DESALINATION

ELSEVIER Desalination 157 (2003) 73-80

www.elsevier.com/locate/desal

Combination of physico-chemical treatment and nanofiltration

to reuse wastewater of a printing, dyeing and finishing textile
industry

A. Bes-Pifi*, J.A. Mendoza-Roca, M.I. Alcaina-Miranda, A. Iborra-Clar,

M.I. Iborra-Clar
Department of Chemical and Nuclear Engineering, Universidad Politdcnica of Valencia,
Camino de Vera s/n, 46071 Valencia, Spain
Tel. + 34 (96) 3879633; Fax + 34 (96) 3877639; email: mbespia@iqn.upv.es

Received 23 December 2002; accepted 30 December 2002

Abstract

The main goal of this work was to study the feasibility of the combination of physico-chemical treatment with
nanofiltration to reuse wastewater of a printing, dyeing and finishing textile industry. For the physico-chemical
treatment two coagulants (one containing Al 3+and another containing Fe2+)were compared by carrying out jar-tests
using different chemical concentrations and pH values. After that, nanofiltration experiments with physico-chemically
treated wastewater were performed at different operating pressures and cross-flow velocities. The results showed
that the COD and conductivity of the nanofiltration permeates were lower than 100 mg/L and 1000 gS/cm respectively.

Keywords: Phisico-chemical treatment; Nanofiltration; Wastewater reuse

1. I n t r o d u c t i o n socks, stockings and panties proved that the

combination of physico-chemical treatment and
Due to high water consumption in the textile
membrane technologies could produce water for
industry it is essential to study its reuse. Previous
reuse in the factory [1]. In this case, an attempt is
experiments of the research group with waste-
made to apply these technologies to the effluent
water o f a textile plmat that mainly manufactures
of another textile plant, optimizing the operating
conditions of the membrane process.
*Corresponding author.
Presented at the European Conference on Desalination and the Environment: Fresh Water for All, Malta, 4-8 May 2003.
European Desalination Socie~, International Water Association.

0011-9164/03/$ See front matter © 2003 Elsevier Science B.V. All rights reserved
PII: S0011-9164(03)00385-0
74 A. Bes-Pid et al. / Desalination 157 (2003) 73-80
Many processes have been studied to treat
textile wastewaters. Biological treatment by
activated sludge offers high efficiencies in COD
removal but it does not eliminate completely the
colour fi'om the water [2]. Chelnicat oxidation by
ozone, or a combination o f UV-radiation and
ozone and H~O2, are of great interest but their costs
are very high to treat raw textile wastewater. Thus,
these techniques should be applied in combination
with conventional treatments [3,4].
Jar-tests are a valuable tool in wastewater
treatment to evaluate tile efficiency of the physico-
chemical treatment [5]. The optimum operating
conditions (pH, chemical concentrations) are
determined by means o f these experiments.
According to the double layer theory, electrical
repulsion forces prevent from colloids aggre-
gation. Ill order to achieve an effective agglo-
meration, the COlnpression of the thickness of the
electrical double layer or a charge reduction of
the particles have to be carried out. This implies
the zeta potential reduction [6]. In this way the
colloids can be settled.
Additional treatments like membrane tech-
niques could be necessary according to the envi-
ronmental laws for tile disposal of treated water
or for its reuse in a textile plant.
The possible approaches for the membrane
purification treatment are nanofiltration or reverse
osmosis, since ultrafiltration membranes can
hardly remove COD and conductivity, having only
a slight effect on colour [7,8]. Nanofiltration does
not reach the retentions of reverse osmosis, but
the permeate quality is good enough for its reuse
in rinse processes (COD <100 mg/L and conduc-
tivity <1000 gS/cm).
In this work, the combination of the physico-
chemical treatment with nanofiltration to reuse
wastewater of a printing, dyeing and finishing
textile industry is proposed.
2. Objectives
The objectives of this work were tile following:
• Evaluation of the efficiency of two coagulants
in the physico-chemical treatment for waste-
water of a printing, dyeing and finishing textile
plant.
• Study of the water quality after treating the
wastewater with a combination of physico-
chemical treatment and nanofiltration mem-
branes.
• Selection of the membrane according to the
salts and COD retention and permeate flow
rate.
• Optimization of the best operating conditions
for nanofiltration process (feed pressure and
cross flow velocity).
3. Material and methods
This work was carried out in three steps. The
first step consisted in the characterization o f the
wastewater samples. The next step was a physico-
chemical treatment by means of jar-tests to reduce
COD. Once the best efficiencies were obtained,
the clarified water was treated with nanofiltration
membranes in a laboratory plant to improve the
quality of the physico-chemically treated waste-
water.
3.1. Wastewater characterization
The parameters analysed were COD, BODs,
pH, and conductivity. COD was determined with
Spectroquant Nova 60 from Merck and BOD 5
with the Oxitop system from WTW.
3.2. Jar-teals
Physico-chemical experiments were carried
out ill a multiple stirrer Jar-Test apparatus from
Selecta. The chemicals used in the jar-tests were
tile commercial products DK-FER 505-1 from
Acideka S.A. and UPAX-33 from Kemira S.A.
The general procedure consisted in introducing
900 mL of the sample in the jars, the coagulant
was added and rapidly mixed (180 rpm) during
3 rain. After that, the paddles were withdrawn so
 A. Bes-Pi6 et al. / Desalination 157 (2003) 73-80 75

