War. Res. Vol. 28, No. 2, pp. 277-282, 1994 0043-1354194 $6.00+0.

00
Printed in Great Britain. All tights reserved Copyright © 1993 Pergamon Press Ltd

TREATMENT OF TEXTILE WASTEWATER BY

ELECTROCHEMICAL METHOD
SI~NG H. Ln~ and CHI F. PENG
Department of Chemical Engineering, Yuan Ze Institute of Technology, Neili, Taoyuan 320,
Taiwan, Republic of China

(First received November 1992; accepted in revisedform May 1993)

Aiwnct--Treatment of textile wastewaters from several dyeing and finishing mills by an electrochemical
method is investigated. The batch experimental results are assessed in terms of color (turbidity) and COD
reductions. Several operating variables, such as the wastewater conductivity, pH, power requirement and
amount of polyelectrolyte added, are explored to ascertain their respective effects on the treatment
efficiency.Optimum operating ranges for each of these operating variables are experimentally determined.
The electrochemical method is found to be quite effective and is highly competitive as an alternative
chemical method for treating textile wastewater. A continuous experimental apparatus is designed and
test runs are performed using the operating conditions obtained in the batch experiments. The preliminary
data show similar satisfactory results to those of the batch runs.

Key words--electrochemical method, textile wastewater, color and C O D reductions, conductivity effect

INTRODUCTION ascertained to insure the competitiveness of this

Dyeing and finishing processes are two important
steps in the textile manufacturing process. These steps
involve the dyeing of man-made or natural fibers
to the desired permanent colors and processing of
these fibers into final commercial products. Hence
dyeing and finishing processings have become an
integral part of the textile manufacturing process.
However, in the dyeing and finishing processes, a
considerable amount of wastewater is generated.
Textile wastewater is notoriously known to contain
strong color, a large amount of suspended solids, a
highly fluctuating pH and a high temperature and
COD concentration (Gurnham, 1965). Because of
these characteristics, treatment of this textile waste-
water has been rather difficult.
Traditional methods for dealing with textile waste-
water consist of various combinations of biological,
physical and chemical methods (Hamza and
Hamoda, 1980; Groves and Buckley, 1980; McKay,
1980, 1984; Brower and Reed, 1987; Paprowicz and
Slodczyk, 1988). Because of the large variability of
the composition of textile wastewaters, most of these
traditional methods are becoming inadequate. Fur-
thermore, treatment cost of textile waste effluents has
been escalating fairly rapidly in recent years. Hence
a search for more cost effective treatment methods is
in order. Ozonation has been proposed in recent
years as a potential alternative (Snider and Porter,
1974; Beszedits, 1980; Green and Sokol, 1985; Gould
and Groff, 1987; Lin and Lin, 1992). This latest
method has been shown to be quite effective in
decolorizing textile wastewater. However, the cost of
ozonation for such purposes needs to be further
method.
A method that has never been considered before
for dealing with textile wastewater is the electrochem-
ical method. This method has been successfully tested
to treat various industrial wastewaters (Beck et al.,
1974; Ramirez et al., 1976; Biwyk, 1980; Matis, 1980;
Ramirez, 1981; Cenkin and Belevtsev, 1985). How-
ever, it has never been attempted to use it for dealing
with textile wastewater before. The purpose of this
study is to conduct experimental investigations of
treating textile wastewater using the electrochemical
method. Several fundamental aspects regarding the
effects of wastewater conductivity, pH, power re-
quirement and chemical coagulants (polyaluminum
chloride) on the treatment efficiency are explored. As
will be seen later, the electrochemical method is quite
effective and is at least as promising as the ozonation
method.
CHARACTERISTICS OF TEXTILE WASTEWATERS
The characteristics of textile wastewater have been
discussed in detail before (Lin and Lin, 1992). Here
only several key aspects are highlighted.
The most notorious part of textile wastewater is its
strong color. Depending on the type of dyestuff used,
the color of the textile wastewater varies from red,
brown, blue, purple and black due to their intensified
and dark varieties. Textile wastewater can change
color from day to day, or even several times a day
because the dyestuff used in the dyeing process
changes frequently due to customers' requirements.
The variation of color also causes frequent fluctu-
ation in the COD content of the textile wastewater.

