Desalination 285 (2012) 188197

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Desalination
journal homepage: www.elsevier.com/locate/desal

Electrochemical degradation of textile dyeing industry efuent in batch and ow

reactor systems
C. Ahmed Basha a,, J. Sendhil b, K.V. Selvakumar c, P.K.A. Muniswaran b, Chang Woo Lee a,
a
Department of Chemical Engineering, College of Engineering, Kyung Hee University 1 Seochun, Gihung, Yongin, Gyeonggi, 446-701, Republic of Korea
b
Department of Chemical Engineering, S.R.M University, Kattankulathur-603 203, Tamil Nadu, India
c
Department of Chemical Engineering, Adhiyamaan College of Engineering, Hosur-635 109, Tamil Nadu, India

a r t i c l e i n f o a b s t r a c t

Article history: Electrochemical oxidation of organic pollutants present in the dye-bath and wash water efuents from the
Received 6 April 2011 textile industry was carried out in batch, batch recirculation and recycle reactor congurations under differ-
Received in revised form 19 June 2011 ent conditions of current density, treatment duration, efuent ow rate and electrode specic surface. COD
Accepted 29 September 2011
reduction of 52.63% to 82.61% could be obtained when the Procion blue dye-bath efuent was treated in
Available online 24 October 2011
the batch reactor for 8 h. In batch recirculation reactor, the reduction was 94.3% for dye-bath efuent and
Keywords:
91.4 for wash water efuent after 6 h of operation at a current density of 5.0 A dm 2 and ow rate of
Batch reactor 100 L h1. The specic energy consumption was found to be 4.32 kWh (kg COD)1 for dye-bath efuent
Batch recirculation reactor and 83.8 kWh (kg COD)1 for wash water efuent. The results for wash water efuent under continuous op-
Recycle reactor eration of recycle reactor conditions showed 52.86% of COD removal at recycle ow rate of 100 L h1 with
Procion blue discharge ow rate of 3 L h1. The specic energy consumption was found to be 11.9 kWh (kg COD)1.
COD reduction 2011 Elsevier B.V. All rights reserved.
Specic energy consumption

1. Introduction The choice of electrode material is important in any electrochemical

Textile processing industries consume large volumes of water and
chemicals generating efuents which when discharged cause unde-
sirable water pollution. Even the presence of very low concentrations
of dyes in efuent interferes with the penetration of light in water
bodies and may affect the aquatic biota [1]. Some dyes and their deg-
radation products have been shown to be toxic, mutagenic and carci-
nogenic in nature [2]. Physicochemical processes such as adsorption,
biosorption, membrane ltration, coagulation by salts, biological oxi-
dation, chemical degradation etc., are some of the generally employed
methods for treating textile industry wastewater. The physicochemi-
cal methods have many disadvantages in terms of efciency, cost, re-
generation or secondary pollution. Conventional activated sludge and
other types of bioreactors fail to remove sufcient color and other
micro-pollutants present in textile efuents [1]. Novel, low cost ef-
cient processes are needed in view of the more stringent environ-
mental regulations and in this context, processes such as,
electrochemical techniques [38], ozonization [9], photo-catalytic
methods [1011], sonication [12], enzymatic treatments [13], and
engineered wetland systems [14] are being tried by researchers for
the treatment of textile wastewater.
Corresponding authors. Tel.: + 82 31 201 3825; fax: + 82 31 204 8114.
E-mail addresses: basha@khu.ac.kr (C.A. Basha), cwlee@khu.ac.kr (C.W. Lee).
study. Dimensionally stable anode (DSA) material has found wide appli-
cation in electrochemical wastewater treatment, the most common
being the Ti/Ru0.3Ti0.7O2 (Cl2-evolution) anode, which has been exten-
sively used in the chlor-alkali industry for long. DSA has been classied
as active or non-active, depending on its chemical nature [1416].
When active electrodes are present, they mediate the oxidation of organ-
ic species by the formation of higher oxidation state oxides of the metals.
When non-active electrodes are present, there is no higher oxidation
state and the organic species are directly oxidized by an adsorbed hy-
droxyl radical, generally resulting in complete combustion of the organic
molecule (e.g., SnO2, PbO2, boron doped diamond, and Ti/Pt).
The biodegradability index (BI) is dened as the ratio of BOD to COD
and is a useful indicator of the total oxidation that occurs during elec-
trolysis [1619]. Morais et al. [17] reported that efuents with BI smaller
than 0.3 are not suitable for biological degradation. According to Cha-
marro et al. [18] the efuent must have a BI of at least 0.4 for complete
biodegradation. It is reported that a waste with BI of >0.4 can be treated
by a biological system while a BI of b0.25 indicates a toxic waste
[1619].
When an active electrode is used for mineralization, BOD initially
marginally increases and COD decreases thus enhancing the BI. When
an inactive electrode is employed, the organic species is directly oxi-
dized by an adsorbed hydroxyl radical, resulting in complete combus-
tion of the organic molecule thereby decreasing the BOD, COD and BI
or marginally enhancing the BI [2022]. Sakalis et al. [23] studied the
electrochemical degradation of azo dyes in batch and continuous ow

