Desalination 157 (2003) 8186

Comparison between nanofiltration and ozonation

of biologically treated textile wastewater for its reuse
in the industry
A. Bes-Pi, J.A. Mendoza-Roca*, L. Roig-Alcover, A. Iborra-Clar,
M.I. Iborra-Clar, M.I. Alcaina-Miranda
Department of Chemical and Nuclear Engineering, Universidad Politcnica of Valencia,
Camino de Vera s/n, 46071 Valencia, Spain
Tel. +34 (96) 387-96 33; Fax +34 (96) 387-7639; email: jamendoz@iqn.upv.es

Received 23 December 2002; accepted 30 December 2002

Abstract
This work is focused on the advanced treatment of the biologically treated wastewater of a textile plant. Nowadays
the factory effluent is treated by an activated sludge process carried out after the wastewater neutralization. The
wastewater treatment plant effluent is not still appropriate for its reuse because of the residual COD and conductivity.
Both nanofiltration experiments at different operating conditions and oxidation reactions with ozone and ozone/UV
irradiation were performed to evaluate the final water quality for its reuse.
Keywords: Nanofiltration; Ozonation; Textile wastewater; Reuse

1. Introduction
The environmental impact of the textile
industry is associated with its high water consumption as well as by the colour, variety and
amount of chemicals which are released in the
wastewater [1]. Conventional treatment methods
*Corresponding author.

for textile wastewater are mainly physicochemical or biological treatments. The quality of
the treated wastewater can be improved if
advanced processes are combined with them.
With adsorption, biorefractory compounds can
be removed. Membrane technologies (nanofiltration and reverse osmosis) are able to separate
both biorefractory organic compounds and

Presented at the European Conference on Desalination and the Environment: Fresh Water for All, Malta, 48 May 2003.
European Desalination Society, International Water Association.

0011-9164/03/$ See front matter 2003 Elsevier Science B.V. All rights reserved

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A. Bes-Pi et al. / Desalination 157 (2003) 8186

salinity. The main problem of theses techniques

is the reject stream management.
Several authors reported about the application
of membrane technologies to obtain water for
reuse from textile wastewater treated previously
with physico-chemical or biological treatment. It
has been proved that nanofiltration could be a
feasible technique for this [2,3]. On the contrary,
chemical oxidation does not produce any waste,
degradating organic compounds. The most commonly used oxidizers are ozone, Fentons reagent
(H2O2/Fe2+) and a combination of theses oxidizers
with UV irradiation.
Ozone is a powerful oxidant for water and
wastewater treatment. Once dissolved in water,
ozone reacts with a great number of organic compounds in two different ways: by direct oxidation
as molecular ozone or by indirect reaction through
formation of secondary oxidants like free radical
species in particular the hydroxyl radical [4]. Both
ozone and hydroxyl radicals are strong oxidants
and are capable of oxidising compounds such as
dyes.
In the bibliography a great number of references about textile wastewater ozonation before
biological treatment can be found [5,6]. The aim
of that is to accomplish an increase in wastewater
biodegradability.
Regarding the ozone application after the
biological treatment, Ciardelli et al. [7] concluded
that 30 g/m3 ozone doses were sufficient to have
good results in terms of colour removal for contact
times of about 60 min. This process was applied
to wastewaters coming from a filling and dyeing
plant used to dye fabrics, hanks, skeins, tops and
flocks of different fibres.
2. Objectives
The objectives of this work were the following:
Study of the combination of activated sludge
process with nanofiltration in order to reuse
water in a printing, dyeing and finishing textile
plant.

Selection of the nanofiltration membrane and

the operating conditions to achieve the best
permeate quality.
Study of the combination of activated sludge
with chemical oxidation using ozone and ozone/
UV radiation.
Comparison between the two advanced treatments mentioned above from the point of view
of the final water quality.
3. Material and methods
Firstly, wastewater from activated sludge process was prefiltered to remove suspension solids.
The next step consisted in analysing the COD,
conductivity and pH of the prefiltered samples.
Nanofiltration experiments were performed in
a laboratory plant with a membrane system of four
plane membranes, each one with 30 cm2 of active
surface. The variation of the permeate flux and
COD and conductivity removal were studied as a
function of the transmembrane pressure and the
feed flow rate. The membranes tested were Desal
DK-5 from Osmonics and NF-90 from Dow
Chemical. Fig. 1 shows a scheme of the nanofiltration plant.

