Chemical Engineering Journal 111 (2005) 63–70

Evaluation of a novel electrochemical pilot plant process for azodyes

removal from textile wastewater
Anastasios Sakalis a , Konstantinos Mpoulmpasakos a , Ulrich Nickel b ,
Konstantinos Fytianos c,∗ , Anastasios Voulgaropoulos a
a Laboratory of Analytical Chemistry, Chemistry Department, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
b Institute of Physical Chemistry, University of Erlangen-Nuremberg, Egerlandstrasse 3, D-91058 Erlangen, Germany
c Laboratory of Environmental Pollution Control, Chemistry Department, Aristotle University of Thessaloniki,

University Campus, 54124 Thessaloniki, Greece

Received 19 November 2004; received in revised form 27 April 2005; accepted 6 May 2005

Abstract

A novel pilot plant for the electrochemical treatment of textile wastewater is discussed in this paper. The process is based on the electrolytic
degradation of azodyes, applying a specific potential with on line measurement of current, pH and temperature. Batch experiments are
performed for single electrolytic cell and continuous flow experiments for serial electrolytic cell apparatus (cascade system), using both
synthetic and real wastewater samples. For synthetic samples treatment, four commercially pure azodyes (Reactive Orange 91, Reactive Red
184, Reactive Blue 182 and Reactive Black 5) are used, while sodium chloride (NaCl) and sodium sulfate (Na2 SO4 ) are tested as supporting
electrolytes. Real wastewater treatment under optimal conditions yield 94.4% dye removal and neutral final pH. Biologically Oxygen Demand
measured after 5 days (BOD5 ) and Chemically Oxygen Demand (COD) values are reduced by 35 and 45%, respectively, while COD/BOD5
ratio is reduced from 4.3 to 3.6 final value. The proposed pilot plant achieves almost complete decoloration requiring no further addition of
electrolyte or any other chemical agent. Thus, it could easily be used as a pretreatment stage prior to biological treatment.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Electrochemical treatment; Pilot plant; Degradation; Decoloration

1. Introduction also because many of the commercial azodyes can produce

hazardous aromatic amines, as well as other highly toxic
Textile industry provides huge quantities of wastewater as by-products through metabolic processes in plants and ani-
a result of many intermediate stages using water [1]. More- mals or directly after the disposal in lakes, rivers or sea
over, each intermediate stage provides different wastewater, [3–6].
so the final wastewater can be considered as a mixture of Concerning the reactive dyes which are mainly used for
intermediate wastewater, containing mainly unfixed dyes as textile dying processes, it is known that 30% of the initial
well as other impurities such as, polyvinyl alcohol, starches, amount of the dye is released in the wastewater due to hydrol-
surfactants, pesticides, biocides and relatively high salinity ysis side reaction, resulting in limited degree of fixation
[2]. [7]. Moreover, azodyes which are synthetic products, show
However, the increased color intensity is the most seri- rather low biodegradability, firstly because of lack of natural
ous problem of the wastewater provided by the Textile biodegradation paths and secondly because of stereochem-
Industries not only because of aesthetical displeasure, but ical interferences concerning the accession of the reductant
or oxidant molecule to the azo-group [8,9]. As a result, tra-
∗ Corresponding author. Tel.: +30 2310 997873; fax: +30 2310 997873.
ditional biological processes are not able to fully decolorize
E-mail address: [email protected] (K. Fytianos). azodye wastewater [10–15].

1385-8947/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2005.05.008
64 A. Sakalis et al. / Chemical Engineering Journal 111 (2005) 63–70

