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-PG*, J.A. Mendoza-Rota, M.I. Alcaina-Miranda, A. Iborra-Clar,
M.I. Tborra-Clar
Deparfment of Chemical and Nuclear Engineering, Universidad Politknica 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 A13+ and another containing Fe*+) 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 ofthe nanofiltration permeates were lower than 100 mg/L and 1000 @/cm respectively.
Keywords: Phisico-chemical treatment; Nanofiitration; Wastewater reuse
1. Introduction
Due to high water consumption in the textile
industry it is essential to study its reuse. Previous
experiments of the research group with waste-
water of a textile plant that mainly manufactures
*Corresponding author.
socks, stockings and panties proved that the
combination of physico-chemical treatment and
membrane technologies could produce water for
reuse in the factory [l]. In this case, an attempt is
made to apply these technologies to the effluent
of another textile plant, optimizing the operating
conditions of the membrane process.
Presented at the European Conference on Desalination and the Environment: Fresh Water for All, Malta, 4-3 May 2003.
Enropea,l Desalination Sociew, International Water Association.
00 I l-9 !64/03/$- See front matter 0 2003 Elsevier Science B.V. All rights reserved
PII: SO01 1-9164(03)00385-O
74 .-I. Bes-PiB et ul. Desalination 157 (2003) :3-80
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 from the water [2]. Chemical oxidation by
ozone, or a combination of UV-radiation and
ozone and H,O,, 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 the efficiency ofthe physico-
chemical treatment [5]. The optimum operating
conditions (pH, chemical concentrations) are
determined by means of these experiments.
According to the double layer theory, electrical
repulsion forces prevent from colloids aggre-
gation. In order to achieve an effective agglo-
meration, the compression 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 the 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 <IO0 mg/L and conduc-
tivity <I 000 @/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 the 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 of the
wastewater samples. The next step was a physico-
chemical treatment by means ofjar-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, BOD,,
pH, and conductivity. COD was determined with
Spectroquant Nova 60 from Merck and BOD,
with the Oxitop system from WTW.
3.2. Jar-tests
Physico-chemical experiments were carried
out in a multiple stirrer Jar-Test apparatus from
Selecta. The chemicals used in the jar-tests were
the commercial products DK-FER 50.5-l from
Acideka S.A. and UPAX- from Kemira S.A.
The general procedure consisted in introducing
900 mL of the sample in the jars, the coagufant
was added and rapidly mixed (1 SO rpm) during
3 min. After that, the paddles were withdrawn so
A. Bes-Pick et al. / Desalination 157 (2003) 73-80 75
that the particles could settle. The influence of
coagulants concentration and pH values were
studied. The coagulant concentrations are referred
to Fe and Al,O, for DK-FER 505-l and UPAX-
33, respectively. The pH of the samples was
changed by addition of HCI 0.1 N and NaOH 0.1
and 0.5 N.
pH values were selected in the alkaline range,
since in this medium the coagulants drive to the
formation of positively charged metal hidroxy
complexes that specifically adsorb onto colloids.
In all tests COD, turbidity, pH and conductivity
of the clarified water and the sludge volume after
30 min sedimentation (V,,) were measured.
3.3. Experiments with membranes
Experiments were carried out using a labora-
tory nanofiltration (NF) plant. The configuration
of the plant can be observed in Fig. I . NF module
is plane and its effective membrane area is
For each membrane, experiments with three
0.012 m?. The tested NF membranes are described
different transmembrane pressures ( 0. 1 0, 0. 15 and
0.20 MPa), and three different feed flow rates (0.2,
in Table 1.
0.3 and 0.4 m3/h) at 25C were performed. The
cross flow velocities related to these flow rates
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;
9-9, manometer; 10, NF module; 11, permeate stream;
12, regulation valve; 13, speed control; 14, rejection stream.
Table 1
Tested NF membranes
Membrane NaCl
MgSO4
Permeability,
retention, retention, Lfmh bar*
% %
Dow NF-90 85-95 >97 0.481
Osmonics Desal - 98 3.863
DL-5
Osmonics Desal - 96 3.562
DK-5
*Experimental values
The operating time of the plant was established
according to the steady state conditions. It was about
8 h in all cases. The permeate fluxes J,, (L/m*h)
and salt retentions R,qA,,, (%) were determined. In
addition, at the end of each experiment, COD was
analysed.
are 1.11, 1.66 and 2.22 m/s respectively. The
series of experiments were carried out using an
experimental design obtained from Statgraphics
Plus 4.0.
4. Results
Table 2 shows the average values of the
measured parameters of the textile wastewater.
These values are typical for textile effluents.
Conductivity and COD are quite important and
they have to be reduced to produce water with
enough quality to be reused.