14

13

12

8
5

10

11

Fig. 1. Scheme of NF laboratory plant. 1, feed tank; 2,

thermometer; 3, stirring; 4, heat exchanger; 5, regulation
valve; 6, filtration system; 7, feed pump; 8, security valve;
99, manometer; 10, NF module; 11, permeate stream;
12, regulation valve; 13, speed control; 14, rejection stream.

A. Bes-Pi et al. / Desalination 157 (2003) 8186

For each membrane, experiments with three

different transmembrane pressures (0.10, 0.15 and
0.20 MPa), and three different feed flow rates (0.2,
0.3 and 0.4 m3/h) at 25C were performed. The
cross flow velocities related to these flow rates
are 1.11, 1.66 and 2.22 m/s respectively. The series
of nanofiltration experiments was carried out using
an experimental design obtained from Statgraphics
Plus 4.0. The duration of each experiment was
long enough to reach the steady state conditions (approximately 8 h). The per-meate fluxes JP (L/m2h)
and salt retentions RSALT (%) were determined. In
addition, at the end of each experiment, COD was
analysed.
The ozonation experiments were carried out
in a laboratory plant consisting of three ozone
generators with a maximum ozone production of
4 g/h each one and a contact reactor of 25 L. The
ozone generators were fed with pure oxygen and
the operating temperature was 25C. Redoxpotential was measured to control the oxidation
reactions. In each experiment 45 L of biologically
treated wastewater were ozonated. Furthermore,
the plant was equipped with a monochromatic
lamp (254 nm) IS-2700. Fig. 2 shows a photograph of the plant, indicating its main elements.

83
Contact reactor
Redox potential
measurement

Ozone generators

UV lamp

Fig. 2. Photograph of the laboratory oxidation plant.

Table 1
Characterisation of biologically treated wastewater from a
textile plant

pH
Conductivity, mS/cm
COD, mg/L

7.88.2
2.83.3
200400

treated textile wastewater. It can be observed that

conductivity and COD are still too high to reuse
the water.

4. Results and discussion

4.1. Nanofiltraton experiments

Table 1 shows the variation ranges of the

measured parameters values of the biologically

In Table 2 salt rejections (RSALT) and permeate

fluxes (JP) at the steady state conditions for the

Table 2
Salt rejections and permeate fluxes at the steady state conditions in the different experiments

Operating conditions

NF-90

DK-5

Feed pressure, bar

Feed flow rate, L/h

RSALT, %

JP, L/m2h

RSALT, %

JP, L/m2h

10
10
10
15
15
15
20
20
20

200
300
400
200
300
400
200
300
400

70.30
76.36
63.15
78.29
80.00
81.40
82.92
81.56
86.75

3.33
3.50
2.31
6.10
5.82
5.55
8.38
8.94
9.19

38.18
43.80
36.64
47.53
47.45
51.40
50.91
56.62
57.06

18.50
19.20
18.70
28.00
27.20
30.30
40.40
45.00
47.00

A. Bes-Pi et al. / Desalination 157 (2003) 8186

tested membranes can be observed.

Figs. 3 and 4 show the standardized Pareto
charts for permeate flux of the membranes tested.
These Pareto charts display a frequency histogram
where the length of each bar is proportional to
the estimated effect and interactions of the feed
flow rate (B) and feed pressure (A) on permeate
flux. The cross line indicates the significance of
each parameter.
For NF-90 and DK-5, it can be seen that only
feed pressure influenced significantly on permeate
flux. No influence of feed flow rate (in the studied
range) on permeate flux was found.
Fig. 5 illustrates the obtained results with the
membranes tested. The graphs only show the

60

NF-90

50

JP (L/m 2h)

84

DK-5

40
30
20
10
0
5

10

15

20

25

P (bar)

Fig. 5. Influence of feed pressure on permeate flux in

NF-90 and DK-5.