Other conventional methods such as physical [16], chem- Table 1

ical [17] and photocatalytic processes [18–20] have individ- Environmental parameters of initial wastewater
ual advantages, but also have constraints causing inadequate Environmental parameter Initial wastewater
effectiveness, if applied individually [1]. Total suspended solids(g/dm3 ) 0.020
For example, adsorption on activated carbon is only suc- pH 8–9
cessful for hydrophobic dyes, coagulation is partially effec- Color, λmax = 525 nm (absorption units) 0.182
Chlorides (g/dm3 ) 0.224
tive for highly soluble dyes and Fenton’s reagent is effective BOD5 (g/dm3 ) 0.142
at pH < 3.5 [21–22], while ozonation is effective at high pH COD (g/dm3 ) 0.608
values [23]. Total organic carbon (g/dm3 ) 0.164
Furthermore, ozonation can result in colorless wastewa-
ter. However, hazardous organic material is slightly reduced,
causing high final total organic carbon (TOC) and COD val-
ues, together with high operational cost [24–26]. 2. Materials and methods
Electrochemical treatment is a relatively new technique
providing certain advantages such as almost complete decol- 2.1. Reagents
oration, operation under moderate pH range, low final tem-
perature, significant COD and BOD5 reduction as well as no All dyes used are of commercial purity grade. Reactive
sludge formation [15,27–31]. However, in most cases [29] Orange 91, Reactive Red 184 and Reactive Blue 182 are
high concentrations of supporting electrolytes, especially obtained from Ciba Co. (Switzerland). Reactive Black 5
NaCl, are required for satisfactory results leading to high is obtained from DyStar Textilfarben GmbH & Co. (Ger-
concentrations of hypochlorite anions, free chlorine and poly- many KG). NaCl and Na2 SO4 used as electrolytes as well as
chlorinated aromatic products, which are extremely harmful reagents used for BOD and COD measurements according
for the environment [1,32–36]. Therefore, novel electro- to standard methods are of analytical purity grade obtained
chemical processes requiring no further electrolyte addition, from Merck (Darmstadt, Germany). Tap water is used for
are essential for environmentally friendly application of this all synthetic solutions in electrochemical treatment for better
technique. simulation with the real wastewater. Doubly distilled water is
Elsewhere a combination of fluidized biofilm process used for all measurements. The real wastewater was obtained
with chemical coagulation and electrochemical oxidation from the co-operating company (Texapret SA, Thessaloniki,
is proposed, without however avoiding sludge formation Greece) and its initial characteristics are shown in Table 1.
[39]. All parameters are measured according to standard methods
In this paper, a pilot plant electrochemical process is pro- for examination of water and wastewater [46].
posed achieving almost complete decoloration and satisfac-
tory COD and BOD5 reduction requiring no further addition 2.2. Electrodes
of supporting electrolyte. The whole process is based on a
previous work of our group [37,38] and is about to operate Carbon fleece used as cathode is Sigatherm PR201-16
as a pre-treatment stage prior to biological treatment, regard- model, obtained from SGL Carbon Group (Germany). It is a
ing that combined processes are the most hopeful solution specially treated and modified carbon, achieving large poros-
for complete mineralization of textile wastewater and safe ity and active surface. Additionally, this type of electrode
disposal to the environment [39,40], since color limits of tex- shows great stability, acid, base and redox resistance, prac-
tile wastewater are rather strict all over world [41–45]. For tically no deactivation through long term use and is easily
this purpose, batch experiments are performed evaluating the cleaned and stored.
efficiency of the electrolytic cell. Four commercial azodyes The anode made of titanium substrate coated with plat-
(C.I names, Reactive Orange 91, Reactive Red 184, Reac- inum film (50 g Pt/m2 ), is obtained from Metakem GmbH
tive Blue 182 and Reactive Black 5) are treated using NaCl (Germany), and shows excellent effectiveness and stability
and Na2 SO4 as supporting electrolytes, while real wastewa- as well as easy cleaning and storage.
ter samples, without any addition of supporting electrolyte,
are treated under batch and continuous flow experiments 2.3. Electrolytic cell—cascade system
using a cascade system. In all cases a constant potential is
applied and specially treated carbon fleece is used as cath- The pilot plant electrolytic cell as well as the cascade sys-
ode, while titanium coated with platinum film (Pt/Ti) is used tem is manufactured by the cooperating Institute of Physical
as anode. Parameters such as temperature, cell current and Chemistry, University of Erlangen (Germany).
pH are checked on line, while BOD5 , COD and COD/BOD5 The capacity of the electrolytic cell is 50 dm3 . The cell
values are determined in case of real wastewater samples. and the electrodes can be seen in Fig. 1.
Color removal is measured in all cases and experimental The inner coat is made of Plexiglas and the outer coat
data for energy consumption and anode efficiency is pre- is made of stainless steel. The aeration of each cell is pro-
sented. vided by a perforated plate made of Plexiglas and placed at
 A. Sakalis et al. / Chemical Engineering Journal 111 (2005) 63–70 65

Fig. 1. (A) Ground plan of the pilot plant electrochemical cell and (B) i: the Pt/Ti anode and ii: the carbon fleece cathode.

