DESALINATION

ELSEVIER Desalination 149 (2002) 137-I 43

www.elsevier.com/locate/desal

Experimental campaigns on textile wastewater for reuse

by means of different membrane processes

M. Marcucci*, G. Ciardelli, A. Matteucci, L. Ranieri, M. Russo

Tecnotessile s.~l., via de1 Gelso 13, I-59100 Prato, Italy
Tel. +39 (0574) 634040, Fax +39 (0574) 634045; email: [email protected]

Received 7 February; accepted 4 April 2002

Abstract

The experimental results of the pilot scale application of different membrane technologies, supported by
clariflocculation and ozonization, for textile wastewater reuse are described. The investigation has been carried out
by treating two different textile effluents: a secondary effluent coming from a biological activated plant and a
wastewater coming directly from several textile departments. In the first case the pilot plant used sand filtration and
microflitration (MF) as pre-treatments for nanofiltration (NF). The MF and NF membranes tested were of the spiral
wound type. The NF permeate can be reused in all production steps, including dyeing with light coloration. In the
second case, the chemical-physical pre-treatment and the advanced treatment of water have been experimented for
different kind of wastewater (from the carbonising process, from dyeing and fulling). The most interesting experimental
results were obtained from the treatment of wastewater from the carbonising process. A scheme process in which
ultrafiltration (UF) with flat membranes operating under vacuum is placed downstream an ozonization treatment has
been evaluated. The UF permeate quality was suitable to the reuse in production processes.

Keywords: Wastewater treatment; Ultrafiltration; Nanofiltration; Ozonization; Colour removal

1. Introduction dustries are also faced with increasing costs for

water supply and wastewater depuration and with
I. I. Textile wastewater characteristics
more stringent controls on industrial effluent
In Europe, increasing water consumption for pollution, in accordance to the European Union
industrial and domestic uses is leading to potential legislation in force [I].
water shortage in many countries. European in- Textile factories are among the largest industrial
consumers of water: typically 0.245 m3 of water
*Corresponding author. are needed to produce 1 kg of finished product

Presented at the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France,
July 7-12, 2002.

001 I-9 164/02/$- See front matter 0 2002 Elsevier Science B.V. All rights reserved
HI: SOOll-9164(02)00745-2
138 M. Marcucci et al. /Desalination 149 (2002) 137-143

[2]. Therefore, textile industry, which is wide- effluents after a suitable pre-treatment, such as
spread throughout Europe, is a good candidate ultrafiltration or microfiltration [5]. Micro-
for development of intensive water recycling and filtration (MF) allows a simple clarification of
minimization of related polluting emissions. the effluent, removing suspended particles (micro-
Textile effluents contain many chemical organism, inorganic particles, colloids). Ultra-
substances coming from desizing, dyeing, printing filtration (UF) is effective for removal of particles
and finishing processes. Moreover textile waste- and molecules of dimensions higher than 10 nm,
water quality is variable with time and may bacteria, viruses and proteins. MF and UF are
include many types of dyes, detergents, sulphide generally proposed as RO pretreatment [6].
compounds, solvents, heavy metals and inorganic The choice of the most suitable membrane
salts, their amounts depending on the kind of process on a technical-economic point of view
process that generates the effluent [3]. for the textile wastewater treatment and reuse is
Textile wastewater is usually treated in an often validated by carrying out experimental
activated sludge plant to allow wastewater dis- campaigns on a pilot scale.
charge within law requirements but not in order In order to maintain the membrane efficiency
to produce a final effluent suitable for reuse in and consequently decrease the costs related to the
the textile processes. In fact, a considerable amount membrane module replacement, it is extremely
of recalcitrant contaminants still remain in bio- important to prevent fouling and module damage
logically treated textile effluents. So, in order to by the use of effective pre-treatments.
have water that can be recycled in production This paper concerns with the application of
cycles (especially dyeing processes), water needs two different membrane technologies in a pilot-
further treatments (called tertiary or advanced scale plant as a tertiary treatment of two different
treatments) [4]. textile effluents:
The techniques which have been experimented l In the first case study, for a secondary effluent
and applied to the textile effluents treatment in coming from a biological activated plant, a MF
order to produce water to be reused in production, step was placed upstream a NF process;
are numerous, such as ozonation, Fenton’s reagent l In the second case study, for a wastewater
oxidation, electrolysis, flotation. The authors coming directly from carbonization depart-
performed several experimental campaigns and, ments, several treatments, such as clarification,
according to their knowledge, membrane techno- sand filtration and ozonization, were placed
logies turned out to be the most interesting ones. as pre-treatment for a UF treatment.
The aim of the study was to verify the econo-
1.2. Membrane processesfor treatment and reuse
mical feasibility of the implementation of the
of textile e&Gents
membrane processes for the treatment and reuse
The interest in membrane processes applied of textile effluents into productive cycles.
to textile wastewater reuse is increasing thanks
to the recent technological innovations that render
them reliable and economically feasible in alter- 2. Materials and methods
native to other systems. 2.1. Textile efluents tested
Several approaches have been proposed to
implement membrane technology to the treatment 2. I. 1. First case study
of textile wastewater from different production The wastewater coming from dyeing depart-
streams. Reverse osmosis (RO) and nanofiltration ments is treated by means of a biological activated
(NF) were studied as treatment of secondary textile sludge plant. Secondary effluents are discharged
 M. Marcucci et al. /Desalination 149 (2002) 137-143 139

