Demirel and Kayan International Journal of Industrial Chemistry 2012, 3:24

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RESEARCH Open Access

Application of response surface methodology and

central composite design for the optimization of
textile dye degradation by wet air oxidation
Muhammet Demirel1 and Berkant Kayan2*

Abstract
Background: The present study is aimed at investigating the degradation of azo dye solution of AR 274 by wet air
oxidation conditions. The central composite design matrix and response surface methodology were applied in
designing the experiments to evaluate the interactive effects of the three most important operating variables. Thus,
the interactive effects of oxygen pressure (3.0 to 5.0 MPa), temperature (100°C to 250°C), and time (30 to 90 min)
on the degradation of dye were investigated.
Results: The predicted values were found to be in good agreement with the experimental values (R2 = 0.9981 and
Adj-R2 = 0.9965), which define the propriety of the model and the achievement of CCD in the optimization of WAO
process.
Conclusions: Intermediates of dye degradation were detected by GC-MS, the possible degradation mechanism for
the WAO of dye was discussed, and the probable degradation pathway was deduced.
Keywords: Degradation, Response surface methodology, Central composite design, Wet air oxidation

Background Thus, azo dyes constitute a significant portion of dyes that

Dye pollutants from textile and dyestuff industries are a are used in industries nowadays. The product obtained
major hazardous source of environmental contamin- from dye degradation could be mutagenic and carcinogenic,
ation. The large quantity of dye wastewater has become thereby causing long-term health concerns. Therefore, the
a serious environmental problem owing to the character- treatment of effluents containing such compounds is
istics of high color, high chemical oxygen demand, and important for the protection of natural waters as well as the
fluctuating pH. The direct discharge of this wastewater environment [9-12]. Conventional methods of dyeing
into water bodies such as lakes and rivers causes pollution wastewater treatment include adsorption, flocculation, ozo-
of the water and affects the flora and fauna. Effluent from nation, advanced oxidation using UV/H2O2 or UV/TiO2,
textile industries contains different types of dyes, which and biological oxidation. Other advanced oxidation treat-
show very low biodegradability owing to their high molecu- ments for dyeing wastewater treatment are wet air oxida-
lar weight and complex structures [1-3]. Some dyes, espe- tion (WAO) and catalytic wet air oxidation (CWAO),
cially azo dyes, are known to be biorefractory pollutants which are operated at subcritical water and pressures of
even with carefully selected microorganism and under water. Previous researches have shown that the treatment
favorable conditions. Azo dyes are characterized by the efficiencies for various dyes using WAO and CWAO are in
presence of one or more azo bonds (−N = N-) and account the range of 50% to 90% at the operating times of 30 to
for 60% to 70% of all textile dyes used. It is estimated that 240 min in different types of reactors [13-17].
approximately 8 × 105 tons (t) of dyes are produced annu- A variety of advanced oxidation process (AOPs) have
ally worldwide, and about 50% of them are azo dyes [4-8]. been attempted for the degradation of dyes, among which
WAO seems to be a clean method as it does not involve
* Correspondence: berkantkayan@aksaray.edu.tr the use of any harmful chemicals and uses only the clean
2
Department of Chemistry, Arts and Sciences Faculty, Aksaray University,
Aksaray 68100, Turkey
reagent of air [7,18]. By using WAO, organic pollutants are
Full list of author information is available at the end of the article either partially oxidized into biodegradable intermediates
© 2012 Demirel and Kayan; licensee Springer. This is an Open Access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and
reproduction in any medium, provided the original work is properly cited.
Demirel and Kayan International Journal of Industrial Chemistry 2012, 3:24
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or mineralized to carbon dioxide, water, and innocuous end
products under elevated temperatures (100°C to 300°C)
and pressures (0.5 to 20 MPa) using an oxidant such as
oxygen. The enhanced solubility of oxygen in aqueous solu-
tions at elevated temperatures and pressures provides a
strong driving force for oxidation. The elevated pressures
are required to keep water in the liquid state. Water also
acts as a moderant by providing a medium for heat transfer
and removing excess heat by evaporation. WAO has been
demonstrated to oxidize organic compounds to CO2 and
other innocuous end products. Carbon is oxidized to CO2;
nitrogen is converted to NH3, NO3, or elemental nitrogen;
and halogen and sulfur are converted to inorganic halides
and sulfates. The degree of oxidation is mainly a function
of temperature, oxygen partial pressure, residence time,
and the oxidizability of the pollutants under consideration
[19-22]. WAO is not only eco friendly but also economical
when compared to other AOPs that use harmful and
expensive oxidizing agents like ozone and hydrogen
peroxide [23-25]. In this research, the aqueous solution of
Acid Red 274 (AR 274) was selected as a model for textile
wastewaters for evaluation under WAO conditions. An-
other part of this study involved the use of response surface
methodology (RSM) and finding an applicable approximat-
ing function for predicting and determining the further
response, and studying the optimum working state. The
factors (variables) of oxygen pressure, temperature, and
experimental time were investigated [26].
