DESALINATION

ELSEVIER

Desalination 178 (2005) 333-341

www.elsevier.com/locate/desal

Treatment of textile plant effluent by nanofiltration and/or

reverse osmosis for water reuse
C. Suksaroj, M. H6ran, C. All6gre, F. Persin*
UMR Cirad 016, Laboratoire G~nie des procOdOs d'~laboration de bioproduits, Universit~ Montpellier II, CC05,
2 Place E. Bataillon, 34980 Montpellier cedex 5, France
TeL +33 (467) 14 3324," Fax +33 (467) 14 4787; email: fpersin@univ-montp2.fr
Received 28 September 2004; accepted 22 November 2004

Abstract

This work concerns the treatment of textile plant effluent after conventional biological processing. The objective
was a feasibility study of the combination of physicochemical treatment with nanofiltration (NF) and/or reverse
osmosis (RO) for water reuse. In fact, dead-end filtration by mierofiltration (MF), ultrafiltration (UF), NF and RO tests
showed that a primary physicochemical treatment (coagulation/flocculation) was necessary to limit membrane fouling.
Two coagulants (organic polyeleetrolyte and/or ferric chloride) were tested and compared by carrying out jar-tests
using different chemical concentrations at pH 6.8. Then, NF and/or RO experiments were performed and investigated
at different operating pressures. Results showed that NF allowed the higher flow rate, 90 L.h-l.m -2 at 18.5 bar
transmembrane pressure. Moreover, the permeate quality obtained in this condition was similar to the RO.
Conductivity, absorbance at 490 nm and the dissolved organic carbon value of the NF permeates were lower than 390
/xS.cm- i, 0 and 2 mg.L- ~of C, respectively. The percent production rate increased with the transmembrane pressure.
NF performed at 18.5 bar transmembrane pressure allowed a higher yield (22.6%) than RO (18.3%).
Keywords: Textile industry; Dyeing; Water reuse; Nanofiltration; Reverse osmosis

1. Introduction

The dyeing and finishing process in the textile

industry uses a large amount o f water in the
presence o f chemical substances such as dyes,
*Corresponding author.

salts and surfactants. These industries generate a

very variable wastewater quality that depends on
process step, dye and textile material (cotton,
synthetic fabric, silk, etc.). Usually a biological
treatment is used to treat wastewater [1], but
many investigations intended to increase membrane processes development [ultrafiltration (UF),

Presented at the conference on Membranes in Drinking and Industrial Water Production, L 'Aquila, Italy, 15-17 November
2004. Organized by the European Desalination Society.
0011-9164/05/$- See front matter 2005 Elsevier B.V. All rights reserved
doi: 10.1016/j.desal.2004.11.043

334

c. Suksaroj et al. / Desalination 178 (2005) 333-341

nanofiltration (NF) and reverse osmosis (RO)]

[2]. Whereas biological processes generate large
amounts of sludge and are not able to remove
water salinity, membrane processes allow treated
water reuse [3-5] even if the product concentration is to be considered. However, fouling by
colour molecules on the membrane surface was
observed. This depends on dye sample, membrane and chemical auxiliary from the dyeing/
finishing process [4]. As mass transport limitation
hinders membrane development, it is necessary to
investigate the reduction of membrane fouling.
A physicochemical precipitation was effective
to reduce dye concentration, chemical oxygen
demand (COD) and turbidity [6-8] and allowed
also the reduction of fouling. Therefore, the combination ofphysicochemical treatment and membranes is interesting to produce reusable water in
the textile industry and to decrease membrane
fouling.
In this work, the feasibility of a physicochemical treatment and NF/RO combination was
studied. The first step consisted of wastewater
sample characterization (from the cotton and
polyester dyeing industry). Then, dead-end filtration by MF, UF, NF and RO permitted initial
membrane fouling measurement. Next, physicochemical treatments by means of jar-tests for
dissolved organic carbon (DOC) and colour
reduction were conducted in order to obtain the
suitable dosage in coagulation/flocculation. The
last step was the separation step by NF or RO at
laboratory scale to improve treated wastewater
quality and lower operating costs.

2. Materials and methods

2.1. Wastewater

The effluents were samples from a textile

industry, Brun d'Arre (France), at the output of
the existing treatment plant which was composed
of screening, acidification, an activated sludge
process and clarifier.

