Desalination 198 (2006) 316–325

Coupling of membrane filtration with biological methods for

textile wastewater treatment
Renata Żyłłaa, Jadwiga Sójka-Ledakowicza, Ewa Stelmachb,
Stanisław Ledakowicza*
a
Textile Research Institute, ul Brzezińska 5/15, Łódź, Poland
Tel. +48 (42) 616-1110; Fax: +48 (42) 679-2638; email: stanleda@p.lodz.pl
b
Faculty of Process and Environmental Engineering, Technical University of Łódź,
ul Wólczańska 213, 93-005 Łódź, Poland

Received 3 November 2005; Accepted 6 February 2006

Abstract
At the first stage of this study, model and real post-dyeing wastewater was concentrated by nanofiltration (NF).
In this process a filtrate characterised by an over 98% colour reduction, expressed in DFZ (spectral absorption
coefficient) and a concentrate of high organic load were obtained. Further on, the NF concentrate was subjected to
anoxic biodegradation. In the anoxic biodegradation of real wastewater, the degree of COD reduction was 50% on
average. The filtrate coming from NF of wastewater was reused as process water in repeated dyeing processes. As
a result of the end-use properties of the dyed products, it was found that the purified filtrate could be applied as
process water for dyeing.

Keywords: Nanofiltration; Concentrate biodegradation; Water reuse

1. Introduction significant amounts of coloured wastewater with

The dyeing process of textiles is characterised
by high water consumption, caused, for instance,
by multiple washing and rinsing cycles. Hence,
*Corresponding author.
a COD load and relatively low toxicity are gene-
rated. Therefore, it is very important to develop a
technology of recovery and reuse of water
coming from textile wastewater.
Nanofiltration (NF) is a known and efficient
method for the separation of pollutants from

Presented at the 2nd Membrane Science and Technology Conference of Visegrad Countries (PERMEA),
Polanica Zdroj, Poland, 18–22 September 2005.
0011-9164/06/$– See front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2006.02.008
 R. Żyłła et al. / Desalination 198 (2006) 316–325
water, that can obtain industrial water from pro-
cess wastewater [1–5]. However, after the process
of NF, a concentrated mixture of dyes and auxili-
ary substances remains, and the problem of its
utilisation has not yet been solved.
The goal of this study was to develop a
method for neutralisation of a filtration concen-
trate by biological methods. An increase of appli-
cation of biological methods to textile wastewater
treatment was recently observed [6–19]. In par-
ticular, biodegradation of azo dyes, which are the
most commonly used in dye houses, were the
subject of investigation. The azo dyes containing
one or many azo bonds (-N=N-) cannot be
degraded under aerobic conditions in municipal
wastewater treatment plants [10]. However, under
anaerobic conditions (negative redox potential),
many bacterial consortia possess enzymes (azo-
reductases) that are able to disrupt the azo-bonds
and release aromatic amines [13]. Many of
aromatic amines are cancerogenic; therefore, they
should be further degraded under aerobic condi-
tions. Based on the literature survey on biode-
gradation of the model [8,12–14,18] and real
[6,15] textile wastewater, one may conclude that
the use of sequential anerobic/aerobic conditions
could allow mineralisation of these xenobiotic
azo-compounds.
This is a precondition to applying the NF
method for process water recovery under indus-
trial conditions. A subject of this study was
wastewater, which was obtained after laboratory
dying (followed by washing and rinsing) of
knitted fabrics with reactive dyes. Real waste-
waters coming from two textile plants where
knitted and woven fabrics were subjected to wet
processing were also the subject of this study.
2. Materials and methods
2.1. Experimental set-up
NF process of wastewater coming from dye
houses was conducted at a constant flow rate
317
(ca. 2 dm3/min) through pressure chamber (4),
equipped with a flat membrane of an active filtra-
tion area equal to 81 cm2 (Fig. 1). The process
was carried out under pressure equal to 1.5 MPa
and temperature 35–40EC with a DL membrane.
The membrane was selected for laboratory-scale
experiments based on former research results
obtained by the Institute for Product Develop-
ment, Denmark. The membrane was manufac-
tured by Desalination Systems, USA, and made
of proprietary polysulphone. A molecular weight
cut-off of about 180 g/mol was expected [20].
The membrane was preconditioned for more than
1 h under the pressure. During the experiments, a
concentrate was recycled to the thermostated tank
(1), while a filtrate was collected in the measuring
cylinder (7).
Experiments with post-filtration concentrate
biodegradation were conducted in the set-up
shown in Fig. 2. The key element of the set-up
was bioreactor (3) with total volume and working
volume of 3 and 2 dm3, respectively, with a
mechanical stirrer (4). The bioreactor was fed
with wastewater from a tank (1) by a peristaltic
pump (2). The pump (5) delivered the reaction
mixture from the bioreactor to the wastewater
tank (6). Possible liquid overflow from the bio-
reactor was transferred to the tank (7) by an
overflow tube. The bioreactor was adapted for
aerobic processes by fitting it with a sparger with
air pump (8). Experiments were conducted at
ambient air temperatures (20–25EC).
2.2. Tested material
The tested material was synthetic domestic
sewage, model and real wastewater from the
textile industry. The synthetic domestic sewage
contained the following ingredients dissolved in
1 dm3 of tap water:
C Casein peptone 0.156 g
C Dry broth 0.105 g
C NH4Cl 0.020 g
C NaCl 0.007 g
318 R. Żyłła et al. / Desalination 198 (2006) 316–325