RSM is a kind of mathematical and statistical technique
for designing experiments, building models, evaluating the
relative significance of several independent variables, and
determining the optimum conditions for desirable
responses [5,27,28]. The two most common designs exten-
sively used in RSM are the central composite design (CCD)
and the Box-Behnken design (BBD). The CCD is ideal for
sequential experimentation and allows a reasonable amount
of information for testing lack of fit while not involving an
unusually large number of design points [29-31].
Methods
Analysis methods
In the present study, AR 274 dye concentration was ana-
lyzed spectrophotometrically on a UV–vis spectrometer
(Shimadzu UV-160A, Shimadzu Corporation, Kyoto, Japan)
at 527 nm by measuring the absorbance of the untreated
samples at maximum wavelength, and the percentage of
AR 274 degradation efficiency percentage was calculated
using the following formula:
Co  Ct
DE% ¼ 100
Co
where Co and Ct represent the initial and remaining AR
274 concentration at given time (t), respectively. The
Page 2 of 10
mineralization of AR 274 solution was monitored
through the diminishment of the TOC, measured on a
Tekmar-Dorhmann Apollo 9000 TOC analyzer (Teledyne
Technologies, Inc., OH, USA).
The mass analysis process, which is the same as the
previous method, was performed for intermediates of
dye degradation [9]. The gas chromatography–mass
spectrometry (GC-MS) analysis was performed using
the 5890A Agilent model gas chromatograph (Agilent
Technologies, Inc., CA, USA), interfaced with the
ECD, NPD, and 5975C mass selective detector. The
aqueous solutions were extracted three times with 15 mL
dichloromethane. A 3-μL sample was analyzed on GC-MS.
A HP5-MS capillary column (30 m × 0.25 mm × 0.25 μm)
was used as the analytical column. Helium was used
as the carrier gas with a flow rate of 2 mL/min. The
GC injection port temperature was set at 250°C (split
mode = 1/5), and the column temperature was fixed at
70°C for 5 min. Subsequently, the column was sequen-
tially heated at a rate of 5°C/min to 120°C and held
for 1 min, at a rate of 8°C/min to 200°C and held for
5 min, and at a rate of 10°C/min to 280°C and held
for 10 min. The MS detector was operated in the EI
mode (70 eV).
Experimental design and optimization
In this study, RSM was used for the optimization of
process variable to enhance the degradation of AR
274 dye combined with the factorial experimental de-
sign of CCD. RSM is a useful method for studying the
effect of several variables influencing the responses by
varying them simultaneously and carrying out a lim-
ited number of experiments. A very limited number of
studies employing the experimental design and
optimization modeling approach for WAO process
have been reported in the literature [32,33]. The CCD
is an effective design that is ideal for sequential
experimentation and allows a reasonable amount of
information for testing the lack of fit while not involv-
ing an unusually large number of design points. It
was first announced by Box and Wilson in 1951, and
is well suited for fitting a quadratic surface, which
usually works well for the process optimization
[31,34-36].
In the present study, a CCD was employed for deter-
mining the optimum conditions for dye removal in
WAO. The experimental results were analyzed using
Design Expert 8.1, and the regression model was
proposed. Oxygen pressure, temperature, and reaction
time were chosen as three independent variables in
ð1Þ
the degradation process. Accordingly, the CCD
matrixes of 20 experiments covering the full design of
five factors were used for building quadratic models as
shown in Table 1 [37]. The experimental data obtained
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from the CCD model experiments can be represented Thus, RSM was used for obtaining a relationship
in the form of the following equation: between factors and the response and for optimizing the
response. Table 2 depicts a complete 23 factorial design
X
n
with four center points in cube, and six axial points and
Y ¼ bo þ bi xi
i¼1
two center points in axial. The experiments were carried
X
n n1 X
X n out in three replicates and six blocks in order to fit the
þ bii xi 2 þ bij xi xj þ ei ; ð2Þ second-order polynomial model [39].
i¼1 i¼1 j¼iþ1 According to the RSM results, polynomial regression
modeling was performed on the responses of the corre-
where Y is the predicted response; n is the number of
sponding coded values of the three different process
factors; xi and xj are the coded variables; bo is the off-
variables, and the results were evaluated. The predicted
set term; bi, bii, and bij are the first-order, quadratic,
response (Y) for the percent TOC of samples treated
and interaction effects, respectively; i and j are the
was obtained using Equation 4:
index numbers for factor; and ei is the residual error
[35,38]. Y ¼ 40:67 þ 5:32X1 þ 23:75X2 þ 3:44X3
The quality of the polynomial model was expressed by þ1:29X1 X2  0:84X1 X3
the coefficient of determination, namely, R2 and Adj-R2.
