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924 FTP
924 FTP
DOI: 10.1002/jctb.924
Abstract: The treatment and reuse of industrial wastewaters by membrane processes has become more
attractive in the last few years due to constraints on water usage. The aim of this study was to investigate
the direct filtration of reactive dye house wastewaters by nanofiltration membranes based on permeate
flux, and sodium chloride and colour removal. Experiments were performed using both synthetic and
industrial dye bath wastewaters with the fluxes of the industrial dye bath wastewaters lower than those
of the synthetic solutions. The effects of operating conditions such as pressure and pH were assessed.
Studies with DS5 DK type (polysulfone–polyamide) membranes showed that nanofiltration membranes
are suitable for direct treatment of wastewaters and the permeate quality was appropriate for reuse in the
dyeing process. Pre-treatment and neutralisation were important for recovery of large amounts of salt
and water from the permeate stream. Neutralisation of the solution with HCl rather than H2 SO4 gave a
better permeate from the point of view of the reuse. The highest permeate flux and colour removal and
the lowest salt removal were achieved with the HCl neutralisation.
2003 Society of Chemical Industry
∗ Correspondence to: Ismail Koyuncu, Istanbul Technical University, Faculty of Civil Engineering, Department of Environmental Engineering,
80626, Maslak, Istanbul, Turkey
E-mail: koyuncu@itu.edu.tr
(Received 17 September 2002; revised version received 3 February 2003; accepted 1 August 2003)
the comparative evaluation of the results from both Table 1. The wastewater composition of the synthetic and industrial
synthetic and actual reactive dye bath wastewaters Procion dye baths
based on permeate flux, sodium chloride recovery and Concentrations Concentrations
colour removal. (g dm−3 ) (g dm−3 )
in synthetic in industrial
Component wastewater wastewater
EXPERIMENTAL Reactive Navy HEXL (RN) 0.2 0.2
Apparatus Reactive Blue HEGN (RB) — 0.2
The Sepa CF laboratory-scale 316SS membrane cell Reactive Crimson HEXL (RC) — 0.04
was supplied by Osmonics Inc and was as described NaCl 30 30
in previous work.15 The feed vessel volume was about Na2 CO3 15 15
50 dm3 . The experimental system had two pumps: a Acetic acid 0.3 0.3
low pressure and a high pressure pump operating in Verolan NBO 0.5 0.5
Slipper 1 1
series so that the low pressure pump supplied sufficient
inlet pressure for the high pressure pump. The high
pressure pump was able to supply a feed pressure up to
10 000 kPa and a feed flow rate up to 1000 dm3 h−1 . A
rotameter was provided to measure the feed flow rate Wastewater composition
up-stream of the membrane cell. Also, pressure gauges The Procion dye bath, containing high concentrations
were used to measure the inlet and outlet pressures. All of NaCl, was simulated for the initial experiments.
experiments were carried out at constant temperature The composition of the Procion dye bath from the
of 25 ± 1 ◦ C and constant cross flow velocity of local cotton textile industry is given in Table 1. The
0.74 m s−1 . Constant temperature was also supplied simulated Procion dye bath solutions were prepared
by using a heat exchanger in the feed tank (Fig 1). step-wise by adding the auxiliary chemicals in five
The concentrate stream was returned to the feed vessel stages (Table 2). It was considered that, for the
while the permeate stream was collected separately. A preparation of the synthetic dye bath, approximately
cartridge filter (10 µm pore size) was used as a pre- 20% of the dyes and 100% of all other chemicals
filter to remove coarse particulates from the dye bath remained in the exhausted dye bath wastewater.16
wastewater prior to nanofiltration. A DS5 DK type Reactive Navy HEXL (RN) used in the synthetic
(polysulfone–polyamide) nanofiltration membrane solutions was supplied by the local textile company.
(0.0155 m2 ) with an approximate molecular weight NaCl, Reactive Navy HEXL, Na2 CO3 , acetic acid,
cut-off of 150–300 Da, supplied by Osmonics as a flat Slipper (Mega Tec Company) and Verolan NBO
sheet, was used in this study. (Rudolf Duraner Company) were added to the
Temperature Concentrate
controller flow Piston clamping
mechanism
Manometer
Back pressure valve
Manometer
Cooling
system
(Tap
water) Manometer Cell holder
High pressure
pump
Flowmeter
Low pressure
pump Computer
Permeate
Prefilter
Balance
Stage no Solutions
1 Distilled water
2 NaCl
3 NaCl + Reactive Navy HEXL (RN)
4 (a) NaCl + Reactive Navy HEXL (RN) + Na2 CO3 (pH = 10.5 (original pH))
4 (b) NaCl + Reactive Navy HEXL (RN) + Na2 CO3 (pH = 7 with HCl)
5 (a) NaCl + Reactive Navy HEXL (RN) + Na2 CO3 + acetic acid + Verolan NBO (ion keeper) + Slipper (broken preventer)
(pH = 10.5 (original pH))
5 (b) NaCl + Reactive Navy HEXL (RN) + Na2 CO3 + acetic acid + Verolan NBO (ion keeper) + Slipper (broken preventer)
(pH = 7 with HCl)
the data logging system as shown in Fig 1, and the 5) a) All chemicals
70 b) All chemicals
permeate conductivity and flux values were used to
60
determine when the permeate composition and flux
50
had reached steady state after changing the applied
40
pressure. The removal efficiency is calculated using
30
the following equation:
20
10
Cp
R(%) = 1 − × 100 (1) 0
0 5 10 15 20 25 30
Cf
Pressure, kPa ( × 100 )
where Cf is feed water concentration and Cp is Figure 2. Flux versus pressure graphs for the synthetic wastewater
permeate water concentration. experiments. (a) Original pH; (b) HCl-neutralisation.
