Documentos de Académico
Documentos de Profesional
Documentos de Cultura
a r t i c l e
i n f o
Article history:
Received 13 November 2011
Received in revised form 24 April 2012
Accepted 6 May 2012
Available online 15 May 2012
Keywords:
Aluminum sulfate
Sodium alginate
Coagulation and occulation
Floc strength
Floc re-growth
a b s t r a c t
The effect of coagulant aid sodium alginate (SA) on coagulation behavior and oc characteristics of aluminum sulfate (AS) was investigated for synthetic dye wastewater treatment. Coagulation performance and
oc characteristics of AS were investigated for comparison. The results showed that AS plus SA exhibited
synergic effect on color removal depending on the dose of AS and SA. Color removal was more enhanced by
SA at low AS doses than at higher ones. Floc properties including oc growth rate, size, strength and reversibility were investigated by Photometric Dispersion Analyzer (PDA). AS plus polymer SA exhibited an
obvious improvement on oc size and oc growth rate. Besides, the ASSA dual-coagulants signicantly
improved the oc recoverability as reected by higher recovery factors compared to AS.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Dye wastewater discharged from textile dye printing industries
is a considerable source of environmental contamination due to its
strong color, high pH and chemical oxygen demand (COD), large
amount of suspended solids (SSs) and low biodegradability [1,2].
The presence of color not only affects scenery, but also disturbs
photosynthetic activity of hydrophytes. In terms of public health,
it has been found that some azo dyes are able to produce carcinogenic aromatic amines in the process of reductive degradation
[1,3]. With regard to aquatic biosphere, dye polluted natural
waters can seriously disturb aquatic biosphere due to the reduced
sunlight penetration and depletion of dissolved oxygen [4]. Thus,
dyes in wastewater should be removed completely before they
are discharged into receiving waters.
Many methods have been reported for removing color from dye
wastewater, among which coagulation is a widely used process
due to its relatively simple operation and low cost [5]. The most
commonly used coagulants in dye wastewater treatment are Al(III)
salts and Fe(III) salts [68]. However, there are some disadvantages
with those in-coagulants. Recent epidemiological, neuropathological and biochemical studies suggest a possible link between the
neurotoxicity of aluminum and the pathogenesis of Alzheimers
disease [9,10]. Ferrite occulants can be costly and the resultant
excessive iron may cause unpleasant metallic taste, odor, color,
corrosion, foaming or staining [11].
Corresponding author. Tel.: +86 531 88361912; fax: +86 531 8664513.
E-mail address: wangyan_sdjn@yahoo.com.cn (Y. Wang).
1383-5866/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.05.009
In view of the above, many factors have been taken into consideration to improve the conditions and reduce the dosage of the
harmful inorganic coagulants. In recent years, Sanghi et al. found
that coagulation aids could enhance the coagulation efciency on
reactive dye wastewater [12] and many synthetic polymers have
been used as the main coagulant aids and some good results have
been reported [13,14]. The most common practice is to add polymer some time after the metal coagulants [15]. However, polymers, used as coagulant aids, have also been reported to contain
contaminants from the manufacturing process which have potentially negative impact on human health [16]. Therefore, there is
an increasing demand for environment-friendly and effective
coagulant aids. Sodium alginate (SA), the sodium salt of alginic
acid, with an average molecular weight of 500,000, is a linear
water-soluble anionic polymer (Fig. 1). It is widely used to produce
microsphere, beads, microcapsule and tablets for drug delivery
system [17]. However, there has been no report on the use of SA
combined with aluminum sulfate (AS) in water treatment. In
principle, the coagulation efciency could be improved when SA
is used in combination with AS, and the dosage of AS could also
be reduced.
Generally, the effectiveness of occulation is measured by the
parameters such as residual turbidity or chromaticity removal
because they are directly related to the solidliquid separation
and water quality. However, they only provide limited information
of occulation process. The information of oc size distribution and
structure would be much needed [18]. The occulation dynamic
monitoring technology, Photometric Dispersion Analyzer (PDA),
was adopted to observe the oc aggregation processes in this
181
1.0
0.9
study. Gregory is the rst researcher to introduce PDA in monitoring the state of aggregation of oc [19], and more researchers
adopted the optical technique to describe the dynamics of occulation in recent years [20].