The statistical significance was verified with adequate þ1:06X2 X3  0:83X1 2  0:069X2 2 þ 0:95X3 2
precision ratio and by the F test [26]. According to the ð4Þ
obtained experimental data, the levels of the three main
A statistical approach using a CCD was used for effi-
parameters investigated in this study are presented in
ciency degradation of dye and for determining the inter-
Table 1. For statistical calculations, the variables Xi (the
action between these factors. For the response surface
real value of an independent variable) were coded as xi
methodology involving CCD, a total of 20 experiments
(dimensionless value of independent variable) according
was conducted for three factors at five levels with three
to the following equation:
replicates at center point. Table 1 provides a list of inde-
ðXi  Xo Þ pendent variables and coded factor levels. The number
Xi ¼ ; ð3Þ of experiments required (N) is given by the expression:
δX
2k (23 = 8; star points) + 2 k (2 × 3 = 6; axial points) + 6
where Xo is the value of Xi at the center point, and δX (center points; 6 replications).
represents the step change [9,30,35]. An RSM is appropriate when the optimal region for
running the process has been identified. The design used
Results and discussion for the optimization and observed responses for 20
Optimization of degradation conditions using the RSM experiments are given in Table 2 for WAO [40]. In
approach Equation 4, Y is the TOC removal percent of dye; and
In the present study, RSM was employed for identifying x1, x2, and x3 are the corresponding coded variables of
the simple and interactive effects of operating variables oxygen pressure, temperature, and time, respectively.
of dye degradation for WAO process. On the basis of
the CCD, there are four important stages for the Analysis of variance
optimization of the experiments: (1) to perform statistically Analysis of variance (ANOVA) values for the quadratic
designed experiments for the experimental plan, (2) regression model obtained from CCD employed in the
recommend the mathematical model basis of the ex- optimization of dye degradation are listed in Table 3. On
perimental data and focus on the data of analysis of the basis of the experimental values, statistical testing
variance, (3) control the efficiency of the model directly was carried out using Fisher's test for ANOVA. The stat-
with diagnostic plots, and (4) estimate the response istical significance of the second-order equation revealed
and verify the model [5,27]. that the regression is statistically significant (P < 0.0001);
however, the lack of fit is not statistically significant at
Table 1 Experimental range and levels of the 99% confidence level. Table 3 depicts the significance of
independent variables the regression coefficients and ANOVA for the regres-
Variables Factor Range and level sion model, respectively. The results indicate that the
−α −1 0 +1 +α response equation proved to be suitable for the CCD
Oxygen pressure (MPa) X1 2.32 3.0 4.0 5.0 5.68 experiment [41,42].
Temperature (°C) X2 48.87 100 175 250 301.13
The model's F value of 595.49 in these tables implies
that the model is significant for the degradation of the
Time (min) X3 9.55 30 60 90 110.45
dye. If the model has a very high degree of adequacy for
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Table 2 Central composite design experiments and experimental results

Experiment number Experimental design Experimental plan Observed% Y Predicted% Y
O2 (MPa) T (°C) t (min) X1 X2 X3
1 −1 −1 −1 3.0 100 30 7.18 7.82
2 +1 −1 −1 5.0 100 30 16.30 17.57
3 −1 +1 −1 3.0 250 30 50.05 50.63
4 +1 +1 −1 5.0 250 30 65.60 65.52
5 −1 −1 +1 3.0 100 90 12.80 14.25
6 +1 −1 +1 5.0 100 90 19.40 20.64
7 −1 +1 +1 3.0 250 90 61.20 61.31
8 +1 +1 +1 5.0 250 90 72.10 72.84
9 −1.682 0 0 2.32 175 60 30.10 29.38
10 +1.682 0 0 5.68 175 60 48.50 47.28
11 0 −1.682 0 4.0 48.87 60 2.60 0.53
12 0 +1.682 0 4.0 301.1 60 80.30 80.43
13 0 0 −1.682 4.0 175 9.55 32.70 32.20
14 0 0 +1.682 4.0 175 110.4 45.20 43.76
15 0 0 0 4.0 175 60 40.50 40.67
16 0 0 0 4.0 175 60 40.70 40.67
17 0 0 0 4.0 175 60 40.00 40.67
18 0 0 0 4.0 175 60 40.80 40.67
19 0 0 0 4.0 175 60 41.00 40.67
20 0 0 0 4.0 175 60 40.70 40.67

predicting the experimental results, the computed F value for the model was 9 and n = 20. It can be observed that
should be greater than the tabulated F value at a level of the tabular F value (F0.05,9,10 = 3.02) is clearly less than the
significance α. Thus, the calculated F value (Fmodel = calculated F value of 595.49. Adequate precision measures
595.49) was compared with the tabulated F value (F0.05, the signal to noise ratio, and a ratio value greater than 4 is
df, (n − df + 1)) at a significance level of 0.05, when the df desirable. Therefore, in the quadratic model degradation
of dye, an adequate precision of 90.78 indicates an
adequate signal for WAO. P values less than 0.05 indicate
Table 3 ANOVA regression model for AR 274 degradation that the model terms are significant, whereas values
using WAO process greater than 0.1 are not significant. The fit of the models
Source Degrees of Sum of Mean F value P value were controlled by the coefficient of determination R2.