to surface water in the respect of law limits. The The total filtrating area of the module was 47 m2.
water requirement of the industry is about Characteristic molecular weight cut-off was
1,500 m”/d and it is satisfied with well water. Due 70,000 Da.
to problems of water shortage, it was decided to
test new advanced wastewater treatments on the
2.3. Pilot plant
pilot scale in order to reuse textile effluents in
manufacturing processes. 2.3. I. First case study
The pilot plant consisted of three stages: sand
2.1.2. Secondary case study filtration, MF and NE
The treatment of wastewater coming from a A part of the effluent from the biological
carbonization textile industry has been evaluated. activated sludge plant was sent to the sand filter
At the present, wastewater coming from pro- (2 bar relative pressure). Filtered water was stored
ductive activities is directly discharged to a in a tank and then sent to the MF module, that
municipal depuration plant. operated at a relative pressure of about 3.5 bar.
The elevated consumption of water used in the The average MF permeate flow was 400 I/h. The
carbonization processes (about 2,000 m3/d) and MF effluent was stored in a second tank and sent
the increase in perspective of the supplying and to the NF module which operated at 6.5-7.0 bar
depuration costs have given a remarkable impulse relative pressure. The NF concentrate was 35-
to start an experimentation on the pilot scale. It 40% of the inlet flow.
has been finalised to work out a specific and The MF membranes were automatically washed
innovative treatment in order to recycle a large with the nanofiltration permeate for 30 s every
amount of water (at least 1,000 m/d). 40 min. The membranes were chemically washed
as soon as the hydraulic performance worsened.
Chemicals used were:
2.2. Membranes
l Alkaline detergent (l-2%) for removal organic
2.2. I. First case study material (fouling);
l Acid detergent (l-2%) for removal inorganic
Microfiltration: a module with two Celgard
particles (scaling).
NADIR PI 50F spiral-wound membranes placed
in series was used for MF. Each membrane was In a preliminary phase a different treatment
101.6 mm in diameter and 1,016 mm in length. was evaluated. It consisted in sand filtration and
The total filtrating area of the module was 11 m2. ozonization, for the treatment of biological effluent
The molecular weight cut-off (MWCO) was in different operative conditions (ozone dosage,
150 kDa. contact times between water and ozone). The
Nanofiltration: an Osmonics Desal DL4040F quality of ozonizated water was not excellent so
membrane of the spiral-wound type was used for membrane filtration technologies were tested.
NF step. The membrane was 98.6 mm in diameter
and 1,016 mm in length. The filtrating area was 2.3.2. Second case study
8.4 m” and the MWCO was 200 Da.
A part of the wastewater (900 I/h) was treated
in a pilot plant composed by:
2.2.2. Second case study
l A chemical-physical pretreatment, consisting
Ultrafiltration: a Filterpar FLAMEC filter in coagulation, flocculation (at controlled pH
FF2C. 1 CS with flat polyvinyldenefluoride (PVDF) condition), settling by means of a lamellar
membranes, operating under vacuum, was used. settler and sand filtration;
140 M. Marcucci et al. /Desalination 149 (2002) 137-143

