Desalination 167 (2004) 387392

Nanofiltration of biologically treated textile effluents

using ozone as a pre-treatment
A. Bes-Pi*, A. Iborra-Clar, J.A. Mendoza-Roca, 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) 387-9633; Fax +34 (96) 387-7639; email:mbespia@iqn.upv.es
Received 29 January 2004; accepted 12 February 2004

Abstract
Water scarcity in Mediterranean areas such as Comunidad Valenciana (Spain) makes water reuse necessary in high
water-consuming industries. Previous studies by our research group showed that nanofiltration (NF) membrane
permeates could be reused in some processes of finishing, dyeing and printing in the textile industry. In this work,
biologically treated textile wastewaters were subjected to ozonation as a pre-treatment stage to NF. The aim was to
reduce organic matter in order to prevent membranes from fouling and to oxidize organic wastewater compounds that
could damage the membrane material. NF experiments were carried out in a laboratory plant equipped with a pressure
vessel containing one spiral-wound membrane element (2.51 m2 of active surface). With ozonation, wastewater COD
was reduced up to three different levels (160, 135 and 82 mg/L). NF experiments with wastewaters of different organic
matter concentrations were carried out studying the effect of increasing the feed concentration periodically. Conductivity retentions higher than 65% were achieved, with no significant flux decay observed during the experiments.
Keywords: Wastewater; Textile industry; Membrane; Ozone; Reuse

1. Introduction
Recycling of wastewater in industries with
high water consumption is especially important in
*Corresponding author.

areas with water shortages such as Comunidad

Valenciana (Spain). Several authors have proposed integrated treatment systems in order to
recycle wastewater in textile factories. All these
systems include a conventional treatment (mainly

Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries: Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European
Desalination Society and Office National de lEau Potable, Marrakech, Morocco, 30 May2 June, 2004.
0011-9164/04/$ See front matter 2004 Elsevier B.V. All rights reserved

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A. Bes-Pi / Desalination 167 (2004) 387392

biological) and membrane technologies [ultrafiltration (UF), nanofiltration (NF) or reverse

osmosis (RO)], which produce permeate streams
of sufficient quality to be reused [1,2].
In 2003 Krull et al. proposed a method based
on a two-stage biological anaerobicaerobic
process followed by a membrane bioreactor and
finally a chemical stage to remove the remaining
colouring of the process water with ozone [3].
Other investigators developed integrated process
schemes where that membranes are the first
treatment stage. In this way, Ambruster et al. in
2001 described a textile wastewater treatment
plant consisting of the following steps: sieving,
conventional filtration, UF and NF. NF permeate
was recycled into the production process. Concentrated streams from the UF and NF stages
were treated in a fixed-bed bioreactor so that they
could be discharged into the municipal wastewater treatment plant [4]. Lee et al. proposed a
similar scheme in 2001. However, these authors
omitted the UF stage previous to NF and included
advanced oxidation processes. These processes
were applied both to NF permeate streams before
their recycling and to concentrate streams from
NF before and after the biological treatment. The
aim was to increase biodegradability and final
quality, respectively [5].
In summary, it can be said that there are two
possibilities of combining biological treatments
with membrane technologies to obtain water to be
reused: either direct wastewater NF (with the
appropriate pre-treatment) and biological treatment of the NF concentrate or biological treatment of raw wastewater and NF or RO
afterwards.
In this work, NF of biologically treated textile
wastewater was studied, including chemical oxidation with ozone before NF in order to reduce
the organic matter in the membrane feeding
stream. This is an advantage not only for NF
membranes (fouling is reduced) but also for the
concentrate stream treatment (evaporation stage).

1.1. Oxidation with ozone

Ozone is a powerful oxidizing agent that may
react with organic compounds either directly or
via radicals formed in a reaction chain as OHradicals. Ozone can be used in wastewater field to
reduce COD, colour, toxicity and pathogens and
to improve wastewater biodegradability the and
coagulationflocculation processes [6,7].
Ledakowicz et al. [8] reported that azo-dyes
used in the textile industry react rapidly with
ozone by direct attack forming decoloured
products. Ciardelli et al. [9] confirmed significant
colour removal (9599%) after applying ozone to
wastewaters from a dyeing and finishing factory
previously treated in an active sludge plant with
filtrated through sand. Regarding COD removal,
ozone treatment with 40 gO3/m3 at contact times
of 15 min and 30 min drove COD reductions
from 160 to 53 and 203 to 123 mg/L, respectively. The most important parameter to evaluate
process feasibility is the quotient between the
generated ozone and the eliminated COD
(kg O3/kg COD). This parameter ranged between
1 and 4 according to the literature [10]. Values
higher than 3 could make the oxidation process
for COD elimination economically unfeasible.
1.2. Objectives
The main objective of this work was the study
of a biologically treated textile wastewater with
ozone as a nanofiltration pre-treatment. First, the
oxidation times and ozone doses had to be determined. Then, the effect of remaining organic
matter in the NF experiments had to be studied in
terms of permeate COD, salt rejection and flux.
2. Materials and methods
This work was carried out in two steps. The
first step consisted of the ozonation of the biologically treated textile wastewater to reduce the

A. Bes-Pi / Desalination 167 (2004) 387392

organic matter. The main reasons were to prevent

membranes from fouling and to oxidize organic
compounds that could affect membrane behaviour. The next step was NF on pre-treated
wastewater.
2.1. Ozonation experiments
The ozonation experiments were carried out in
a laboratory plant equipped with three ozone
generators (4 g/h each one) fed with pure oxygen
and a contact reactor of 25 L. The oxidized
wastewater volume was 50 L in each experiment.
The experiments were controlled continuously by
the oxidationreduction potential (ORP)
measurement.