freedom squares square
Based on the ANOVA results, the models report high R2
Model 9 8,302.34 922.48 595.49 <0.0001
value of 99.81% for dye degradation using WAO. Also, an
X1 1 386.63 386.63 249.58 <0.0001 acceptable agreement with the adjusted determination
X2 1 7,705.46 7,705.46 4,974.12 <0.0001 coefficient is necessary. In this study, the Adj-R2 value of
X3 1 161.35 161.35 104.16 <0.0001 99.65% was found. The values of R2 and Adj-R2 are close
X21 1 9.90 9.90 6.39 0.0153 to 1.0, which is very high and advocates a high correlation
X22 1 0.068 0.068 0.044 0.1523
between the observed values and the predicted values.
This indicates that the regression model provides an excel-
X23 1 13.08 13.08 8.44 0.0253
lent explanation of the relationship between the independ-
X1X2 1 13.21 13.21 8.53 0.9725 ent variables and the response. The diagnostic plots given
X1X3 1 5.64 5.64 3.64 0.6877 in Figures 1, 2, and 3 were used for estimating the
X2X3 1 8.99 8.99 5.80 0.7608 adequacy of the regression model. The calculated chi-
Residual 10 15.49 1.55 square value of the model (χ2 = 0.25) was found to be less
Lack of fit 5 14.90 2.98 25.33 0.0015
than the tabulated value (χ20.05 = 30.14), which revealed that
there is no significant difference between the observed
Pure error 5 0.59 0.12
data and the model response [5,9,32-37]. The actual and
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Figure 1 The actual and predicted TOC removal percentage.
the predicted TOC removal percentage values are given in
Figure 1. It can be observed that there are tendencies in
the linear regression fit, and the model adequately explains
the experimental range studied. The actual TOC removal
percentage value is the measured result for a specific run,
and the predicted value is evaluated from the independent
variables in the CCD model [5,9]. The normal percentage
probability and studentized residual plot are shown in
Figure 2. The data points indicate that neither response
transformation was required nor there was any apparent
problem with normality. Figure 3 depicts the studentized
residual and predicted TOC removal percentage of dye
degradation.
Figure 2 The studentized and normal percentage probability
plot of degradation of AR 274.
Page 5 of 10
Figure 3 The predicted TOC removal (%) of AR 274 and
studentized residual plot.
Interactive effect of processes of independent variables
To understand the impact of each variable, three dimen-
sional (3D) plots were made for the estimated responses,
which were the bases of the model polynomial function
for analysis to investigate the interactive effect of the
two factors on the TOC removal percentage within the
experimental ranges given in Figures 4, 5, and 6. The
inferences so attained are discussed below [43].
Interactive effect of oxygen pressure and temperature
To investigate the integrated effect of temperature and
oxygen pressure, RSM was used and the result was given
in the form of 3D plots. As indicated in Figure 4, the
temperature and pressure conditions have considerable
influence on the extent of degradation achieved. Figure 4
Figure 4 3D surface plot of TOC removal versus oxygen
pressure (MPa) and experiment temperature (°C). Fixed reaction
time t = 60 min.
Demirel and Kayan International Journal of Industrial Chemistry 2012, 3:24
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Figure 5 3D surface plot of TOC removal versus experiment
temperature (°C) and experiment time (in min). Fixed oxygen
pressure (4.0 MPa).
indicates that the increasing pressure of oxygen partially
speeded up the dye degradation, and the dye degradation
rate increased until the oxygen was exhausted in the
reaction medium. The oxygen pressure is part of the
driving force for mass transfer; therefore, the degradation
rate increases with the increasing oxygen amount. However,
with the oxygen amount below the stoichiometric amount,
it contributes little to the concentration of the dissolved
oxygen [4]. The degradation rate is found to be affected by
this situation. The TOC removal percentage of dye is found
to increase with rising temperature for degradation
processes. At the lowest temperature of 100°C, the
removal of TOC is rather insignificant. At temperatures
above 150°C, TOC removal after 30 min is almost
dependent on temperature. For example, as shown in
Figure 4 (at 3.0 MPa oxygen pressure, temperature 100°C),
the percentage of TOC removal was 7.18%, which
increased to 50.0% at 3.0 MPa and 250°C temperature
when using the WAO process. The increased percentage
Figure 6 3D plot of TOC removal versus oxygen pressure (MPa)
and experiment time (min). Fixed temperature T = 175°C.