Fig. 1. Schematic of nanofiltration and

reverse osmosis set-up. 1 thermostat;
2 pump, 3 control valves, 4 pressure
chamber with membrane, 5 manometer,
6 rotameter, 7 measuring cylinder.

The model textile wastewater was obtained

after dyeing (followed by washing and rinsing) of
knitted cotton fabric with reactive “low tempera-
ture” dyes — Helaktyn Blue F-R (CI Reactive
Blue 4), Helaktyn Yellow F-5G (CI Reactive
Yellow 1), Helaktyn Red F-5B (CI Reactive
Red 2) in a Pyrotec S laboratory dyeing machine
(Roaches, UK) — according to the procedures
recommended by the manufacturers of these dyes
at a bath of ratio 1:10 (i.e., 1 g textile and 10 cm3
water). The wastewater was then subjected to NF,
and consequently a concentrate was obtained with
a concentration ratio of 1:3.
The real textile wastewater came from two
textile plants. Textile plant no. 1, with a dye-
house and a finishing department, is a manu-
Fig. 2. Schematic of the experimental set-up. 1 waste- facturer of knitted fabrics from cellulose fibres
water tank, 2,5 peristaltic pump, 3 bioreactor of working and their blends with synthetic fibres. Plant no. 2
volume 2 dm3, 4 stirrer, 6 post-reaction tank, 7 overflow
deals mainly with finishing of viscose lining,
tank, 8 aeration pump connecting with air sparger.
polyester fabrics and mixed synthetic and cotton
fabrics. The initial parameters of wastewater
produced under laboratory conditions and of
C CaCl2 @ 6H2O 0.0075 g
these delivered by textile plants are compared in
C MgSO4 @ 7H2O 0.002 g
Table 1.
C KH2PO4 0.020 g
C K2HPO4 0.050 g
 R. Żyłła et al. / Desalination 198 (2006) 316–325 319

Table 1
Physicochemical parameters of wastewater coming from selected textile plants

DFZ COD Conductivity pH

[mg O2/dm3] [mS]
436 nm 525 nm 620 nm

Wastewater from laboratory dyeing 112 200 82 580 25.9 9.52

Plant no. 1 Wastewater I 150 135 117 2039 7.3 9.3
Wastewater II 204 183 121 2699 5.1 9.1
Plant no. 2 91 87 73 542 1.95 7.85

