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Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, Peoples Republic of China
Engineering Research Center for Eco-Dyeing & Finishing of Textiles, Ministry of Education of China, Zhejiang Sci-Tech University, Hangzhou 310018,
Peoples Republic of China
c
The Development Center of Water Treatment Technology, Hangzhou 310012, Peoples Republic of China
b
h i g h l i g h t s
a r t i c l e
i n f o
Article history:
Received 14 September 2014
Received in revised form 9 November 2014
Accepted 13 November 2014
Available online 15 November 2014
Keywords:
Textile efuent
Nanoltration
Submerged ltration
Color removal
COD reduction
a b s t r a c t
Raw and biologically treated textile efuents were submerged ltrated using lab-fabricated hollow ber
nanoltration membrane with a molecular weight cut-off of about 650 g/mol. Permeate ux, chemical
oxygen demand (COD) reduction, color removal, membrane fouling, and cleaning were investigated and
compared by varying the trans-membrane pressure (TMP) and volume concentrating factor (VCF). It
was found that both raw and biologically treated textile efuents could be efciently treated through
submerged nanoltration. The increase of TMP resulted in a decline in water permeability, COD reduction,
color removal, and ux recovery ratio, while the increase of VCF resulted in both increased COD reduction
and color removal. Under the TMP of 0.4 bar and VCF of 5.0, uxes of 1.96 and 2.59 l/m2 h, COD reductions
of 95.7 and 94.2%, color removals of 99.0, and 97.3% and ux recovery ratios of 91.1 and 92.9% could be
obtained in ltration of raw and biologically treated efuents, respectively. After ltration, the COD and
color contents of the raw efuent declined sharply from 1780 to 325 mg/l and 1.200 to 0.060 Abs/cm,
respectively, while for the biologically treated efuent, they decreased from 780 to 180 mg/l and 0.370
to 0.045 Abs/cm, respectively.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Efuents from textile industry are generally loaded with spent
dyes and chemical additives, and high in both biochemical oxygen demand (BOD) and chemical oxygen demand (COD) [1,2].
The extremely polluted textile efuents must be properly treated
Corresponding author at: Zhejiang Sci-Tech University, Department of Chemistry, Hangzhou 310018, Peoples Republic of China. Tel.: +86 571 86843217;
fax: +86 571 86843217.
E-mail addresses: yuschn@163.com, yuschn@mail.hz.zj.cn (S. Yu).
http://dx.doi.org/10.1016/j.jhazmat.2014.11.009
0304-3894/ 2014 Elsevier B.V. All rights reserved.
122
Table 1
Properties of the lab-fabricated thin-lm composite hollow ber nanoltration
membrane used in this study.
Parameter
Unit
Value
l/m2 h bar
g/mol
mV
%
%
mm
mm
9.2
650
2.5
10.5
8.0
0.40
0.51
0.3
40
0.8
1.0
0.8
Tested with de-ionized water under TMP of 0.8 bar and 25.0 C.
Obtained from the retention cure of PEG with different molecular weights
according to the method described in [37].
c
Obtained from the measured streaming potential according to the
HelmholtzSmoluchowski equation with the Fairbrother and Mastin substitution
[38].
d
Tested with 500 mg/l salt aqueous solution under TMP of 0.8 bar, 25.0 C, and
pH 7.0.
a
Vf
Vf Vp
(1)
where Vf and Vp are the volumes of the initial feed solution and
total withdrawn permeate stream, respectively. The volume of the
initial feed solution (Vf ) for volume reduction experiment was 9.0 l.
The performance at certain VCF was studied by checking the permeate water ux, color removal as well as COD reduction. After
each run of certain VCF, the fouled membrane module was washed
with owing de-ionized water for 60 min and measured for the ux
of de-ionized water (Jwc ) under the same TMP of 0.4 bar.
