Waste Management 20 (2000) 569±574

www.elsevier.nl/locate/wasman

Short communication

Testing an electrochemical method for treatment of

textile dye wastewater
A.G. Vlyssides a,*, D. Papaioannou b, M. Loizidoy a, P.K. Karlis a, A.A. Zorpas a
a
Department of Chemical Engineering, National Technical University of Athens, 9, Heroon Polytechniou St., Zographou, 157 00 Athens, Greece
b
Department of Regional and Economic Development, Panteios University of Athens, 136 Sygrou Av., Athens, Greece
Accepted 29 February 2000

Abstract
Wastewater from total dyeing and ®nishing stages (TDFW) and wastewater only from dyeing stage (DW) from a Textile cellu-
losic reactive azo dyeing process were treated separately by an electrochemical method using Ti/Pt as anode and Stainless Steel 304
as cathode. In this technique, sodium chloride was used as an electrolyte and the mixture was passed through an electrolytic cell.
Due to the strong oxidizing potential of the chemicals produced (chlorine, oxygen, hydroxyl radicals and other oxidants) the COD,
BOD of the wastewaters were substantially decreased using this electrochemical technique. A number of experiments were run in a
batch 5 litre apparatus and the results of the electrochemical treatment on the two kinds of wastewaters are reported here. The
results indicate that the electrochemical method used is feasible for treatment of textile dyeing wastewaters. # 2000 Elsevier Science
Ltd. All rights reserved.
Keywords: Textile; Color removal; Wastewater; Electrolysis treatment