2.3. Biological process conditions
The process of sludge adaptation was carried
out for 7 days under anoxic conditions in order to
adapt microorganisms to textile wastewater
degradation. Biodegradation under anoxic con-
ditions with the use of model textile wastewater
was started by adding a mixture of model textile
wastewater (10%) and model domestic sewage
(90%) in the amount of 1 dm3 to the bioreactor
with adapted active sludge. The domestic sewage
was used as an external source of carbon in the
degradation processes. The percent of textile
wastewater was increased by 10% every 3–
4 days. A similar process was carried out for real
textile wastewater that came from one of the
textile plants in Łódź, Poland, decreasing only the
amount of exchanged mixture of wastewater to
0.8 dm3.
The anoxic phase for each biodegradation
process lasted for 22.4 h every day. During this
time, the content of the bioreactor was mixed so
slowly that no aeration occurred through the
vortex at the impeller shaft (the frequency of
impeller rotations was 110 min!1 for model
wastewater and 80 min!1 for real wastewater).
Next, mixing was stopped and the process of
sedimentation began. The phases of sedimen-
tation and removal of supernatant lasted 40 min
each. The amount of removed supernatant was
ca. 1 dm3 for model wastewater and 0.8 dm3 for
real wastewater. The resulting loss of liquid in the
bioreactor was completed each time with an
appropriate mixture of textile wastewater and
domestic sewage.
2.4. Analytical methods
The efficiency of NF and anoxic biodegra-
dation processes was estimated on the basis of:
1. Spectral absorption coefficient (DFZ,
Durchsichtsfarbzahl in German), determined on
the basis of absorbance measurements by the
spectrophotometric method at three wavelengths
(λ = 436, 525 and 620 nm), according to the DIN-
38404/1 standard [21] (in the case of biological
processes after filtration on a filter paper and
0.45 µm filter), using the formula
1000 ⋅ E (λ )
DFZ = (1/m)
d
where E(λ) is the absorbance at a given wave-
length λ, and d is the measuring cuvette thickness
(mm).
2. Chemical oxygen demand (COD) by the
dichromate method according to Polish Standard
No. PN-74/C-04578, corresponding to German
Standard DIN EN 1899-1 and DIN 38409-H 41
[22].
The following parameters were determined for
the wastewater in the bioreactor:
C Redox potential using SenTix ORP electrode
connected to Multi Lab 2 apparatus;
320 R. Żyłła et al. / Desalination 198 (2006) 316–325

C Dry matter content in the suspension (drying

to constant mass at the temperature 105EC),
refers to anoxic processes;
C organic dry matter content (roasting at
550EC), refers to anoxic processes.

In addition, pH and electrolytic conductivity, as

a salt content index, were determined using a
multi-functional computer-aided device equipped
with a CD-210 conductivity sensor.
Microscopic observations of microflora re- Fig. 3. Reduction of colour, COD and conductivity of
sponsible for biodegradation processes in the analysed wastewater.
bioreactor were also carried out. For this purpose,
an Olympus BX40 optical microscope connected
to a digital camera with a resolution of 760×
560 pixels was used. The image was magnified
1200 times.