Page 6 of 10
TOC removals were also monitored for oxygen pressure
ranging from 3.0 to 5.0 MPa for the WAO process. With
oxygen pressure reaching up to 5.0 MPa from 3.0 MPa at
250°C, the TOC removal percentage was found to increase
until to 65.6% from 50.0 using WAO process. The
degradation of dye would increase if the oxygen pressure
is kept high; however, after the stoichiometric quantity is
achieved, the oxygen quantity is not an effective factor for
dye degradation [4,16]. As can be seen in Figure 4, TOC
removal percentage increased remarkably with increasing
temperature at all applied oxidant concentrations, and
temperature has a significant impact on the dye degrad-
ation. Thus, with the increase of temperature, an improve-
ment in dye degradation performance was determined [4].
At wet air oxidation conditions, the free radical easily
occurs at high temperature and oxygen-rich conditions.
The free-radical generation consists of O2 attacking the
C-H bond of the organic molecule. The following
reactions could occur by the addition of molecular oxygen
[4,44-49].
RH þ O2 ! R þ HO2 ðinitiationÞ ð5Þ
R þ O2 ! RO2 ðpropagationÞ ð6Þ
RO2  þ RH ! ROOH þ RðpropagationÞ ð7Þ
ROOH ! RO þ OHðautocatalytic decompositionÞ ð8Þ
RO þ RH ! ROH þ R ðpropagationÞ ð9Þ
OH þ RH ! R þ H2 O ðpropagationÞ ð10Þ
2ROO ! ROOR þ O2 ðterminationÞ ð11Þ
These reactions generate organic radicals and other
free radicals, which in turn initiate the chain reactions of
dye degradation with the help of dissolved oxygen. Several
operating parameters influence the aforementioned
formation of free radicals, and thereby the degradation
rate of pollutants, among which temperature plays the
most important role in the case of sufficient oxygen
supply [7,50,51].
Interactive effect of temperature and time
Figure 5 presents 3D plots indicating the effect of
temperature and time on percentage TOC removal
under the predefined conditions given by Design Expert.
As indicated in Figure 5, the maximum 80.3% TOC
removal occurs at 60 min of experimental time and at
300°C ± 2°C in WAO conditions. The degradation rate
slightly increases with the increase in the experimental
time at moderate temperature; however, when the
temperature increases, the effect of time is almost insig-
nificant, and temperature becomes the main factor
owing to the interaction between the oxidant and
temperature. Thus, the degradation rate is almost
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Figure 7 Major degradation pathway proposed for WAO of Acid Red 274.
primarily controlled by the temperature, the details of
which are described above. Therefore, it appears that
time might be less important for the degradation rate of
dye. The same effect was observed in the study reported
previously [9].
Interactive effect of oxygen pressure and time
As seen in Figure 6, the response surface and 3D plots
were enhanced as a function of oxidant pressure and
Figure 8 GC-MS analysis of the organic intermediates of AR
274 after 5-min WAO treatment. Reaction conditions: T = 200°C;
[AR 274]o = 1,000 mg/L.
Page 7 of 10
experimental time. In addition, the TOC removal percent-
age rate increased with increased oxygen pressure and time
at constant temperature. With the increasing experimental
time, the interaction probability of formed radicals with
dye, according to Equations 5 to 11, increased. The dye
degradation by WAO was regarded as a free radical
mechanism. With increasing time, the free radicals such as
R and ROO would be increased, which promotes the
degradation rate [7]. However, regardless of the experimen-
tal time, this interaction would be limited to the amount of
oxygen. As free radical occurs easily at oxygen-rich condi-
tions, depending on the time decrease, the amount of
oxygen in the radicals will reduce and the degradation rate
will gradually slow down.
Figure 9 Molecular structure of reactive Acid Red 274 dye.
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Figure 10 Scheme of the wet air oxidation system.
Identification of degradation products
The degradation products obtained in the present study
were similar to that obtained from the previous study
wherein the degradation of AR 274 was realized using
H2O2 in subcritical water [9]. This result is normal as
common reagents were occurring in both studies. In this
process, the attack of the azo bond would be the initial
step of dye degradation, which pioneers the fast removal
of color [7]. Figure 7 depicts the GC-MS analysis of
short-time oxidized solutions in WAO condition revealing
the formation of benzamide (A1), benzoic acid (A2),
hydroquinone (A3), benzoquinone (A4), 1-naphthol (B1),
naphthalene-1,6-diol (B2), naphthalene-1,2,4,6-tetraol (B3),
phthalic anhydride (B4), 2,6-dihydroxynaphthalene-1,4-
dione (B5), phthalic acid (B6), o-cyclohexylphenol (C1), and
catechol (C2). In the process, C-N and C-O bonds were
cleavaged owing to temperature effects and attacks of
hydroxyl radicals. The main intermediates identified during
WAO treatment of AR 274 by GC-MS was shown on GC
chromatogram in Figure 8. For a longer duration of oxida-
tion, all aromatic compounds would be further transformed
into small molecules.