277
278 SHENG H. LIN and CHI F. PENG
Such a strong color, if untreated, would have a
m a r k e d negative impact o n the e n v i r o n m e n t o f the
receiving water body.
The large p H swing in the textile wastewater is
a n o t h e r strong negative point. The p H variation is
primarily caused by different kinds o f dyestuff used
in the dyeing process. The pH of the wastewater
can change from 2 to over 12 ( G u r n h a m , 1965). Such
a big pH variation is particularly troublesome be-
cause of the rather limited p H tolerance of the
activated sludge process or chemical treatment pro-
cess. Hence p r o p e r pH a d j u s t m e n t has become a
necessary part of the textile wastewater treatment
process.
In comparison to most industrial wastewaters, the
t e m p e r a t u r e of textile wastewater is unusually high.
During the dyeing process, rinse waters of up to 90°C
are used in various steps. The near 40°C temperature
of the textile wastewater is a t t r i b u t a b l e to these hot
rinse waters. The high t e m p e r a t u r e renders immediate
treatment of the textile wastewater released directly
from the dyeing process impractical a n d usually
entails proper prior heat dissipation to lower the
temperature to 30°C or below.
O t h e r i m p o r t a n t pollutants of textile wastewater
may consist of small a m o u n t s of polyvinyl alcohol
(PVA), carboxymethyl cellulose ( C M C ) a n d starch
used for sizing of the chemical or m a n - m a d e fibers.
The sizing agents have a very high C O D content of
over 10,000 mg/1, depending on their concentrations.
They enter the wastewater after the desizing process
and contribute significantly to the C O D content of
the textile wastewater.
A l t h o u g h the pH, BOD, total solids a n d the
a m o u n t o f wastewater produced vary widely from
one operation to another, mixing of these waste-
waters in the equalization tank forms a final waste
effluent which possesses more stable physical and
chemical properties. In general, the final textile waste
effluent can be broadly categorized into three types o f
wastewater according to their C O D content a n d the
color intensity (Lin a n d Lin, 1992), these are the high,
medium and low strength wastewaters. The high
strength wastewater has a C O D concentration ex-
ceeding 1600 mg/l and a strong dark color with very
low transparency. The m e d i u m strength wastewater
has a C O D content between 800 a n d 1600 mg/l while
the low strength wastewater has the lowest C O D
concentration o f less t h a n 800 mg/1. Table 1 lists the
average characteristics of these three textile waste-
waters. The color in the wastewater usually varies in
intensity according to the above strength classifi-
cation. But in m a n y circumstances, the low or
Table 1. Characteristics of typical textile wastewater
BOD COD
Type (rag/l) (rag/I) pH
High strength 500 1500 10
Medium strength 270 970 9 137
Low strength 100 460 10
m e d i u m strength wastewater may also have a very
strong color. The degree of difficulty in treating these
wastewaters is largely in p r o p o r t i o n to their relative
strength. Fortunately, most textile wastewaters be-
long to the medium a n d low strength varieties. The
majority of textile wastewaters employed in this study
belonged to these two types.
EXPERIMENTAL STUDIES
The batch experimental apparatus is shown in Fig. I. The
cathode and anode consist of four pieces of cast iron each,
situated approx. 1.5 cm apart from each other and dipped
in the wastewater. The power input was controlled by an
ammeter and the total power consumption was integrated
and registered by a power integrator. In each run, approx.
1000 cm 3 of textile wastewater was placed in the electrolytic
cell. The total effective surface area of the cast iron elec-
trodes was 324 em 2. The initial pH of most of the textile
wastewaters in the electrolytic cell was adjusted to around
7, except for those samples intended to investigate the pH
effect on the COD removal efficiency. The conductivity of
raw textile wastewater was adjusted by dilution with deion-
ized water or by adding sea water. Experimental runs using
the same wastewater and operated under the same operating
conditions were repeated for a complete set of color and
