Вы находитесь на странице: 1из 8

Separation and Purication Technology 95 (2012) 180187

Contents lists available at SciVerse ScienceDirect

Separation and Purication Technology


journal homepage: www.elsevier.com/locate/seppur

Coagulation performance and oc characteristics of aluminum sulfate using sodium


alginate as coagulant aid for synthetic dying wastewater treatment
Caihong Wu, Yan Wang , Baoyu Gao, Yanxia Zhao, Qinyan Yue
School of Environmental Science and Engineering, Shandong University, No. 27, Shanda South Road, Jinan 250100, Shandong, Peoples Republic of China

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

C. Wu et al. / Separation and Purication Technology 95 (2012) 180187

1.0
0.9

Fig. 1. Chemical structure of sodium alginate.

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

COD removal effciency, %

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

Color removal effciency, %


Fig. 2. Relationship between the removal efciency of color and COD of the tested
D.Y. RGFL solution.

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

Disperse yellow (RGFL)

Molecular structure

kmax (nm)

OH

445

C. Wu et al. / Separation and Purication Technology 95 (2012) 180187

removal efciency and COD removal efciency of the tested D.Y.


RGFL, different concentrations of D.Y. RGFL solution were tested.
The results were shown in Fig. 2. From this gure, it can be found
that the COD removal efciency is linear with the color removal
efciency. In this study, the color removal efciency was used to
evaluate coagulant performance. The absorbance of the liquid
was also measured by TU-1810 spectrophotometer. The zeta potential of ocs was measured by JS94H Micro-Electrophoretic
Mobility Detector.
2.5. Floc formation
In this study, Photometric Dispersion Analyzer 2000 (PDA2000)
was used to monitor the formation of oc during coagulation
occulation process. During the coagulation periods, the suspension
was continuously sampled by peristaltic pump (LEAD-1, Baoding
Longer Precision Pump Co., Ltd., China). The inow and outow
tubes were positioned opposite one another at a depth just above
the paddle in the holding ports.
In the oc formation phase, three parameters were adopted to
analyze the data collected by PDA2000 during the coagulation
occulation process: a oc growth rate of the growth region, a
time-weighted average steady-state ratio value and a timeweighted ratio variance (TWV) of the steady-state ratio value.
These parameters of PDA 2000 have been reported in detail in
some literatures. The slope of the growth region indicated the rate
at which ocs developed. The oc growth rate is a measure of coagulation rate and can be determined as [21]:

Floc growth rate

Dsize
Dtime

In this work, the time-weighted average steady-state ratio value


(denoted as Ratio) indicated the oc size in the steady-state region,
which was highly correlated with oc size and always increased as
ocs grow larger [23]. The parameter was computed as [28]:

PN
Ratio

i1 ratioi  timei
PN
i1 timei

The time-weighted ratio variance was computed using data from


the nal steady-state portion of the ratio curve. It indicated the difference of oc size in steady-state region and was calculated as
[21]:

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

3. Results and discussion


3.1. Effect of SA on coagulation performance
Fig. 3 presents the color removal efciencies as a function of the
coagulant doses. Through jar testing procedures it was found that
higher color removal efciency was achieved at the same pH range
when both the coagulations were used to treat D.Y. RGFL water.
The range of pH was 68. (This part of the experiment did not appear in this manuscript) In order to approach the actual wastewater pH as mentioned in Section 1, the dosing of acid and alkali was
reduced in practice. In this study, all the pH of test water was 8.
The main nding was that SA addition during coagulation could
enhance color removal. This is consistent with the previous research which showed that better removal could be achieved when
polymer was used in combination with a conventional coagulant
[25]. Color removal increased, to varying degrees, with the addition
of SA depending on the doses of SA and AS, and was more enhanced by SA at low AS doses than at higher ones. When AS was
used alone, color removal efciency increased gradually with
increasing coagulant doses. The maximum color removal (86.0%)
was obtained at AS of 6.5 mg/L. In this study, sodium alginate doses
of 0.5, 1.0, and 2.0 mg/L were selected for investigation. Color removal rst increased with increasing SA doses compared to AS,
and then the synergistic improvement decreased when dose of
SA was greater than 1.0 mg. That is to say, AS and SA mixture
had the most apparent synergistic improvement in color removal
when 1.0 mg SA was used (Fig. 3). SA of 1.0 mg improved color

100

2.6. Floc breakage and re-growth

Strength factor

the aggregating capacity of the ruptured ocs after breakage. The


larger the strength factor, the less sensitive the ocs are to breakage as a result of increased shear rate, which are therefore considered as stronger. Likewise, ocs with larger recovery factors show
better recoverability after high shear, that is, better re-growth after
breakage.
Coagulationocculation tests were performed by a jar test,
after the slow stir phase of occulation, and the effect of increased
shear rate on ocs breakage and re-growth was investigated by
increasing the rpm on a jar tester for a further 3 min. Each experiment was repeated twice at 50, 100, 200, 300 and 400 rpm,
followed by another slow mixing at 40 rpm for 5 min for ocs to
re-form. The dynamic oc sizes were monitored as stated in Section 2.5.

d2
 100
d1

d3
 100
d1

where d1 is the average oc size of the steady phase before breakage


or shear phase, d2 is the oc size after the oc breakage period, and
d3 is the oc size after re-growth to the new steady phase.
Here, the strength factor indicates resistance of the formed ocs
to shear force, while the recovery factor shows the sensitivity of

Color removal effciency, %

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.