that the particles could settle. The influence of Table 1

coagulants concentration and pH values were Tested NF membranes
studied. The coagulant concentrations are referred
to Fe 2+ and AI20 3 for DK-FER 505-1 and UPAX- Membrane NaC1 MgSO 4 Permeability,
retention, retention, L/m2h bar*
33, respectively. The pH of the samples was % %
changed by addition of HCl 0.1 N and NaOH 0.1
Dow NF-90 85-95 >97 0.481
and 0.5 N.
Osmonics Desal - - 98 3.863
pH values were selected in the alkaline range, DL-5
since in this medium the coagulants drive to the Osmonics Desal - - 96 3.562
formation of positively charged metal hidroxy DK-5
complexes that specifically adsorb onto colloids. *Experimental values
In all tests COD, turbidity, pH and conductivity
of the clarified water and the sludge volume after
are 1.11, 1.66 and 2.22 m/s respectively. The
30 rain sedimentation (V3o) were measured.
series of experiments were carried out using an
experimental design obtained from Statgraphics
3.3. Experhnents with membranes
Plus 4.0.
Experiments were carried out using a labora- The operating time of the plant was established
tory nanofiltration (NF) plant. The configuration according to the steady state conditions. It was about
of the plant can be observed in Fig. 1. NF module 8 I1 in all cases. The permeate fluxes Jl, (L/m2h)
is plane and its effective membrane area is and salt retentions RmL,v (%) were determined. In
0.012 m 2. The tested NF membranes are described addition, at the end of each experiment, COD was
in Table 1. analysed.
For each membrane, experiments with three
different transmembrane pressures (0.10, 0.15 and
4. Results
0.20 MPa), and three different feed flow rates (0.2,
0.3 and 0.4 m3/h) at 25°C were performed. The Table 2 shows the average values o f the
cross flow velocities related to these flow rates measured parameters of the textile wastewater.
These values are typical for textile effluents.
14 Conductivity and COD are quite important and
2 3
they have to be reduced to produce water with
enough quality to be reused.
Figs. 2 and 3 show the COD obtained after
13 jar-tests on varying the D K - F E R 505-1 and
UPAX-33 concentrations. In Fig. 2 it can be
[ 8 12
7 Table 2
@ Wastewater characterization
11 Parameter Feedwater
Fig. 1. Scheme of NF laboratory plant. 1, feed tank; 2, T, °C 20
thermometer; 3, stirring; 4, heat exchanger; 5, regulation pH 12.0
valve; 6, filtration system; 7, feed pump; 8, security valve; Conductivity, mS/cm 4.53
9-9', manometer; 10, NF module; 11, penneate stream; BODs, mg/L 490
12, regulation valve; 13, speed control; 14, rejection stream. COD, mg/L 1630
76 A. Bes-Pid et al. / Desalination 157 (2003) 73-80

1600 ..............................................................................................................................................
1600 ................................................................................................................

