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: [email protected]
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

a COD load and relatively low toxicity are gene-
The dyeing process of textiles is characterised
rated. Therefore, it is very important to develop a
by high water consumption, caused, for instance,
technology of recovery and reuse of water
by multiple washing and rinsing cycles. Hence,
coming from textile wastewater.
Nanofiltration (NF) is a known and efficient
*Corresponding author. 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) 316–325 317

water, that can obtain industrial water from pro- (ca. 2 dm3/min) through pressure chamber (4),
cess wastewater [1–5]. However, after the process equipped with a flat membrane of an active filtra-
of NF, a concentrated mixture of dyes and auxili- tion area equal to 81 cm2 (Fig. 1). The process
ary substances remains, and the problem of its was carried out under pressure equal to 1.5 MPa
utilisation has not yet been solved. and temperature 35–40EC with a DL membrane.
The goal of this study was to develop a The membrane was selected for laboratory-scale
method for neutralisation of a filtration concen- experiments based on former research results
trate by biological methods. An increase of appli- obtained by the Institute for Product Develop-
cation of biological methods to textile wastewater ment, Denmark. The membrane was manufac-
treatment was recently observed [6–19]. In par- tured by Desalination Systems, USA, and made
ticular, biodegradation of azo dyes, which are the of proprietary polysulphone. A molecular weight
most commonly used in dye houses, were the cut-off of about 180 g/mol was expected [20].
subject of investigation. The azo dyes containing The membrane was preconditioned for more than
one or many azo bonds (-N=N-) cannot be 1 h under the pressure. During the experiments, a
degraded under aerobic conditions in municipal concentrate was recycled to the thermostated tank
wastewater treatment plants [10]. However, under (1), while a filtrate was collected in the measuring
anaerobic conditions (negative redox potential), cylinder (7).
many bacterial consortia possess enzymes (azo- Experiments with post-filtration concentrate
reductases) that are able to disrupt the azo-bonds biodegradation were conducted in the set-up
and release aromatic amines [13]. Many of shown in Fig. 2. The key element of the set-up
aromatic amines are cancerogenic; therefore, they was bioreactor (3) with total volume and working
should be further degraded under aerobic condi- volume of 3 and 2 dm3, respectively, with a
tions. Based on the literature survey on biode- mechanical stirrer (4). The bioreactor was fed
gradation of the model [8,12–14,18] and real with wastewater from a tank (1) by a peristaltic
[6,15] textile wastewater, one may conclude that pump (2). The pump (5) delivered the reaction
the use of sequential anerobic/aerobic conditions mixture from the bioreactor to the wastewater
could allow mineralisation of these xenobiotic tank (6). Possible liquid overflow from the bio-
azo-compounds. reactor was transferred to the tank (7) by an
This is a precondition to applying the NF overflow tube. The bioreactor was adapted for
method for process water recovery under indus- aerobic processes by fitting it with a sparger with
trial conditions. A subject of this study was air pump (8). Experiments were conducted at
wastewater, which was obtained after laboratory ambient air temperatures (20–25EC).
dying (followed by washing and rinsing) of
knitted fabrics with reactive dyes. Real waste- 2.2. Tested material
waters coming from two textile plants where
knitted and woven fabrics were subjected to wet The tested material was synthetic domestic
processing were also the subject of this study. sewage, model and real wastewater from the
textile industry. The synthetic domestic sewage
contained the following ingredients dissolved in
2. Materials and methods 1 dm3 of tap water:
C Casein peptone 0.156 g
2.1. Experimental set-up C Dry broth 0.105 g
NF process of wastewater coming from dye C NH4Cl 0.020 g
houses was conducted at a constant flow rate 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 bioreactor was completed each time with an
appropriate mixture of textile wastewater and
The process of sludge adaptation was carried
domestic sewage.