2.2. Wastewater characterization

The analysed parameters were COD, DOC,

pH, conductivity, absorbance, chloride, nitrate,
sulphate and mineral carbon. The absorbance was
determined by UV-visible absorption using a
Hitachi (U-2001) spectrophotometer (1 cm cell
width) after sampling filtration with a 2 #m filter.
Chloride, sulphate and nitrate were measured by
ionic chromatography, whereas carbonate and bicarbonate were obtained by titration.
2.3. Jar-tests

The physicochemical experiments were carried out on a Flocculator SW1 jar test. Chemical
coagulant was added to 500 ml of solution under
rapid mixing conditions (150 rpm) during 2 rain.
Then the solution was mixed under slow energetic conditions to favour particle flocculation
(35 rpm for 30 min). Supernatant was analysed
after a 30-min settling. Two different flocculants
were used. The first one was a cation organic
polymer (PE, from Ciba), widely used in the Brun
d'Arre wastewater treatment plant. This flocculant is relatively expensive compared to the
second one, ferric chloride.

2.4. Membranes

The characteristics of the membranes are

given in Table 1.
2. 5. Experimental units

Three different pilots were used. The first one

was a NF spiral-wound module (Fig. 1); the
second one, a RO spiral-wound module; the last
one flat-sheet modules equipped with a MF, UF,
NF or RO membrane.
NF and RO pilots were provided with a feed
tank (40 L) and carried out at controlled temperature. A volumetric pump ensured cross flow
circulation, and transmembrane pressure (Ptm)

335

C. Suksaroj et al. / Desalination 178 (2005) 333-341

Table 1
Characteristics of membranes

Membrane
reference

Molecule
cut-off (Da)

Material

Area (m2)

Permeability
(L.h-~.m-2.bar-~)

Osmonics Desal 5 DK

150-300

Polyamide/polysulfone

Filmtec Cycron

Non-porous
membrane

Polyamide

0.0044 (flat)
2.5 (spiral-wound)
0.0044 (flat)
1.2 (spiral-wound)

4.4
4.8
1.3
1.1

(20C)
(25C)
(20C)
(25C)

Flow rneter
Permeate

Recirculation,~i
Nanofiltration/
reverse osmosis
in spiral-wound module

Feed tank 40 L
Pressure gage

Pressme gage
Retentate : Concentrate
__@____~
Flow meter

Pressure control valve

Control t e m p e r a t u r ~
by cooling water ] Thermometer

Fig. 1. Pilot used in spiral-wound module system.

was monitoring by two pressure gauges. The RO

osmosis pilot was a ship desalinator (sea recovery
system controller).
The flat-sheet pilot was used in dead-end filtration mode. Ultra, micro, nano and RO filtration
were performed with the same membrane and
then with the spiral-wound pilot. The pressure
was achieved and ensured by nitrogen gas injection, and permeate flux was measured by continuous weighing on an electronic balance.
3. Results and discussion

3.1. Characteristics o f wastewater

Table 2 shows the influent and effluent

characteristics of the industrial plant. The influent

is a wastewater mixture from dye baths and
flushing waters. For each value a range is given,
confirming the large variability of the wastewater,
variability related to great dyeing diversity. It can
be noticed that conductivity and COD values
measured on effluent are lower than 28003300 #S/cm and 200-400 mgL -1 due to the dilution of wash water [9].
Biological treatment allowed a good COD and
DOC removal efficiency, but mineral parameters
seem not to be effective with the biological process. Absorbance reduction was also observed,
but this effluent was still coloured and did not
permit direct discharge or reuse.

336

C. Suksaroj et al. / Desalination 178 (2005) 333-341

Table 2
Wastewater characterization
Parameters

Before
biological
treatment

After
biological
treatment

pH
Conductivity at 25C,

9.5-9.7
1400-2100

7.4-8.3
1400-1800

SS, mg.L -~
Turbidity, NTU
Absorbance at 490 nm

4-50
3-42
0.1-0.53

15-26
1-9
0.1-0.16

DOC, mg.L < of C

COD, mg.L -1 of O2

48-50
285-460

9.5-9.6
10-65

Carbonate, retool.L-~
Hydrogenocarbonate,
mmol.L
Chloride, mg.L ~
Nitrate, mg.L -t
Sulphate, mg.L -1

0.9-3.9
3.3-4.2

ND
4.6-5.6

#S.cm J

removal from 40-50% after 0.05 #m filtration.

The low initial absorbance and colour were due to
the biological process, which degraded these
compounds. However, membrane fouling was
still observed and no mineral compound reduction was observed.

3.2.2. Reverse osmosis and nanofiltration

NF and RO membranes were tested on the
effluent with and without pretreatment by coagu2.8

initial
2.4

ca
o

172-382
2.5-14.4
180-250

0.05pm

1.2

<:

0.8
0.4

ND, not detected.