0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.09.054
 C.A. Basha et al. / Desalination 285 (2012) 188197
Fig. 1. A schematic view of batch experimental set-up (1. Regulated power supply, 2.
Reference electrode, 3. Noble oxide coated catalytic anode, 4. Cathode 5. Magnetic stirrer.).
experiments using Ti/Pt anode for both real and synthetic wastewater
samples and reported an increase in BI value from 0.23 to 0.28 due to
partial combustion of the organic molecule. When commercial pesti-
cides were treated in a laboratory scale electrolysis using Ti/Pt as
anode and stainless steel 304 as cathode the BI ratio was found to in-
crease considerably from 0.125 to 0.36 [24] indicating that the electro-
chemical oxidation can be a possible pretreatment method for
pesticide detoxication.
Electrochemical oxidation of refractory organic contaminants pre-
sent in efuents by noble oxide coated anode tends to increase BOD
(by forming group OH, CHO, CO, and COOH) decrease COD and
marginally increase BI. The dye house of a textile processing industry
releases two types of wastewater, viz., dye-bath wastewater and
wash wastewater in volume ratios of 15% and 85% respectively. The
dye-bath wastewater causes more pollution and its treatment is
more difcult due to its intense color, high COD, low
biodegradability and high-salt content.
In the present study, the dye-bath and wash water efuents of a
textile industry were subjected to electrochemical oxidation in
batch reactor, batch recirculation ow reactor and continuous
recycle reactor with the objective of reducing the color and the
COD. Experiments were conducted under different conditions of
current density, ow rate, specic electrode surface and electrolysis
time and the performance was analyzed in terms of specic power
consumption. The dye-bath and wash water efuents were treated
separately instead of treating them after mixing them as generally
practiced. Ultimately a sort of pinch technology can be devised, to in-
tegrate electrochemical technique (the knowledge of specic energy/
charge required), with the conventional biological treatment method
for complete mineralization of the efuent.
Table 1
Characteristics of selected dye bath and wash water.
Characteristics Dye-bath efuent
Color Purple blue
Initial COD (mgL1) 5800
Initial BOD (mg L1) 181
BI (= BOD / COD) 0.03
Chloride content (mgL1) 38995
Total dissolved solids (mgL1) 52,000
Suspended solids (mgL1) 2000
pH 9 8
189
2. Materials and methods
All the reagents, used in this study, were of analytical grade. Pro-
cion Blue hydrolyzed dye-bath wastewater and wash water samples
were collected from a dyeing industry located in Tiruppur, Tamilnadu,
India. The efuent samples were analyzed according to American
Public Health Association (APHA) procedures [25] and their charac-
teristics are given in Table 1. Experiments were carried out using a
RuOxTiOx coated [26] titanium substrate insoluble anode (TSIA)
and a stainless steel cathode.
2.1. Batch reactor
Fig. 1 gives the schematic diagram of the batch reactor. It consists
of a cylindrical glass container closed with a lid in which electrodes of
size 7.7 cm 6.5 cm are tted with constant gap between them. The
lid is designed so as to facilitate sample collection and to enable the
connection of reference electrode through the salt bridge. The electri-
cal energy for the system was drawn from a regulated power supply
and a magnetic stirrer was employed for stirring the efuent. Exper-
iments were conducted at room temperature under galvanostatic
conditions with a mixture of reactive hydrolyzed dyes efuent of ini-
tial COD 5800 mg L 1 and BOD 181 mg L 1 under various operating
conditions of reactor holdup volumes (300 mL, 400 mL, and
500 mL), and current density (1.0, 2.0, 3.0, 4.0, and 5.0 A dm 2). The
electrode area exposed to the efuent varied with the volume of ef-
uent thereby varying the current passed to give the required current
density. All experiments were carried out for 8 h and the cell voltage,
anode potential and cathode potential were noted down periodically.
The samples were collected every hour, kept at acidic conditions and
analyzed for COD. After electrolysis, chlorides, hypochlorites and
chlorates concentrations were determined and percentage reduction
of COD, energy consumption and rate constant were computed
experimentally.
2.2. Batch recirculation reactor
The electrolytic ow reactor set-up, operated in batch recircula-
tion mode is shown in Fig. 2a and b. It consists of an expanded
mesh of titanium (coated with TiOxRuOx) anode and stainless steel
at plate cathodes in between a PVC frame. The anode mesh is xed
in between two parallel cathode plates (7 cm 7 cm) with an inter-
electrode gap of 1.25 cm. The available effective electrode area is
39.2 cm 2 for anodic reactions. The electrodes are connected to a 5 A,
30 V DC regulated power supply, an ammeter and a voltmeter in
order to supply a constant current. The reactor with a holdup volume
of 0.588 dm 3 has an inlet and outlet and is connected using silicon
rubber tubes to a reservoir of 2.5 L volume, a magnetically driven
self-priming centrifugal pump and a rotameter. The set-up can be op-
erated either in batch recirculation or in continuous recycle mode
wherein streams 10 and 12 are in closed state for the former and
are in open state for the latter.
1.5 L of dye-bath efuent having initial COD of 5800 mg L 1 and
BOD of 181 mg L 1 was taken and experiments were carried out at
two different current densities of 2.5 A dm 2 and 5.0 A dm 2. At
each current density, experiments were conducted for ve different
Wash water
ow rates of 20, 40, 60, 80 and 100 L h 1. The electrode plates were
Dark olive green cleaned manually by washing with distilled water before every run.
560
All the experiments were carried out for 6 h in batch recirculation
30
0.05 mode under galvanostatic conditions during which the cell voltage
1500 was noted and the samples were collected periodically for COD
3200 analysis. The dye-bath efuent feed and the samples obtained when
800 treated under the current density of 5.0 A dm 2 and ow rate of
80 L h 1 were subjected to spectral analysis.
190 C.A. Basha et al. / Desalination 285 (2012) 188197