out for 7 days under anoxic conditions in order to
adapt microorganisms to textile wastewater
degradation. Biodegradation under anoxic con- 2.4. Analytical methods
ditions with the use of model textile wastewater
The efficiency of NF and anoxic biodegra-
was started by adding a mixture of model textile
dation processes was estimated on the basis of:
wastewater (10%) and model domestic sewage
1. Spectral absorption coefficient (DFZ,
(90%) in the amount of 1 dm3 to the bioreactor
Durchsichtsfarbzahl in German), determined on
with adapted active sludge. The domestic sewage
the basis of absorbance measurements by the
was used as an external source of carbon in the
spectrophotometric method at three wavelengths
degradation processes. The percent of textile
(λ = 436, 525 and 620 nm), according to the DIN-
wastewater was increased by 10% every 3–
38404/1 standard [21] (in the case of biological
4 days. A similar process was carried out for real
processes after filtration on a filter paper and
textile wastewater that came from one of the
0.45 µm filter), using the formula
textile plants in Łódź, Poland, decreasing only the
amount of exchanged mixture of wastewater to 1000 ⋅ E (λ )
DFZ = (1/m)
0.8 dm3. d
The anoxic phase for each biodegradation
process lasted for 22.4 h every day. During this where E(λ) is the absorbance at a given wave-
time, the content of the bioreactor was mixed so length λ, and d is the measuring cuvette thickness
slowly that no aeration occurred through the (mm).
vortex at the impeller shaft (the frequency of 2. Chemical oxygen demand (COD) by the
impeller rotations was 110 min!1 for model dichromate method according to Polish Standard
wastewater and 80 min!1 for real wastewater). No. PN-74/C-04578, corresponding to German
Next, mixing was stopped and the process of Standard DIN EN 1899-1 and DIN 38409-H 41
sedimentation began. The phases of sedimen- [22].
tation and removal of supernatant lasted 40 min The following parameters were determined for
each. The amount of removed supernatant was the wastewater in the bioreactor:
ca. 1 dm3 for model wastewater and 0.8 dm3 for C Redox potential using SenTix ORP electrode
real wastewater. The resulting loss of liquid in the 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
Fig. 4. Permeate flux decrease for wastewater coming
98% reduction of the filtrate colour was achieved, from selected textile plants.
which confirms a nearly complete retention of
dye particles in the concentrate (Fig. 3). Only
NaCl and Na2CO3 salts were transferred freely to It was found that the composition of waste-
the filtrate. Some salt remained on the filter. water coming from different plants had a sig-
Further on, the model concentrate was subjected nificant effect on filtration rate (Fig. 4). Waste-
to biodegradation under anoxic conditions. water I taken from plant no. 1 from an averaging
During the second stage of the investigation, tank contained reactive and direct dyes, salts and
the wastewater coming from selected textile alkalis and certain amounts of auxiliary com-
plants was subjected to NF processes to recover ponents, including cationic ones. Wastewater II
process water. Fig. 3 shows a reduction degree of was taken from a channel at the moment of
colour, COD and conductivity of the analysed removal of a post-dyeing bath from the apparatus
wastewater. The reduction of colour and COD (reactive dyeing, black); hence, its composition
during NF exceeded 90%, irrespective of the could be considered approximately as the com-
analysed wastewater composition. However, dur- position of a post-dyeing bath. It follows from
ing the NF process, deterioration of the DFZ Fig. 4 that permeate flux of wastewater II was
parameter of the filtrate was observed. higher than in the case of averaged wastewater I.