389

2.2. Nanofiltration experiments

Membrane experiments were performed in a
laboratory plant equipped with a pressure vessel
that contained one spiral-wound membrane
element. The operating conditions of the experiments were a transmembrane pressure of 12 bar,
300 L/h of feed flow rate and a temperature of
25C. NF experiments lasted was 6 days. Fig. 1 is
a photograph of the laboratory plant.
Permeate fluxes JP (L/m2h) and salt retention
RSALT (%) were determined periodically. Permeate
and reject streams were recycled into the feed
tank. However, 5 L of permeate were withdrawn
from the system every 24 h in order to increase
the feed concentration up to a volume concentration factor (VCF) of 2.5. The COD of these
samples were analyzed.
The membrane tested was DK2040 (2.51 m2
of active area) from Osmonics according to previous results obtained by the research group [2].
3. Results
3.1. Wastewater characterization
Characterization of the biologically treated
textile wastewater is shown in Table 1. As can be
seen, both COD and conductivity are still high to
reuse the water in the textile factory.
3.2. Ozonation experiments
Fig. 2 shows the ozonation results in terms of
wastewater COD and ORP variations with the
Table 1
Textile wastewater characterization after activated sludge
process
Parameter

Fig. 1. Photograph of the laboratory plant.

Conductivity, mS/cm
COD, mg/L
pH

2.59
205
8.36

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A. Bes-Pi / Desalination 167 (2004) 387392

Fig. 2. COD and ORP evolution during ozonation of the

biologically treated wastewater.

Fig. 3. Evolution of permeate fluxes over the time for the

experiments with different feeding streams.

ozonation time. It can be seen that COD

decreases rapidly at the beginning of the experiment (from 205 to 88 mg/L in 60 min). Thus, if
maximal ozone production from generators is
considered (12 g/h), the O3/COD ratio was 2.1.
After 1 h, COD remained approximately constant
until t = 450 min. Then, wastewater COD went
down to 65 mg/L. From this time on, COD hardly
decreased and the experiment was stopped after
650 min of ozonation. The O3/COD ratio for
reducing COD from 88 to 65 mg/L was 67.5.
Thus, it makes no sense, from an economical
point of view, to oxidize with ozone down to
65 mg/L COD.
For ORP it was observed that this parameter
rose sharply at the beginning of the experiment.
Then its increase gradually became lower with
time since oxidation reactions hardly occurred.
According to these results, it was decided to
carry out further ozonation experiments in order
to obtain wastewater samples with three different
COD levels (after 30, 45 and 60 min of oxidation
time). Wastewater COD values after these experiments were 160, 135 and 82 mg/L, respectively.
Longer ozonation times were rejected as explained above.
It has to be highlighted that all ozonation
experiments were performed with the same
wastewater. Oxidation of samples taken on other
days, even from the same factory, would produce,
to some extent, different results in terms of the

O3/COD ratio. The main reason is the application

of different dyes in the factory.
3.3. NF experiments
Fig. 3 shows the evolution of the permeate
flux over the time for the experiments carried out
with three different feeding streams (F1, F2 and
F3) containing 160 mg/L, 135 mg/L and 82 mg/L
of COD, respectively, at the beginning of the NF
experiments.
It was observed that flux decay was higher for
the experiment with F1 due to higher COD concentration. At the end of the experiments high
permeate fluxes were achieved with samples F2
and F3 (37 L/m2h and 39 L/m2h, respectively).
Fig. 4 details the variation of salts retention
with the time. In all cases salts rejection remained
practically constant with a slight tendency to
improve because of the increasing feeding stream
concentration. The values ranged between 64%
and 69%.
Table 2 shows the values of permeate fluxes,
salt retention and permeate COD after 24 h and
144 h (VCF = 1 and VCF = 2.5). For a VCF of 1,
the highest salt retention was produced with F1,
which corresponds with the highest COD. For a
VCF of 2.5, the same tendency was observed.
This is due to the influence of organic matter
content in conductivity rejection and vice versa
[11]. High COD values resulted in an increase of

A. Bes-Pi / Desalination 167 (2004) 387392

Fig. 4. Evolution of salt retention over time for the

experiments with different feeding streams.
Table 2
Comparison between flux, retention salt and COD in the
permeate at different VCF values
Feeding VCF = 1.0

1
2
3

since too high ozone doses were required. However, prior to an economical feasibility study, it
should be proved that these results are similar for
different wastewater samples that include other
dyes and detergents.
NF of the sample with the lowest organic
matter concentration (F3) presented the lowest
flux decline during the process. Consequently, a
combination of ozonation and NF results in an
increase of membrane life.
Salt retention was very similar for the three
feeding streams, reaching slightly higher values
for samples with higher organic matter concentrations. Solely for the F3, permeate COD
remained lower than 50 mg/L even with the
maximum VCF (2.5).

VCF = 2.5

Flux, Rsalt,
L/m2h %

COD,
mg/L

Flux, Rsalt, COD,

L/m2h %
mg/L

37.6
40.1
42.5

67
54
<50

32.5
36.8
39.2

66.9
64.8
64.0

391

68.8 122
67.0 98
64.6 <50

the layer thickness surrounding the membrane,

leading to a decrease in the available area for the
salt passage. As expected, for a given feeding
stream, the higher the VCF, the higher the
permeate COD values achieved.
On the other hand, permeates obtained with F3
were in all cases lower than 50 mg/L. Therefore,
ozonated wastewater samples until a COD of
82 mg/L generate permeates with sufficient
quality to be reused for either VCF.
4. Conclusions
A COD removal efficiency of 43% was
accomplished with low ozone doses at 60 min
using three ozone generators of 4 gO3/h, each one
for a biologically treated textile wastewater. It
was not worth continuing with the COD removal

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