3. Results and discussion

3.1. Nanofiltration
During the first stage, the mixture of waste-
water coming from the dyeing process and
washing and rinsing performed under laboratory
conditions was subjected to NF. As a result, over
98% reduction of the filtrate colour was achieved,
which confirms a nearly complete retention of
dye particles in the concentrate (Fig. 3). Only
NaCl and Na2CO3 salts were transferred freely to
the filtrate. Some salt remained on the filter.
Further on, the model concentrate was subjected
to biodegradation under anoxic conditions.
During the second stage of the investigation,
the wastewater coming from selected textile
plants was subjected to NF processes to recover
process water. Fig. 3 shows a reduction degree of
colour, COD and conductivity of the analysed
wastewater. The reduction of colour and COD
during NF exceeded 90%, irrespective of the
analysed wastewater composition. However, dur-
ing the NF process, deterioration of the DFZ
parameter of the filtrate was observed.
Fig. 4. Permeate flux decrease for wastewater coming
from selected textile plants.
It was found that the composition of waste-
water coming from different plants had a sig-
nificant effect on filtration rate (Fig. 4). Waste-
water I taken from plant no. 1 from an averaging
tank contained reactive and direct dyes, salts and
alkalis and certain amounts of auxiliary com-
ponents, including cationic ones. Wastewater II
was taken from a channel at the moment of
removal of a post-dyeing bath from the apparatus
(reactive dyeing, black); hence, its composition
could be considered approximately as the com-
position of a post-dyeing bath. It follows from
Fig. 4 that permeate flux of wastewater II was
higher than in the case of averaged wastewater I.
Thus, when designing a wastewater treatment
 R. Żyłła et al. / Desalination 198 (2006) 316–325
installation with a NF stage, one should consider
separation of streams for the elimination of com-
pounds which can deteriorate the efficiency and
permeate flux.
Wastewater from plant no. 2 contained mainly
suspension and direct dyes and relatively low salt
concentrations. The permeate flux for this waste-
water was higher than in the case of wastewater
coming from plant no. 1. However, the permeate
flux decreased with time, reaching half of the
initial value after 240 min.
3.2. Biodegradation of model wastewater in
anoxic processes
The degree of colour reduction was estimated
at three wavelengths: 436 nm, 525 nm and
620 nm (Fig. 5). The highest degree of colour
reduction was observed at wavelength 525 nm.
With an increase of the percentage of textile
wastewater in the mixture, there is an increase of
differences in colour reduction measured at
wavelength 525 nm compared to the values
obtained at wavelengths 436 and 620 nm. This
provides evidence of a different degree of biode-
gradation of each of the three dyes that are
present in model textile wastewater.
Apart from that, it was observed that with an
increase of mass fraction of textile wastewater in
the mixture, a distinct drop in the relative colour
reduction followed. A significant scatter of COD
results for biodegraded wastewater that might be
caused by temperature changes (the bioreactor
was not thermostated) was observed. Despite the
scatter of results of the COD measurement, it was
found that these data could be described approxi-
mately by a straight line, depending on the
percentage of textile wastewater in the mixture
(Fig. 6). The slope of the COD curve for initial
wastewater and of the curve representing COD of
biodegraded wastewater, depending on the per-
centage of textile wastewater in the mixture, are
similar. This means that, irrespective of the
percentage of textile wastewater, COD is reduced
321
approximately by a constant value in this range of
organic load. This indicates that besides bio-
chemical reduction of dyes, microorganisms
adsorb dye molecules. However, the active sludge
was saturated with the dyes, but in order to draw
explicit conclusions, further investigations are
necessary.
An increase of dry matter content was
observed during the process, which follows from
an increase of the amount of inorganic salts, with
a growth of textile wastewater percentage. In
parallel, the organic dry matter decreased two-
fold, and this could explain a decrease of process
efficiency. This was most probably caused by too
short a time of active sludge adaptation to
changed process conditions (an increased fraction
of textile wastewater). This could be also due to
the formation of toxic compounds that have an
unfavourable effect on microflora in the bio-
reactor during biodegradation.
3.3. Anoxic biodegradation of wastewater from
textile plant no. 1
During a subsequent stage of investigation, a
concentrate obtained from NF of wastewater
coming from plant no. 1 was subjected to anoxic
biodegradation. Initially, wastewater I was sup-
plied to the bioreactor, while at the end of the
process, when the percentage of textile waste-
water in the mixture was 70% and above,
wastewater II was applied.
Fig. 7 shows the degree of colour reduction
depending on the percent of textile wastewater.
With an increase of wastewater I concentration,
the colour reduction decreased. The content of
dry organic matter also decreased; however, later
(on the 30th day), it slightly increased (Table 2).
As in the case of model wastewater, a different
colour reduction degree was observed depending
on the wavelength at which absorbance measure-
ments were taken. The values of reduction degree
obtained at wavelengths 525 nm and 620 nm
were similar. Colour reduction degree measured
322 R. Żyłła et al. / Desalination 198 (2006) 316–325

Fig. 5. Colour reduction degree of model textile wastewater for different wavelengths.