The aim of the present work was to test the effect of SA used as
coagulation aids in disperse yellow (D.Y. RGFL) wastewater treatment with AS. The coagulant performance was investigated in
terms of color removal efciencies and zeta potentials. In this
study, the evolution of oc ratio as a function of coagulation time
was measured by PDA. Floc aggregates were characterized in terms
of size, oc growth rate, breakage and subsequent regrowth potential. The relationship between oc properties and coagulation
mechanism was also discussed.
2. Materials and methods
2.1. Coagulants
In this study, the following stock solutions of coagulants were
prepared; (1) aluminum sulfate (Alum 1000 mg/L as Al, analytic
reagent, Sinopharm Chemical Reagent Co. Ltd., Beijing, China),
(2) Sodium alginate (cSA, 1000 mg/L, Medicine Group Chemical
Reagent Co. Ltd., Tianjin, China). All the solutions were prepared
using deionized water and stored at 4 C.
2.2. Test water
The raw water in the coagulation experiment was prepared by
adding designated amounts of D.Y. RGFL in tap water. The dye
was obtained from Jinan No. 2 Textile Dyeing Mill, China. The synthetic dye wastewater was prepared by adding 0.1 g of D.Y. RGFL
powder in 1.0 L tap water and the concentration of D.Y. RGFL
reached 100 mg/L which was close to that in actual printing and
dyeing wastewater [21]. The characteristic wavelength for the
dispersed dye water was determined by a spectrophotometer
(TU-1810, Pgeneral Instrument Co. Ltd., Shanghai, China). The maximum absorbance wavelength (kmax = 445) was used for all absorbance readings. The relationship between absorbance value at kmax
and dye concentration was linear, constituting a basis of conversion of absorbance value at kmax data into an equivalent dye concentration. Color removal efciency was calculated by comparing
the absorbance values of the treated wastewater and the absorbance value of the original dye wastewater, with distilled water
serving as a Ref. [21]. The characteristics of D.Y. RGFL were shown
in Table 1.
2.3. Wastewater characteristics and analytical methods
Wastewater to be tested was obtained from the Binzhou Textile Company, Shandong Province, China. The wastewater was
0.8
B
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
dark yellow in color, which was caused by two main dyes disperse yellow and reactive yellow, and it also contained high
concentrations of organic matter including dyes, additive, surfactant and others. Dyes can contribute about 20% COD. The
characteristics of the wastewater were: COD = 2860 mg L1,
Abs (sum) = Abs(330) + Abs(400) + Abs(445) = 2.756, pH = 10.26.
The color and COD of inuent were measured throughout the
experiment. Color measurements were conducted with TU-1810.
As the wastewater contained different kinds of dyes, the traditional
method of applying the maximum absorbance was not utilized.
Color content was determined by measuring the absorbance at
three wavelengths (330 nm, 400 nm, 445 nm) and taking the sum
of these absorbencies. The COD of the test water sample was measured on the TL-1A COD reactor.
2.4. Jar test
Coagulation experiments were preformed in 1.5 L plexiglass
beakers using a conventional Jar-test apparatus (ZR4-6, Zhongrun
Water Industry Technology Development Co. Ltd., China). Standard
jar tests were conducted at room temperature (20 1 C). During
the rapid stirring at 200 rpm (G = 51.6 s1), predetermined amount
of coagulant was dosed to obtain a certain AS and SA concentration. The doses of AS ranged from 4.0 to 6.5 mg/L as Al, while SA
dose (calculated as mg/L of SA) was 0.5, 1.0, and 2.0 mg/L, respectively. When organic polymer was used as coagulant aids, the best
results were obtained when the polymer was added after the addition of the primary coagulant [22]. In this comparative experiment,
AS was added rstly at the start of rapid mixing phase (200 rpm),
followed by SA after 30 s. This dual-coagulant was denoted as
ASSA. The wastewater samples were mixed rapidly for 2.5 min
after dosing, followed by slow stirring at 40 rpm (G = 11.8 s1) for
20 min and sedimentation for 30 min. After occulation, supernatant samples were withdrawn from about 20 mm below the wastewater surface for measuring absorbance and analyzing color
removal efciency. In order to investigate the relation of color
Table 1
Dye characteristics.