l An ozonization treatment; 3. Results and discussion

l A finishing sand filtration;
3. I. Membranes hydraulic performance
l An ultrafiltration.
3. I. 1. First case study
The high values of turbidity, total suspended
The working cycle of the both membrane
solids and COD of the wastewater induced to
steps, MF and NF, operating under pressure, was
adopt a complex pretreatment for the UF process
monitored for 530 h measuring the permeate flows
(clariflocculation + sand filtration + ozonization).
before and after the cleaning of the membranes
During the trials the definition of the coagulant
with chemical detergents. The characteristic
and the relative optimal dosage were determined.
variations with time of MF and NF permeate flow-
The filtered effluent was sent to an oxidation
rate and operating pressures are shown in Fig. 1.
process in order to remove the organic pollutants
The dotted lines indicate the interruption of the
and the colour by ozone. It has been necessary to
operating cycle in correspondence of the chemical
introduce an ultrafiltration treatment after ozon-
washing of the membranes (every -100 h). After
ization, because of the presence of a residual
the chemical washing, the initial permeate flux is
turbidity in the ozonized water, imputable to the
re-established. The MF and NF operating pressures
presence of oxidised compounds.
remain nearly constant with the increasing of the
membrane fouling.
2.4. Efluents analysis
Chemical oxygen demand (COD), pH, con- --t MF + NF

ductivity, total hardness, turbidity, total suspended

solids (SST), colour, chlorides and surfactants
were determined in both experimental campaigns
to evaluate the efficiency of the proposed treat-
ments .

100 1~

2.5. Dyeing tests 0 50 100 150 200 250 300

Time (h)
2.5.1. First case study
Fig. 1. Characteristic MF and NF permeate flow-rate and
Several dyeing tests, using the ozonizated operating pressures for the first case study.
water (first approach) and NF permeate, were
carried out on the pilot scale by means of a labo-
ratory machine that dyes 10 g of hank. The dyeing
tests were made for dark, medium and light 3.1.2. Second case study
colours on 100% wool.
The UF membrane process must assure an
optimal permeate quality maintaining good per-
2.5.2. Second case study
formance in terms of permeate flux and operating
The UF permeate was used in dyeing experi- pressures. The time dependence of the UF
ments for dark, medium and light colours on the operating pressure is shown in Fig. 2. The positive
laboratory scale. The fibres used for the tests were values correspond to the back-washing phase.
wool and cotton. The same tests were carried out It can be asserted from the periodic observ-
on an industrial scale using a 10 kg dyeing machine. ations of the UF working cycle that:
 M. Marcucci et al. /Desalination 149 (2002) 137-143 141

0. 6 Table 1
Average values of chemical-physical analyses at the various
sampling points, in the first case study

Parameters Sampling point

1 2 3 4
PH 6.7 6.2 6.4 6.1
COD, mg/l O2 66 62 42 12
TSS, mg/l 21 9 c.5 <5
Time (min)
Turbidity, NTU 4.1 2.4 0.9 0.5
Fig. 2. Characteristic operating pressure of the FLAMEC Conductivity, us/cm 1150 - - 582
FF2C. 1 CS UF module in the second case study. Total hardness, “F 9 9 8 2
Mg2+, mg/l 6 5 4 2
Ca”, mg/l 29 26 26 5
Sulphates, mg/l 260 - - 11
The absolute value of the UF operating and Chlorides, mg/l 100 100 88 78
back-washing pressure gradually increased BIAS”, mg/l 1.1 - 1.1 0.4
and stabilised according with the fouling of MBASb, mg/l 0.9 - 0.6 0.3
the membrane; Colouf removal, % Ref. 0 13 94
The back-washing started every 30 min even “Non-ionic surfactants as bismuth-iodine active substances
if the absolute value of the operating pressure (IRSA method 5 160-IS0 7875/2 1st ed., 1984).
was almost constant as evidence of the good hAnionic surfactants as methilene blue active substances
purification efficiency of the ultrafiltration’s (IRSA method .5150-IS0 7875/l 1st ed., 1984).
pre-treatment; ‘Integral of the absorbance curve in the whole visible range
The membranes were never chemically washed (400-800 nm).
“Absorbance at 420 nm.
since there was not a significant increase of
the operating pressure;
The FLAMEC FF2C. 1 CS module guarantees (100%) and turbidity (78%). COD is removed
a constant UF permeate flux. partially by sand filtration and MF (30%) and
quite completely after NF. Colour, one of the most
3.2. Contaminants removal important parameters in checking textile waste-
water quality for reuse, is removed almost com-
3.2. I. First case study
pletely by NF (81%). The histogram in Fig. 3
To test the performance of the pilot plant con- represents the contributions of the various treatment
figuration, sampling of the effluents was performed stages to the total removal of some polluting
at the following four points: parameters. The percentages are referred to the
. Sand filtration inlet; sand filter input.
l Sand filtration outlet;
l Microfiltration permeate outlet; 3.2.2. Second case study
l Nanofiltration permeate outlet.
Sampling of the effluent was performed to test
Table 1 reports the average results of the the purification efficiency of the plant configur-
chemical-physical analyses of the effluents ation. The following sampling points were chosen:
showing the efficiency of the plant system in Untreated wastewater from carbonization process;
producing a NF permeate of good quality. l Ozonization inlet;
The use of sand filtration and of MF is funda- l UF inlet;
mental in the reduction of suspended solids l UF permeate.
142 M. Marcucci et al. /Desalination 149 (2002) 137-143

