+Model

CEJ-5227; No. of Pages 9 ARTICLE IN PRESS

Chemical Engineering Journal xxx (2007) xxx–xxx

Electrochemical degradation of Levafix CA reactive dyes

in textile dyeing wastewater using iron electrodes
Bahadır K. Körbahti ∗

D
University of Mersin, Faculty of Engineering, Chemical Engineering Department, Çiftlikköy, 33343 Mersin, Turkey
Received 20 November 2006; received in revised form 28 February 2007; accepted 30 March 2007

TE
Abstract
In this study, the electrochemical treatment of Levafix CA reactive dyes in textile dyeing wastewater was investigated on iron electrodes in the
presence of NaCl electrolyte. The effects of initial dye concentration, electrolyte concentration and current density on color removal and turbidity
removal were studied at 28 ◦ C room temperature. In the study, complete color removal and effective turbidity removal achieved, and the rate of color
removal obtained as Levafix Yellow CA > Levafix Blue CA > Levafix Red CA at all reaction conditions. The mass transfer coefficients calculated as
7.72 × 10−6 , 9.05 × 10−6 and 7.81 × 10−6 m/s and the mass fluxes were evaluated as 4.77 × 10−3 , 4.61 × 10−3 and 3.79 × 10−3 kg/m2 s for Levafix
Blue CA, Levafix Red CA and Levafix Yellow CA, respectively. At optimized reaction conditions, mean energy consumption were calculated as
8.3, 9.0 and 7.7 kWh/kg COD removed for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively.
AC
© 2007 Elsevier B.V. All rights reserved.

Keywords: Electrochemical wastewater treatment; Electrolysis; Textile wastewater; Dyeing wastewater; Mass transfer; Energy consumption

1. Introduction [10]. In the literature, the electrochemical treatment of textile

wastewater has also been studied [3–9,11–14]. Although the
Textile manufacturing is one of the largest industrial produc- electrochemical methods used for dye degradation have been
R

ers of wastewater and approximately generates about 125–150 L
wastewater per kilogram of textile product [1]. Dyes and auxil-
iary chemicals used in textile mills are improved to be resistant
to environmental influences for better performance. As a result,
ET
successful, this study meets the lack of data on the electrochem-
ical degradation of industrial Levafix CA reactive dyes. In the
study, Levafix CA reactive dyes were chosen because of increas-
ing regional use in textile industry due to their high fastness

they are hardly to remove from wastewater generated during the
dyeing processes [1,2]. Textile wastewater is well known with
its high chemical oxygen demand, strong color, large amount
of suspended solids, variable pH values, salt content and high
temperature. Therefore, the treatment systems combined with
physical, biological and chemical methods are inefficient for
the effective treatment of industrial textile wastewater due to
R
profile and meet most requirements set by textile manufacturers
for fastness to light, perspiration, chlorine and repeated washing.
In this study, the electrochemical treatment of textile dye-
ing wastewater that produced in the industrial mercerized and
non-mercerized cotton and viscon processes containing Lev-
afix Blue CA, Levafix Red CA and Levafix Yellow CA reactive
dyes was investigated, and the effect of operating parameters

the variation of wastewater characteristics and heavy COD load
[3–9].
In recent years, electrochemical oxidation is becoming an
alternative wastewater treatment method and replacing the con-
ventional processes, because many industrial processes produce
toxic wastewaters, which are not easily biodegradable and
requiring costly physical or physico-chemical pretreatments
∗ Tel.: +90 324 3610001x7374; fax: +90 324 3610032.
E-mail address: korbahti@mersin.edu.tr.
of current density, electrolyte concentration, initial dye concen-
tration and electrolysis time on COD removal, color removal
and turbidity removal efficiency were analyzed from batch runs.
The textile dyeing wastewater was synthetically prepared for the
standardization throughout the study.
In the study, the electrochemical treatment of textile dyeing
wastewater was investigated in the presence of NaCl electrolyte
using iron electrodes. The electrochemical reactions that take
place during the electrolysis of NaCl solution are rather compli-
cated, only assumptions can be made based on the products that
can be determined as Cl2 , ClO2 , O3 , OH• , O• , H2 O2 , O2 , H2 and