0
200

3.2. Dead-end filtration study

3.2.1. Microfiltration and ultrafiltration
Figs. 2 and 3 show the relationship between
absorbance removal and filtration membrane pore
size. Experiments were performed through three
successive membranes on influent and effluent:
first a 1.2 #m (GF/C) filtration was done, then the
permeate was filtrated through a 0.1 #m cellulose
nitrate and a 0.05/zm cellulose nitrate filter. For
the influent, colour removal efficiency was more
than 90% whereas COD reduction was about 50%
after 0.05 #m filtration. Direct filtration by the
0.05/zm membrane only also showed the same
high percentage of colour removal, but the fouling sensitivity and colour fixing on the membrane
occurred both in series and direct filtration. The
reduction of mineral compounds was not observed. It seems unsuitable to use a direct treatment membrane process on influents. On the
other hand, effluent filtration showed colour

....

"" 1.6

172-402
ND
344-535

400

600

800

Wave length (nm)

Fig. 2. lnfluent (before biological treatment) filtration

effect on absorbance removal.
2.8
;nitial

2.4

1.2pm

=
t~
J~
0

1.6

....

0.1pm

......

O,05#m

.~ 1.2
<

0.4
0
200

400

600

800

Wave length (nm)

Fig. 3. Effluent (after biological treatment) filtration

effect on absorbance removal.

337

C. Suksaroj et al. / Desalination 178 (2005) 333-341

lation/flocculation (described in Section 3.3). As

expected, the NF flux under low transmembrane
1.2-

pressure showed good permeability balances with

good selectivity from RO. For a homogeneous
comparison, the ratio of permeate value vs. water
flux against elapsed time is given in Fig. 4.

With pretreatments (Desal 5 DK)

10.

NF runs were performed for the Desal 5 DK

--D--Without pretreatment (Desal 5 DK)

membrane at 12.5 bar and for the Cycron membrane (RO) at t 5 bar. The results indicate that the
permeate flux of pre-treated effluent was higher
than without pre-treatment. The specific fluxes
from NF and RO were comparable. However, the

o.8.
o.e.

0.4"

NF permeate flux (17.9 L.h-~.m -~ at 12.5 bar) was

0.2,
0,0

1000

2000
3000
Time (s)

4000

5000

Fig. 4. Normalised permeate flux vs. time for nanofiltration with the Desal 5 DK (12.5 bar) and for the Cycron
membrane (15 bar).
0,4
0,35

0.3

approximately more than twice that of RO

(9.8 L.h-~.m-~ at 15 bar) for pretreated effluent.
The DOC and absorbance values of the permeate
solution were achieved during the experiment,
and similar values were obtained in both final
treated water - - either NF or RO. The
t0

~ A b s at 490 nm
~:',
~
~!I!~ A b s at 250.......nm

0.25

@
O

Ob

0.2

2~ o.~5

<

0
0

0.1

0.5

10

0.1

PE (mg/L)

10

at variablepHs.
10

ImAbs at 490 nm,

~~

Fig. 7. Influence ofpolyelectrolyte concentration on DOC

0.35

PE (mg/L)

Fig. 5. Influence of polyelectrolyte concentration on

absorbance at variable pHs.
0.45
0.4

0.5

~ DAbsit250nr

~6
6 ~

0.25
"~ 0 , 2

o.15

0.1

O
O
C3

2 --L- o,,

~:i:

0.05-

0
0

28

56

70

84

112

Ferric chloride coagulant (mg/L of Fe)

Fig. 6. Influence of ferric chloride concentrationon

absorbanceat pH 6.9

28

56

70

84

112

Ferric chloride coagulant (mg/L of Fe)

Fig. 8, Influenceof ferricchlorideconcentrationon DOC

at pH 6.8.

338

C. Suksaroj et al. / Desalination 178 (2005) 333-341

Table 3
Supernatant characteristics according to PE and Fe mixture concentration
Initial
PE, mg.L-'
Fe, mg.L-t
pH
7.4-8.3
Conductivity at 25C, #S.cm -~ 1400-1800
Turbidity, NTU
1-9
Absorbanceat490nm*
0.1-0.16
absorbance at 250 nm*
DOC*, mg.L-~ of C
9.5-9.6

1
28
7.4
1472
13.8
0.067
0.452
8.4

2
28
7.4
1463
16.4
0.065
0.477
8.8

5
28
7.4
1455
6.9
0.024
0.238
8.5

~i
~
~
~
~
~i~
0~2~
8~

~
~
~
N
~
~
~! ~ ~6)
~
~
0~16
~
~:!~8~
~2
~.(8

1
84
6.8
1496
11.7
0.050
0.301
6.4

2
84
6.8
1486
1.9
0.031
0.230
5.6

*After filtration (2 #m).