Experimental
Materials
The azo dye C.I. Acid Red 274, commercial name Supranol
Red 3BW (CAS no: 61931-18-8), was obtained from Dystar
Colours Distribution GmbH (Germany) and was used
without further purification. The solution of AR 274 was
prepared in 1,000 mg/L initial concentration with distilled
Page 8 of 10
water for all treatments. The molecular structure of AR
274 (C35H28N3O9Na2S2, Mw = 744 g/mol) was shown in
Figure 9. Oxygen was used as the oxidant in the WAO
process, which was supplied by Linde Gas (Linde Group
Turkey, Adana, Turkey) with 99.9% purity.
Wet air oxidation process
The experimental process is described in detail in Kayan
et al. [44]. A brief overview of the process is as follows:
Wet air oxidation process was carried out at temperature
ranging from 100°C to 250°C with oxygen pressure of 3.0
to 5.0 MPa in a 150-mL stainless steel reactor with mag-
netic stirrer and heater as shown in Figure 10. The glass
vessel was placed in the reactor and filled with 1,000 mg/L
of AR 274 solution, and subsequently the reactor was
placed on a magnetic stirrer and heater. Oxygen was
directly supplied through a tube into the liquid phase.
Ordinarily, the reactor was filled with 150 mL of reaction
solution. The reaction solution was heated to the targeted
temperature, and all the valves of the reactor were tightly
closed during preheating. Upon reaching the targeted
temperature, the amount of pure oxygen gas fed in the
reactor in the liquid phase and its partial pressure were
maintained with a gas relief valve. Samples were taken out
periodically and analyzed for AR 274 degradation using a
UV–vis spectrophotometer. The reaction temperature was
measured using a thermocouple and controlled using a
regulator. After the sample collection treatment, the
reactor was cooled to room temperature using a water
bath and sampled for total organic carbon (TOC) analysis
Demirel and Kayan International Journal of Industrial Chemistry 2012, 3:24
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of the final effluent in 90-min reaction time. The quantity
of dissolved oxygen in water was calculated using an oxy-
gen solubility model for the required degradation of AR
274 in distilled water [52].
Conclusions
The degradation of the azo dye was obtained by wet
air oxidation system. Wet air oxidation seems a very
attractive technique for the treatment of waste streams
that are toxic and dilute. When molecular oxygen was
used as an oxidant in WAO system, effective degrad-
ation or mineralization efficiency was obtained at high
temperature. This clearly indicated that temperature
had an effect on dye degradation. An increase in the
pressure of oxygen partially speeded up the dye deg-
radation and increased the dye degradation rate until
the oxygen was exhausted in the reaction medium.
This result indicated that temperature was the main
factor, and the interactions of other parameters were
discussed in detail. The degradation process was opti-
mized using RSM based on CCD. The optimum values
of oxygen pressure, temperature, and reaction time
were 3.3 MPa, 255°C, and 111 min, respectively, where
67.02% TOC removal could be obtained from the
proposed model. The ANOVA showed high coefficient of
the determination values (R2 = 0.9981 and Adj-R2 = 0.9965).
In this way, the degradation mechanism of WAO of Acid
Red 274 dye was discussed, and the probable degradation
pathway was deduced.
Abbreviations
ANOVA: analysis of variance; AR 274: Acid Red 274; AOPs: advanced
oxidation processes; CCD: central composite design; CWAO: catalytic wet air
oxidation; GC-MS: gas chromatography–mass spectrometry; RSM: response
surface methodology; WAO: wet air oxidation; TOC: total organic carbon.
Competing interests
The authors declare that they have no competing interests.
Authors' contributions
BK conceived of the study, coordinated in the research, and participated in
the experimental design and optimization. MD participated in the
degradation experiments, the preparation of graphs and tables, and in the
statistical analysis of the data. All authors read and approved the final
manuscript.
Acknowledgments
We wish to thank Dr. Belgin Gözmen for GC-MS analysis and other supports.
We also would like to thank Prof. Dr. A. Murat Gizir for the ever positive
support and for the continuous encouragement.
Author details
1
Department of Chemistry, Arts and Sciences Faculty, Mersin University,
Mersin 33342, Turkey. 2Department of Chemistry, Arts and Sciences Faculty,
Aksaray University, Aksaray 68100, Turkey.