1385-8947/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2007.03.083

Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
2 B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx
CO2 [15,16]. The possible electrochemical reactions are shown
in Eqs. (1)–(11). The discharged chlorine gas on the anode was
in excess amount in the reactor for textile dyeing wastewater
treatment in the presence of NaCl and the irreversible hydroly-
sis reaction [17–19] and ionization reaction [18,19] take place
subsequently Cl2 gas discharged on the anode [15–18]. HOCl is
replenished in the medium with the electrochemical reaction of
NaCl in solution. Hypochlorous acid, HOCl, is a strong oxidant,
which oxidizes the wastewater while OCl− is also consumed by
reaction (4) [15,16,20].
2Cl− → Cl2 + 2e−
Cl2 + H2 O  HOCl + H+ + Cl−
HOCl  H+ + OCl−
TE
6OCl− + 3H2 O → 23 O2 + 6H+ + 4Cl− + 2ClO3 − + 6e−
Moreover, with sufficient power supply, Fe2+ ions added to
the solution by the anodic reaction (reaction (5)), and some of the
organic molecules and suspended solids removed by Fe(OH)3
sedimentation or H2 flotation [3].
AC
4Fe → 4Fe2+ + 8e−
4Fe2+ + 10H2 O + O2 → 4Fe(OH)3 + 8H+
Two major mechanisms of precipitation (pH < 6.5) and
adsorption (pH > 6.5) are considered between dye molecules
and electrolysis by-products in Eqs. (7)–(10) [6,7], Fe(m) and
R
Fe(p) are corresponding to monomeric Fe and polymeric Fe,
respectively.
Precipitation : Dye + Fe(m) → [Dye ⊕ Fe(m)]
ET
Dye + Fe(p) → [Dye ⊕ Fe(p)]
Adsorption : Dye + Fe(OH)n → [particle]
[Dye ⊕ Fe(p)] + Fe(OH)n → [particle]
Electrogenerated ferric ions may form monomeric
R
ions, ferric hydroxo complexes with hydroxide ions and
polymeric species of FeOH2+ , Fe(OH)2 + , Fe2 (OH)2 4+ ,
Fe(OH)4 − , Fe(H2 O)2 + , Fe(H2 O)5 OH2+ , Fe(H2 O)4 (OH)2+ ,
Fe(H2 O)8 (OH)2 4+ , Fe2 (H2 O)6 (OH)4 2+ depending on the pH
range, which transform into Fe(OH)3 finally [21]. In Eqs. (9)
and (10), n is equal to 2 or 3 [6].
In electrochemical reactions azo linkage also electroreduce,
where Ar and Ar are aryl groups in Eq. (11) [22].
Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
2. Materials and methods
2.1. Chemicals and materials
Levafix Blue CA, Levafix Red CA and Levafix Yellow
CA reactive dyes (DyStar) and sodium chloride (Merck) were
obtained in extra pure grade and double distilled water was
used for the preparation of model textile dyeing wastewater. The
Levafix CA reactive dyes are bifunctional and CA (Combined
Anchor) refers to the use of chlorine-free tri-fluoropyrimidine,
mono-fluorotriazine and new vinyl sulphone anchor groups. The
(1) dyes had COD concentrations of 950, 690 and 740 mg/g, respec-
tively, with pH values between 6 and 8. The chemical structures
D
(2) of commercial Levafix CA reactive dyes are not disclosed.
(3)
2.2. Experimental set-up and procedure
The model textile dyeing wastewater was prepared in rel-
atively high dye concentrations between 400 and 2000 mg/L,
(4) whereas dye content of textile wastewater used in the literature
were between 10 and 373 mg/L [6–9,11–13].
The batch electrochemical reactor was designed in our labo-
ratory. The reactor was made of Pyrex® glass having a volume of
600 mL (reaction volume of 400 mL) with a heating and cooling
coil around. The three pairs of iron electrodes (OD = 12 mm)
(5) were used as anode and cathode. The total anode area was
84.823 cm2 and the spacing between the electrodes was 15 mm.
(6) A glass stirrer with two blades 3 cm diameter impeller was
driven with a Heidolph-RZR 1 model mixer for homogeniza-
tion at 750 rpm. The reaction temperature was monitored with
a glass thermometer immersed inside the reactor. The reaction
temperature was controlled with circulating water recycled from
a temperature controlled water bath (New Brunswick, G-86).
The current was applied by a constant voltage/current controlled
dc power source, NETES NPS-1810D.
(7) The model textile dyeing wastewater was loaded into the
batch electrochemical reactor and the Plexiglas® reactor cover
(8) was placed tightly. Five milliliters of sample was taken from the
reactor with an injector to determine the initial chemical oxy-
(9) gen demand (COD), color and turbidity prior to reaction. The
reaction started with the application of specified current density,
(10)
and the recycling water for temperature control was pumped
through the reactor coil. The reaction temperature was kept con-
stant at 28 ◦ C room temperature. At appropriate time intervals,
5 mL samples were taken from the reactor in order to analyze
the specimen during electrochemical degradation.
2.3. Analysis
The samples were taken from the electrochemical reactor
at appropriate time intervals and centrifuged at 5000 rpm for
10 min to have supernatant for analysis and measurements. The
color of the reaction medium was monitored by a Labomed
(11) UV-Vis double beam UVD-3200 model spectrophotometer at
610, 526 and 416 nm for Levafix Blue CA, Levafix Red CA
and Levafix Yellow CA reactive dyes, respectively. The turbid-
ity was measured by a Hach 2100 AN IS model turbidimeter at
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx
860 nm. COD analysis performed with Palintest PL464 test kits
after color and turbidity analysis. In the Palintest COD method,
the water sample is oxidized by digesting in a sealed reaction
tube with sulphuric acid and potassium dichromate in the pres-
ence of a silver sulphate catalyst. The amount of dichromate
reduced is proportional to the chemical oxygen demand (COD).
The absorbance of the COD samples was read at 605 nm at
Labomed UV-Vis double beam UVD-3200 model spectropho-
tometer and the COD values was calculated using a calibration
curve prepared previously.
3. Results and discussion
Azo dyes are synthetic products and show rather low
biodegradability, which traditional biological processes are not
able to fully decolorize azo dyes wastewater [14]. In the elec-
TE
trochemical treatment of textile dyeing wastewater, pollutants
can be destroyed by direct anodic oxidation, indirect oxidation
or cathodic reduction processes.
In the study, the batch runs were conducted for the deter-
mination of the effects of operating variables of initial dye
concentration, electrolyte concentration and current density on
color removal and turbidity removal of textile dyeing wastewa-
ter. The increase in current density and electrolyte concentration
AC
resulted in enhanced color removal and turbidity removal in all
runs. In the study, complete color removal obtained at 40 min
reaction duration. Effective turbidity removal achieved also,
however turbidity values fluctuated due to the possible forma-
tion of low molecular weight complex by-products during the
electrochemical treatment. The pH of the reaction medium was
not controlled just monitored throughout the study. As a general