DOC value was approximately 2 mg.L-1 of C and

absorbance value at 490 nm was 0.003. It can be
concluded that both types of membrane processes
were effectiveness on organic pollution and
colour removal, and pretreatment with coagulation was effective in the reduction of membrane
fouling.
3.3. Determination o f optimum chemical coagulation conditions

The main parameters that induce fouling were

caused by coloured compounds and were evaluated through absorbance and DOC measurement.
Two values of wavelength were chosen and
reported: the first one is in the visible range,
490 nm; the other one is in UV range, 250 nm
(this value is close to the wavelength used for
organic carbon measurement in water). Two different types of coagutant/flocculants were tested:
(1) ferric chloride used at corrected pH (pH = 6.9,
which is the optimum pH zone for this coagulant
[10]); (2) PE is used like a flocculant. Figs. 5-8
show the absorbance at 490 nm and 250 nm and
the DOC obtained after jar-tests according to
polyelectrolyte and ferric chloride concentrations.
The addition of PE at pH close to 7.4 not only
allowed a decreasing of DOC from 9.1 to

6.9 mg.L -1 C but also permitted absorbance at

490 nm removal (57%). The PE seemed to have
more influence on decolourization. As PE is
expensive, no more concentrated solutions were
tested.
A DOC decreasing (47%) was obtained for Fe
addition at pH 6.9 under the highest dosage test
(112 mg.L-1 Fe), but the absorbance decrease at
490 nm was poor (17%). In fact, DOC values
were not related foreseeable by absorbance values
due to the mixing of dyes and the additive compound in wastewater.
Kim [8] obtained slightly different results
where Fe addition was more efficient on colour
removal. In fact, their effluents that contained
only dye compounds and additive compounds
also limited colour removal.
Since Fe was not able to remove colour, but
was still economical, experiments were carried
out on Fe and PE mixtures in order to achieve
DOC and absorbance reduction (Table 3).
Coagulant injections slightly increased the
conductivity value (1% when PE increased from
1 to 5 mg.L -1 and 2% when Fe increased from
28 to 84 mg.L-~). At constant Fe concentration,
the addition of PE allowed better turbidity
removal whereas the addition of Fe allowed DOC
removal, if Fe concentration were sufficient. In

C. Suksaroj et al. /Desalination 178 (2005) 333-34I

the case of 84 mg.L -I Fe and 2 mg.L -z PE, DOC

value and turbidity value decreased to 38% and
58%, respectively. Even if the ratio of 56 mg.L-:
Fe and 5 rag.L-: PE provided better turbidity
reduction (64%) and absorbance removal (92%),
this performance must be balanced with low DOC
reduction (27%) and high costs.
All these experiments showed that a mixture
of 84 mg.L -~ Fe and 2 mg.L -~ PE presented
good conditioning upstream before membrane
treatment

3.4. Crossflow filtration step

Filtrations were performed in the spiral-wound
module, continuously being fed with pretreated
effluent. The relationship between permeate flux
and transmembrane pressure of pure water and
pretreated effluent is illustrated Fig. 9.
As expected, the permeability of NF
was higher than the permeability of RO
(4.77 L.h-:.m-2.bar i c o m p a r e d with
0.95 L.h-l.m-2.bar-I). In each process the permeate flux of pure water and pretreated effluent
was slightly different. Therefore, the combination
of pretreatment and spiral-wound filtration was
an interesting process for membrane filtration
improvement. However, the experiment must be
carried out during a long time in order to observe
possible membrane fouling. In the case of RO,

339

it was noted that the permeate flux behaviour

between pure water and pretreated effluent was
different than in NF. Nevertheless, the RO
membrane had a high removal efficiency, and
most of the compounds contained in the
pretreated effluent were eliminated. The filtration
results, given in Figs. 10 and 11, show the relationship between conductivity and the retention
factor vs. transmembrane pressure for NF and
RO, respectively.
The retention factor (RF) was calculated
according to Eq. (1) where CR and Cp are the
retentate concentration (mol.L-1) and the permeate concentration (tool.L-1).
C

R F : 1 ____2_P

cR

(1)

0.8
0

0.6

._

"~ 0.4

n- 0.2
O
0

10

20

30

T r a n s m e m b r a n e pressure (bar)

Fig. 10 Retention factor vs, transmembrane pressure for

the Cycron and DS 5 DK membrane with C1 (A, A);
NO B (O, O ) ; SOl- (0, <7); HCOS; (x, *); DOG (11, Fq).