2.3. Analytical methods
Permeate volume collected over a certain period was measured
to determine the permeate ux. The COD concentrations were
determined by a HACH DR1010 (USA) direct reading spectrophotometer using a HACH COD reactor, according to the standard
methods [39]. Conductivity of all the samples was measured by
a conductance meter (DDSJ-308A, Cany Precision Instruments Co.,
Ltd., China). Color of each sample was analyzed by spectrophotometer (UV759, Shanghai) and calculated using the Eq. (2) [20]:
Color =
(2)
where A530 , A590 , and A617 are the absorbance values measured at
three different wave lengths of 530, 590, and 617 nm, respectively.
2.4. Calculations
The volumetric permeate water ux (Jw ) in terms of liter per
square meter per hour (l/m2 h) was calculated by the Eq. (3):
Jw =
V
A t
(3)
where A is the effective area of the membrane module for permeation, and V is the volume of permeate collected over a time interval
t.
Membrane water permeability (WP) was calculated from the
volumetric water ux (Jw ) measured under certain TMP through
the Eq. (4):
WP =
Jw
TMP
(4)
123
Jwc
100
Jwi
(5)
where Jwi and Jwc are the pure water uxes of the fresh and watercleaned membrane measured under the same TMP, respectively.
The observed COD reduction and color removal were calculated
using the Eq. (6):
R(%) =
Cf Cp
100
Cf
(6)
TMP
w Rm
(7)
TMP
w (Rm + Rf )
(8)
Unit
Conductivity
COD
Color
pH
s/cm
mg/l
Abs/cm
2250
1780
1.200
6.8
40
30
0.001
0.2
Biologically treated
textile efuent
2690
780
0.370
7.0
40
30
0.0008
0.2
124
Pure water
Pure water
Txtile effluent
Cleaning
Flux ( l/m2 h)
0.7bar
0.6bar
0.8bar
6
0.5bar
4
0.4bar
3
a
2
5
0
300
600
900
1200
1500
1800
0.4
0.5
0.6
0.7
0.8
TMP (bar)
Pure water
Pure water
Txtile effluent
Cleaning
0.8bar
Flux ( l/m2 h)
0.7bar
0.6bar
0.5bar
4
0.4bar
3
b
2
0
300
600
900
1200
1500
1800
) and
) bar.
Table 3
Fluxes (Jwi , Jws , and Jwc ) to the raw and biologically treated textile efuents under 25.0 C and different TMPs.
TMP (bar)
Jwi (l/m2 h)
0.4
0.5
0.6
0.7
0.8
3.68
4.60
5.51
6.45
7.35
Jws (l/m2 h)
Jwc (l/m2 h)
Jws /Jwi
Raw efuent
Raw efuent
Raw efuent
2.81
3.26
3.73
4.27
4.72
3.11
3.73
4.31
4.94
5.49
3.54
4.31
4.99
5.78
6.44
3.56
4.34
5.06
5.85
6.50
0.764
0.709
0.677
0.662
0.642
0.845
0.811
0.782
0.766
0.747
0.030
95
90
85
0.4 bar
0.5 bar
0.6 bar
0.7 bar
0.8 bar
80
75
100
125
0.020
0.015
0.4 bar
0.5 bar
0.6 bar
0.7 bar
0.8 bar
0.010
0.005
a
0.000
70
0
0.025
300
600
900
1200
300
600
900
1200
0.4 bar
0.5 bar
0.6 bar
0.7 bar
0.8 bar
95
90
85
80
75
0.030
100
0.025
0.020
0.015
0.4 bar
0.5 bar
0.6 bar
0.7 bar
0.8 bar
0.010
0.005
b
0.000
70
0
300
600
900
1200
300
600
900
1200
Fig. 4. Time-dependent color contents of the ltrated raw (a) and biologically
treated (b) textile efuents under 25.0 C and different TMPs of 0.4 (), 0.5 ( ),
0.6 (
) bar.
) bar.