Fig. 2. a) Schematic diagram of batch recirculation/continuous recycle ow reactor system (1. Reservoir, 2. Pump, 3. Rotameter, 4. Flow cell, 5. Anode, 6. Cathode 7. Digital Voltmeter, 8.
Digital Ammeter, 9. D.C. Regulated Power Supply, 10. Treated wastewater outlet, 11. Recirculation Stream, 12. Wastewater inlet to system. (For batch recirculation system, streams 10 and
12 will be absent). b) Experimental set-up.
 C.A. Basha et al. / Desalination 285 (2012) 188197
The experiments were repeated with untreated wash water efu-
ent of COD 560 mg L 1 and BOD 30 mg L 1 under the same operating
conditions of current density and ow rate.
2.3. Recycle reactor
The untreated wash water of COD 560 mg L 1 and BOD
30 mg L 1 was subjected to electrolysis at the current density of
5.0 A dm 2 and a recycle ow rate (Q) of 80 L h 1. 2 L of treated
wash water was taken initially in the reservoir to which untreated
wash water was fed at different ow rates (q): 10, 20, 30, 40 and
50 mL min 1. The treated wastewater outlet ow rate was adjusted
to attain steady state reservoir level and to establish the required re-
cycle ow rate Q and ow rate through the reactor (Q + q). DC
power was supplied to the electrodes to maintain a constant current
of 1.96 A, corresponding to a current density of 5 A dm 2. All the ex-
periments were carried out till steady state was reached and main-
tained for 30 min and after treatment samples collected were
analyzed for COD.
2.4. Analysis
COD was determined by the dichromate closed reux method
using thermo reactor TR620-Merck. The interference of Cl noticed
in the range of its concentration (up to 4 mg L 1) during the estima-
tion of COD was overcome by the addition of HgSO4 along with AgSO4
as recommended [25]. BOD was estimated using the Winkler's meth-
od, following the American Public Health Association (APHA) proce-
dures [25]. Experiments were repeated until the error found was
less than 3%. The initial BI values of dye-bath and wash water
efuents were 0.03 and 0.05 respectively which were noticeably
low. Absorbance of untreated and treated samples of dye-bath
efuent was measured at appropriate wavelengths using UVVisible
Spectrophotometer (Spectroquant NOVA 60, Merck). The
temperature of the efuent during electrolysis was constant at
35 C. The concentrations of hypochlorite and chlorate were
5 mg L 1 and 15.25 mg L 1 respectively.
3. Electro-oxidation theoretical approach
In the presence of chloride, oxidation of organic compounds is me-
diated by active chloro species. The main reactions at the electrodes
are:
k1
anode : 2Cl Cl2 2e 1 pound (Eq. (12)),
cathode : 2H2 O 2e H2 2OH : 2 4x y2z
Cl2 gas is discharged on the anode rapidly as per reaction (1) in
the aqueous medium. Hydrolysis and ionization reactions are given
by Eqs. (3) and (4) respectively.
k2
Cl2 H2 O HOCl H Cl 3 
k
HOCl
3
;
H OCl : 4
k3
The side-reactions at the anode which evolve O2 and form chlorate,
compete with Cl2 evolution as per the reactions,
H2 O2H O2 2e 5
6OCl 3H2 O3=2O2 6H 4Cl 2ClO3 6e 6
Hypochlorous acid (HOCl) is replenished in the medium with simul-
taneous electrochemical reaction of NaCl in the reaction solution. HOCl
191
is a strong oxidant, which can oxidize the wastewater while OCl is
consumed by reaction (6). In solutions of neutral to moderate pH values
a cycle of chloridechlorinehypochloritechloride occurs that causes
the initial concentration of chlorides to remain stable. However, in
strong alkaline solutions, the cycle of chloridechlorinechloride is
blocked due to the production of stable ClO3 . At low pH chlorides are re-
duced with the production of free chlorine while at high pH the chlo-
rides are oxidized and chlorates are produced.
Considering the electrochemical oxidation mechanism proposed
by the Comninellis group [27], which assumed the action of the elec-
trochemical oxidation extended to a reaction cage in the vicinity of
the electrode surface, rather than limited at the surface itself, the dis-
tinction between direct and mediated oxidation becomes even less
stringent [28]. The Cl2-mediated mineralization has been shown to
give good results at low-oxygen-overvoltage electrodes [29, 30]. The
addition of chloride ions in the electrolyte allows an increase of the
removal efciency, and a degradation of pollutants can be obtained
due to the participation of active chlorine. Different authors have al-
ready published the possible direct and indirect roles for the chlo-
ride anion in the electrochemical reaction [2733].
The generated gaseous Cl2 dissolves to produce hypochlorite ions re-
peatedly. The hypochlorite ions can mineralize the dye waste, thereby
improving the biodegradability to an extent, especially during the
early stage of the treatment.
k4
Dye OCl R CO2 N2 H2 O Cl : 7
The indirect electrooxidation rate of organic pollutants depends on the
diffusion rate of the oxidants into the solution, ow rate of the efuent,
temperature and pH. In bulk, a reaction sequence of chloridechlorine
hypochloritechloride takes place. The pseudo-steady state theory can
be applied to each of the intermediate product (HOCl and OCl) as
given in Eqs. (3), (4) and (7). The rates of reaction in the bulk solution
can be written as:
rCl2 k2 Cl2  8
h i
rHOCl k2 Cl2 k3 HOCl k3 H OCl k4 DyeOCl  0 9
rOCl k3 HOClk3 HOCl k4 DyeOCl  0 10
rOrganic k4 DyeOCl : 11
From the equation of the chemical mineralization of the organic com-
 