1200 1200
d~ :::
: I"" !1
800 E 800
rm
O © , :
o
400 t) 400
:!:<:

0 0 ............. ~--- --~--- --7---

500 600 700 8 00 200 300 400 500

DK-FER 505-1 coagulant (mg/L) UPAX-33 coagulant (mg/L)

Fig. 2. Influence of DK-FER 505-1 concentration on COD Fig. 3. Influence of UPAX-33 concentration on COD of
of treated water. treated water.

observed that DK-FER 505-1 concentrations of a COD removal of 70.5% at pH 12 (the raw waste-
500 mg/L and 600 mg/L produced only a slight water pH).
COD reduction. This occurred because of the in- In Fig. 5 it is shown that the best yield was
sufficient reduction in the zeta potential of the waste- reached at pH 11.0 (COD removal o f 66.0%). The
water. The maximum COD removal yield (72.5%) other tested pH did not i m p r o v e the C O D
was reached with a concentration of 700 mg/L. efficiency.
Higher coagulant concentrations did not improve Thus, experiments showed that DK-FER 505-1
the efficiency. In Fig. 3, for UPAX-33 the selected coagulant provided the best results for the physico-
coagulant concentration was 300 mg/L. For this chemical treatment of this textile wastewater. The
value the COD of the clarified water was 680 mg/L optimum operating conditions were: pH = 12.0 and
(i.e. 58.0% removal). Cve2+ = 700 mg/L. In Table 3 the characteri-zation
Fig. 4 and Fig. 5 show the COD obtained after of the clarified water after the test at these
jar-test for different wastewater pH values. In conditions can be observed. It is important to
Fig. 4 it can be observed that the COD removal emphasize that a total colour removal was
slightly increased with wastewater pH, reaching accomplished.

1000 ......................................................................................................................................................................... 1000 .......................................................................................................................................................................

800 800
d 3
600 600
v E
db E)
O 400 0 400
O 0
20O 200

0 0
9 10 11 12 10.0 10.5 11,0 11.4
pH pH

Fig. 4. Influenceofwastewater pH on COD &treated water Fig. 5. Influenceofwastewater pH on COD &treated water
using 700 mg/L of DK-FER 505-1. using 300 mg/L of UPAX-33.
 ,4. Bes-Pid et al. / Desalination 157 (2003) 73-80 77

Table 3
Clarified water characterization (Jar-test conditions: C~2+
= 700 rag/L; pH = 12)

pH 6.14
Conductivity, mS cm-' 3.80 AB
Turbidity, NTU 4.7
V3o, mL/L 260 BB
COD, mg/L 448
AA

Nanofiltration experiments were made using 0 2 4 6 8 0

wastewater treated with DK-FER 505-1 as feed
Standardized effect
water.
in Table 4 salts rejections (RS~Lr)and permeate Fig. 6. Standardized Pareto chart for permeate flux of
fluxes (@) at the steady state conditions for the NF-90.
tested membranes can be observed.
Figs. 6-8 show the standardized Pareto charts i . . . . i . . . . i . . . . i . . . . i . . . . i

for permeate flux of the membranes tested. These

Pareto cimrts display a frequency histogram where
the length of each bar is proportional to the B:Q
estimated effect and interactions of the feed flow
BB
rate (B) and feed pressure (A) on permeate flux.
The cross line indicates the significance.of each AA
parameter.
For NF-90 it can be observed that feed pressure AB
and feed flow rate were significant variables. Feed i , , . , i , . . , i . . . , i , , , . J . . . . i

pressure variations produced an important 0 1 2 3 4 5

increase on permeate flux, while the influence of Standardized effect
the feed flow rate was substantially lower. Fig. 7. Standardized Pareto chart for permeate flux of
However, it can be seen that only feed pressure DK-5.