COD measurements at various treatment times.
The color of the treated textile wastewater was deter-
mined using an apparatus similar in basic structure to the
candle turbidimeter (APHA, 1985) which is used for
measuring the Jackson unit. The color (or turbidity) of the
raw and treated wastewater was determined in terms of its
transparency (centimeter). According to the Taiwan EPA
stipulations, the acceptable transparency of all treated in-
dustrial wastewaters needs to exceed 15 cm. The COD was
measured by the standard method (APHA, 1985).
After the batch experiments were completed, a continuous
electrolytic reactor system was designed based on the experi-
ences gained in the batch studies. The continuous system
was intended to investigate the performance of the electro-
chemical treatment for potential practical implementation.
The experimental setup is shown in Fig. 2. The electrolytic
reactor was made of Pyrex glass with the dimensions
17.5 × 17.5 x 25 era. With the wastewater flow rate kept at
0.75 l/rain, the reactor permits an equivalent residence time
of about t0 rain. The pH of the textile wastewater was
monitored continuously and adjusted if necessary. PAC was
then added before the wastewater entered the electrolytic
reactor. Before the continuous experiments were started, the
system was filled with raw textile wastewater. Hence samples
taken at the exit of the electrolytic cell showed a transient
period. The COD and other parameters were measured
using the same methods as the batch runs.
DISCUSSION OF RESULTS
The mechanism o f the electrochemical process in
aqueous systems is quite complex (Pietcher and
Walsh, 1990). It is generally believed t h a t there are
three possible mechanisms involved in the process:
electrocoagulation, electroflotation a n d electrooxida-
SS Temperature Oil Conductivity
(mg/l) (°C) (mg/l) (#S)
250 28 50 2900
28 21 2500
91 31 10 2100
 Electrochemical treatment of textile wastewater
Iciott
2 1
°ti °
4 5
+
Fig. 1. Batch experimental setup.
tion. Oxidation and reduction of the electrochemical
process occur, respectively, at the anode and cathode
of the iron electrodes according to (Pletcher and
Walsh, 1990):
Anode: 4Fe~-4Fe 2+ + 8 e-
4Fe 2+ + 10H20+ O 2~,-~4Fe(OH)3 + 8H +
Cathode: 8H + + 8 e-~-4H2
With sufficient power supply, the dye molecules are
reduced at the cathode to small organic molecules.
Some of the small organic molecules and the sus-
pended solids are captured by Fe(OH)3 which is
removed by sedimentation or by H 2 flotation. This
perhaps accounts for the rather satisfactory decol-
orization and COD reduction of the textile waste-
water by the electrochemical process. In fact, during
the experiments, either batch or continuous, small
amounts of sludge were scraped off from the top and
the bottom of the electrolytic cell, evident of the
sedimentation and flotation actions.
Textile pH control
Feed
pump
Fig. 2. Continuous experimental setup.
WR 28/2---C
279
3
1. D.C. power supply
2. Digital ammeter
3. Power integrator
4. Parallel iron-anodes
5. Parallel iron-cathodes
6. Magnetic bar-stirrer
7. Sampling valve
8. Electrolytic cell
9. Digital magnetic stirring controller
The textile wastewater samples were obtained from
three large dyeing and finishing mills in northern
Taiwan. The wastewaters had a COD within the
range of 800-1600mg/l and were strongly colored
with a transparency invariably less than 4 cm. The
suspended solids were consistently less than 200 mg/1
due primarily to partial sedimentation occurring in
the equalization tanks. The pH of the wastewater was
also partially adjusted in the equalization tanks and
was usually within the range of 6-9. Due to signifi-
cant heat dissipation in these tanks, the wastewater
temperature had been maintained below 35°C which
facilitates the ensuing treatments.
Figure 3 displays the transparency of the treated
wastewater as a function of time for a typical run of
medium strength wastewater. The transparency im-
proves slowly with treatment until 6min. Marked
improvement was then observed up to l0 min and
beyond that not much improvement was realized. In
fact, the color of the treated wastewater had become
PAC
r_ Effluent
Electrolytic cell
280 SHENOH. Dr~ and Cm F. PENO