Received: 28 May 2012 Accepted: 31 August 2012
Published: 2 October 2012
Page 9 of 10
References
1. Wang A, Qu J, Liu H, Ge J (2004) Degradation of azo dye acid red 14 in
aqueous solution by electrokinetic and electrooxidation process.
Chemosphere 55:1189–1196
2. Verma AK, Dash R, Bhunia P (2012) A review on chemical coagulation/
flocculation technologies for removal colour from textile wastewaters. J
Environ Manage 93:154–168
3. Martinez SS, Uribe EV (2012) Enhanced sonochemical degradation of azure
B dye by the electro-Fenton process. Ultrason Sonochem 19:174–178
4. Lei L, Dai Q, Zhou M, Zhang X (2007) Decolorization of cationic red X-GRL
by wet air oxidation: performance optimization and degradation
mechanism. Chemosphere 68:1135–1142
5. Zhang Z, Zheng H (2009) Optimization for decolorization of azo dye acid
green 20 by ultrasound and H2O2 using response surface methodology. J
Hazard Mater 172:1388–1393
6. Muruganandham M, Swaminathan M (2004) Solar photocatalytic
degradation of a reactive azo dye in TiO2–suspension. Sol. Energy. Mat. Sol.
Cells 81:439–457
7. Zhou M, He J (2007) Degradation of azo dye by three clean advanced
oxidation processes: wet oxidation, electrochemical oxidation and wet
electrochemical oxidation-A comparative study. Electrochem. Acta.
53:1902–1910
8. Zollinger H (1991) Color chemistry—synthesis, properties and application of
organic dyes and pigments. VCH Publisher, New York
9. Kayan B, Gözmen B (2012) Degradation of Acid Red 274 using H2O2 in
subcritical water: application of response surface methodology. J Hazard
Mater 201–202:100–106
10. Devi LG, Kumar SG, Reddy KM, Munikrishnappa C (2009) Photo degradation
of methyl orange an azo dye by advanced Fenton process using zero
valent metallic ion: influence of various reaction parameters and its
degradation mechanism. J Hazard Mater 164:459–467
11. Erdemoglu S, Karaaslan S, Sayılkan F, Izgi B, Asiltürk M, Sayılkan H, Frimmel F,
Güçer Ş (2008) Photocatalytic degradation of Congo Red by hydrothermally
synthesized nanocrystalline TiO2 and identification of degradation products
by LC–MS. J Hazard Mater 155:469–476
12. Özcan A, Oturan MA, Oturan N, Şahin Y (2009) Removal of Acid Orange 7
from water by electrochemically generated Fenton's reagent. J Hazard
Mater 163:1213–1220
13. Söğüt OÖ, Akgün M (2009) Removal of CI basic blue 41 from aqueous
solution by supercritical water oxidation in continuous-flow reactor. J of
Industrial and Eng Chem 15:803–808
14. Tang C, Chen V (2004) The photocatalytic degradation of reactive black 5
using TiO2/UV in an annular photoreactor. Water Res 38:2775–2781
15. Bhargava SK, Tardio J, Prased J, Folger K, Akolekar DB, Grocott SC (2006) Wet
oxidation and catalytic wet oxidation. Ind. Eng. Chem. Res. 45:1221–1258
16. Kim SC, Park HH, Lee DK (2003) Pd-Pt/Al2O3 bimetallic catalysts for the
advanced oxidation of reactive dye solutions. Catal. Today 87:51–57
17. Chang DJ, Chen IP, Chen MT, Lin SS (2003) Wet air oxidation of a reactive
dye solution using CoAlPO4-5 and CeO2 catalysts. Chemosphere 52:943–949
18. Rajeshwar K, Ibanez JG, Swain GM (1994) Electrochemistry and the
environment. J Appl Electrochem 24:1077–1091
19. Mishra VS, Mahajani VV, Joshi JB (1995) Wet air oxidation. Ind. Eng. Chem.
Res. 34:2–48
20. Copa WM, Gitchel WB (1989) Wet oxidation standard handbook of
hazardous waste treatment and disposal. Mc Graw-Hill, New York
21. Laughlin RGW, Gallo T, Robey H (1983) Wet air oxidation for hazardous
waste control. J Hazard Mater 8:1–9
22. Zimmermann FJ (1950) Wet oxidation of hazardous organics in
wastewaters. US Patent. 2665249
23. Kim KH, Ihm SK (2011) Heterogeneous catalytic wet air oxidation of
refractory organic pollutants in industrial wastewaters: a review. J Hazard
Mater 186:16–34
24. Luck F (1996) A review of industrial catalytic wet air oxidation processes.
Catal. Today 27:195–202
25. Luck F (1999) Wet air oxidation: past, present and future. Catal. Today
53:81–91
26. Rauf MA, Marzouki N, Körbahti BK (2008) Photolytic decolorization of Rose
Bengal by UV/H2O2 and data optimization using response surface method. J
Hazard Mater 159:602–609
27. Box GEP, Draper NR (1978) Empirical model-building and response surfaces.
Wiley, New York
Demirel and Kayan International Journal of Industrial Chemistry 2012, 3:24 Page 10 of 10
http://www.industchem.com/content/3/1/24

28. Draper N, John JA (1988) Response surface design for quantitative and
qualitative variables. Technometrics 30:423–428
29. Somayajula A, Asaithambi P, Susree M, Matheswaran M (2011)
Sonoelectrochemical oxidation for decolorization of reactive red 195.
