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Article history:
Received 3 May 2010
Received in revised form 25 June 2010
Accepted 28 June 2010
Keywords:
Polypyrrole
Polyaniline
Paper mill wastewater
Sawdust
Treatment
Composite
a b s t r a c t
This paper deals with a new application of polyaniline (PAn) and polypyrrole (PPy) synthesized chemically.
Coated on sawdust via cast method the polypyrrole/sawdust (PPy/SD) and polyaniline/sawdust (PAn/SD) were
used as effective adsorbents for the removal of heavy metals, anions, color and COD (chemical oxygen demand)
from mill paper wastewater. The products were investigated in terms of morphology and chemical structure
using scanning electron microscopy and Fourier-transform infrared spectroscopy (FTIR), respectively. It was
found that PPy/SD and PAn/SD are very simple to prepare and can be used as effective adsorbents in the removal
of anions, heavy metals, color and COD from paper mill wastewater.
2010 Elsevier B.V. All rights reserved.
1. Introduction
High consumption of water is one of the most important
environmental concerns in paper industry. In an attempt to overcome
this problem, zero liquid efuent technologies are being developed.
In these technologies circuits are closed and water is continuously
recycled [13]. Such wastewater contains a large amount of pollutants
characterized by biochemical oxygen demand (BOD), chemical oxygen demand (COD), suspended solids (SS), toxicity, and colorants
which cause bacterial and algal slime growths, thermal impacts,
scum formation, color problems, and a loss of both biodiversity and
aesthetic beauty in the environment [4]. The main treatment processes used at pulp and paper mill plants are primary clarication
(sedimentation or otation), secondary treatment (activated sludge
process or anaerobic digestion) and/or tertiary processes (membrane
processes as ultraltration) [5]. Activated sludge plants have been
the most common wastewater treatment process for the removal of
organics in our country; however, there are several problems with the
process. It produces sludges with very variable settlement properties,
it is sensitive to shock loading and toxicity, and its capacity to remove
poorly biodegradable toxic substances is limited [6]. Different type of
catalysts such as Fenton agent and TiO2, have been used to degrade
pollutants from board paper industries and revealed that the Fenton
reagent gave a higher degree of total COD and BOD depletion compared to TiO2 [7]. In the same year, the occulation performances of
polyacrylamides have been reported for treating pulp and paper mill
wastewater. They revealed that cationic polyacrylamides, like Organopol 5415, with a very high molecular weight and low charge density
achieved a reduction of 95, 98 and 93 % in turbidity, total suspended
solid (TSS) and total COD, respectively, with a sludge 13858947/$
volume index (SVI) of 14 mL/g at the optimum dosage of 5 mg/l [8].
Buzzini and coworkers reported a system based upon precipitation
with a microbial community which provided approximately 8086%
and 7578% total COD removal with and without recirculation of the
efuent, respectively [9].
Since the discovery of conducting polymers three decades ago, a
large volume of research work has been performed associated with
the physics and chemistry of conducting polymers. PPy and PAn is the
most environmentally stable known conducting polymer and also one
of the most commonly investigated conducting polymer due to its
high electrical conductivity and simple preparation [10]. Conducting
polymers found applications in various elds such as microelectronics, composite materials, optics and biosensors [11] and as adsorbent
[12,13]. The ion exchange capacities of conducting Polymers were
well understood and it was found to depend on the polymerization
conditions, the type and size of the dopants incorporated during the
polymerization process as well as on the ions present in the electrolyte solution, the polymer thickness and ageing of the polymer [14].
Review of the literature revealed that PPy synthesized in solutions
with small dopants such as Cl, ClO4, NO3, etc., mainly exhibits
280
Table 1
Textile wastewater characterization.
Compound
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
300
21
155
1.5
33
0.5
0.3612
2700
16
2.1. Instrumentation
2.5. Characterization of mamrez tree sawdust
A digital scale FR200, a PH meter, a scanning electron microscope
(SEM) model XL30, a Fourier-transform infrared (FTIR) spectrometer
model shimadzu 4100 have been used in these experiments. Also a
manual Photometer SQ300 Merck as spectrophotometer and Merck
Spectroquant Test Kits were used for the analysis of COD (catolog
2
no.: 114555), NO
(no.: 1.14779),
2 (no.: 100609), NO3 (no.: 100614), S
2
SO
(no.:
114548).
Atomic
absorption
spectrometer
(AAS)
(Model 929,
4
Unicam) was used to analyze the concentration of heavy metal ions.
Conductivity was measured by the four-point method using a current
source.
Keithley 238, a scanner Keithley 706 with switching cards, and
a Solartron-Schlumberger 7081 Precision Voltmeter. The densities of
the samples were determined by the Archimedes method by weighing
the pellets in the air and immersed in decane.
2.2. Preparation of PAn/SD composite
1 g of KIO3 was added to 100 mL of sulfuric acid (1 M) and mixed
by a magnetic stirrer to make a uniform solution. Then, 1 g of SD and
1 mL fresh distilled aniline monomer was added to stirred solution.