Name
Type
D.Y. RGFL
Molecular structure
kmax (nm)
OH
445
Dsize
Dtime
PN
Ratio
i1 ratioi timei
PN
i1 timei
Time-weighted varianceTWV
s
PN
PN
2
i1 Ratioi Ratio timei =
i1 timei
100%
Ratio
Floc strength factor (Sf) and recovery factor (Rf) are well-established parameters for describing oc strength and recovery ability
and can be calculated as follows [24]:
Recovery factor
100
Strength factor
d2
100
d1
d3
100
d1
182
(a)
80
60
40
Al2(SO4 )3
20
Al2(SO4)3 + 0.5 mg SA
Al2(SO4)3 + 1.0 mg SA
Al2(SO4)3 + 2.0 mg SA
-20
4.0
4.5
5.0
5.5
6.0
6.5
Dosage, mg/L
Fig. 3. Effect of dosage of coagulant on the color removal efciency.
183
184
5.0
4.0
(a)
4.5
3.5
2.5
Al2(SO4)3
4.0
Al2(SO4)3 + 1.0 mg SA
3.5
3.0
2.0
Ratio
-2
3.0
(b)
1.5
2.5
2.0
1.5
1.0
0.5
1.0
Al2(SO4)3
0.5
Al2(SO4)3 + 1.0 mg SA
0.0
0.0
-0.5
4.0
4.5
5.0
5.5
6.0
4.0
6.5
4.5
5.0
Dosage, mg/L
0.7
6.0
6.5
(c)
Al2(SO4)3
0.6
Al2(SO4)3 + 1.0 mg SA
0.5
TWV
5.5
Dosage, mg/L
0.4
0.3
0.2
0.1
0.0
4.0
4.5
5.0
5.5
6.0
6.5
Dosage, mg/L
Fig. 5. Effect of SA on oc growth rate (a), Ratio (b) and TWV (c) as a function of coagulant dose in color removal.
respectively. Jar tests were performed as mentioned above to evaluate the inuence of SA on oc breakage and re-growth at low and
high doses. The results were shown in Fig. 6. Compared to AS,
ASSA coagulant exhibited faster oc growth rate with larger oc
size. The oc in the ASSA occulation process showed a sharp increase in size during the rst 200 s, achieving the largest oc size.
The sharp growth of oc size in the rst 200 s was likely due to the
aggregation of particles. The extended stirring resulted in the
breakage of aggregated ocs. The ocs formed by ASSA were lager
than those of AS. As shown in Fig. 6a and b, for AS, when AS dose of
4.5 mg/L was used, ocs showed apparent decrease immediately
after the mixing speed was up to 400 rpm. Once the original slow
stir speed (40 rpm) was reintroduced, the ocs began to re-grow.
However, the ocs could not re-grow to anywhere near their previous size. When the SA was used as the coagulant aid, the ocs
did not show sharp decrease with increasing shear speed. After
re-growth, the ocs could re-grow to its previous size.
To investigate oc variations in detail, oc strength and recovery factors, as calculated by Eqs. (4) and (5), were used to interpret
the oc strength and recoverability (Table 2). For ASSA, compared
to the lower dose, the higher dose produced weaker ocs, which
could be attributed to the large ocs being more exposed to micro
scale energy-dissipating eddies that led to oc breakage. The reason for the contrary variation trend of AS may be that AS addition
increased the number of bonds in ocs which provided more contact between dye particles and coagulant molecules. Flocs formed
by ASSA presented better reformation capacity than those by AS
for both doses investigated. For ASSA, after the ocs were broken,
the SA with the special structure attraction and Van der Waals on
newly exposed ocs surface may bond the oc fragments together,
resulting in the good recoverability of the ASSA ocs. Compared
to ASSA, the ocs formed by AS showed poor oc recovery after
oc breakage, which suggested that the adsorption/entrapment
of the hydrolysates of AS on microocs was signicantly weakened
in the oc re-growth process. Yukselen and Gregory [33] have
reported that the chemical bonds broken during oc breakage process may lead to the irreversibility of oc breakage for hydrolyzing
coagulants, and this is a possible reason for the poor recoverability
of ocs formed by AS.
3.3.2. Effect of shear rate
A series of jar tests were conducted to investigate the effect of
high shear on oc breakage and re-growth. In this study, AS dose
of 6.5 mg/L and SA dose of 1.0 mg were selected to investigate
the effect of shear rate on oc properties. The suspension was exposed to an increasing shear rate from 50 rpm to 400 rpm after the
slow stir phase as mentioned above. Fig. 7 shows the oc breakage
and re-growth proles versus coagulation time.