B:Q

evolution of permeate flux with feed pressure P,

since only this variable was significant according
to the Pareto charts. The permeate flux values
correspond with the average values calculated for
the tested feed flow rates.
It can be observed that DK-5 yielded permeate
flux rates substantially higher than NF-90. At
20 bar, the average permeate flux was 44 L/(m2h).
Similarly, the obtained salt rejection values
have been studied using the same types of graphs.
Figs. 6 and 7 show the standardized Pareto charts
for retention salts of the membranes tested. In both
cases salts retentions did no depend on the feed
flow rate.
In Fig. 8, it is shown that for both membranes
the variation of salt retentions with the feed
pressure was very similar, reaching higher values
with NF-90 (approximately 15% higher than with
DK-5).
Related to permeate COD, the measured values
were lower than 50 mg/L in all experiments for
both membranes.

AB

4.2. Oxidation experiments

BB

After previous experiments with ozone, the

operating time was fixed at 3.5 h and it was decided
to work with two ozone generators (maximum
ozone production of 8 g/h) due to the estimated
O3/COD ratio necessary for the oxidation. In
Table 3, the results of the chemical oxidation with

A:P
AB
BB
B:Q
AA
0

10

15

20

25

30

Standardized effect
Fig. 3. Standardized Pareto chart for permeate flux of
NF-90.

A:P
AA

10

15

20

25

30

Standardized effect
Fig. 4. Standardized Pareto chart for permeate flux of
DK-5.

A. Bes-Pi et al. / Desalination 157 (2003) 8186

A:P

A:P

AB

AB

BB

B:Q

B:Q

BB

AA

AA
0

10

15

20

25

30

Standardized effect

NF-90

DK-5

RSALT (%)

80
60
40
20
0
5

10

15

Standardized effect

Fig. 6. Standardized Pareto chart for salts retention of

NF-90.

100

85

20

25

P (bar)

Fig. 8. Influence of feed pressure on salts retention in

NF-90 and DK-5.

Fig. 7. Standardized Pareto chart for salts retention of

DK-5.

ozone and ozone/UV are shown. It can be seen

the significant influence of the UV irradiation on
the COD elimination. In fact, after 30 min the
COD was already lower than 50 mg/L. However,
only with ozone, the COD was 286 mg/L after
the same time. In this experiment it was observed
that COD decreased substantially after 90 min.
In addition, the table shows the measured
redox potential values, which indicate the evolution of the oxidation reactions. It can be observed
that final measured value was very similar in the
two experiments (320 mV).
Table 4 compares the final effluent quality of
the two treatments applied. It can be observed that
better results were achieved with nanofiltration.
However, the management of the reject stream of
the membrane process must be studied.

Table 3
Experiments results in the chemical oxidation of the biologically treated textile wastewater
Time, min
15
30
45
60
90
120
150
210

Experiment with O3

Experiment with O3/UV

COD, mg/L

Redox potential, mV

COD, mg/L

Redox potential, mV

326
286
276
184
63
84
98
70

209
244
264
266
276
302
307
319

<50

<50
<50
<50
<50
<50

209

225
239
297
320
325

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A. Bes-Pi et al. / Desalination 157 (2003) 8186

Table 4
Comparison between the treated effluents with nanofiltration and oxidation

Process

COD,
mg/L

Conductivity,
mS/cm

Nanofiltration (NF-90)
P = 20 bar; Q = 200400 L/h

<50

0.390.51

Ozone + UV after 30 min

<50

3.04

5. Conclusions

It can be concluded that:

Nanofiltration of the biologically treated
wastewater of a printing, dyeing and finishing
textile plant produced permeates with very low
COD (<50 mg/L).
Salt rejection was higher for NF-90 than for
DK-5. Though the permeate flux rates of NF90 were lower than for the other, this was the
selected membrane since the salt rejections
were substantially higher than for the other
membrane. NF-90 permeates could be reused
as rinse water in the textile plant (COD
<100 mg/L and conductivity <1.0 mS/cm).
Salt rejections and permeate flux rates were
dependent basically on feed pressure. However, for the studied feed flow rate range, no
influence was found on the studied variables.
A high COD removal was achieved with
chemical oxidation with ozone and with ozone/
UV. The advantage of this technique in comparison with nanofiltration is that there is no
reject stream generation. Nevertheless, the
oxidation does not reduce the water conductivity. Thus, the reuse of the treated water
is not possible.

The combination of UV irradiation with ozone

led to a significant reduction in the operating
time to reach the same COD removal efficiency.
Acknowledgment
We thank Colortex 1967 S.L. for its support
in the investigation project.
References
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