trend, pH sharply increased in 10 min up to pH 10–11 from 6.
R
This increasing pH trend was observed in all runs and was most
likely due to hydrolysis, ionization and HOCl/OCl− consump-
tion reactions of Eqs. (2)–(4). The data points for duplicate runs
at any time were not different from each other more than 4%.
ET
3.1. The effect of initial dye concentration
The effect of initial dye concentration on color removal is
shown in Fig. 1. The Levafix CA dyes removed at rather long
reaction durations as the initial dye concentration increased.
In the study, the formation of colorless compounds obtained
R
with the degradation of azo groups in the dye molecule. The
chromophore groups of dyes are easily destroyed by direct and
indirect oxidation, later the subsequent intermediates and other
organics undergo further anodic oxidation at a much lower rate
Table 1
The dimensionless numbers, mass transfer coefficients, mass fluxes and energy consumptions corresponding to the electrochemical treatment of textile dyeing
wastewater in a batch electrochemical reactor
Reactive dye Reaction time (min) Fractional COD conversion
Levafix CA Blue 40 0.325
Levafix CA Red 40 0.369
Levafix CA Yellow 40 0.328
Calculated dimensionless numbers for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes: Re = 11,747; Sc = 45; Sh = 148.
Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
3
Fig. 1. The effect of initial dye concentration on color removal (current density:
D
6 mA/cm2 ; electrolyte concentration: 2 g/L NaCl; reaction temperature: 28 ◦ C).
as reported in the literature [4]. In Fig. 1, color removal obtained
at 400 mg/L initial dye concentration as 95% for Levafix Blue
CA and Levafix Red CA, and 97% for Levafix Yellow CA at
10 min reaction duration.
In the study, the complete degradation of the initial dye
obtained with the presence of some organic side products accord-
ing to fractional COD conversion in Table 1, which was obtained
at optimized conditions using response surface methodology
(RSM) [23]. The decrease of COD shows that further degra-
dation of the initial colorless products took place along with the
decoloration during the electrochemical treatment. It could be
concluded that the rate of COD removal is lower than that of
color, indicating the azo bond degradation is the first step of the
electrochemical degradation mechanism with the comparison
of COD removal and color removal which is also stated in the
literature [4,12–14].
In the literature, it was reported that the degradation products
in the electrochemical oxidation of azo dyes are typically car-
bon dioxide, nitrate and sulphate, with the possible formation of
aromatic esters, phenols, aromatic carboxylic acids, cyclic and
aliphatic hydrocarbons as intermediates [4]. Usually, the oxida-
tion of the azo group occurs, followed by the oxidation of the
decomposition products [13].
Fig. 2 shows the effect of initial dye concentration on tur-
bidity removal. The lowest turbidity removal obtained at 55%
with 1200 mg/L Levafix Blue CA dye and the highest obtained
at 96% with 1200 mg/L Levafix Yellow CA as shown in Fig. 2.
The turbidity removal obtained after 40 min reaction duration
at 400 mg/L initial dye concentration as 83%, 89%, 91%, at
1200 mg/L initial dye concentration as 60%, 83%, 94% and at
2000 mg/L initial dye concentration as 74%, 90%, 96% for Lev-
afix Blue CA, Levafix Red CA and Levafix Yellow CA reactive
dyes, respectively.
km (m/s) J (kg/m2 s) E (kWh/kg COD removed)
7.72 × 10−6 4.77 × 10−3 8.3
9.05 × 10−6 4.61 × 10−3 9.0
7.81 × 10−6 3.79 × 10−3 7.7
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
4 B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx
Fig. 2. The effect of initial dye concentration on turbidity removal (current
density: 6 mA/cm2 ; electrolyte concentration: 2 g/L NaCl; reaction temperature:
28 ◦ C).
3.2. The effect of electrolyte concentration
TE
In textile dyebaths, NaCl is the main salt used for the optimal
fixation of the dyes on the textile substrate. Therefore, the real
textile wastewater contains the required quantity of NaCl [14,24]
to carry out the electrochemical treatment without any further
addition of electrolyte, which would increase the ionic strength.
The conductivity of dye solutions was adjusted using NaCl in
the range of 0–4 g/L in the present study. The addition of NaCl
AC
into textile dyeing wastewater increased the conductance and
electric current of the electrochemical process.
Reactive dyes are ionic and particularly anionic dyes attracted
to the electrodes during electrolysis. Therefore, reactive dyes
could ensure the conductance and current flow in the reaction
medium without NaCl addition (NaCl = 0 g/L). It is known that
almost all azo dyes are polysulphonated compounds in order to
be water-soluble. These anions together with other ionic degra-
R
dation products cause the increase of the current, however NaCl
enhances the decoloration process [14].
The effect of electrolyte concentration on color removal is
shown in Fig. 3. The applied potential was stabled at 6 V in order
ET
to observe the effect of electrolyte concentration. The supplied
current density was 1 mA/cm2 without NaCl, 6 and 11 mA/cm2
with 2 and 4 g/L NaCl, respectively. The increase in electrolyte
concentration increased color removal as shown in Fig. 3, where
R
Fig. 3. The effect of electrolyte concentration on color removal (applied poten-
tial: 6 V corresponding to 1 mA/cm2 without NaCl, 6 and 11 mA/cm2 with 2 and
4 g/L NaCl concentration, respectively; dye concentration: 1200 mg/L; reaction
temperature: 28 ◦ C).
Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
D
Fig. 4. The effect of electrolyte concentration on turbidity removal (applied
potential: 6 V corresponding to 1 mA/cm2 without NaCl, 6 and 11 mA/cm2 with
2 and 4 g/L NaCl concentration, respectively; dye concentration: 1200 mg/L;
reaction temperature: 28 ◦ C).
the fastest color removal obtained at 4 g/L electrolyte concen-
tration. In the study, complete color removal obtained at 2 and
4 g/L electrolyte concentrations after 25 min reaction duration.
Since in typical cotton dyeing operations 2–3 g/L NaCl elec-
trolyte exist in the textile wastewater as a remaining dyebath
additive [24], this investigated electrochemical treatment pro-
cess could be employed to the real textile dyeing wastewater
without any further electrolyte addition.
In the literature, Awad and Galwa obtained the highest elec-
trocatalytic activity in the presence of 2 g/L NaCl in which the
degradation of Acid Blue and Basic Brown dyes occurred by
both direct and indirect oxidation. The authors concluded that
the electrocatalytic effect with NaOH and H2 SO4 was not as
good as that in NaCl due to the absence of chloride [8].
In Fig. 4, similar turbidity profiles observed between 0 and