Thus, when designing a wastewater treatment
 R. Żyłła et al. / Desalination 198 (2006) 316–325 321

installation with a NF stage, one should consider approximately by a constant value in this range of
separation of streams for the elimination of com- organic load. This indicates that besides bio-
pounds which can deteriorate the efficiency and chemical reduction of dyes, microorganisms
permeate flux. adsorb dye molecules. However, the active sludge
Wastewater from plant no. 2 contained mainly was saturated with the dyes, but in order to draw
suspension and direct dyes and relatively low salt explicit conclusions, further investigations are
concentrations. The permeate flux for this waste- necessary.
water was higher than in the case of wastewater An increase of dry matter content was
coming from plant no. 1. However, the permeate observed during the process, which follows from
flux decreased with time, reaching half of the an increase of the amount of inorganic salts, with
initial value after 240 min. a growth of textile wastewater percentage. In
parallel, the organic dry matter decreased two-
3.2. Biodegradation of model wastewater in fold, and this could explain a decrease of process
anoxic processes efficiency. This was most probably caused by too
short a time of active sludge adaptation to
The degree of colour reduction was estimated changed process conditions (an increased fraction
at three wavelengths: 436 nm, 525 nm and of textile wastewater). This could be also due to
620 nm (Fig. 5). The highest degree of colour the formation of toxic compounds that have an
reduction was observed at wavelength 525 nm. unfavourable effect on microflora in the bio-
With an increase of the percentage of textile reactor during biodegradation.
wastewater in the mixture, there is an increase of
differences in colour reduction measured at
wavelength 525 nm compared to the values 3.3. Anoxic biodegradation of wastewater from
obtained at wavelengths 436 and 620 nm. This textile plant no. 1
provides evidence of a different degree of biode- During a subsequent stage of investigation, a
gradation of each of the three dyes that are concentrate obtained from NF of wastewater
present in model textile wastewater. coming from plant no. 1 was subjected to anoxic
Apart from that, it was observed that with an biodegradation. Initially, wastewater I was sup-
increase of mass fraction of textile wastewater in plied to the bioreactor, while at the end of the
the mixture, a distinct drop in the relative colour process, when the percentage of textile waste-
reduction followed. A significant scatter of COD water in the mixture was 70% and above,
results for biodegraded wastewater that might be wastewater II was applied.
caused by temperature changes (the bioreactor Fig. 7 shows the degree of colour reduction
was not thermostated) was observed. Despite the depending on the percent of textile wastewater.
scatter of results of the COD measurement, it was With an increase of wastewater I concentration,
found that these data could be described approxi- the colour reduction decreased. The content of
mately by a straight line, depending on the dry organic matter also decreased; however, later
percentage of textile wastewater in the mixture (on the 30th day), it slightly increased (Table 2).
(Fig. 6). The slope of the COD curve for initial As in the case of model wastewater, a different
wastewater and of the curve representing COD of colour reduction degree was observed depending
biodegraded wastewater, depending on the per- on the wavelength at which absorbance measure-
centage of textile wastewater in the mixture, are ments were taken. The values of reduction degree
similar. This means that, irrespective of the obtained at wavelengths 525 nm and 620 nm
percentage of textile wastewater, COD is reduced 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 The degree of COD reduction was 50% on ave-
with an increase of industrial wastewater percen- rage. Initially, the COD reduction degree was
tage. Introducing wastewater II to the system (i.e., increasing (it was ca. 60%); next at the textile
the wastewater coming from dyeing processes), a wastewater fraction amounting to 50%, there was
significant increase of the colour reduction degree a decrease of the COD reduction degree (to about
was obtained. This can provide evidence of lower 40%). This value was kept for growing textile
toxicity of wastewater II. An increase of dry wastewater concentrations.
organic matter for the wastewater was observed.
 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 The filtrate coming from the NF of wastewater
observations of microorganisms in the bioreactor that was formed as a result of reactive dyeing of
were also carried out. While analysing the mix- knitted cotton fabric, carried out in laboratory
ture of wastewater that contained 30% textile conditions, was used as process water in repeated
wastewater, in the field of microscope view dyeing processes. The quality of dyeing was
single cysts of roundworms, small protozoans, assessed taking into account end-use properties of
slowly flowing ciliates and anoxic bacteria were the products, such as relative dyeing intensity in
observed. At 90% load of real textile wastewater, relation to process water (Table 3), resistance to
numerous flowing flagellates with single and washing, and wet and dry friction. This assess-
double flagella, single ciliates and numerous 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 Refereneces

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