the bottom of the cell. A compact air pump (oil free model, (40 dm3 ) for volume adjustment and three parallel electrolytic
∼300 dm3 min−1 ) is used for air supply. cells placed in different height.
Five cathode plates and six anodes of 15 Pt/Ti parallel The main wastewater tank is made of Plexiglas and the ini-
cylindrical wires adapted on stainless steel frames are sequen- tial wastewater has a constant suitable temperature obtained
tially settled on suitable copper substrates which are adapted through heat exchanger. The power supply is provided by
on the cell and connected via cables parallelly with two pairs two parallely connected pairs of batteries per electrolytic cell
of batteries providing 12 V potential. The distance between (12 V, 200 A dc, 2.4 kW) and compact air pumps are used for
the electrodes is adjustable and anodes are electrically iso- air supply. An underwater pump (flow rate: 2–10 dm3 min−1 )
lated from the copper substrate of the cathodes by suitable is used for the adjustment of the continuous flow of the
Teflon isolators and vice versa. All geometrical data for the wastewater from the main tank to the electrolytic cells, while
electrodes are presented in Table 2. hydrostatic pressure ensures the flow through the electrolytic
The cascade system is basically consisted of a main cells due to different height of each cell. A recycling loop
wastewater tank with 1000 dm3 capacity, a smaller tank is used in order to keep constant the height of the wastewa-

Table 2
Dimensions of electrodes
Each electrode Electrolytic cell (five cathodes–six anodes) Cascade system (three electrolytic cells)
Dimension of cathode (m) 0.280 × 0.440 5 × 0.280 × 0.440 3 × 5 × 0.280 × 0.440
Cathode surface (m2 ) 0.120 0.120 0.120
Cathode total surface (m2 ) 0.240 1.2 3.6
Dimension of anode (m) 15 × 0.003a × 0.340 15 × 0.003a × 0.340 15 × 0.003a × 0.340
Anode surface (m2 ) 0.048 0.048 0.048
Anode total surface (m2 ) 0.048 0.29 0.864
a Diameter of each anode wire.
66 A. Sakalis et al. / Chemical Engineering Journal 111 (2005) 63–70

ter in the adjustment tank ensuring the constant hydrostatic

pressure between the adjustment tank and the electrolytic cell
circuit, thus providing constant flow through the cells.

2.4. Experimental procedure

Initially, batch experiments are performed in a single

electrolytic cell, with synthetic wastewater samples con-
taining 5 × 10−4 M azodye diluted in tap water as well as
specific concentration of supporting electrolyte. Regarding
the electrolyte concentration, the short time of treatment, the
possibility of the electrode deactivation and the overheat of
the effluent [37], the optimal potential value is 12 V. This
potential value provides total current of approximately 130 A
and the wastewater is treated for a specific period of time.
Sampling is performed every 20 min, since shorter time of Fig. 2. The % color removal during the treatment of synthetic azodye sam-
ples using either 0.02 M NaCl or 0.02 M Na2 SO4 as supporting electrolytes.
sampling drives to usual and expected data as demonstrated Concentration of each azodye: 5 × 10−4 M. Applied potential: 12 V. Dis-
in previous work [37]. UV–vis spectra of each sample are tance between electrodes: 3 cm. Measured wavelength: Reactive Orange 91:
recorded using a Jasco V-530 spectrophotometer (Japan) 416 nm, Reactive Blue 182: 612 nm, Reactive Black 5: 590 nm, Reactive
with 10−2 m path length cells. Additionally, temperature, pH Red 184: 540 nm.
(Consort C830, Belgium) and current (ECT-689 clamp-on
multimeter, Schmidt Scientific Taiwan Ltd.) are measured inorganic products, which can further be biologically treated
on line. for complete mineralization of the wastewater. The com-
In a second stage, batch experiments of real wastewater are plete absence of the initial dye, together with the presence
performed using also single electrolytic cell. Besides all the of some organic and inorganic products, is proved by exten-
above-mentioned parameters, BOD5 , COD and COD/BOD5 sive research for the identification of the final degradation
values are also measured for every sample in each experi- products of the treated wastewater using suitable hyphenated
ment, while data for the energy consumption and the anode analytical techniques such as Liquid Chromatography–Mass
efficiency are presented. Spectrometry (LC/MS) [38]. It is well known that the electrol-
Finally continuous flow experiments are performed test- ysis of NaCl results in some very strong oxidants, such as free
ing the pilot plant cascade system. The decoloration process chlorine (Cl2 ) and hypochlorite anions (ClO− ) [29,47,48,49].
starts under batch conditions, till constant UV–vis absorption, On the contrary, Na2 SO4 electrolysis drives mainly to the for-
approximately after 30 min of treatment, when the continu- mation of SO2 especially in acidic media, which is just a mod-
ous flow process starts. A flow rate of 6 dm3 min−1 is chosen erate reductant. The whole decoloration proceeds mainly via
as optimal value and sampling from all cells is performed direct redox reactions on the electrodes, enhanced by indirect
every 10 min for the batch process and every 15 min for the redox reactions by the produced oxidants or reductants. The
continuous flow process. Decoloration process, current and stronger the oxidants or reductants are, the better enhance-
temperature are monitored in each of the three cells. ment they can achieve. Consequently, the dye molecule can
more easily be degraded in aquatic media containing chlo-
ride anions (Cl− ). Additionally, each dye shows different
3. Results and discussion degradeability for both electrolytes due to stereochemical and
resonance inductive effects. However, the final degradation
3.1. Batch experiments especially using NaCl is rather satisfactory.
Concerning the current and temperature values during the
Experiments using synthetic wastewater samples are ini- decoloration process, both show smaller increase in case that
tially performed in order to clarify the influence of the nature NaCl is used as electrolyte (Fig. 3). This means that treatment
of the electrolyte on the efficiency of the method. In Fig. 2 under Na2 SO4 , produces more ionic products, increasing the
the decoloration progress using either NaCl or Na2 SO4 for ionic strength of the wastewater. It is known that almost
all azodyes is presented. all azodyes (including those used in this work) are poly-
It is obvious that NaCl causes quicker and more complete sulphonated compounds in order to be water-soluble. In our
decoloration than Na2 SO4 for all dyes. Especially for Reac- previous work [38], significant quantities of HOSO3 − were
tive Blue 182 after 100 min of treatment, 99% of the initial identified in the final wastewater, as a result of the degradation
color is removed from the wastewater, while for Reactive Red of the dye molecules. These anions together with other ionic
184, more than 99.5% of the color is removed after 120 min of degradation products cause the increase of the current. In the
treatment. This rapid decoloration indicates that initial dyes case of NaCl, the increase is smaller probably because many
are fully degraded, giving smaller and colorless organic or of the ionic products are rapidly further degraded in non-ionic
 A. Sakalis et al. / Chemical Engineering Journal 111 (2005) 63–70 67