Figs. 2 and 3 show the COD obtained after
jar-tests on varying the DK-FER 505-l and
UPAX- concentrations. In Fig. 2 it can be
Table 2
Wastewater characterization
Parameter Feedwater
T, C 20
PH
12.0
Conductivity, mS/cm 4.53
BODS, mg/L 490
COD, mg/L 1630
76 .4 Bes-Pick et al. Desalination 157 /2003) 73-80
1600
1600
-
-
-
-
-
1200
2
2
800
0
s
400
0
-
- :_
r
500 600 700 8 00 200 300 400 500
UPAX- coagulant (mg/L) DK-FER 505-I coagulant (mg/L)
Fig. 2. Influence of DK-FER 505-I concentration on COD Fig. 3. Influence of UPAX- concentration on COD of
of treated water. treated water.
observed that DK-FER 505-l concentrations of
500 mg/L and 600 mg/L produced only a slight
COD reduction. This occurred because of the in-
sufficient reduction in the zeta potential ofthe waste-
water. The maximum COD removal yield (72.5%)
was reached with a concentration of 700 mg/L.
Higher coagulant concentrations did not improve
the efficiency. In Fig. 3, for UPAX- the selected
coagulant concentration was 300 mg/L. For this
value the COD ofthe clarified water was 680 mg/L
(i.e. 58.0% removal).
Fig. 4 and Fig. 5 show the COD obtained after
jar-test for different wastewater pH values. In
Fig. 4 it can be observed that the COD removal
slightly increased with wastewater pH, reaching
a COD removal of 70.5% at pH 12 (the raw waste-
water pH).
In Fig. 5 it is shown that the best yield was
reached at pH 11 .O (COD removal of 66.0%). The
other tested pH did not improve the COD
efficiency.
Thus, experiments showed that DK-FER 505- 1
coagulant provided the best results for the physico-
chemical treatment of this textile wastewater. The
optimum operating conditions were: pH = 12.0 and
C + = 700 mg/L. In Table 3 the characteri-zation
of the clarified water after the test at these
conditions can be observed. It is important to
emphasize that a total colour removal was
accomplished.
1000
800
i -
m 600
5
8 400
200
0
800
I T
- 5~ 600
c.
8 400
200
0 l__-I
I
J-
10
PH
Il__L
11 12
I
_-
10. 5 11. 0
PH
Fig. 4. Influence ofwastewater pH on COD oftreated water Fig. 5. Influence ofwastewater pH on COD oftreated water
using 700 mgiL of DK-FER 505-I. using 300 mg/L of UPAX-33.
A. Bes-Pick et al. / Desalination 157 (2003) 73-80 77
Table 3
Clarified water characterization (Jar-test conditions: CFc2+
= 700 IngiL; pH = 12)
PH
6.14
Conductivity, mS cm 3.80
Turbidity, NTU 4.7
v;(), lllL/L 260
COD, rng/L 448
A:P
B:Q
AB
BB
AA
Nanofiltration experiments were made using
wastewater treated with DK-FER 505-I as feed
water.
In Table 4 salts rejections (I?,,,,) and permeate
fluxes (J,,) at the steady state conditions for the
tested membranes can be observed.
0 2 4 6 8 10
Standardized effect
Fig. 6. Standardized Pareto chart for permeate flux of
NF-90.
Figs. 6-8 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 it can be observed that feed pressure
and feed flow rate were significant variables. Feed
pressure variations produced an important
increase on permeate flux, while the influence of
the feed flow rate was substantially lower.
However, it can be seen that only feed pressure
A:P
B:Q
BB
AA
AB
J...Il.l..1,.,.Il..,l....C
0 1 2 3 4 5
Standardized effect
Fig. 7. Standardized Pareto chart for permeate flux of
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,
R,SA,.,, J /J , &AI./, J ,s RSAL~,
bar L/h % Limh % Llmh %
IO 200 83.0 2.8 28.2 25.6 42.8
10 300 77.0 2.5 34.7 25.7 35.0
10 400 72.3 2.0 30.3 21.8 37.0
15 200 85.2 5.3 33.1 40.1 43.3
15 300 78.6 5.5 38.0 42.7 42.5
15 400 83.8 4.8 36. I 37.7 39.7
20 200 87.8 8.7 35.14 51.3 55.0
20 300 86.2 7.6 48.39 67.8 60.9
20 400 85.2 7.5 40.27 52.0 44.8
J/3
L/m*h
-
21.6
18.4
16.9
29.2
28.1
26.3
45.2
55.8
34.5
A. Bes-Pici et al. / Desalination 157 (2003) 73-80 78
A:P
BB
AB
B:Q
AA
0 2 4 6 8
L
Standardized effect
Fig. 8. Standardized Pareto chart for permeate flux of
DL-5.
influenced significantly on permeate flux for
DL-5 and DK-5.
In order to illustrate the obtained results, a
response surface graph was plotted if both feed
pressure (P) and feed flow rate (Q) were signifi-
cant variables (Fig. 9). If only the feed pressure
was significant, a graph showing the evolution of
this variable was performed (Fig. IO).
Fig. 9 shows the increase of the permeate
fluxes with the feed pressure. No influence ofthe
feed flow rate was observed at 10 and 15 bar.