The reaction took place for 4 h at room temperature. Finally, the
product was ltered to separate the impurities, and the products
were isolated on lter paper and washed several times with deionized
water and dried at room temperature.
2.3. Preparation of PPy/SD composite
5 g FeCl4 was added to 100 mL of water and then a uniform solution was resulted using magnetic mixer. Then, 1 g of SD and 1 mL fresh
distilled pyrrole monomer was added to stirred solution. The reaction
was carried out for 4 h at room temperature. Finally, the product was
ltered to separate the impurities, the products were isolated on lter
paper and washed several times with deionized water and dried at
room temperature.
In order to remove any dissolvable color materials in SD, PAn/SD
and PPy/SD, they were washed with acetone and sodium hydroxide
(0.3 M) until the washing liquid was colorless.
The composite has been grinded before use and their size were
between 1 and 2 mm.
2.4. Removal technique
Adsorption experiments were performed by agitating 0.5 g of sorbent with 50 mL of paper mill wastewater at 30 0.5 C in magnetic
mixer. The rotating speed was 700 rpm throughout the study. At the
end of predetermined time intervals, the sorbent was ltered and the
281
Table 2
Various physical parameters for the adsorbent (mamrez tree sawdust).
Parameters
Values
35
620
1.25
5.75
16.45
76.25
Table 3
Conductivity and density of sawdust, conducting polymers, and their composites at
20 C.
Compound
SD
PAn/SD
PPy/SD
PAn
PPy
Conductivity (S cm 1)
1.4 10
0.30
0.16
2.1
0.9
14
Density (g cm 3)
1.25
1.30
1.34
1.38
1.45
282
For studying affects SD on conductive polymer properties, conductivities and densities of composites, SD, PAn and PPy were measured
(Table 3). PAn and PPy have identical densities therefore composites
densities are equal. PA/SD, PPy/SD composites have much higher conductivities than conductivity of SD.
Experiments were done using PA/SD, PP/SD during 25 min with 5minute intervals. As can be seen (Tables 4 and 5) increasing the time
(5 to 20 min) removal efciency increased but after 20 min it increased
not signicantly.
For studying effect of SD size on removal efciency, SD indifferent
sizes (2050 m, 100150 m, 12 mm, 2030 mm) was coated with
polymer and applied for wastewater treatment. Amount of adsorbent
was 0.5 g, wastewater volume was 50 mL and the treatment process
was in 20 min. The results are indicated in Tables 6 and 7. As can be
seen decreasing SD size of 2030 mm to 12 mm removal efciency
increased but decreasing more, removal efciency decreased. The
reason could be for small size SD, polymer diffuses into SD so is not
coated on SD surface that made removal efciency decreased.
In Table 8, the removal efciency of wastewater is shown using
PAn, PPy and SD. As can be seen in Table 8, SD has low efciency in
the removal of anions and COD, but its performance to remove metals
and color is considerable. PPy and PAn have noticeable efciency
in the removal of metals, anions, color and COD. However, in all
experiments, the removal efciency of PPy and PAn are lower than
composites. Therefore it can be concluded that SD in the composites
does not play signicant role in the anions and COD removal but the
Table 4
Analyze of mill paper waste water after removal using PPy/SD in different time of reaction.
Compound
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
52.4
50.15
55.35
60.46
56.65
60.11
62.55
38.72
61.28
68.4
65.5
70.64
72.5
67.14
71.5
74.58
52.47
73.65
78.54
75.82
81.43
85.27
77.41
84.72
86.68
61.44
82.38
84.5
83.67
87.45
94.2
87.1
92.17
93.22
65.41
89.55
84.82
84.1
88.32
94.54
87.85
92.25
94.05
65.55
90.1
Table 5
Analyze of mill paper waste water after removal using PAn/SD in different time of reaction.
Compound
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
45.41
45.78
47.65
53.25
44.85
56.7
55.42
31.24
52.45
62.5
58.74
64.25
67.42
62.34
67.86
69.56
42.52
70.75
74.15
72.51
79.45
80.34
73.68
80.38
79.35
53.25
79.21
80.1
81.3
79.8
85.6
82.7
86.72
84.44
58.71
84.15
80.65
82.04
80.42
86.4
83.84
88.2
85.65
59.34
85.04
Table 6
Wastewater treatment using PPy/SD with different particle size.
Compound
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
81.75
79.25
83.42
89.5
82.68
85.4
85.52
57.32
84.31
84.5
83.67
87.45
94.2
87.1
92.17
93.22
65.41
89.55
72.3
74.25
74.84
80.16
70.64
83.67
83.45
51.22
80.86
61.93
57.25
55.45
75.23
53.22
80.24
75.32
34.54
76.78
Table 9
The removal efciency of PAn, SD and PPy, SD (not in composite form).