Fig. 3. Diagrams of temperature and current, during the electrochemical

treatment of 5 × 10−4 M Reactive Black 5 synthetic sample, using either
0.02 M NaCl or 0.02 M Na2 SO4 as supporting electrolytes. Applied poten-
tial: 12 V. Distance between electrodes: 3 cm. Measured wavelength: 590 nm.

final products (N2 , CO2 , SO2 /SO3 ). Final wastewater with as

low ionic strength as possible is basic demand for both high
biodegradability and safe disposal in the environment.
In dye baths, NaCl is the main salt used for the optimal
fixation of the dyes on the textile substrate. Therefore, the real
wastewater contains the required quantity of NaCl to carry out
the electrochemical treatment, without any further addition
of electrolyte, which would increase the ionic strength.
In Fig. 4, the spectra of real wastewater treatment samples
are presented.
It is shown that after 75 min of treatment there is almost
complete decoloration. This means that the concentration of
salts contained already in the wastewater is adequate for fast
and complete color removal. It is significant that just after
15 min, the decoloration is almost completed. Fig. 5. (a) Anode efficiency during the decoloration process. Applied poten-
tial: 12 V. Distance between electrodes: 3 cm. (b) Energy consumption during
The anode efficiency during the treatment, measured in the decoloration process. Applied potential: 12 V. Distance between elec-
kg COD h−1 m−2 A−1 , is optimal around 45 min of treat- trodes: 3 cm. (c) DFZ values (DFZ = A(1000)/d, A = absorbance, d = cell
ment as seen in Fig. 5a. After 45 min the anode efficiency length in mm) for 436 nm (yellow), 525 nm (red) and 620 nm (blue), dur-
is decreased mainly due to the significant decrease of the ing the electrochemical treatment for the real wastewater sample. Applied
Cl− which are oxidized during the treatment. As a result, the potential: 12 V. Distance between electrodes: 3 cm. Measured wavelengths:
436, 525 and 620 nm.
formation of strong oxidants which enhance the decoloration
and degradation process is also reduced.
As can be seen in Fig. 5b, the energy consumption, which for the removal of 1 kg of COD, so the treatment proceeds
is measured in kW h kg−1 COD, is reduced during the first efficiently and with low energy demand. After 45 min of
45 min of the treatment. This means that less energy is needed treatment the energy consumption is increased rapidly, so
the whole treatment loses its efficiency and becomes energy
consuming. Therefore, 50 min of treatment are enough for
the complete treatment of the wastewater and from the eco-
nomic point of view, they are chosen as the optimal period of
treatment.
The whole decoloration process can be seen in Table 3,
where crucial environmental parameters are measured.
The initial pH is decreased approaching pH 7. This is very
important because finally treated wastewater should be neu-
tral prior any disposal. Furthermore, BOD5 and COD are
decreased up to 36 and 45%, respectively, while COD/BOD5
ratio is decreased from 4.3 to 3.7, indicating that the final
Fig. 4. The UV–vis spectra of real wastewater sample during the electro-
chemical treatment. Applied potential: 12 V. Distance between electrodes: wastewater is much more biodegradable than the initial one.
3 cm. Additionally, the decrease of COD and BOD5 means that not
68 A. Sakalis et al. / Chemical Engineering Journal 111 (2005) 63–70