Fig. 6. Dependence of COD on model textile wastewater percentage.

at the wavelength 436 nm decreased remarkably
with an increase of industrial wastewater percen-
tage. Introducing wastewater II to the system (i.e.,
the wastewater coming from dyeing processes), a
significant increase of the colour reduction degree
was obtained. This can provide evidence of lower
toxicity of wastewater II. An increase of dry
organic matter for the wastewater was observed.
The degree of COD reduction was 50% on ave-
rage. Initially, the COD reduction degree was
increasing (it was ca. 60%); next at the textile
wastewater fraction amounting to 50%, there was
a decrease of the COD reduction degree (to about
40%). This value was kept for growing textile
wastewater concentrations.
 R. Żyłła et al. / Desalination 198 (2006) 316–325 323

Fig. 7. Colour reduction degree of real wastewater from plant no. 1 at different wavelengths.

Table 2 Table 3
Content of dry matter and dry organic matter in textile Comparison of relative dyeing intensity of products dyed
wastewater in purified filtrate

Time Wastewater Dry matter Dry organic Dye type Relative dying intensity, %
[days] fraction , % [g·dm!3] matter [g·dm!3]
Helaktyn Blue F-R 94.3
6 10 3.8 2.55 Helaktyn Red F-5B 104.4
9 20 4.45 2.36 Helaktyn Yellow F-5G 96.4
16 30 4.32 2
20 40 5.54 2.11
23 50 6.64 2.39 anoxic bacteria were observed. These observa-
27 60 7.26 2.48 tions confirm a correct operation of the bioreactor
30 70 8.64 2.96 and a proper active sludge adaptation.
37 90 9.83 3.6