185
(a)
40
30
AS
AS-SA
35
(a)
25
30
20
20
Ratio
Ratio
25
400rpm
15
15
G 50 RPM
G 100 RPM
G 200 RPM
G 300 RPM
G 400 RPM
10
40rpm
10
5
0
0
0
200
400
600
800
1000
1200
1400
1600
1800
-200
2000
200
400
600
800
(b)
60
AS
AS-SA
(b)
50
40
Ratio
Ratio
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
-5
time, sec
time, sec
400rpm
30
G 50 RPM
G 100 RPM
G 200 RPM
G 300 RPM
G 400 RPM
20
40rpm
10
200
400
600
800
1000
1200
1400
1600
1800
2000
-200
200
400
600
Table 2
Strength and recovery factors of ocs after different dosages.
Coagulant
Dosage, mg/L
4.5
Strength factor, %
AS
ASSA
12.52
76.36
21.9
56.84
Recovery factor, %
AS
ASSA
24.29
127.27
40.49
89.28
time, sec
time, sec
Fig. 6. Growth, breakage and regrowth proles of ocs formed by different AS doses
combined with 1.0 mg SA: (a) 4.5 mg/L; (b) 6.5 mg/L (the oc formed after oc
growth period was exposed to high shear force of 400 rpm for 3 min, shear force
was then reintroduced for a further 5 min for oc re-growth).
800
Fig. 7. The changes of oc size versus time for AS (a)/ASSA (b) coagulant at
different shear rate.
ring rate. Once the slow stir (40 rpm) which made ocs re-form
was reintroduced, the ocs began to re-grow and reached a new
steady state. The ocs could re-grow to their previous sizes at
the steady phase.
Table 3 shows the strength and recovery factors calculated by
Eqs. (4) and (5). It can be found that the shear did not break ocs
to the same degree for different shear values. For AS coagulant,
strength factors decreased with the increase of shear rate. However, it should be noted that the strength and re-formation of ocs
were not only controlled by shear rate but also by characteristics of
different coagulants. Flocs formed by ASSA had better ability to
resist shear with the higher strength factor under the same conditions and presented a better re-formation capacity based on the
higher recovery factor values as shown in Table 3.
Table 3
Strength and recovery factors of ocs after different shear rate.
Coagulant
G, rpm
100
200
300
400
Strength factor, %
AS
86.4
ASSA
94.6
50
65.02
93.67
37.73
91.08
34.18
83.93
22.91
60.67
Recovery factor, %
AS
89.96
ASSA
96.89
73.89
97.42
68.64
91.34
66.25
86.48
62.56
83.38
186
ulant AS. The results were shown in Fig. 8. It can be seen that
ASSA is more efcient in removing color and COD than AS. For
ASSA, the maximum color removal rate is 93.4%, while for AS
the maximum color removal rate is 88.6%. For ASSA and AS, the
maximum COD removal efciency is 80.1% and 72.9%, respectively.
100
(a)
Color removal effciency,%
90
80
70
4. Conclusions
60
AS
AS-SA
50
40
30
10
20
30
40
50
60
70
Dosage, mg/L
100
90
(b)
80
70
60
50
Acknowledgements
AS
AS-SA
40
This study was supported by Independent Innovation Foundation of Shandong University (2010TS070), Jinan City University
Institute Innovation Program (201102044) and the Star Plan of Jinan (20100308).
30
20
10
20
30
40
50
60
70
Dosage, mg/L
Fig. 8. The color removal efciency (a) and COD removal efciency (b) of AS or
ASSA for textile wastewater treatment.
References
[1] J.W. Lee, S.P. Choi, R. Thiruvenkatachari, W.G. Shim, H. Moon, Evaluation of the
performance of adsorption and coagulation processes for the maximum
removal of reactive dyes, Dyes Pigments 69 (2006) 193203.
[2] B.Y. Shi, G.H. Li, D.S. Wang, C.H. Feng, H.X. Tang, Removal of direct dyes by
coagulation: the performance of preformed polymeric aluminum species, J.
Hazard. Mater. 143 (2007) 567574.
[3] D.T. Sponza, M.M. Isik, Toxicity and intermediates of C.I. Direct Red 28 dye
through sequential anaerobic/aerobic treatment, Process Biochem. 40 (2005)
27352744.
[4] V.K. Gupta Suhas, Application of low-cost adsorbents for dye removal a
review, J. Environ. Manage. 90 (2009) 23132342.
[5] T. Chen, B.Y. Gao, Q.Y. Yue, Effect of dosing method and pH on color removal
performance and oc aggregation of polyferric chloridepolyamine dualcoagulant in synthetic dyeing wastewater treatment, Colloids Surf., A. 355
(2010) 121129.