Table 4
Salt rejections and permeate fluxes at the steady state conditions in the different experiments

Operating conditions NF-90 DL-5 DK-5

Feed pressure, Feed flow rate, RsAz,7; Jp, Rs::,'r, J:,, RS'ALT~ Jl',
bar L/h % L/m2h % L/m2h % k/m2h
10 200 83.0 2.8 28.2 25.6 42.8 2 1.6
10 300 77.0 2.5 34.7 25.7 35.0 18.4
l0 400 72.3 2.0 30.3 21.8 37.0 16.9
l5 200 85.2 5.3 33.1 40.1 43.3 29.2
15 300 78.6 5.5 38.0 42.7 42.5 28.1
15 400 83.8 4.8 36.1 37.7 39.7 26.3
20 200 87.8 8.7 35.14 5 1.3 55.0 45.2
20 300 86.2 7.6 48.39 67.8 60.9 55.8
20 400 85,2 7.5 40.27 52.0 44.8 34.5
78 A. Bes-Pi~ et aL / Desalination 157 (2003) 73-80

A:P 118-10
1( m6-8
BB 114-6
¢-q
D 2-4
AB
20
B:Q
B
AA
0 ~ar)
0 2 4 6 8 400
Q (L/h)
Standardized effect
Fig. 8. Standardized Pareto chart for permeate flux of Fig. 9. Influence of feed pressure and feed flow rate on
DL-5. permeate flux in NF-90.

influenced significantly on permeate flux for 80.

• DL-5 x DK-5
DL-5 and DK-5.
In order to illustrate the obtained results, a r-
60,
c,l
response surface graph was plotted if both feed E
40
pressure (P) and feed flow rate (Q) were signifi- J
v
n
cant variables (Fig. 9). If only the feed pressure --3
20
was significant, a graph showing the evolution of
this variable was performed (Fig. 10). 0
Fig. 9 shows the increase of the permeate 5 11 ~ 20 25
fluxes with the feed pressure. No influence of the P (bar)
feed flow rate was observed at 10 and 15 bar.
Fig. 10. Influence of feed pressure on permeate flux in
However, at 20 bar a slight influence was noticed.
DL-5 and DK-5.
Thus, the highest permeate flux was achieved at
20 bar and 200 L/h.
In Fig. 10 the permeate fluxes vs. tile feed pres- Figs. 11-13 show the standardized Pareto charts
sure have been represented for DL-5 and DK-5. for retention salts of the membranes tested. In all
The permeate flux values correspond with the cases salts retentions did no depend on the feed
average values calculated for the tested feed flow flow rate.
rate. As it can be expected, the highest feed pres- As can be seen in Fig. 14, the higher feed pres-
sure, tile highest permeate flux. sure, the higher salts retentions. The highest salts
Similarly, the obtained salts rejection values retentions were obtained with NF-90. DL-5 and
have been studied using the same types of graphs. DK-5 yielded very similar values for each tested
Figs. 11-13 show the standardized Pareto charts pressure.
for retention salts of the membranes tested. In all Table 5 summarizes the results o f the permeate
cases salts retentious did no depend on the feed analysis. By means of DK-5 and NF-90, it was
flow rate. possible to produce water with sufficient quality
Similarly, the obtained salts rejections values to be reused in the textile plant. The low permeate
have been studied using the same types of graphs. COD values (50 mg/L) can be highlighted.
 A. Bes-Pid et al. / Desalination 157 (2003) 73-80 79

I
:::~u I

AB

AB
I i i i i I i i • , i . . . . i . . . . i , , ! i I

0 1 2 3 4 5 0 1 2 3 4
Standardized effect Standardized effect
Fig. 11. Standardized Pareto chart for retention salts of Fig. 12, Standardized Pareto chart for retention salts of
NF-90 membrane. DL-5.