35 of textile wastewaters is not needed in most practical

applications. Hence, in all subsequent tests, the pH of
30 e l e the samples was not adjusted except for some unusual
cases in which the pH fell out of this range.
25 The conductivity of raw textile wastewaters was
found to vary from as low as 1000 to over
3000 #mho/cm. In order to examine the effect of
o~ 20

..../'/
g- 15
[-
lO
I I I I
2 4 6 8
Time (rain)
Fig. 3. T r a n s p a r e n c y as a function o f time.
very light with a transparency over 20cm. This
corresponds to about 8 min of electrolytic treatment.
The Taiwan EPA stipulates that treated industrial
wastewater needs to meet the requirement of 15 cm
transparency, as mentioned earlier. Hence electrolytic
treatment of 8 rain amply satisfies this requirement.
Due to the potential pH variation in the textile
wastewater, the effect of pH on the electrochemical
treatment efficiency was examined next. Figure 4
shows the results of a typical run on the pH effect.
The pH of the raw textile wastewater collected from
the textile mills was adjusted using sodium hydroxide
or sulfuric acid to the desired pH for each experimen-
tal run. It is apparent that the pH effect of the
wastewater on the COD removal is not very signifi-
cant within the range of 5-10. This result is particu-
larly meaningful since the majority of textile
wastewaters from the equalization tanks have a pH
within that range, implying that adjustment of the pH
50
conductivity on the COD removal efficiency, the
textile wastewater was artificially adjusted to the
range between 1000 and 6000#mho/cm using sea
'water or deionized water. Results of a typical run are
displayed in Fig. 5. COD removal is seen to increase
rapidly with increasing conductivity between 1000
and 2000#mho/cm. It increases mildly beyond
2000 #m.ho/cm and peaks out at 3000 #mho/cm. It is
I I also apparent that corresponding to the range of
10 12
conductivity between 2000 and 3000 #mho/cm, there
is a rapid decrease in power requirement. Hence, it
can be concluded that a conductivity in the range
between 2000 and 3000 #mho/cm appears to be the
optimum operating range in terms of optimum COD
removal and power utilization. CoincidentaUy, over
80% of the textile wastewater samples gathered
from the various dyeing and finishing mills fell within
this range of conductivity. Hence adjustment of
the conductivity is usually not necessary. Only on
rare occasions did the wastewater samples have a
conductivity much more than 3000 or less than
2000 #mho/cm. In these cases, the conductivity could
be easily adjusted to the optimal operating range.
Figure 6 displays the COD removal as a function
of time and power requirement. Two plateaux appar-
ently exist in this figure. The first plateau of COD
removal occurs at 4 rain after the electrolytic process
began and with a COD removal efficiency of about
50%. The measured transparency, not shown in the
figure, barely reached 15 cm even at 8 min. However,
beyond that time, considerable improvement in the
Power (Wh)
1 2 3 4
80 I r I I

75
48
7O

"~ 46
o~ 65
O

~ 44 ~ e
¢~ 6o
0
O
• Power

42 55 ~, Conductivity

50 I 1 I t l
40 t I I I I 1000 2000 3000 4000 5000 6000
6 7 8 10 11
Conductivity Otmho/cm)
pH
Fig. 5. Effect o f w a s t e w a t e r c o n d u c t i v i t y o n the C O D
Fig. 4. Effect o f w a s t e w a t e r p H o n the C O D removal. removal.
 Electrochemical treatment of textile wastewater 281

Power (Wh) 55 J •
0 1 2 3 4 5 6 7 f • ~ •
60 I I I I I I I 50

50 - ~ [ 45

/
"-" 40
40
>
0
;> I~ 35
0
.o
~ 3o
~ 3o
O 20
25
• Power
20 '--
10 A Time
15 I I [ I I [ t I I I I
I I I I I I I I I I I I I I 0 10 20 30 40 50 60 70 80 90 100 110
0 2 3 4 5 6 7 8 9 10 11 12 13 14 15 PAC (mg/I)
Time (min)
Fig. 8. Effect of PAC on COD removal.
Fig. 6. COD removal as a function of time.