Ultrasonics Sonochem. doi:10.1016/j.ultsonch.2011.12.019
30. Myers RH (1971) Response surface methodology. Allyn and Bacon, Boston
31. Montgomery DC (1996) Design and analysis of experiments, 4th edition.
Wiley, New York
32. Singh KP, Gupta S, Singh AK, Sinha S (2011) Optimizing adsorption of crystal
violet dye from water by magnetic nanocomposite using response surface
modeling approach. J Hazard Mater 186:1462–1473
33. Sahu JN, Acharya J, Meikap BC (2009) Response surface modeling and
optimization of chromium (VI) removal from aqueous solution using tamarind
wood activated carbon in batch process. J Hazard Mater 172:818–825
34. Özer A, Gürbüz G, Çalımlı A, Körbahti BK (2009) Biosorption of copper(II)
ions on Enteromorpha prolifera: application of response surface
methodology (RSM). Chem. Eng. Journal 146:377–387
35. Moghaddam SS, Alavi Moghaddam MR, Arami M (2010) Coagulation/flocculation
process for dye removal using sludge from water treatment plant: optimization
through response surface methodology. J Hazard Mater 175:651–657
36. Myers RH, Montgomery DC (2002) Response surface methodology: process
and product optimization using designed experiments, 2nd edition. Wiley,
New York
37. Moghaddam SS, Alavi Moghaddam MR, Arami M (2011) Response surface
optimization of acid red 119 dye from simulated wastewater using Al based
waterworks sludge and polyaluminium chloride as coagulant. J. Environ.
Manag. 92:1284–1291
38. Körbahti BK, Tanyolaç A (2009) Continuous electrochemical treatment of
simulated industrial textile wastewater from industrial components in a
tubular reactor. J Hazard Mater 170:771–778
39. Lim CL, Morad N, Teng TT, Norli I (2011) Chemical oxygen demand (COD)
reduction of a reactive dye wastewater using H2O2/pyridine/ Cu(II) system.
Desalination 278:26–30
40. Brereton RG (2003) Chemometrics: data analysis for the laboratory and
chemical plant. Wiley, New York
41. Guaracho VV, Kaminari NMS, Ponte MJJS, Ponte HA (2009) Central
composite experimental design applied to removal of lead and nickel from
sand. J Hazard Mater 172:1087–1092
42. Olmez-Hanci T, Kartal Z, Arslan-Alaton İ (2012) Electrocoagulation of
commercial naphthalene sulfonates: process optimization and assessment
of implementation potential. J Environ Manage 99:44–51
43. Kasiri MB, Khataee AR (2011) Photooxidative decolorization of two organic
dyes with different chemical structures by UV/H2O2 process: experimental
design. Desalination 270:151–159
44. Kayan B, Gözmen B, Demirel M, Gizir AM (2010) Degradation of acid red 97
dye in aqueous medium using wet oxidation and electro-Fenton
techniques. J Hazard Mater 177:95–102
45. Joklegar HS, Samant SD, Joshi JB (1991) Kinetics of wet air oxidation of
phenol and substituted phenols. Water Res 25:135–145
46. Chang S, Liu Y (2007) Degradation mechanism of 2,4,6-trinitrotoluene in
supercritical water. J Environ Sci 19:1430–1435
47. Legrini O, Oliveros E, Braun AM (1993) Photochemical process for water
treatment. Chem. Rev. 93:671–698
48. Mantzavinos D, Hallenbrand R, Livingston AG, Metcalfe IS (1997) Wet
oxidation as a pretreatment method for wastewaters contaminated by
bioresistant organics. Water. Sci. Techol. 36:109–116
49. Suresh KB, James T, Jaidev P, Karl F, Deepak BA, Stephen CG (2006) Wet
oxidation and catalytic wet oxidation. Ind. Eng. Chem. Res. 45:1221–1258
50. Gözmen B, Kayan B, Gizir AM, Hesenov A (2009) Oxidative degradation of Submit your manuscript to a
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51. Alaton IA (2003) A review of effects of dye-assisting chemicals on advanced 7 Convenient online submission
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52. Tromans D (2000) Modelling oxygen solubility in water and electrolyte
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