3.4. Water reuse in the dyeing processes

During anoxic processes, the microscopic
observations of microorganisms in the bioreactor
were also carried out. While analysing the mix-
ture of wastewater that contained 30% textile
wastewater, in the field of microscope view
single cysts of roundworms, small protozoans,
slowly flowing ciliates and anoxic bacteria were
observed. At 90% load of real textile wastewater,
numerous flowing flagellates with single and
double flagella, single ciliates and numerous
The filtrate coming from the NF of wastewater
that was formed as a result of reactive dyeing of
knitted cotton fabric, carried out in laboratory
conditions, was used as process water in repeated
dyeing processes. The quality of dyeing was
assessed taking into account end-use properties of
the products, such as relative dyeing intensity in
relation to process water (Table 3), resistance to
washing, and wet and dry friction. This assess-
ment led to the conclusion that purified filtrate
324 R. Żyłła et al. / Desalination 198 (2006) 316–325
could be reused as process water in dyeing
processes.
4. Conclusions
The wastewater from laboratory-scale dying
of knitted cotton fabrics with reactive low
temperature dyes was subjected to NF. The
process of NF was also applied to real wastewater
coming from two textile plants where knitted and
woven fabrics were subjected to wet processing.
The results of the membrane experiments
showed that due to NF of the textile wastewater,
over 90% reduction of colour (DFZ) and COD
was obtained. The concentrate produced in NF
underwent further anoxic biological processes.
The degree of colour bioreduction decreased with
an increase of wastewater percentage in the
mixture. The highest colour reduction degree for
model textile wastewater was reported at a wave-
length of 525 nm. In the case of anoxic biode-
gradation of real wastewater, the degree of COD
reduction was 50% on the average.
It can be concluded that a concentrated mix-
ture of dyes and auxiliary substances (after NF)
can be utilized by applying anoxic biological
process. The filtrate coming from NF of waste-
water was reused as process water in repeated
dyeing processes. It was found that the filtrate
could be applied as process water for dyeing.
Further investigations on biodegradation of con-
centrate in anaerobic–aerobic systems are being
conducted that focus on integration of both bio-
logical steps with NF (extent of filtration) and
recycling of filtrate in order to close the water
cycle and minimise waste in the textile industry.
Acknowledgements
The study was partially financed by the Polish
Ministry of Education and Sciences (MES), Grant
No. 3 O9D 03029.
Refereneces
[1] G. Ciardelli, L. Corsi and M. Marcucci, Membrane
separation for wastewater reuse in the textile
industry, Resources, Conserv. Recycl., 31 (2000)
189–197.
[2] S. Chakraborty, M.K. Purkait, S. DasGupta, S. De
and J.K. Basu, Nanofiltration of textile plant effluent
for color removal and reduction in COD, Sep. Purif.
Technol., 31 (2003) 141–151.
[3] C. Tang and V. Chen, Nanofiltration of textile
wastewater for water reuse, Desalination, 143 (2002)
11–20.
[4] I. Koyuncu, D. Topacik and E. Yuksel, Reuse of
reactive eyehouse wastewater by nanofiltration:
Process water quality and economical implications,
Sep. Purif. Technol., 36 (2004) 77–85.
[5] T.-H. Kim, Ch. Park and S. Kim, Water recycling
from desalination and purification process of reactive
dye manufacturing industry by combined membrane
filtration, J. Cleaner Prod., 13 (2005) 779–786.
[6] R. Minke and U. Rott, Anaerobic treatment of split
flow wastewater and concentrates from the textile
processing industry, Water Sci. Technol., 40(1)
(1999) 169–176.
[7] I.M.C. Goncalves, A. Gomes, R. Bras, M.I.A. Ferra,
M.T.P. Amorim and R.S. Porter, Biological treat-
ment of effluent containing textile dyes, JSDC, 116
(2000) 393–398.
[8] C. O’Neill, F.R. Hawkes, D.L. Hawkes, S. Esteves
and S.J. Wilcox, Anaerobic–aerobic biotreatment of
simulated textile effluent containing varied ratios of
starch and azo dye, Water Res., 34(8) (2000) 2355–
2361.
[9] T. Panswad and W. Luangdilok, Decolorization of
reactive dyes with different molecular structures
under different environmental conditions, Water
Res., 34(17) (2000) 4177–4184.
[10] A. Stolz, Basic and applied aspects in the microbial
degradation of azo dyes, Appl. Microbiol. Bio-
technol., 56 (2001) 69–80.
[11] B. Manu and S. Chaudhari, Anaerobic decolorisation
of simulated textile wastewater containing azo dyes,
Bioresource Technol., 82 (2002) 225–231.
[12] C.B. Shaw, C.M. Carliell and A.D. Wheatley,
Anaerobic/aerobic treatment of coloured textile
effluents using sequencing batch reactors, Water
Res., 36 (2002) 1993–2001.
 R. Żyłła et al. / Desalination 198 (2006) 316–325
[13] D.T. Sponza and M. Isik, Decolorization and azo dye
degradation by anaerobic/aerobic sequential process,
Enzyme Microb. Technol., 31 (2002) 102–110.
[14] I.K. Kapdan, M. Tekol and F. Sengul, Decolorization
of simulated textile wastewater in an anaerobic/
aerobic sequential treatment system, Process Bio-
chem., 38 (2003) 1031–1037.
[15] S. Sen and G.N. Demirer, Anaerobic treatment of
real textile wastewater with a fluidized bed reactor,
Water Res., 37 (2003) 1868–1878.
[16] E. Forgacs, T. Cserhati and G. Oros, Removal of
synthetic dyes from wastewaters: a review, Environ.
Inter., 30 (2004) 953–971.
[17] Y.H. Lee and S.G. Pavlosthatis, Decolorization and
toxicity of reactive anthraquinone textile dyes aunder
methanogenic conditions, Water Res., 38 (2004)
1838–1852.
325
[18] N. Supaka, K. Juntongjin, S. Damronglerd, M.-L.
Delia and P. Strehaiano, Microbial decolorization of
reactive azo dyes in a sequential anaerobic–aerobic
system, Chem. Eng. J., 99 (2004) 169–176.
[19] M. Isik and D.T. Sponza, Substrate removal kinetics
in an upflow anaerobic sludge blanket reactor
decolorising simulated textile wastewater, Process
Biochem., 40 (2005) 1189–1198.
[20] J. Sójka-Ledakowicz, T. Koprowski, W. Mach-
nowski and H.H. Knudsen, Membrane filtration of
textile dyehouse wastewater for technological water
reuse, Desalination, 119 (1998) 1–10.
[21] DIN 38 404/1, Bestimmung der Färbung mit
optischen Geräten.
[22] Polish Standard No. PN-74/C-04578, corresponding
to German Standard DIN EN 1899-1 and DIN
38409-H 41.