than 5 rain for this case and by 8 min it far exceeded

wastewater transparency was observed to begin and
25 cm. The encouragingresults prompted us to ex-
at 10 min the transparency far exceeds 25 cm. This is
plore further the effect o f P A C on this process. Figure
also reflected by a corresponding increase in C O D
8 shows the C O D removal as a function of the P A C
removal in this figure. In comparison, the improve-
concentration. A P A C concentration o f 40 mg/l ap-
ment in C O D removal does not seem to be as
pears to yield the optimum results in terms o f c o l o r and
pronounced as that o f the transparency between 8
C O D reductions. Besides, the power requirement for
and 10min. As a consequence, 8-10 min are deemed
this case is at least 30% less than that without PAC.
necessary to achieve good color and C O D reductions.
The current density was observed by the previous
Polyelectrolytes are widely used as a synthetic
investigators to influence the treatment efficiency o f
coagulant in chemical treatment o f wastewaters. To
the electrochemical process (Biwyk, 1980; Matis,
test whether it helps improve the electrochemical
1980; Cenkin and Belevtsev, 1985). Hence, the cur-
treatment, a small a m o u n t o f polyaluminum chloride
rent was varied to determine its effect on the C O D
(PAC) was added to the electrolytic cell in several
removal in the present work. F r o m Fig. 9, it is
runs. Figure 7 demonstrates the results with addition
apparent that the C O D removal improves steadily
o f 5 mg/l PAC. Comparison o f Fig. 5 indicates that
with increasing current and peaks at around 3 amps.
the P A C significantly improves the C O D reductions.
With a total electrode surface area of 324 cm 2, this
The transparency was observed to reach 15 cm in less

Power (Wh) Power (Wh)

0 1 2 0 1 2 3 4
60 I I 66 I r I t

64 -
50

62 m
40
60

O
>.
0
i= 30

20
i
~ 56
58

54
10 / A Time
52 •/ I
_l I I I [ I I I I I I I I I 50 I J I
0 1 2 3 4 5 6 7 8 9 101112131415 0 1 2 3
Time (min) Current (amp)
Fig. 7. COD ~moval as a function of time with 5 mg/1 PAC. Fig. 9. Effect of current on COD removal.
282 Sr~NG H. LI~ and Cm F. I~NG
60
5o
~ 4o
~ 3o
20
10
0 40 80 120 160 200 240 280
Time (min)
Fig. 10. COD removal of the continuous run.
optimum current is equivalent to a current density of
92.5 amp/m 2 which is within the range of the operat-
ing range of current density adopted by the previous
investigators (Biwyk, 1980; Matis, 1980; Cenkin and
Belevtsev, 1985). The power requirement is also seen
to follow the same pattern. In fact, all experimental
runs discussed in the previous figures were conducted
with this optimal current density.
Typical results of C O D removal for the continuous
runs were demonstrated in Fig. 10. To attain the best
results, the optimum operating conditions determined
in the batch experiments were adopted. It is apparent
that a transient period of about 50 min existed at the
beginning as anticipated. The steady C O D removal
fluctuated around 51% which is in line with that
obtained in the batch runs operated under similar
conditions. The transparency of the treated waste-
waters at the steady state was consistently above
20cm. The satisfactory results clearly reflect the
applicability of the electrochemical process for con-
tinuous treatment of textile wastewater.
CONCLUSIONS
The electrochemical method has been employed in
the present study to treat the textile wastewater.
Several aspects, such as the wastewater conductivity,
pH, power requirement and addition of polyelec-
trolyte, are explored to determine their effect on the
treatment efficiency. It has been observed that most
of the textile wastewaters gathered from the dyeing
and finishing mills have a conductivity within the
optimum operating range and hence adjustment of
the conductivity is usually not necessary. The pH
effect of the textile wastewater on the treatment
efficiency is found not to be significant when it is
within the range between 5 and 10 and hence in the
majority of cases, adjustment of the pH prior to
electrochemical treatment is not necessary. Addition
of a small amount of polyaluminum chloride (PAC)
up to 40 mg/l has been observed to significantly
enhance the treatment efficiency. A current density of
about 92.5 amp/m 2 is also found to yield a maximum
C O D removal. A continuous experimental setup is
also designed to test the applicability of the process.
The continuous runs operating at the optimum oper-
ating conditions obtained above show equally satis-
factory results as those of the batch runs, indicating
the strong potential of the electrochemical process for
the textile wastewater treatment.
Acknowledgements--The authors wish to sincerely thank
the Far Eastern Textile Company, Republic of China for
financial support of this project. Technical help by the
personnel of the Far Eastern, Hoyu, Wufon and Yang Ming
Textile Companies is greatly appreciated.
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