However, at 20 bar a slight influence was noticed.
Thus, the highest permeate flux was achieved at
20 bar and 200 L/h.
In Fig. IO the permeate fluxes vs. the feed pres-
sure have been represented for DL-5 and DK-5.
The permeate flux values correspond with the
average values calculated for the tested feed flow
rate. As it can be expected, the highest feed pres-
sure, the highest permeate flux.
Similarly, the obtained salts rejection values
have been studied using the same types of graphs.
Figs. 1 l-l 3 show the standardized Pareto charts
for retention salts of the membranes tested. In all
cases salts retentions did no depend on the feed
flow rate.
Similarly, the obtained salts rejections values
have been studied using the same types ofgraphs.
200
300
1 .,;()
P (bar)
400
Q (L/h)
Fig. 9. Influence of feed pressure and feed flow rate on
permeate flux in NF-90.
80 .__- __,,__.-.__ ._.______ .I_. _,.__ .__..____ .._.. __ ___ ._
??DL-5 X DK-5
01
5 Cl 3 20 25
P (bar)
Fig. 10. Influence of feed pressure on permeate flux in
DL-5 and DK-5.
Figs. 1 I - I3 show the standardized Pareto charts
for retention salts of the membranes tested. In all
cases salts retentions did no depend on the feed
flow rate.
As can be seen in Fig. 14, the higher feed pres-
sure, the higher salts retentions. The highest salts
retentions were obtained with NF-90. DL-5 and
DK-5 yielded very similar values for each tested
pressure.
Table 5 summarizes the results ofthe permeate
analysis. By means of DK-5 and NF-90, it was
possible to produce water with sufficient quality
to be reused in the textile plant. The low permeate
COD values (50 mg/L) can be highlighted.
A. Bes-Pick el al. I Desalinarion I57 (2003) 73-80 79
A:P
B:Q
AB
BB
AA
0 I 2 3 4 5
Standardized effect
A:P
B:C
AA
BB
AB
J... .... ...C
0 1 2 3 4
Standardized effect
Fig. 11. Standardized Pareto chart for retention salts of
NF-90 membrane.
Fig. 12. Standardized Pareto chart for retention salts of
DL-5.
A:P
BB
B:Q
AA
AB
3 1 2 3
Standardized effect
I
I OC
80
;;
&
- 60
kl
2 40
20
. DL-5 XDK-5 + NF-90
5 10 15 20 25
4
P (bar)
Fig. 13. Standardized Pareto chart for retention salts of
DK-5,
Fig. 14. Influence offeed pressure on salts rejection in tested
membranes.
Table 5
Analysis of permeate streams at the best operating conditions for each membrane
Membrane
NF-90
Desal DL-5
Desal DK-5
Selection of operating conditions
Feed pressure, Feed flow rate,
bar L/h
20 200
20 200-400
20 200400
Variables
Flux,
L/m*h
8-l 0
60-80
50-60
&AI. 1:
%
85-90
45-50
5565
Effluent analysis
Conductivity, COD,
mS/cm mg/L
0.46 48
1.90-2.09 98
1.33-1.71 50
80 .A Bes-Pi6 et al. / Desalination 157 (2003) 73-80
5. Conclusions
By means of a physico-chemical treatment
using the coagulant DK-FER 505-I at pH I2 and
with a concentration CFe+ = 700 mg/L, COD of a
textile effluent can be reduced to values lower
than 500 mg/L (72.5% COD removal efficiency).
With UPAX- worse efficiencies were achieved.
Nanofiltration of the physico-chemically
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 ofNF-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 of the retentate stream has to be deeply
studied.
Acknowledgment
We thank Colortex 1967 S.L. for its support
in the investigation project.
References
[II
PI
[31
[41
[51
[61
171
PI
A. Bes-Pia, J.A. Mendoza-Rota, M.I. Alcaina-
Miranda, A. Jborra-Clar and M.I. Jborra-Clar, Reuse
ofwastewater ofthe textile industry after its treatment
with a combination of physico-chemical treatment and
membrane technologies, Desalination, 149 (2002)
169-174.
M. Crespi Rose11 and J.A. Huertas Lopez, lndutria
textil: depuracion biologica o fisicoquimica?, Revista
de la Jndustria Text& 233 (1995) 42-61.
C. Ciardelli, G. Campanelli and A. Botino, Ozone
treatment of textile wastewater for reuse, Wat. Sci.
Technol., 44(5) (2001) 61-67.
S Baig and P.A. Liechti, Ozone treatment for bio-
refractory COD removal, Wat. Sci. Technol., 43 (200 1)
197-204.
0.0. Hart, GR. Groves, CA. 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.
Y.H. Kim, Coagulants and Flocculants. Theory and
Practice, 1995.
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.
A. Rozzi, M. Antonelli and M. Arcari, Membrane
treatment ofsecondary textile effluents for direct reuse,
Wat. Sci. Technol., 40(4-5) (1999) 409-416.