RsOBS, % ( × 100 )
b) All chemicals
increasing pressure for the five steps (Fig 2) with 0.3
the highest flux, about 110 dm3 m−2 h−1 at 2400 kPa,
achieved for distilled water (step 1). The fluxes 0.2
decreased, however, with the addition of components
to the dye bath. Thus a flux of 73 dm3 m−2 h−1 was 0.1
obtained at 2400 kPa for the 30 g dm−3 NaCl solution,
and addition of 0.2 g dm−3 Reactive Navy HEXL (RN) 0
further slightly affected the flux. In addition, there 0 5 10 15 20 25 30
As with the synthetic wastewater experiments, feed for the industrial wastewaters. With this concentration
solutions were neutralised with 0.1 mol dm−3 HCl and the NaCl unit cost of 0.041 $ per kg, the annual
and 0.01 mol dm−3 H2 SO4 . The permeate flux (Jv ) income from NaCl reuse will be about $75 000 for
increased with increasing pressure for all experiments. 200 m3 day−1 capacity. From this basic calculation the
The fluxes for the industrial dye bath wastewater were pay back period for the nanofiltration plant will be
lower than for the synthetic wastewaters. This was about 2 years assuming a capital cost of $150 000.
probably the result of particulate materials present in Additional financial benefits from water and energy
the industrial wastewater. Flux values for the original reuse can decrease this pay back period. In addition,
solution and neutralised solution with HCl decreased the NaCl content of the reactive dye houses varies
by about 28% and 23% respectively compared with the between 20 and 80 g dm−3 and all the different dye
results of synthetic wastewaters. The lowest flux value wastewaters will be collected together and treated by
of 37.5 dm3 m−2 h−1 was obtained with the original the nanofiltration plant. Therefore the salt content
solution. The highest flux value of 54 dm3 m−2 h−1 , of the feed solution will increase to an average value
however, was obtained with the neutralised solution of 40 g dm−3 , and can decease the salt removal to
by using 0.1 mol dm−3 HCl. Flux values for the 10%.9,17 In addition, the rate of salt removal can
solution neutralised with 0.01 mol dm−3 H2 SO4 were further be lowered in real operation because of the high
about 47 dm3 m−2 h−1 . It was slightly lower than recovery rate. Thus, overall, the use of a nanofiltration
that for the solution neutralised with HCl. These plant to treat reactive dye wastewaters is an attractive
low flux values at high pH were probably the proposition.
consequence of the hydrophobicity of dye molecules
at the membrane surface. Furthermore, sulfate ions
in solutions neutralised with H2 SO4 increased the
osmotic pressure of the feed and this caused lower flux CONCLUSIONS
values for the solutions neutralised with H2 SO4 than The results of this study confirm previous observations
with HCl. that nanofiltration is suitable for the direct treatment
Chloride ion removal was also determined for the of industrial wastewaters. Permeate quality was
industrial wastewaters. Similar to the flux values, salt appropriate for the reuse of the permeate in the dyeing
removal from industrial wastewater was lower than process. Nevertheless, further experiments should be
from the synthetic solutions with chloride rejection performed to study the effect of reuse of water on the
from the original solution of about 28% at 2400 kPa. dyeing process. Pre-treatment and neutralisation were
There were small differences in Cl− removal between important parameters for recovery of high amounts of
experiments conducted with the original solution and salt and water from the permeate stream. The results
the solution neutralised with H2 SO4 . The lowest Cl− from industrial dye bath experiments were different
removal, about 15% at 2400 kPa, was observed with from the results of the synthetic experiments. The
the solution neutralised with HCl (Fig 5). While the fluxes of the industrial wastewaters were lower than
feed Cl− concentration increased with the addition of the synthetic solutions, and cartridge filtration had to
0.1 mol dm−3 HCl, the osmotic pressure differences be used before nanofiltration to remove particulate
between the feed and permeate decreased further. It material. Experiments also showed that neutralisation
can therefore be concluded that HCl-neutralisation with HCl rather than H2 SO4 gave better permeate
increased NaCl recovery. quality with respect to reuse, with the highest flux
A basic economic evaluation has been carried out and colour removal and the lowest salt removal. Basic
to estimate the annual income from the reuse of economic evaluation showed a pay back period for the
NaCl. Permeate NaCl concentration is estimated as nanofiltration plant to be less than 2 years.
25.5 g dm−3 based on 15% salt removal at 2400 kPa
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