[6] B.Y. Gao, Y. Wang, Q.Y. Yue, J.C. Wei, Q. Li, Color removal from simulated dye
water and actual textile wastewater using a composite coagulant prepared by
polyferric chloride and polydimethyldiallylammonium chloride, Sep. Purif.
Technol. 54 (2007) 157163.
[7] J. DeWolfe, B. Dempsey, M. Taylor, J.W. Potter, Guidance Manual for Coagulant
Changeover, American Water Works Association Press, Denver, 2003. pp. 56.
[8] R.J. Francois, Strength of aluminium hydroxide ocs, Water Res. 21 (1987)
10231030.
[9] W.A. Banks, M.L. Niehoff, D. Drago, P. Zatta, Aluminum complexing enhances
amyloid protein penetration of blood-barrier, Brain Res. 1116 (2006) 215221.
[10] S. Polizzi, E. Pira, M. Ferrara, M. Buginani, A. Papaleo, R. Albera, S. Palmi,
Neurotoxic effects of aluminum among foundry workers and Alzheimers,
disease, Neuroxicology 23 (2002) 761774.
[11] W.W. Li, W.Z. Zhou, Y.Z. Zhang, J. Wang, X.B. Zhu, Flocculation behavior and
mechanism of an exopolysaccharide from the deep-sea psychrophilic
bacterium Pseudoalteromonas sp. SM9913, J. Chem. Technol. Biotechnol. 99
(2008) 68936899.
[12] R. Sanghi, B. Bhattacharya, V. Singh, Use of Cassia Javahikai seed gum and
gum-g-polyacrylamide as coagulant aid for the decolorization of textile dye
solutions, J. Chem. Technol. Biotechnol. 97 (2006) 12591264.
[13] A.L. Ahmad, S.S. Wong, T.T. Teng, A. Zuhairi, Improvement of alum and PACl
coagulation by polyacrylamides (PAMs) for the treatment of pulp and paper
mill wastewater, Chem. Eng. J. 137 (2008) 510517.
187
[27] D.H. Bache, E. Rasool, D. Moffatt, F.J. McGilligan, On the strength and character
of alumino-humic ocs, Water Sci. Technol. 40 (1999) 8188.
[28] E. Pefferkorn, Clay and oxide destabilization induced by mixed alum/
macromolecular occulation aids, Adv. Colloid Interface Sci. 120 (2006) 3345.
[29] B.Y. Gao, Y.B. Chu, Q.Y. Yue, B.J. Wang, S.G. Wang, Characterization and
coagulation of a polyaluminum chloride (PACl) coagulant with high Al13
content, J. Environ. Manage. 76 (2005) 143147.
[30] X. Zhan, B.Y. Gao, Q.Y. Yue, Y. Wang, B.C. Cao, Coagulation behavior of
polyferric chloride for removing NOM from surface water with low
concentration of organic matter and its effect on chlorine decay model, Sep.
Purif. Technol. 75 (2010) 6168.
[31] M. Boller, S. Blaser, Particles under stress, Water Sci. Technol. 37 (1998) 929.
[32] D.C. Hopkins, J.J. Ducoste, Characterizing occulation under heterogeneous
turbulence, J. Colloid Interf. Sci. 264 (2003) 184194.
[33] M.A. Yukselen, J. Gregory, The reversibility of oc breakage, Int. J. Miner.
Process. 73 (2004) 251259.
[34] P. Jarvis, B. Jefferson, S.A. Parsons, Breakage, regrowth, and fractal nature of
natural organic matter ocs, Environ. Sci. Technol. 39 (2005) 23072314.
[35] V. Chaignon, B.S. Lartiges, A. El Samrani, C. Mustin, Evolution of size
distribution and transfer of mineral particles between ocs in activated
sludges: an insight into ocs exchange dynamics, Water Res. 36 (2002) 476
484.
[36] M.I. Aguilar, J. Saez, M. Llorens, A. Soler, J.F. Ortuno, Microscopic observation of
particle reduction in slaughterhouse wastewater by coagulationocculation
using ferric sulphate as coagulant and different coagulant aids, Water Res. 37
(2003) 22332241.
[37] P. Jarvis, B. Jefferson, S.A. Parsons, The duplicity of oc strength, in:
Proceedings of the Nano and Micro Particles in Water and Wastewater
Treatment Conference, International Water Association, Zurich, Switzerland,
2003, pp. 6370.