1. Introduction Because of the large variability of the composition of

Textile dye and ®nishing processes are among the
major industrial water users; in many areas, this industry
has the wastes most dicult to treat satisfactory. Textile
dye and ®nishing wastewater is known to contain strong
color, high pH, temperature and COD and low biodegra-
dability [1]. In previous work [2], typical characteristics
and chemical compounds of textile wastewaters have
been reported, after an extensive analysis of e‚uents
from a Greek textile industry. The new dyes, which
impart a color to textile wastewater, are particularly
important in wastewater treatment. The new dyes must
yield a color that is bright and last throughout the lifetime
of the fabric. Therefore, when a new dye is made that is
stable under all conditions (exposure to sunlight, water,
soap, soil, etc), it becomes more dicult to treat the dye in
wastewater. The removal of dyes (color) is, therefore, a
challenge to both the textile industry and the wastewater
treatment facilities that must treat these wastewaters [3].
Dyeing wastewaters are usually treated by conven-
tional methods such as biological oxidation [4], adsorption
[5], or coagulation by aluminium or iron salts [6].
* Corresponding author. Fax: +30-1772-3163.
E-mail address: avlys@tee.gr (A.G. Vlyssides), antoniszorpas@-
iname.com (A.A. Zorpas)
0956-053X/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0956-053X(00)00028-3
textile wastewaters, most of these traditional methods
are inadequate. Ozonation has been proposed as a
potential alternative [1,7±9]. Ozonation has been shown
to be quite e€ective in decolorizing textile wastewater,
however, it is not e€ective for COD and BOD5 reduction.
In addition, the cost of ozonation for such purposes
needs to be further ascertained to ensure the competi-
tiveness of this method [10].
In recent years, there has been increasing interest in
the use of electrochemical methods for the treatment of
wastewaters [11±14]. The organic and toxic pollutants
present in treated wastewaters such as dyes and phenols
are usually destroyed by a direct anodic process via the
production of oxidants such as hydroxyl radicals, ozone
etc. Electrochemical methods have been successfully
applied in the puri®cation of several industrial waste-
waters [1,12,15,16] as well as land®ll leachate [17], and
domestic sewage [18]. In the past graphite was fre-
quently used as an anode during electrochemical treat-
ment as it is relatively economical and gives satisfactory
results [19]. Titanium electrodes covered with very thin
layers of electrodeposited noble metals have recently
been used for electro-oxidation [20]. Apart from plati-
num and ruthenium, rhodium [21] can also be applied as
electrocatalysts for electro-oxidation of pollutants pre-
sent in wastewaters, making it possible to destroy
570 A.G. Vlyssides et al. / Waste Management 20 (2000) 569±574
organic pollutants which are dicult to eliminate bio-
logically, such as phenols and surfactants. Iridium mix-
tures are also successfully used [22] for this purpose.
This study deals with the treatment of total e‚uent
(TDFW) and the dyeing stage (DW) only e‚uent by an
electrochemical method using a Ti/Pt anode. Samples
for this research were collected from a textile mill loca-
ted in Thrace. The characteristics of wastewaters used in
this study are presented in Table 1.
2. Theoretical considerations
The time of oxidation depends upon the stability and
concentration of compounds; concentration of NaCl
used; temperature; pH of the solution; time of recircu-
lation; size of the anode; and the current and voltage
applied [12,13].
The electrochemical reactions, which take place dur-
ing the electrolysis of a brine solution, are complicated
and not entirely known. For the time being only
assumptions can be made, based on the products that
are produced (Cl2, ClO2, O3, OH , O , ClOH , H2O2,
O2, H2, CO2). The radicals OH , O and ClOH have a
very short life owing to their high oxidation potential
and they are either decomposed to other oxidants (Cl2,
O2, ClO2, O3, and H2O2) or they oxidize organic com-
pounds (direct oxidation). The primary (Cl2, O2) and
secondary (ClO2, O3, and H2O2) oxidants that are pro-
duced from the destruction of radicals have quite a long
life and are di€used into the area away from the elec-
trodes continuing the oxidation process (indirect oxida-
tion) [23±25].
The direct electro-oxidation rates of organic pollu-
tants are dependent on the catalytic activity of the
anode; on the di€usion rates of organic compounds in
the active points of the anode and the applied current
density [23±25]. The indirect electro-oxidation rates are
dependent on the di€usion rate of secondary oxidants
into the solution, temperature and the pH. An e€ective
pollutant degradation is based on the direct electro-
chemical process because the secondary oxidants are not
Table 1
Characteristics of wastewater used
Sl. No. Character DW
1 Total suspended solids (TSS) (mg/l) 34
2 pH 11.82
3 BOD5 (mg/l) 1540
4 COD (mg/l) 3325
5 TOC (mg/l) 1810
6 Total Kjeldahl nitrogen (TKN), (mg/l) 314
7 Chlorides (mg/l) 24 200
8 ADMI color units 41 530
able to completely convert all organics into water and
carbon dioxide. From previous investigations [13,16,18],
in acid solutions, oxygen, free chlorine and maybe some
amounts of ozone and chlorine oxides are the main
secondary oxidants as byproducts of the direct oxida-
tion process. In moderate alkaline solutions a cycle of
chloride±chlorine±hypochlorite±chloride takes place,
which produces OClÿ, oxygen and some amounts of
hydrogen peroxide and maybe ozone. In strong alkaline
solutions the cycle of chloride±chlorine±chloride is
reduced owing to the production of ClOÿ 3 that is a
stable chlorate anion. Therefore, in low pH the chlor-
ides are reduced during the electrolysis process produ-
cing free chlorine, while at high pH the chlorides are
reduced producing chlorates. Only in moderate alkaline
to neutral conditions do the initial concentrations of
chlorides remain stable [15] with the continuous pro-
duction of free hydroxyl radicals.
3. Materials and methods
3.1. Experimental plant
The experimental set-up (Fig. 1) consisted of the elec-
trolytic cell, the recirculation vessel, the wastewater feed
system, and the cooling system for the electrolytic cell.
3.1.1. Electrolytic cell
The electrolytic cell consisted of the cathode, which
was a stainless steel 304 cylinder of 5 cm diameter, and
of the anode, which was located in the centre of the
cylinder and which was made of titanium alloy, mea-
suring 18 cm long and 1 cm diameter, covered by plati-
num alloy foil approximately 0.25 mm thick.
3.1.2. Recirculation vessel
The recirculation vessel (V) included a vessel of 5
litres, which contained the wastewater to be treated, and
a peristaltic pump (P) of 10 l/min ¯ow rate, which con-
tinuously recirculated the reactor content into the elec-
trolytic cell.
3.1.3. Cooling system
The cooling system included a temperature indicator
controller (TIC), an electric valve for the water and a
cooling water jacket, which was located in the cell. The
TDFW cylinder wall and the cooling jacket constituted the
cathode. When the temperature of the water increased
18
10
over 45 C, cooling water circulated in the jacket until
450 the temperature returned to the desired value.
1250
740 3.2. Material
34
350
3450
The characteristics of wastewaters used in this study
are presented in Table 1.
 A.G. Vlyssides et al. / Waste Management 20 (2000) 569±574 571