w y
Cx Hy Nw Oz O2 xCO2 N2 H2 O 12
4 2 2
it is possible to obtain the relation between the dye [dye] concentration in
mol CxHyNwOz L1 and the chemical oxygen demand [COD] in mol O2
L1:

4
Dye COD: 12
4x y2z
From the above equations, rate equation can be expressed as:
rCl2 rDye k4 DyeOCl  kCODOCl : 13
3.1. Design and performance of batch reactor
During electrolysis, if a constant operating current density is ap-
plied, the rate of degradation of organic contaminant will remain con-
stant under a given set of experimental conditions, but it will vary if
192 C.A. Basha et al. / Desalination 285 (2012) 188197

the applied current density is changed. The reaction rate for the re- COD of wastewater due to bulk movement of efuent and electro-
moval of COD in a batch reactor can be expressed as: chemical oxidation reactions. Since there is no accumulation of COD
of wastewater in the liquid phase of the reactor, it can be assumed
dC i that the reactor is under steady state, C/t = 0, and C = C for COD
kh aC 14
dt zF of wastewater entering the reactor [at x = 0] and C = C for COD of
wastewater leaving the reactor [at x = L]. The steady state solution
C
expkh at 15 of Eq. (18) yields
Co
   
C k aA L k A
where C represents COD of the efuent in the batch reactor, i is the exp h C exp h e : 19
C Q Q
current passed during electrolysis time t, a is specic electrode area
(Ae / VR), Ae electrode area, VR reactor volume, kh is pseudo rst
Considering the reservoir as a perfect backmix system, the mass
order heterogeneous rate constant, F is the Faraday constant
balance equation for the reservoir is
(96485.3 C mol 1) and z is the number of electrons transferred per
mole of reaction. The unconverted species (1 X) or (C / Co) [by de- dC
ning the extent of degradation, X = (Co C) / Co], decreases expo- Vres Q CC 20
dt
nentially with time, according to Eq. (15).
The rate of degradation is controlled by the operating current densi- where Vres is the volume of the reservoir tank.
ty and it is assessed in terms of the heterogeneous rate constant kh The mass balance Eq. (20) is solved after substitution of the ex-
(cm s 1) by monitoring the extent of COD removal. In electrochemical pression for C from Eq. (19), knowing the initial COD of wastewater,
conversion, the high molecular weight aromatic compounds and ali- C = Co at t = 0 in the reservoir. The following resultant equation then
phatic chains are broken to intermediate products for further proces- gives the variation of COD of wastewater in the reservoir.
sing. In electrochemical oxidation, the organics are oxidized to CO2
and H2O. The current efciency of the electrolysis can be calculated    
using the following expressions: C t k A
exp 1exp h 21
Co Q
COD  VR Co  X  VR
Current Efficiency CE : 16
16It=2F 16It=2F where is the residence time (Vres / Q).
The unconverted species (1 X) or (C/ Co) decreases exponentially
Process performance is dened in two ways, one with respect to with time, according to Eq. (21). The slope
of the plot of ln (1 X)
the extent of reaction completion and the other with respect to the versus t, gives the value 1exp kQh Ae = from which the value of kh,
energy consumption, E (kW h kg 1). the heterogeneous rate constant, can be computed. Experiments have
shown that the electrolysis time, current density and recirculation
3 3
VIt  10 VIt  10 ow rate considerably inuence the performance of the process. The ac-
Specific Energy Consumption; Et : 17
COD  VR Co  X  VR tual utilization of energy for processing a unit quantity of the targeted
reaction is specic power consumption and it is found by monitoring
Computation of the current efciency (CE) indicates the path and the cell voltage and extent of COD removal and can be written as:
course of the targeted reaction by monitoring the extent of COD re-
moval (Eq. (16)). The utilization of energy in processing a unit quan- VIt  103
Specific Energy Consumption; Et
tity of the targeted reaction is found by Eq. (17). COD  Vres
VIt  103
22
3.2. Design and performance of batch recirculation reactor Co  Xt  Vres