126
98
1.0
96
0.8
Jws/Jwi
94
FRR( %)
0.9
92
0.7
90
0.6
88
0.5
0.4
86
0.4
0.5
0.6
0.7
0.8
TMP (bar)
Fig. 5. FRR values in ltration of raw ( ) and biologically treated (
ents, respectively, under 25.0 C and different TMPs.
) textile efu-
Rf = Rfr + Rr
(9)
) and bio-
logically treated ( ) textile efuents, respectively, at TMP of 0.4 bar and 25.0 C,
under which Jwi = 3.70 l/m2 h.
Therefore, the hydraulic resistance of the fouling layer (Rf ) is composed of two resistances in series [43]:
Jwc =
VCF
(10)
Table 4
Hydraulic resistances (Rm , Rf , Rfr , and Rr ) in ltration of raw and biologically treated textile efuents, respectively, under 25.0 C and different TMPs.
TMP (bar)
Rm 1013 (m1 )
0.4
0.5
0.6
0.7
0.8
4.39
4.39
4.40
4.38
4.39
Rf 1013 (m1 )
Rr 1013 (m1 )
Raw efuent
Raw efuent
Raw efuent
1.36
1.80
2.10
2.24
2.45
0.80
1.02
1.23
1.34
1.49
1.19
1.51
1.64
1.73
1.83
0.65
0.76
0.84
0.89
0.92
0.17
0.29
0.46
0.51
0.62
0.15
0.26
0.39
0.45
0.57
100
127
100
95
96
FRR (%)
98
90
94
92
90
85
1
88
VCF
Fig. 7. Inuence of VCF on COD reduction of the ltrated raw (
) and biologically
treated (
99
100
98
97
96
95
94
1
VCF
Fig. 8. Inuence of VCF on color removal of the ltrated raw (
treated (
VCF
) and biologically
Table 5
Hydraulic resistances (Rm , Rf , Rfr , and Rr ) in ltration of raw and biologically treated textile efuents, respectively, under TMP of 0.4 bar, 25.0 C and different VCFs.
VCF
Rm 1013 (m1 )
1.0
2.0
3.0
4.0
5.0
4.37
4.38
4.37
4.38
4.37
Rf 1013 (m1 )
Rr 1013 (m1 )
Raw efuent
Raw efuent
Raw efuent
1.38
2.04
2.68
3.29
3.87
0.79
1.16
1.44
1.70
1.84
1.20
1.78
2.37
2.92
3.46
0.62
0.94
1.18
1.40
1.51
0.18
0.26
0.31
0.37
0.41
0.17
0.22
0.26
0.30
0.33
128
Fig. 10. Photograph of the samples of (a) raw textile efuent, (b) ltrated raw textile efuent obtained at TMP of 0.4 bar and VCF of 5.0, (c) biologically treated textile efuent,
and (d) ltrated biologically treated textile efuent obtained at TMP of 0.4 bar and VCF of 5.0.
Table 6
Characteristics of the representative ltrated raw and biologically treated textile efuents under TMP of 0.4 bar and VCF of 1.0 and 5.0, respectively.
Parameter
Conductivity
COD
Color
pH
Unit
s/cm
mg/l
Abs/cm
VCF = 1.0
VCF = 5.0
2180
153.0
0.017
6.83
2610
132.0
0.015
7.02
2210
325
0.060
6.86
2630
182
0.045
6.95
is also lower to the raw efuent at each VCF compared with the
biologically treated efuent.
4. Conclusions
Raw and biologically treated textile efuents have been treated
through submerged ltration using lab-fabricated hollow ber
nanoltration membrane with a molecular weight cut-off of about
650 g/mol. The treatment efciencies to both the raw and biologically treated textile efuents were high and attractive for practical
application. Raw textile efuents containing high contents of dyes
of biodegradable difculty are more suitable for direct submerged
nanoltration.
The water permeate ux, COD reduction and color removal were
largely affected by TMP and VCF. The increase of TMP resulted in
a decline in water permeability, COD reduction and color removal,
129