4 g/L NaCl as obtained in the effect of initial dye concentra-
tion. Turbidity removal could not obtain in the runs without
NaCl at the end of 40 min reaction. Turbidity removal resulted at
2 g/L electrolyte concentration as 60%, 83%, 94% and at 4 g/L
electrolyte concentration as 77%, 74%, 90% for Levafix Blue
CA, Levafix Red CA and Levafix Yellow CA reactive dyes,
respectively.
Do and Yeh was reported that oxygen evolution was the major
reaction in the absence of chloride, but the oxygen formation in
solution did not produce significant oxidation [18]. The results of
the present investigation have shown that efficient color removal
occurred in the presence of NaCl as a conductive electrolyte.
3.3. The effect of current density
In all electrochemical processes, current density is the most
important parameter for controlling the reaction rate within the
electrochemical reactor. In order to investigate the effect of cur-
rent density on the efficiency of color removal and COD removal,
electrolysis process was carried out between 4 and 8 mA/cm2
current densities. In the literature, Fernandes et al. studied the
electrochemical oxidation of C.I. Acid Orange 7 between 1.25
and 10 mA/cm2 [13], and Awad and Galwa [8] investigated the
electrocatalytic degradation of Acid Blue and Basic Brown dyes
between 0 and 45 mA/cm2 current densities.
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx
Fig. 5. The effect of current density on color removal (dye concentration:
1200 mg/L; electrolyte concentration: 2 g/L NaCl; reaction temperature: 28 ◦ C).
The increase in current density increased color removal as
shown in Fig. 5. The rate of color removal obtained as Levafix
TE
Yellow CA > Levafix Blue CA > Levafix Red CA at all applied
current densities. Color removal obtained at 4 and 6 mA/cm2 cur-
rent densities after 20 min reaction duration as 57%, 3%, 93%
and 98%, 81%, 98% for Levafix Blue CA, Levafix Red CA and
Levafix Yellow CA reactive dyes, respectively. At 8 mA/cm2
current density complete color removal obtained for all reac-
tive dyes after 20 min reaction. In Fig. 5, the removal of Levafix
AC
Red CA dye improved from 3% to 81% with the increase in
current density from 4 to 6 mA/cm2 . In the literature, Danesh-
var et al. stated that an increase in the current density up to
6–8 mA/cm2 enhanced the color removal efficiency in their study
[6].
In Fig. 6, the turbidity removal obtained after 40 min reac-
tion duration at 4 mA/cm2 current density as 69%, 78%,
91%, at 6 mA/cm2 current density as 60%, 83%, 94% and at
8 mA/cm2 current density as 76%, 79%, 79% for Levafix Blue
R
CA, Levafix Red CA and Levafix Yellow CA reactive dyes,
respectively.
Oxidized iron production increased from electrodes via rais-
ing current density, which is also reported in the literature [6].
ET
Therefore, when current density increases, there is an increase in
the amount of iron dissolved in the liquid phase and an increase
in the production of Fe(OH)3 [6]. It could be concluded that the
increase in current density greatly enhances the removal effect
at low potential differences. In the literature, it was reported
that at high voltages most of current is consumed by oxygen
R
Fig. 6. The effect of current density on turbidity removal (dye concentration:
1200 mg/L; electrolyte concentration: 2 g/L NaCl; reaction temperature: 28 ◦ C).
Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
5
evolution and side reactions [9]. Electrolyte decomposition and
gas evolution secondary reactions can also take place during the
mineralisation of organic compounds, resulting in a loss of cur-
rent efficiency and leading to a decreasing of the removal yield
[13]. The results showed that an increase in the current density
increased the color removal efficiency, which is also stated in
the literature [6,8,13,14].
3.4. Experimental optimization
In the previous study, color removal and turbidity removal
data were processed to obtain the interaction between the process
variables and the response using response surface methodology
D
(RSM) [23]. The total number of experiments for each dye with
four independent factors was 30 (=2k + 2k + 6), where k is the
number of factors equals to 4. Twenty-four experiments were
augmented with six replications at the design center for each dye
in order to evaluate the pure error and were carried in randomized
order as required in many design procedures.
The experimental results were evaluated using Design-Expert
6.0 (trial version) and the quadratic approximating functions
were obtained in the previous study [23].ANOVA results indi-
cated that those quadratic models could be used to navigate the
design space with significant model F values and adequate pre-
cision [23]. In Figs. 7–9, the residual plots were examined for
the adequacy checking of the approximating models, which is
an important part of the data analysis procedure [25,26].
The normal probability and studentized residuals plot is
shown in Fig. 7 for color removal and turbidity removal. Resid-
uals are the difference between actual and predicted values for
each point, shows how well the model satisfies the assumptions
of the analysis of variance (ANOVA). Studentized residuals
in Fig. 7 are the residuals divided by the estimated standard
deviation of that residual. It measures the number of standard
deviations separating the actual and predicted values. The nor-
mal probability plot indicates whether the residuals follow a
normal distribution, in which case the points will follow a
straight line. S-shaped curve was not formed according to Fig. 7,
indicating that neither response transformation needed nor there
was apparent problem with normality.
Fig. 8 shows the studentized residuals versus predicted color
removal and turbidity removal plot. The general impression is
that the plot should be a random scatter, suggesting the vari-
ance of original observations is constant for all values of the
response. If the variance of the response depends on the mean
level of color removal percent and turbidity removal percent,
then this plot often exhibits a funnel-shaped pattern [25,26].
This is also indicating that no need for transformation of the
response variable.
In Fig. 9, outlier t for the batch runs for color removal and tur-
bidity removal is shown. The outlier t is a measure of how many
standard deviations the actual value deviates from the predicted
value. Most of the standard residuals should lie in the interval of
±3.50 and any observation with a standardized residual outside
of this interval is potentially unusual with respect to its observed
response [25,26]. According to Fig. 9, the outlier t values below
the interval of ±3.50 indicated that the approximation of the fit-
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
6 B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx

D
TE
AC
R

Fig. 8. The predicted color removal and turbidity removal and studentized resid-
Fig. 7. The studentized residuals and normal % probability plot for color removal
ET

uals plot.
and turbidity removal.

ted model to the response surface was fairly good without data 3.5. Dimensional analysis and mass transfer coefficient
recording error.
In the optimization phase, current density and electrolyte con- Dimensional analysis is used to plan the experiments and to
centration were minimized while color removal and turbidity interpret the results in the form of dimensionless groups and
removal were maximized at 2000 mg/L initial dye concentra-
R

equations [27]. The dimensionless Re, Sc and Sh numbers in

tion [23]. The optimized conditions obtained for the highest the stirred batch electrochemical reactor was calculated and
desirability at 6.7, 5.9, 5.4 mA/cm2 current density and 3.1, given in Table 1. In engineering, modified Eq. (12) gives a fairly
2.5, 2.8 g/L NaCl concentration for Levafix Blue CA, Levafix good fit to the published data over a wide range of Reynolds
Red CA and Levafix Yellow CA reactive textile dyes, respec- numbers and Schmidt numbers [27]. The average Sherwood
tively [23]. In Table 1, the fractional COD conversion values number for parallel electrodes in turbulent flow could be given as
at optimized conditions indicate the removal degree for Levafix [22,27,28]:
CA reactive dyes treated using iron electrodes that color dis-
appearance does not mean complete degradation or complete Sh = 0.023Sc1/3 Re4/5 (12)
removal of pollutants in wastewater. In terms of COD removal,
some of literature studies apparently achieved better results than In Eq. (12), Re and Sc numbers defined as [27]:
this work, however, the initial dye concentrations used in this
study were relatively high in contrast to those in the literature nDa2 ρ
Re = (13)
[6–9,11–13]. μ

Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx
TE
AC
R
Fig. 9. The outlier t plot for color removal and turbidity removal.
ET
μ In Eq. (16), JA is the mass flux in kg/m2 s, CAi and CAf the ini-
Sc =
DAB ρ
Re number in Eq. (13) defined for agitation of liquids, and cal-
culated from the diameter and peripheral speed of the impeller.
In Eqs. (13) and (14), n, Da , ρ, μ and DAB are corresponding
to rotational speed in r/s, diameter of impeller in m, density
in kg/m3 , viscosity in kg/m s and diffusion coefficient of the
R
wastewater in m2 /s, respectively. The flow pattern was turbu-
lent according to calculated Re number of 11,747 which was
greater than 104 . The Re number 11,747 indicated that the
flow system in the stirred batch electrochemical reactor was
well mixed and the inertia forces were greater than viscous
friction forces. Sc number of 45 indicated the momentum trans-
port was much effective than the mass transport by diffusion,
where Sh number obtained from Eq. (12) as 148 in stirred
batch electrochemical reactor with the diffusion coefficient of
2.12 × 10−8 m2 /s, calculated using Wilke–Chang correlation
[27].
Mass transfer coefficient for a loaded reactor and stirred for a
given time, during which the reaction occurs to a certain extent
Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
7
could be determined by Eq. (15) [22,28,29]:
  