In batch recirculation operation valves are closed to prevent the where X(t) is the extent of conversion, Co (initial COD in mg L 1), due
ow of streams 10 and 12 (Fig. 2a). There is a gradual depletion of to passing current I (A) for time t (h); Vres is volume of the reservoir
the COD of wastewater in the reservoir of batch recirculation system. (L); and V represents the cell voltage in volts.
In order to design and control the reactor, the development of a
model is essential, which enables the prediction of the variation of 3.3. Design and performance of recycle reactor
COD of wastewater with time in the reservoir. The basic assumption
made in deriving the model equation is that the COD of wastewater In the recycle operation valves are opened to allow the ow of
is changing along the ow direction in the reactor which was based streams 10, 11 and 12 (Fig. 2a). The material balance around the res-
on the residence time distribution experiments conducted using a ervoir gives concentration of the reactant entering the reactor as
tracer. A plug ow model may be considered for the reactor in
which these reactions take place. qC0 QC RC0 C
C 23
The concentration variation of COD of wastewater in the electro- qQ R1
chemical reactor can be written as:
where Q is the recycle ow rate of the treated efuent, q is the inlet
C Q C (fresh)/discharge(treated) efuent volumetric ow rate, and R is the
kh aC 18
t Ac x ratio, dened as R = q / Q. The material balance around the reactor is
 
k A
where Ac is the cross sectional ow area of the electrochemical reac- C Cexpkh aR Cexp h e 24
Q q
tor, L is the length of the reactor, Ae is the electrode area, VR = AcL,
volume of the reactor, a is the specic surface area [Ae / VR] for reac- where Q + q is the total ow rate of the efuent passing through the re-
tion, Q is the volumetric ow rate, C is the COD of wastewater and actor. From Eqs. (23) and (24) we get,
kh is the heterogeneous rate constant. Left hand side represents the 
kL Ae
rate of change of COD of wastewater in the reactor. Two terms of RCo Cexp Q1R
C : 25
the right hand side of the Eq. (18) represent the rate of depletion of R1
 C.A. Basha et al. / Desalination 285 (2012) 188197 193

Table 2
Effect of reactor holdup and current density on the performance of the batch electrochemical reactor: initial COD 5800 20 mg L 1; electrolysis time 8 h; active electrode area
50 cm2.

VR Current density Current Cell voltage Potential COD reduction Current efciency Power consumption kh 104
mL A dm2 A V % % k Wh (kg COD)1 cm s1
Anodic Cathodic
V V

300 1 0.5 2.9 1.13 1.73 71.71 9.29 2.63

2 1 3.3 1.62 1.73 89.66 65.33 16.92 4.73
3 1.5 3.58 1.77 1.84 96.73 46.98 25.52 7.12
4 2 3.84 1.83 1.98 99.15 36.12 35.61 9.92
5 2.5 4.31 2.09 2.24 99.83 29.09 49.62 13.3
400 1 0.5 2.78 1.23 1.51 56.95 8.41 2.34
2 1 3.26 1.75 1.52 80.53 78.23 13.95 4.54
3 1.5 3.53 1.805 1.71 91.93 59.54 19.86 6.99
4 2 3.87 1.87 1.99 97.01 47.12 27.51 9.73
5 2.5 4.22 2.13 2.11 99.03 38.48 36.73 12.87
500 1 0.5 2.86 1.18 1.63 46.86 8.41 2.19
2 1 3.21 1.38 1.83 73.26 88.97 12.08 4.57
3 1.5 3.69 1.58 2.19 87.38 70.74 17.47 7.18
4 2 3.83 1.62 2.22 94.49 57.37 22.36 10.06
5 2.5 4.21 1.78 2.27 97.81 47.51 29.68 13.27

The above equation can be rearranged as 4. Results and discussion

    4.1. Electrolysis of dye-bath efuent in batch reactor

kh Ae 1X
ln : 26
Q 1 R R 11XR The results of the experiments conducted in the batch reactor are
reported in Table 2 and shown in Figs. 3 and 4a, b and c.
 Fig. 3 shows the effect of current density on cell voltage, anode
1X
The slope of the plot ln R11XR versus 1 / (1 + R)Q, gives the and cathode potentials with time for reactor holdup volume of
value khAe as per Eq. (26) from which kh, the rate constant, can be 300 mL. The cell voltage, anode and cathode potentials varied re-
computed for the given conversion. The specic power consumption markably with the current density and marginally with time at all
can be found by current densities. However, there was no signicant change in them
with the current density and time when reactor holdup volumes are
400 mL and 500 mL (not shown).
VI  103 VI  103 Fig. 4(a), (b) and (c) depicts the % COD reduction with electrolysis
Specific Energy Consumption; E 27 time for various current densities at the three different reactor holdup
COD  RQ Co  X  RQ
volumes of 300, 400 and 500 mL respectively. In all cases it can be
seen that the % removal of the organic matter has increased exponen-
where X is the extent of conversion, Co is the initial COD in mg L 1, I tially with time. The increase in pollutant removal beyond 5 h of
is the passing current and V is the applied cell voltage. treatment is marginal when cell is operated at current densities

4.5

4 VR=300 mL, a=0.1668

1.0 A/dm, C.V

3.5 1.0 A/dm, A.P
1.0 A/dm, C.P
2.0 A/dm, C.V
Voltage (V)

3 2.0 A/dm, A.P

2.0 A/dm, C.P
3.0 A/dm, C.V
2.5 3.0 A/dm, A.P
3.0 A/dm, C.P
4.0 A/dm, C.V
2 4.0 A/dm, A.P
4.0 A/dm, C.P
5.0 A/dm, C.V
1.5 5.0 A/dm, A.P
5.0 A/dm, A.P

1
0 60 120 180 240 300 360 420 480
Time (min)