Compound
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
66.74
73.35
77.21
81.65
76.72
82.68
79.78
50.45
78.35
80.1
81.3
79.8
85.6
82.7
86.72
84.44
58.71
84.15
66.56
70.12
68.23
78.45
63.75
81.25
80.56
45.75
77.64
283
58.45
51.51
50.46
74.87
48.53
77.86
72.37
30.25
76.78
Table 8
The analyze of wastewater after treatment using PAn, PPy and SD.
Compound
Removal efciency
(%) using PAn
and SD (not in the
composite form)
Removal efciency
(%) using PPy and
SD (not in the
composite form)
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
67.52
78.68
76.5
73.7
79.3
75.42
71.51
52.4
70.14
75.8
81.24
84.3
82.5
83.25
80.04
78.7
62.74
80.12
Table 10
Desorption data using H2SO4, NaOH and distillated water.
Compound
Removal
efciency
of PAn (%)
Removal
efciency
of PPy (%)
Removal
efciency
of SD (%)
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
63.5
78.2
72.27
69.43
81.7
72.54
57.41
57.45
64.38
74.73
84.16
85.24
76.23
84.11
72.45
61.37
64.52
78.65
56.34
7.45
11.24
71.76
9.8
78.41
71.12
3.07
74.75
Compound
Desorption
efciency
using
NaOH (%)
Desorption
efciency
using
H2SO4 (%)
Desorption
efciency using
distillated
water (%)
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
32.5
93.74
92.25
24.27
88.54
25.45
38.24
42.86
92.5
85.52
18.14
25.78
88.2
14.74
87.94
48.56
58.3
47.8
51.35
38.74
44.58
42.5
57.2
52.46
82.45
88.74
61.5
4. Conclusion
The composite of conducting polymer showed considerable potential in the removal of heavy metals, color and anions from paper mill
wastewater and have the ability to remove COD; but the removal
efciency of COD is lower than removal efciency of anions, metals and
color. Composites regeneration operation is performed using NaOH,
deionized water and H2SO4. After regeneration, composites were used
for wastewater treatment. Ability of these composites has no considerable difference, with the fresh composites for removing color, COD,
anions and heavy metals. Also, the efciency of these composites are
higher than PAn PPy and SD to treat the wastewater.
Table 11
Analyze of mill paper waste water before and after removal by regenerated PPy/SD and
PAn/SD.
Fig. 8. (a) Wastewater, wastewater after treated with (b) PPy/SD, (c) PAn/SD.
Compound
Removal efciency
of PAn/SD (%)
Removal efciency
of PPy/SD (%)
Mg (mg/l)
S 2 (mg/l)
2
SO
(mg/l)
4
Fe (mg/l)
1
1
Total N (NO
3 , NO2 ) (mg/l)
Cu (mg/l)
Color (adsorbance, at 600 nm)
COD (mg/l)
Zn (mg/l)
77.85
79.01
76.1
81.08
82.7
83.14
83.33
52.71
84.73
82.71
83.22
84.35
90.05
86.43
86.54
91.86
59.43
87.42
284
Acknowledgements
The research upon which this paper is based was supported by
a grant from the Khosro Katal. Saied Farhadi at Tarbiat Modares
University is acknowledged for his assistance with experimental design
and analysis.
References
[1] H. Lunsing, W.E. De Haan, Experiences in the Dutch paper and board industry in
reducing the fresh water consumption, Pap. Technol. Ind. 11 (1993) 305308.
[2] C. Negro, A. Blanco, B. Vicedo, J. Tijero, Overview ZLE for pulp and paper mills,
Invest. Tecnica Papel 142 (1999) 413417.
[3] A. Koppol, M. Bagajewicz, B. Dericks, M. Savelski, On zero water discharge
solutions in the process industry, Adv. Environ. Res. 8 (2003) 151171.
[4] D. Pokhrel, T. Viraraghavan, Treatment of pulp and paper mill wastewater a
review, Sci. Total Environ. 333 (2004) 3758.
[5] G. Thomson, J. Swain, M. Kay, C.F. Forster, The treatment of pulp and paper mill
efuent: a review, Bioresour. Technol. 77 (3) (2001) 275286.
[6] R. Nagarathnamma, P. Bajpai, K. Pramod, Studies on decolorization, degradation
and detoxication of chlorinated lignin compounds in kraft bleaching efuents by
Ceriporiopsis subvermispora, Process Biochem. 34 (1999) 939948.
[7] A.M. Amat, A. Arques, F. Lopez, M.A. Miranda, Solar photo-catalysis to remove
paper mill wastewater pollutants, Sol. Energy 79 (2005) 393401.
[8] S.S. Wong, T.T. Teng, A.L. Ahmad, A. Zuhain, G. Najafpour, Treatment of pulp and
paper mill wastewater by polyacrylamide (PAM) in polymer induced occulation,
J. Hazard. Mater. 35 (2005) 378388.
[9] A.P. Buzzini, I.K. Sakamoto, M.B. Varesche, E.C. Pires, Evaluation of the microbial
diversity in an UASB reactor treating wastewater from an unbleached pulp plant,
Proc. Biochem 41 (2006) 168176.