−km A
xSBR = 1 − t (15)
VR
In Eq. (15), VR reaction volume of 400 mL, A electrode area
in m2 , km mass transfer coefficient in the reaction medium in
m/s, t reaction time in s and xSBR fractional COD conversion
given in Table 1. The mass transfer coefficients calculated as
7.72 × 10−6 , 9.05 × 10−6 and 7.81 × 10−6 m/s for Levafix Blue
CA, Levafix Red CA and Levafix Yellow CA, respectively.
In the literature, Morão et al. studied the electrochemical
oxidation of multicomponent mixtures of organic compounds
D
using boron doped diamond anode and obtained mass transfer
coefficient for phenol, phenyl-methanol, 1-phenyl-ethanol and
m-cresol degradation as 1.9 × 10−5 , 1.9 × 10−5 , 1.7 × 10−5 and
2.1 × 10−5 m/s, respectively [30]. Panizza and Cerisola investi-
gated the electrochemical oxidation of 2-naphthol using lead
dioxide, boron-doped diamond and Ti–Ru–Sn ternary oxide
anodes, and determined the mass transfer coefficient about
0.7 × 10−5 to 2.0 × 10−5 m/s [31]. Spitzer and Bertazzoli deter-
mined the mass transfer coefficients in the electrochemical
recovery of copper, gold and silver between 0.24–0.29 × 10−4 ,
0.40–3.3 × 10−4 , and 0.97–4.8 × 10−4 m/s, respectively on the
vitreous carbon cathode, and on the Ti cathode determined
between 0.28–0.47 × 10−4 and 0.68–1.33 × 10−4 m/s for gold
and silver recovery, respectively [32]. Fernandes et al. studied
the electrochemical oxidation of C.I. Acid Orange 7 on a boron
doped diamond electrode and evaluated an average mass trans-
fer coefficient of 1.46 × 10−5 m/s [13]. In the literature, mass
transfer coefficients for Pt, C and Ag electrode reactions was
also given between 9 × 10−8 and 6.6 × 10−4 m/s [22].
The convective mass flux could be determined by Eq. (16)
[27]:
JA = km (CAi − CAf ) (16)
(14) tial and final COD concentrations in kg/m3 . The initial and final
COD concentrations were determined at t = 0 and at t = 40 min,
respectively. Mass transfer coefficients and mass fluxes were
evaluated using Eqs. (15) and (16), and given in Table 1. The
mass fluxes were calculated as 4.77 × 10−3 , 4.61 × 10−3 and
3.79 × 10−3 kg/m2 s for Levafix Blue CA, Levafix Red CA and
Levafix Yellow CA, respectively.
3.6. Energy consumption
The mean energy consumption during the electrochemical
treatment of textile dyeing wastewater in the stirred batch reactor
were evaluated using Eq. (17) and given in Table 1. In Eq. (17),
E is the mean energy consumption in kWh/kg COD removed, i
the current in A, V the applied potential in V, t the reaction time
in h and COD is the COD removed in kg from t = 0 to the end
of reaction time.
iVt
E= (17)
COD
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
8 B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx
The mean energy consumption at 28 ◦ C reaction temperature
in 40 min reaction duration at optimum conditions were calcu-
lated as 8.3 kWh/kg COD removed, 9.0 kWh/kg COD removed
and 7.7 kWh/kg COD removed for Levafix Blue CA, Levafix
Red CA and Levafix Yellow CA, respectively. The obtained
mean energy consumption values are reasonable for electro-
chemical treatment of textile dyeing wastewater. In the literature,
the mean energy consumption in a recirculation tubular batch
reactor consisted of stainless steel 304 cathode and Ti/Pt anode
placed at the center of the reactor was determined as 21 kWh [5],
1.273–12.3 kWh [15], 4.8–200 kWh [33], 1.273–12.3 kWh [34]
and 12.4 kWh per kg COD removed [35] for the electrochemi-
cal treatment of textile dye wastewater [5], olive oil wastewater
[15], tannery waste liquors [33], noncyanide strippers wastes
[34] and domestic wastewater [35], respectively.
4. Conclusion
TE
The electrochemical degradation of Levafix Blue CA, Levafix
Red CA and Levafix Yellow CA reactive dyes was investigated
in textile dyeing wastewater using iron electrodes. The batch
runs were conducted for the investigation of the effects of initial
dye concentration, electrolyte concentration and current den-
sity on color removal and turbidity removal of textile dyeing
AC
wastewater. In the study, the flow pattern was analyzed and deter-
mined as turbulent according to Re number of 11,747. The mass
transfer coefficients calculated as 7.72 × 10−6 , 9.05 × 10−6
and 7.81 × 10−6 m/s and the mass fluxes were evaluated as
4.77 × 10−3 , 4.61 × 10−3 and 3.79 × 10−3 kg/m2 s for Levafix
Blue CA, Levafix Red CA and Levafix Yellow CA, respec-
tively. At optimized conditions, the mean energy consumption
were evaluated in 40 min reaction duration as 8.3 kWh/kg COD
R
removed, 9.0 kWh/kg COD removed and 7.7 kWh/kg COD
removed for Levafix Blue CA, Levafix Red CA and Levafix
Yellow CA reactive dyes, respectively. During the electrochem-
ical treatment, rapid decoloration achieved throughout the study
ET
indicating that the reactive dyes were completely degraded into
smaller and colorless organic and inorganic molecules without
any coagulant addition or any further physicochemical processes
in order to enhance the electrochemical treatment performance.
Since in typical cotton dyeing operations 2–3 g/L NaCl elec-
trolyte exist in the textile wastewater as a remaining dyebath
additive, such investigated electrochemical treatment process
R
could be employed to the real textile dyeing wastewater. The
results of this study indicate that this electrochemical reactor
could be a feasible and an effective alternative system for the
electrochemical treatment of textile dyeing wastewater and it
could also be used at an oxidation pretreatment stage. Although
high electrolyte concentration, high current density and low ini-
tial dye concentration is improving treatment effect, some more
research is required on this subject in order to mineralize organic
pollutants and side products completely.
References
[1] U.S. EPA, Profile of the Textile Industry, EPA310R97009, Washington,
DC, 1997.
Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083
[2] U.S. EPA, Preliminary Industry Characterization: Fabric Printing, Coating,
and Dyeing, North Carolina, 1998.
[3] S.H. Lin, C.F. Peng, Treatment of textile wastewater by electrochemical
method, Water Res. 28 (1994) 277–282.
[4] J. Naumczyk, L. Szpyrkowicz, F. Zilio-Grandi, Electrochemical treatment
of textile wastewater, Water Sci. Technol. 34 (1996) 17–24.
[5] A.G. Vlyssides, M. Loizidou, P.K. Karlis, A.A. Zorpas, D. Papaioannou,
Electrochemical oxidation of a textile dye wastewater using a Pt/Ti elec-
trode, J. Hazard. Mater. B70 (1999) 41–52.
[6] N. Daneshvar, A. Oladegaragoze, N. Djafarzadeh, Decolorization of basic
dye solutions by electrocoagulation: an investigation of the effect of oper-
ational parameters, J. Hazard. Mater. B 129 (2006) 116–122.
[7] A. Alinsafi, M. Khemis, M.N. Pons, J.P. Leclerc, A. Yaacoubi, A. Ben-
hammou, A. Nejmeddine, Electro-coagulation of reactive textile dyes and
textile wastewater, Chem. Eng. Process. 44 (2005) 461–470.
D
[8] H.S. Awad, N.A. Galwa, Electrochemical degradation of Acid Blue and
Basic Brown dyes on Pb/PbO2 electrode in the presence of different con-
ductive electrolyte and effect of various operating factors, Chemosphere
61 (2005) 1327–1335.
[9] Z.M. Shen, D. Wu, J. Yang, T. Yuan, W.H. Wang, J.P. Jia, Methods to
improve electrochemical treatment effect of dye wastewater, J. Hazard.
Mater. B 131 (2006) 90–97.
[10] C. Pulgarin, N. Adler, P. Péringer, Ch. Comninellis, Electrochemical detox-
ification of a 1,4-benzoquinone solution in wastewater treatment, Water
Res. 28 (1994) 887–893.
[11] L. Szpyrkowicz, C. Juzzolino, S.N. Kaul, A comparative study on oxida-
tion of disperse dyes by electrochemical process, ozone, hypochlorite and
Fenton Reagent, Water Res. 35 (2001) 2129–2136.
[12] M. Cerón-Rivera, M.M. Dávila-Jiménez, M.P. Elizalde-González, Degra-
dation of the textile dyes Basic yellow 28 and Reactive black 5 using
diamond and metal alloys electrodes, Chemosphere 55 (2004) 1–10.
[13] A. Fernandes, A. Morão, M. Magrinho, A. Lopes, I. Gonçalves, Electro-
chemical degradation of C.I. Acid Orange 7, Dyes Pigments 61 (2004)
287–296.
[14] A. Sakalis, K. Mpoulmpasakos, U. Nickel, K. Fytianos, A. Voulgaropou-
los, Evaluation of a novel electrochemical pilot plant process for azo dyes
removal from textile wastewater, Chem. Eng. J. 111 (2005) 63–70.
[15] C.J. Israilides, A.G. Vlyssides, V.N. Mourafeti, G. Karvouni, Olive oil
wastewater treatment with the use of an electrolysis system, Bioresour.
Technol. 61 (1997) 163–170.
[16] A.G. Vlyssides, C.J. Israilides, M. Loizidou, G. Karvouni, V. Mourafeti,
Electrochemical treatment of vinasse from beet molasses, Water Sci. Tech-
nol. 36 (1997) 271–278.
[17] S.H. Lin, C.T. Shyu, M.C. Sun, Saline wastewater treatment by electro-
chemical method, Water Res. 32 (1998) 1059–1066.
[18] J.S. Do, W.C. Yeh, Paired electrooxidative degradation of phenol with in
situ electrogenerated hydrogen peroxide and hypochlorite, J. Appl. Elec-
trochem. 26 (1996) 673–678.
[19] G. Tchobanoglous, F.L. Burton (Eds.), Metcalf&Eddy, Inc., Wastewater
Engineering: Treatment Disposal and Reuse, 3rd ed., McGraw-Hill Inc.,
New York, 1991.
[20] Ch. Comninellis, A. Nerini, Anodic oxidation of phenol in the presence of
NaCl for wastewater treatment, J. Appl. Electrochem. 25 (1995) 23–28.
[21] M. Kobya, O.T. Can, M. Bayramoglu, Treatment of textile wastewaters by
electrocoagulation using iron and aluminum electrodes, J. Hazard. Mater.
B 100 (2003) 163–178.
[22] K. Rajeshwar, J.G. Ibanez, Environmental Electrochemistry, Academic
Press, San Diego, 1997.
[23] B.K. Körbahti, Response surface optimization of electrochemical
treatment of textile dye wastewater, J. Hazard. Mater., in press.
doi:10.1016/j.jhazmat.2006.11.031.
[24] U.S. EPA, Best Management Practices for Pollution Prevention in the
Textile Industry, EPA625R96004, Ohio, 1996.
[25] D.C. Montgomery, Design and Analysis of Experiments, 4th ed., John
Wiley & Sons, New York, 1996.
[26] R.H. Myers, D.C. Montgomery, Response Surface Methodology: Process
and Product Optimization Using Designed Experiments, 2nd ed., John
Wiley & Sons, New York, 2002.
+Model
CEJ-5227; No. of Pages 9 ARTICLE IN PRESS
B.K. Körbahti / Chemical Engineering Journal xxx (2007) xxx–xxx 9