Fig. 3. Variation of cell voltage, and anode and cathode potentials in batch reactor at different current densities. Conditions: initial COD 5800 mg L 1; active electrode surface
50 cm2, reactor holdup 300 mL.
194 C.A. Basha et al. / Desalination 285 (2012) 188197

100 100
a a
80 Dye-bath Effluent
COD Reduction (%)

-2
80 Current Density = 2.5 A dm
Co = 5800 mg L-1
60 kL=4.3x10-3u0.1213

COD Reduction (%)

60
40

-1 20 L/h
VR =300 mL, a=0.1668 cm 40 L/h
20
40 60 L/h
1.0 A/dm2 2.0 A/dm2 3.0 A/dm2
80 L/h
4.0 A/dm2 5.0 A/dm2
100 L/h
0
0 60 120 180 240 300 360 420 480
Time (min) 20
100
b
80 0
COD Reduction (%)

0 1 2 3 4 5 6
Time (h)
60
100
b
40
80

COD Reduction (%)

-1
VR=400 mL, a= 0.1251 cm
20
1.0 A/dm2 2.0 A/dm2 3.0 A/dm2 60
4.0 A/dm2 5.0 A/dm2
0 Dye bath effluent
0 60 120 180 240 300 360 420 480 40 Current Density = 5.0 A dm-2

Time (min) Co = 5800 mg L-1 20 L/h

kL=4.6x10-3u0.1 40 L/h
100 60 L/h
20
c 80 L/h
100 L/h

80
COD Reduction (%)

0
0 1 2 3 4 5 6
60 Time (h)

40
VR=500 mL, a=0.1001 cm
20
1.0 A/dm2 2.0 A/dm2
4.0 A/dm2 5.0 A/dm2
0 The variation of heterogeneous rate constant kh (cm s 1) with
0 60 120 180 240 300 360
Time (min)
Fig. 4. Effect of electrolysis time and current density on percentage removal of COD in
the batch system. Conditions: initial COD 5800 mg L 1; active electrode surface
50 cm2. Reactor holdup a) 300 mL; b) 400 mL; c) 500 mL.
above 3 A dm 2. It can also be seen that with increase in current den-
sity COD reduction is increased but the current efciency is de-
creased. Increasing the current density from 1 to 5 A dm 2
increased the COD removal from 71.71% to 99.83% after 8 h of treat-
ment but the current efciency dropped to 29% when the reactor
holdup was 300 mL. Comparison of Fig. 4(a), (b) and (c) shows that
an increase in reactor holdup has not increased the COD removal sig-
nicantly but it has resulted in higher current efciency and lesser
power consumption. A more noticeable fact in Table 2 is that an in-
crease in current density decreases the current efciency and in-
creases power consumption. The possibility of loss of electrical
energy in the form of heat and unwanted reactions is greater at
higher levels of current density. Thus, in general, a higher current
density operation will give high capacity utilization, at the expense
of higher energy loss. The results also show that COD removal de-
creases with a decrease in the specic electrode area.
Fig. 5. Variation of COD reduction with electrolysis time at different ow rate in batch
recirculation system for dye-bath efuent at the applied current density of a)
2.5 A dm2 b) 5.0 A dm2.
-1
3.0 A/dm2
420 480 current density and reactor holdup (VR) was also studied for the
batch operation. kh is found to increase with current density, proba-
bly due to the generation of more oxidizing agents at higher current
density values. Also kh (cm s 1) is found to increase with the de-
crease in the specic electrode surface area. This may be due to
poorer extent of reaction though the amount of reactant available
for reaction is more. The operation is more energy efcient when
the specic electrode surface is low. In general operation at lower
specic electrode surface is advantageous because of the high capac-
ity of operation and/or degradation of higher amounts of pollutants at
better energy gures, but with poor extent of completion of the
process.
4.2. Electrolysis of dye-bath efuent in batch recirculation reactor
Electrolysis of dye-bath efuent of 5800 mg L 1 initial COD was
carried out in a batch recirculation reactor at ve different ow
rates of 20, 40, 60, 80 and 100 L h 1 and at the current density of
2.5 A dm 2 or 5.0 A dm 2. It is seen from Fig. 5 that the percentage
COD reduction increases as the electrolysis time increases. The
degradation rate was higher during the initial 2 h of electrolysis for
all ow rates. The increase in the rate and the subsequent increase
in the percentage COD reduction are larger in the beginning of the
 C.A. Basha et al. / Desalination 285 (2012) 188197 195

2.2 100
E(t), kW h (kg COD)-1
2
a Washwater Effluent
-2
Current Density = 5 A/dm
1.8 Dye-bath Effluent
80 -1
Co = 560 mg L
Current Density=2.5 A dm -2

COD Reduction (%)