i . . . . i . . . . i . . . . g . . . . i

100
• DL-5 ~DK-5 , NF-90
80

v
60
co
rl," 40
AA
20
AB
................... i. . . . . . . . . . . . . . . . . . . . . . r ..................... T . . . . . . . . . . . .

i , , , , i . . . . ~ , , 1 1 I i i i i
5 10 15 20 25
0 1 2 3 4
P (bar)
Standardized effect
Fig. 13. Standardized Pareto chart for retention salts of Fig. 14. Influence of feed pressure on salts rejection in tested
DK-5. membranes,

Table 5
Analysis of permeate streams at the best operating conditions for each membrane

Membrane Selection of operating conditions Variables Effluent analysis

Feed pressure, Feed flow rate, Flux, RsAt.v: Conductivity, COD,
bar L/h L/mZh % m S/cm rng/L
NF-90 20 200 8-10 85-90 0.46 48
Desal DL-5 20 200-400 60-80 45-50 1.90-2.09 98
Desal DK-5 20 200-400 5040 55-65 1.33-1.71 50
80 A. Bes-Pid et al. / Desalination 157 (2003) 73-80
5. Conclusions
By means o f a physico-chemical treatment
using the coagulant DK-FER 505-1 at pH 12 and
with a concentration CFe2+ : 700 mg/L, COD o f a
textile effluent can be reduced to values lower
than 500 mg/L (72.5% COD removal efficiency).
With UPAX-33 worse efficiencies were achieved.
N a n o f i l t r a t i o n o f the p h y s i c o - c h e m i c a l l y
treated wastewater produced a permeate with a
COD lower than 100 mg/L for the three tested
membranes. ',
Salts rejection and permeate flux rates were
dependent basically on feed pressure. However,
for the feed flow rate range that was studied, no
influence was found on the studied variables.
Though the permeate flux rates o f NF-90 were
lower than for the other membranes, this was the
selected membrane, since the salts rejections were
substantially higher than for the other membranes.
Prior to an industrial operation, the manage-
ment o f the retentate stream has to be deeply
studied.
Acknowledgment
We thank Colortex 1967 S.L. for its support
in the investigation project.
References
[1] A. Bes-Pifi, J.A. Mendoza-Roca, M.I. Alcaina-
Miranda, A. Iborra-Clar and M.I. Iborra-Clal, Reuse
ofwastewater of the textile industry after its treatment
with a combination ofphysico-chemical treatment and
membrane technologies, Desalination, 149 (2002)
169-174.
[2] M. Crespi Rosell and J.A. Huertas Ldpez, Indutria
textil: depuracidn biol6gica o fisicoquimica?, Revista
de la lndustria Textil, 233 (1995) 42--61.
[3] G. Ciardelli, G. Campanelli and A. Botino, Ozone
treatment of textile wastewater for reuse, Wat. Sci.
Technol., 44(5) (2001) 61~57.
[4] S Baig and RA. Liechti, Ozone treatment for bio-
refractory COD removal, Wat. Sci. Technol., 43 (200l)
197-204.
[5] O.O. Hart, G.R. Groves, C.A. Buckley and B. South-
worth, A guide for the planning, design and implemen-
tation of wastewater treatment plants in the textile
industry. Part I: Closed loop treatment/recycle system
for textile sizing/desizing effluents. Pretoria, 1983.
[6] Y.H. Kim, Coagulants and Flocculants. Theory and
Practice, 1995.
[7] M. Marcucci, G. Nosenzo, G. Capanelli, 1. Ciabatti,
D. Corrieri and G. Ciardelli, Treatment and reuse of
textile effluents based on new ultrafiltration and other
membrane technologies, Desalination,. 138 (2001)
75-82.
[8] A. Rozzi, M. Antonelli and M. Arcari, Membrane
treatment of secondary textile effluents for direct reuse,
Wat. Sci. Technol., 40(4-5) (1999) 409-416.