Table 3
Profiles of the main environmental parameters during the real wastewater batch treatment
Time of treatment (min) pH COD (g/dm3 ) BOD5 (g/dm3 ) COD/BOD5 Remained color (%) Temperature (◦ C)
(λ = 525nm)
0 10.2 0.608 0.142 4.3 100 26
15 9.5 0.560 0.137 4.1 9.6 25
30 9.2 0.496 0.110 4.5 7.1 30
45 8.8 0.400 0.097 4.1 6.0 45
60 8.5 0.352 0.096 3.7 5.1 60
75 8.4 0.336 0.091 3.7 5.0 75

only decoloration takes place during the treatment, but also

further degradation of the initial colorless products. This is the
main task of the electrochemical process in order to create
a more degradable wastewater for further biological treat-
ment. Concerning the color removal, there is a decrease up to
95% after 75 min of treatment. Additionally, after only 15 min
of treatment almost 90% of the initial color was removed.
Practically, the final wastewater is colorless and much more
biodegradable than the initial one.
In Fig. 5c, DFZ values of real wastewater sample are
plotted versus time of treatment. These values are used by
Germany as the official system for the color measurement and
are depended on Beer’s law. So, DFZ = A(1000)/d, where A
is the color absorption and d the distance of the used UV–vis
cell in mm. After 75 min of treatment DFZ value at 436 nm
is 8.9, at 525 nm is 3.9 and at 620 is 1.5. Besides 436 nm,
the DFZ values at 525 and 620 nm in final wastewater are
below German standards (7, 5 and 3 m−1 DFZ values). This
means that the concentration of salts contained already in the
wastewater is adequate for fast and complete dye removal.

3.2. Continuous flow experiments

Batch conditions are initially applied in order to stabilize

the wastewater in the electrolytic cells. Since color removal is
constant in all three cells, the flow rate is gradually increased
up to 6 dm3 min−1 . This flow rate is chosen as the optimal Fig. 6. (a) The % remaining color during the decoloration process using
real wastewater sample treated in the cascade system. (I) batch condition.
value for the continuous flow procedure, following the criteria
(II) continuous flow condition, flow rate: 6 dm3 min−1 . Applied potential:
that decoloration over 90% should be achieved in the shortest 12 V. Distance between electrodes: 3 cm. Measured wavelength: 525 nm. (b)
possible time. In Fig. 6a the decoloration process measured The temperature profile for the three cells, during the real wastewater cas-
at 525 nm is presented for both conditions. cade system treatment. Applied potential: 12 V. Distance between electrodes:
Under batch treatment, the percentage of the color removal 3 cm.
is increased up to 90% after 30 min in all three cells. Subse-
quently, the flow rate is increased up to 6 dm3 min−1 resulting the temperature is not further increased and it is stabilized at
in rapid increase of the remaining color mainly in the first low values. Compared with the batch experiment (Fig. 3)
electrolytic cell. In approximately 10 min, the color removal the final temperature is significantly lower, because of the
in all cells is stabilized and in the third cell it is around 10% of wastewater flow, which decreases considerably the final tem-
the initial amount, thus practically after 40 min of treatment, perature, thus providing suitable final wastewater for envi-
the effluent from the third cell can be driven to the biological ronmental disposal or further biological treatment.
treatment. Under continuous flow conditions, an amount of
50 dm3 wastewater needs around 30 min of treatment in the
three cells before the subsequent biological process. 4. Conclusions
The temperature profile for the three cells is presented
in Fig. 6b. In all cells the final temperature does not exceed A novel pilot plant electrochemical method is evaluated in
38 ◦ C. After 30 min of treatment (continuous flow is applied), this study. Initial batch experiments using synthetic wastewa-
 A. Sakalis et al. / Chemical Engineering Journal 111 (2005) 63–70 69

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