1.6 Co = 5800 mg L -1
-3 0.27
kL=3.1x10 u
1.4
60
1.2

1 20 L/h 40 L/h 60 L/h

80 L/h 100 L/h 40
0.8
1 2 3 4 5 6 20 L/h
40 L/h
Time (h) 60 L/h
20
80 L/h
4.7 100 L/h
b
E(t), kW h (kg COD)-1

4.2
Dye-bath Effluent
3.7 Current Density = 5 A dm -2
Co = 5800 mg L -1
3.2
2.7
20 L/h
2.2
80 L/h
1.7
1 2 3 4
Time (h)
Fig. 6. Variation of specic energy consumption with electrolysis time at different ow
rate in batch recirculation system for dye-bath efuent at the applied current density of
a) 2.5 A dm2 b) 5.0 A dm2.
process which decreased gradually to approach zero increase in the
later hours of electrolysis.
Fig. 5a and b shows that the rate of degradation of organic con-
taminants increases with the increase in ow rate and the percentage
COD reduction increases to reach a constant value at the current den-
sities 2.5 A dm 2 and 5.0 A dm 2 respectively. The rate of organic
contaminant degradation is dependent on its bulk concentration. At
higher ow rates the rate of destruction of organic contaminant is sig-
nicantly more and this may be due to the increased production of
oxidants in the process. As the electrolyte circulation rate increases,
the transport of the Cl ion from the bulk to the electrode surfaces in-
creases. This would facilitate Cl2 generation, as well as the dissolution
of Cl2 to form OCl for reaction with the organic contaminant. The
heterogeneous rates constant were computed for the oxidation of
the organic contaminant. It is 4.286 10 3 u 0.1213 at the current den-
sity of 2.5 A dm 2 and 4.551 10 3 u 0.0971 at the current density of
5.0 A dm 2. Here u represents the velocity in cm s 1.
0
0 1 2 3 4 5 6
Time (h)
Fig. 8. Variation of COD reduction with electrolysis time at different ow rate in batch
recirculation system for wash water efuent at the applied current density of
5.0 A dm2.
40 L/h 60 L/h
100 L/h
The COD removal in 6 h of operation was increased from 88.66 to
5 6 93.93% as the ow rate was increased from 20 to 100 L h 1 when the
current density was 2.5 A dm 2. At a current density of 5.0 A dm 2
the increase was from 79.87 to 91.38% when the ow rate was in-
creased from 20 to 100 L h 1. The cell voltages did not vary signi-
cantly with the circulation ow rates at both current densities,
around 2.7 V for the current density 2.5 A dm 2 and 3.1 V for the cur-
rent density 5 A dm 2. The improvement in voltage (2.792.75 V for
the current density 2.5 A dm 2 and 3.133.04 V for the current den-
sity 5.0 A dm 2) and in COD removal considerably affected the power
consumption when the ow rate Q was increased from 20 to
100 L h 1.
When ow rate was increased from 20 to 100 L h 1, at the current
density 2.5 A dm 2 the specic energy consumption decreased from
2.1 to 1.98 kWh (kg COD) 1 and at current density 5 A dm 2 it de-
creased from 4.63 to 4.33 kWh (kg COD) 1. The enhanced current
density not only decreases the reduction of pollutant removal
(93.93% for the current density 2.5 A dm 2 and 91.38% for the current
density 5 A dm 2 in 6 h) but also largely increases the specic energy
consumption (from 1.98 kWh kg 1 for the current density
2.5 A dm 2 to 4.33 kWh kg 1 for the current density 5 A dm 2 at
ow rate is 100 L h 1 as depicted in Fig. 6a and b). From the results,
it was clear that the applied current density and efuent initial COD con-
centration inuence the electrolysis more than the circulation ow rates.
The increase in heterogeneous rate constant due to the increase in
current density is observed to be marginal (from 4.982 103 cm s 1

95
E(t), kW h (kg COD)-1

85 Washwater Effluent
Current Density = 5 A dm-2
75 Co = 560 mg L-1

65

55

20 L/h 40 L/h 60 L/h

45
80 L/h 100 L/h

35
1 2 3 4 5 6
Time (h)

Fig. 9. Variation of specic energy consumption with electrolysis time at different ow