n sand filter OMF q NF the removal of turbidity (49%), which is of

strategic importance for the success of the puri-
fication process;
70
!gT High removal of colour (93%), especially by
Ti, 60
g 50 means of the ozonization step (7 1%);
E
c
40
30
High removal of turbidity (27%) and total
20 suspended solids (30%) by means of UF mem-
10
0
brane process;
A satisfactory removal of COD (66%);
Residual concentration of non-ionic surfact-
ants of 19 mg/l due to high initial concen-
Fig. 3. Contributions of: a) sand filter; b) microfiltration; tration.
c) nanotiltration; to the removal of some parameters, The The removal of mean parameters with the last
percentages are referred to the filter input.
plant configuration (with UF as the advanced
treatment) are shown in Fig. 4.
Table 2 reports the analytical data concerning
n Pretreatment OOzanization n UF
the pilot plant configuration with UF as final
membrane process.
According with the analytical data, the follow-
ing issues were made evident:
l Good performance of the first stage of the
treatment (clariflocculation) concerning with

Table 2
Average values of some parameters at the various sampling
points
Fig. 4. Contributions of the three stages of depuration
Parameters Sampling point treatment: a) chiariflocculation + sand filtration; b) ozoni-
zation; c) ultrafiltration; to the removal of some parameters.
1 2 3 4
The percentages are referred to the pretreatment input.
PH 6.9 8.9 7.8 7.3
COD, mgil O2 1017 660 512 352
TSS, mgil 173 121 56 15 3.3. Dyeing experiment results
Turbidity, NTU 123 63 34 0.8
Conductivity, pslcm 2702 2938 2956 2778 3.3.1. First case study
Total hardness, “F - 25
Dyeing experiments with 100% ozonizated
BIAS”, mgil 30.5 33.1 20.0 19.2
0.9
water and 100% NF permeate were compared
MBASb, mg/l 2.2 1.9 1.3
Colourd removal 0.092 0.027 0.009 0.007 with the same with the softened freshwater. In
order to evaluate in a scientific way the results of
“Non-ionic surfactants as bismuth-iodine active substances the laboratory-scale dyeing trials, tests on colour
(IRSA method 5160-IS0 7875/2 1st ed., 1984).
measurement were realised by means of a Gretag
“Anionic surfactants as methilene blue active substances
(IRSA method 5 150-IS0 7875/l 1th ed., 1984).
Macbeth Coloreye 2 180 UV spectrophotometer.
‘Integral of the absorbance curve in the whole visible range They gave different results:
(400-800 nm). l 100% ozonizated water can be used only in
“Absorbance at 420 nm. some dyeing steps processes (washing, dyeing
 M. Marcucci et al. /Desalination 149 (2002) 137-143 143

with dark colour) or mixed with freshwater; mentation of the membrane processes on the
l 100% NF permeate is reusable in all dyeing industrial scale. With same wastewater flow of
cycle, even for light colours. 1,500 m3/d, the unit costs for the two proposed
treatments are:
3.3.2. Second case study l 0.34 c /m3 in the first case study
l 0.40 c /m3 in the second case study,
Both the dyeing tests, with 50% UF permeate
and 50% well water, on laboratory and industrial which would be a very competitive costs if com-
scale gave successful results. A comparison among pared to present costs for water supply and depura-
dyeing with freshwater and with a mixed of tion within law limits, guaranteeing a payback of
recycled and well water did not show any differ- the investment cost of about 3 years.
ences.

4. Conclusions Acknowledgements

On the basis of the pilot scale trials results The authors are grateful to Fildrop (Firenze,
membrane processes show to be promising methods Italy), Filterpar (Bergamo, Italy), Ingrid Ciabatti
for the purification aimed at reuse of textile waste- and Guido Vemaglione for technical support.
water.
In the two case studies examined in this work
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