3.3. Methodology
The eciency of the electrolytic cell was studied when
HCl 36% was added in such amounts per liter of raw
wastewater (both of TDFW and DW) so as the pH of
the process was kept to a constant 5.0. NaCl was used
as an electrolyte in such amounts as its concentration
was 1% for TDFW, and 4% for DW. The temperature
was kept at 42 C during all experiments. Four experi-
ments under the same conditions were run and the
results that are presented in this work are the average of
the four separate experiments. Each experiment was a
batch operation and its active time lasted for 18 min.
The total time for some experiments lasted more than
18 min, however, and the active time did not change.
Every 2 min samples were taken from the reactor and
COD, BOD5, and ADMI color units were measured.
Water and Wastewater [26]. The color was measured
using the ADMI Tristimulus Filter (Tentative) Method,
section 2120 D of Standard Methods. A Hitachi 2000
spectrophotometer with 1 cm path length was used to
measure transmittance of samples.
4. Results
4.1. COD Removal
Fig. 2 shows that the COD reductions during the
electrolytic oxidation follow a linear decrease for the
DW, while for the TDFW they follow an exponential
reduction asymptotic at concentration of 100 mg/l. For
TDFW the COD reduction came up to about 90%
while for DW to 77%.

3.4. Methods of analysis 4.2. Color removal

COD, and BOD5 measurements were determined The electrolytic method of oxidation for color
according to the Standard Methods for Examination of removal is more ecient for the DW than for TDFW,

Fig. 1. Experimental laboratory pilot-plant. C=electrolytic cell; E=electromagnetic valve; P=recirculating pump; TICR=temperature indicator
controller recorder; pHIR=pH indicator recorder; RIR=redox indicator recorder.

Fig. 2. COD reduction during the electrolytic oxidation.

572 A.G. Vlyssides et al. / Waste Management 20 (2000) 569±574

as depicted in Fig. 3. For DW, after only 6 min of elec- results indicate that the electrolytic oxidation improves
trolysis, the color reduction was about 100%. the biodegradability of both e‚uents.

4.3. BOD5 removal 4.4. Energy consumption

BOD5 reduction for DW follows a linear trend Fig. 5 shows the energy consumption during the elec-
between 1600 and 450 units (Fig. 4), BOD5 reduction trochemical oxidation. For TDFW the rate of energy
for TDFW also shows a linear trend initially. The consumption was increased linearly but for DW the energy

Fig. 3. Color reduction during the electrolytic oxidation.

Fig. 4. BOD5 reduction during the electrolytic oxidation.

Fig. 5. Energy consumption during the electrolytic oxidation.

 A.G. Vlyssides et al. / Waste Management 20 (2000) 569±574
Fig. 6. Anode eciency during the electrolytic oxidation.
consumption increased for 14 min, after which it started to
decrease. It must be noted that current and voltage were not
stable during the experiments. From the COD reduction of
the TDWF it is noted that this e‚uent constitutes an
organic load that is dicult to oxidize. This explains the
continuously increasing demand for Kw. The DW e‚uent
seems to consist of a more easily oxidized organic load
and this can result in a decline in the demand of Kw. This
decline can be also explained by the higher conductivity of
this e‚uent, since it contains 4% of NaCl as electrolyte.
4.5. Anode eciency
The eciency of the anode of the electrode is shown in
Fig. 6. It has been calculated in kilograms (kg) of COD
removed (CODr) per h per ampere per square meter.
5. Conclusions
The electrolytic method that was examined gave
satisfactory results for the reduction of the organic load
and the color of the e‚uent. It must be noted that color
reduction is of prime importance for the textile indus-
tries. Only with 18 min active treatment time COD,
BOD5 and color% reductions exceeded in almost all
cases 80%. The color reduction for DW was almost
100%. The di€erence in the treatment behavior of the
two e‚uents can be explained by the di€erences of
concentrations of both the contaminants and the
amount of NaCl that was used as electrolyte. From the
overall results it can be concluded that the electro-
chemical treatment of both these wastes proved feasible.
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