Fig. 7. Effect of electrolysis on color removal for dye-bath efuent at the applied rate in batch recirculation system for wash water efuent at the applied current density
current density of 5 A dm2. of 5.0 A dm2.
196 C.A. Basha et al. / Desalination 285 (2012) 188197
Table 3
Effect of discharge ow rate on the performance of continuous recycle ow reactor for wash water with the initial concentration 560 mgL1under current density 5.0 A dm2 and
recycle ow rate 80 L h1.
Discharge ow rate Cell voltage COD reduction
q (Lh1) (V) (%)
0.6 5.3 75.71
1.2 5.3 67.86
1.8 5.3 61.07
2.4 5.4 56.79
3.0 5.4 52.86
for the current density 2.5 A dm2 to 5.107 103 cm s 1 for the
current density 5 A dm2) and in all cases BI increased (0.48) after 1 h
of electrolysis.
Raw and treated samples of dye-bath efuent were subjected to
absorbance measurements for different wavelengths using UV
Visible Spectrophotometer. Fig. 7 exhibits the absorption behavior
of both untreated and treated dye-bath efuent for different
wavelengths varying from 340 nm to 865 nm. The absorption of the
untreated efuent shows a peak at wavelength 605 nm, indicating
that color is present in the sample due to the selected dye. The
absorption of the treated efuent at the wavelength 605 nm is
nearly zero. This indicates the absence of coloring substance (dye)
in the efuent, which has disappeared due to electrolysis.
4.3. Electrolysis of wash water in batch recirculation reactor
Electrolysis of wash water efuent of 560 mg L 1 initial COD was
carried out at the current density of 5.0 A dm 2 for ve different ow
rates of 20, 40, 60, 80 and 100 L h 1. It is seen from Fig. 8 that the COD
decreased exponentially with electrolysis time. Higher degradation
rate was observed during the initial period at all ow rates. The %
COD removal increased from 79.87 to 91.38% in 6 h of operation as
the ow rate was increased from 20 to 100 L h 1. The value of the
heterogeneous rate constant kh at the current density of 5.0 A dm 2
was determined as 3.135 10 3 u 0.2747 using Eq. (21).
The observed cell voltage was around 5.5 V for the current density
5 A dm 2. When the ow rate was increased from 20 to 100 L h 1
the cell voltage and COD removal were found to improve, resulting
in decreased power consumption. This may be due to the improved
ionic conductivity of bulk movement and the reduction of resistance
on the electrode surface resulting in the enhancement of heteroge-
neous rate constant at higher ow rates. It can be seen from Fig. 9
that the specic energy consumption decreased from 97.3 to
83.8 kWh (kg COD) 1 in 6 h of operation when the ow rate in-
creased from 20 to 100 L h 1.
4.4. Electrolysis of wash water in recycle reactor
The results obtained when wash water efuent was treated in a
continuous recycle ow reactor at the circulation ow rate of
80 L h 1 and current density of 5 A dm 2 are shown in Table 3. The
percentage COD reduction decreased from 75.71 to 52.86% when
the discharge ow rates increased from 0.6 to 3 L h 1 at a constant
recycle ow rate of 80 L h 1 indicating that an increase in withdraw-
al ow rate decreases the % COD reduction. This may be is due to the
shorter residence time at the higher withdrawal ow rates. The COD
of the efuent was found to decrease from its initial value of
560 mg L 1 to a value of 240 mg L 1 at the withdrawal ow rate of
2.4 L h 1 and below this rate the COD limit is below the limits of tol-
erance. It is seen that with increased withdrawal ow rates, power
consumption decreases and the value of rate constant kh increases.
In general, the operation of the reactor at higher withdrawal ow
rates provides good energy gures but poor reaction performance
with an enhancement in biodegradability (see Table 3). The perfor-
mance of recycle reactor is poorer when compared to the batch
BI Power consumption Heterogeneous rate constant
[kWh (kg COD)1] cm s1
0.63 40.83 0.013512
0.61 22.78 0.018514
0.59 16.88 0.020828
0.52 13.87 0.023482
0.51 11.92 0.025262
recirculation reactor on power consumption gures and rate con-
stant. The study of variation of rate constant with the efuent circula-
tion ow rate can be of much interest in this system.
5. Conclusion
Batch studies provide a good number of combinations (Table 2) of
the operating parameters of current density and reactor holdup for
good the overall system performance. For dye bath, at the current
density of 4.0 A dm 2, 300 mL reactor holdup, electrolysis duration:
8 h yield 99.17% COD removal with specic energy consumption of
35.6 kWh (kg COD) 1. For dye bath, at the current density of
4.0 A dm 2, 300 mL reactor holdup, electrolysis duration: 8 h yield
99.17% COD removal with specic energy consumption of 35.6 kWh
(kg COD) 1.
Batch recirculation mode of operation was superior for dye-bath
efuent, for COD removal with the specic energy consumption
(93.93% and 1.98 kWh (kg COD) 1) in 6 h of operation at the ow
rate of 100 L h 1 and the current density 2.5 A dm 2. For wash
water the % COD removal was 91.38% in 6 h of operation (ow rate
100 L h 1, current density 5.0 A dm 2) with the specic energy
consumption of 83.8 kWh (kg COD) 1.
The recycle system of operation has the best performance of the
conventional reactor congurations studied. The capacity utilization
of the system improved considerably under continuous recirculation
condition than the batch recirculation. The best operating point (Q
80 L h 1, q 2.4 L h 1) of the best reactor conguration (recycle reac-
tor) was further investigated by estimating the biodegradability
index, resulting in a considerable improvement to 0.52 0.01. This
shows that the remaining 40% of the COD can be easily digested bio-
logically. Thus, the advantage of the process is two-fold; it not only
removes the bulk quantity of organic matter (57%), but also makes
the remaining matter more easily biodegradable.
It is concluded that the complete removal of COD could be
achieved in batch reactor and in recirculation reactor if the electroly-
sis time is long enough, but the specic energy will be very large com-
pared with continuous operation. The purpose behind this
investigation is to estimate the energy demand for the electrochemi-
cal mineralization that enhances biodegradability and the results
would be helpful for optimization of electrochemical oxidation tech-
nology. Electrochemical oxidation of intermediates to carbon dioxide
and water is difcult and less energy efcient, because the rate of
electrochemical CC bond scission seems to decrease with decreasing
molecular size. Present studies indicate that electrochemical degrada-
tion may not be a viably economic proposal if employed alone be-
cause of the high energy consumption and low conversion. Efforts
can be now made to devise a technique in which a conventional tech-
nique such as biological treatment is integrated with electrochemical
oxidation with the knowledge of specic energy/charge required for
complete mineralization of efuent.
Acknowledgements
One of the authors (CAB) thanks the Korean Federation of Science
and Technology Societies Grant funded by Korea Government (MEST,
 C.A. Basha et al. / Desalination 285 (2012) 188197
Basic Research Promotion Fund) (No. 101S-4-3-0270) for the nan-
cial support of this work.
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