120
- - {> - -Permeate flux (DS5-DK)
~
Water flux (DS5-DK)

100
~,~" 80

'

- " '0" - - Permeate flux (cycren)

---C----Water flux (cycron)

kl-

O..

700

600,

-~"

400,

"~
m
tO

300,

500,

2= 6O

2O

800.
'~=

'"

10
15
20
25
30
T r a n s m e m b r a n e pressure (bar)

35

4O

Fig. 9. Permeate flux vs. transmembrane pressure

(T=25C).

Cycron

100 1

-o

DS5-DK
"

200 -

0
0

+
"~0"'-"----O

10

i
t

15

|
i

|
i

2O

25

|
]

30

Transmembrane pressure (bar)

Fig. 11. Conductivity vs. transmembrane pressure for the
Cycron and Desal 5 DK membranes.

C. Suksaroj et al. / Desalination 178 (2005) 333-341

340

The results show that the permeate conductivity

value was much lower than the effluent conductivity value. Colour removal was completed
both for NF and RO, but in the case of RO, the
permeate conductivity value was almost constant
and very low (8.5 #S.cm -I at 13.5 bar). Even if
the conductivity decreased with increasing
transmembrane pressure in NF, this value
(390 #S.cm -1 at 13.5 bar) was higher than RO.
The chloride value was 1.9 rag.L-I compared with
109 mg.L~ in NF at 13.5 bar. According to permeate recycling in the dyeing process, a good
physicochemicalcharacteristic was required. This
condition governs the transmembrane pressure
until meeting the mineralization value requirement. The hydrogenocarbonatereduction rate was
significant for the RO process but decreased
slightly for NF.
The rejection rates of the other species
(chloride, nitrate, sulphate and DOC) were higher
than 90% for RO while the HCO~ and DOC
retention values varied from 60% to 90% due to
the transmembrane pressure tested range for NF.
However, the DOC rejection rate in NF can reach
the RO rejection rate by imposing transmembrane
pressure up to 18.5 bar. In this condition, NF
allowed a high flow rate whereas the permeate
quality was sufficient to reuse treated water in the
dyeing process.

30.0

25.0,

~ 20.0.
~J
c 15.0.
o

Cycron

10.0,

5.0.

0.0

10

15

20

25

Transmembrane pressure (bar)

Fig. 12. Production rate vs. transmembrane pressure.

30

3.5. Production rate

Fig. 12 shows the percent production from NF
and RO with pretreated effluent. The production
rate increased with the transmembrane pressure.
NF at 18.5 bar transmembrane pressure allowed
a higher permeate yield (22.6%) than RO
(18.3%).
The percent production (I1) was calculated
according to Eq. (2) where Q~ and Qp were the
feed in flow rate (L.h-t) and the permeate flow
rate (L.h-1).

Y : QP 100

Qo

(2)

4. Conclusions

Although the textile plant effluent was treated

by a biological treatment process, the quality was
not sufficient to reuse it on site. The membrane
process (RO and NF) was successfully used to
obtain a permeate quality which allowed water
reuse in the dyeing process, but this process
required a physicochemical pretreatment. The
using of a mixed ferric chloride-cationic polymer
solution could achieve a very low DOC and
absorbance values which reduced the fouling
problem. Under these conditions, the best results
were obtained with 84 mg.L -~ Fe and 2 mg.L -j
PE. Moreover, the higher flow rate, 90 L h- 1 m 2 at
18.5 bar, was obtained with NF; the percent
production rate was 22.6% for NF and 18.3% for
RO. At this pressure, the permeate quality of NF
and RO was sufficient even if the minerar values
of the permeate from RO are lower than NF.
However, the permeate quality (low DOC concentration, absorbance and weak mineralization)
allowed successful recycling in the dyeing
process project.
This work needs to be studied further. Another
sampling test should be done due to the variation
of effluent quality. Moreover, retentate treatment

C. Suksaroj et al. / Desalination 178 (2005) 333-341

should be considered. In fact, since the filtration

step was only a mass transport, the chemical
oxidation process should be studied as a retentate
treatment from the membrane process.

Acknowledgement
We would like to thank Brun d'Arre in
Herault, France, for wastewater sampling and
some of the chemicals.

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