[27] W.L. McCabe, J.C. Smith, P. Harriott, Unit Operations of Chemical Engi-
neering, 6th ed., McGraw-Hill, Inc., Boston, 2001.
[28] D.J. Pickett, Electrochemical Reactor Design, Elsevier, Amsterdam, 1979.
[29] H.S. Fogler, Elements of Chemical Reaction Engineering, 2nd ed., Prentice-
Hall, Inc., New Jersey, 1992.
[30] A. Morão, A. Lopes, M.T. Pessoa de Amorim, I.C. Gonçalves, Degra-
dation of mixtures of phenols using boron doped diamond electrodes for
wastewater treatment, Electrochim. Acta 49 (2004) 1587–1595.
[31] M. Panizza, G. Cerisola, Influence of anode material on the electrochemical
oxidation of 2-naphthol. Part 2. Bulk electrolysis experiments, Electrochim.
Acta 49 (2004) 3221–3226.
[32] M. Spitzer, R. Bertazzoli, Selective electrochemical recovery of gold and
silver from cyanide aqueous effluents using titanium and vitreous carbon
cathodes, Hydrometallurgy 74 (2004) 233–242.
[33] A.G. Vlyssides, C.J. Israilides, Detoxification of tannery waste liquors with
an electrolysis system, Environ. Pollut. 97 (1997) 147–152.
[34] A.G. Vlyssides, P.K. Karlis, A.A. Zorpas, Electrochemical oxidation of
noncyanide strippers wastes, Environ. Int. 25 (1999) 663–670.
[35] A.G. Vlyssides, P.K. Karlis, N. Rori, A.A. Zorpas, Electrochemical treat-
ment in relation to pH of domestic wastewater using Ti/Pt electrodes, J.
Hazard. Mater. B 95 (2002) 215–226.

D
TE
AC
R
ET
R

Please cite this article in press as: B.K. Körbahti, Electrochemical degradation of Levafix CA reactive dyes in textile dyeing wastewater using
iron electrodes, Chem. Eng. J. (2007), doi:10.1016/j.cej.2007.03.083