radiation time of 60min , and pH of 4 under this conditions 90.92 % of
BOD removal and 92.75% of COD removal was taken place.

Table 5: ANOVA for the responses

Source BOD removal COD removal
F value P value F value P value
Model 180.372 < 0.0001 110.854 < 0.0001
A 154.625 < 0.0001 89.8713 < 0.0001
B 0.81984 0.3953 1.20052 0.3095
C 57.5421 0.0001 34.8946 0.0006
AB 19.9587 0.0029 19.572 0.0031
AC 56.0073 <0.0001 36.7646 0.0005
BC 14.5393 0.0066 4.45613 0.0727
A² 885.03 < 0.0001 554.365 < 0.0001
B² 51.5798 0.0002 36.9707 0.0005
C² 282.784 < 0.0001 157.62 < 0.0001

Conclusions
Response surface methodology coupled with three factor and three level BBD design was employed to
optimize the process variables such as catalyst dose, pH, radiation on COD and BOD removal. A
mathematical model and ANOVA was developed to correlate the influencing parameter on the pollutant
removal and used to predict the treatment efficiency. Operating conditions was found at catalyst dose 55
mg/ 100ml, radiation time of 60min , and pH 4 , under this conditions 90.92 % of BOD removal and
92.75% of COD removal was taken place. It shows that effectiveness of photo catalytic oxidation method
for sea food industry waste water treatment.

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CITE THIS ARTICLE

R.Sorna Prema, S. Kandasamy. Photo Catalytic Oxidation: A Novel Route for Removing Pollutant Present In The
Seafood Industry Effluent. Res. J. Chem. Env. Sci. Vol 5 [1] February 2017. 31-39

RJCES Vol 5 [1] February 2017 39 | P a g e © 2017 AELS, INDIA