C. Wu et al. / Separation and Purication Technology 95 (2012) 180187

removal by an additional 73.8%, over AS alone, at AS dose of


4.5 mg/L. At high AS doses, this improvement was less than
10.0%. Based on the above results, the dose of coagulant aid, like
occulating agents, should be optimized, because higher or lower
dose would deteriorate the coagulant/occulation behavior. Lower
dose of SA means inadequate molecules to adsorb the suspended
dye or dyealum particles, and to bridge between them. While
higher SA doses would inhibit small ocs from growing due to
the stronger repulsion force between them.
Changes in the zeta potential values of colloid microocs are generally used to evaluate the destabilization ability of coagulation reagents. The result of the experiment indicated that the relationship
of zeta potential versus the dose of different coagulants. It can be
found that the effect of SA on oc zeta potential was barely observed,
and the zeta potential was all negative within the dose range investigated. The zeta potentials were 40 mV -30 mV. Previous studies
have shown that the coagulation of organic matter by hydrolyzing
metal salts is generally described as a combination of charge neutralization, entrapment, adsorption and complexation with coagulant metal hydrolysis species into insoluble aggregates [26,27].
Pefferkorm [28] pointed out that if the charge neutralization is the
only path for coagulation, the zeta potential should be in excellent
correlation with the coagulant dose and the optimal removal efciency is achieved when zeta potential of ocs is close to zero.
According to the theories above, within the doses investigated,
the zeta potential results imply that charge neutralization was very
weak for AS and the corresponding ASSA. This indicated that
charge neutralization was not the mechanism involved in color removal, and that physical entrapment of colloids within coagulant
precipitates and adsorption might play an important role. However, it is not consistent with the reports that the coagulation with
AS was achieved by charge neutralization, bridge-formation and
sweep coagulation mechanism [29].
3.2. Dynamic analysis of oc formation process
Floc formation process with AS and ASSA coagulants was monitored by PDA. The current explanation on oc formation is as follows: after the addition of coagulant, primary particles destabilize
and come together to form small occules which further aggregate
to microocs. During oc aggregation, the larger oc structure
changes continually because the ocs internal bonds break under
shear and reform at more favorable points where the attractive
force is greater or the repulsive force is lower; when a balance
between the rate of aggregation and the rate of breakage under a
given shear condition is reached, the process of oc formation is
completed and the size of ocs reaches a steady plateau [30].

183

Fig. 4 shows the PDA monitor responses collected every 1 s. The


curves were plotted using the typical ratio obtained from the
experiments and it can be divided into three regions: lag region,
growth region and steady-state region. The growth region describes the stage of oc growth. The steady-state region describes
the balance between oc growth and breakage where the oc size
distribution no longer changes with time.
In this study, three parameters (Floc growth rate, ratio and TWV)
were obtained by the abovementioned Eqs. (1)(3) to assess oc
characteristics and the results were shown in Fig. 5. The oc growth
rate and ratio with different coagulant doses were investigated as
shown in Fig. 5a and b. Based on the discussion above, the slope of
the growth region indicated the rate at which ocs developed and
ratio could be used as a reliable indicator of oc size. Floc growth
rate and ratio increased with the increase of dose for both AS and
ASSA, which was consistent with the order of color removal. As
shown in Fig. 5, it was apparent that ASSA had higher oc growth
rate with higher oc size and more apparent oc TWV compared to
AS. For AS, in this study, aluminum hydroxide precipitates formed
the primary particles of the ocs. At low dose of AS, the adsorption
of organics prevented primary particles from contacting one another due to steric repulsive forces and the thick hydrodynamic layers [30]. As a result, the oc growth rate at the low dose appeared to
be slower than that at high dose. As the AS dose was increased, the
dye molecules only partially covered the primary particles and the
repulsion between each other was weak, which allowed primary
particles to come into close contact with one another. Therefore,
the microocs and colloids aggregated quickly at the rapid mixing
stage. For ASSA, increase in oc size with ASSA could be attributed
to the bridging ability of sodium alginate. The initial microocs
were formed due to the reaction of dye molecule with AS. When
SA was dosed, microocs aggregated into larger ones due to the
adsorption/bridging ability of SA. A higher ratio implied larger
aggregate sizes. Boller and Blaser [31] reported that larger particles
generally settled down more quickly than smaller particles of similar density. So, as to ASSA, a short retention time coupled with larger oc size formation can lead to smaller and more compact
occulation and sedimentation units. In contrast, the ocs formed
by AS coagulant were more stable and the breakage of ocs seldom
occurred during the growth period.
The steady-state variance values (TWV) for two coagulants in
treating D.Y. RGFL were displayed in Fig. 5c. In general, a larger variance value indicates a wider range of oc size distribution. Fig. 5c
shows that the variance increased with the increase of coagulant
dosage, and then reached a relatively constant value when AS
was the primary coagulant. However, when SA was used as the
coagulant aid, the TWV was much larger than that of AS, which
was consistent with the color removal and Ratio results. The results suggested that the ASSA coagulant which gave higher color
removal also gave larger oc and a wider range of oc size distribution in the treatment of D.Y. RGFL. As other researchers have observed [32], large variance may indicate the formation of ocs with
porous structure and low fractal dimension value. Moreover, ocs
formed under sweep and bridging tend to have open structure and
possibly a wider distribution of oc sizes. In contrast, charge neutralization created tighter and more condensed ocs with less variance in the distribution of oc size, which conrmed that charge
neutralization was not the mechanism of ASSA. In this case,
ASSA produced ocs with more porous and open structure
depending on its stronger bridging and sweep ability.
3.3. Floc breakage and oc recovery

Fig. 4. Typical ratio curve as a function of coagulation time.

3.3.1. Effect of coagulant dose


The effect of dose on coagulation behavior of AS and ASSA
was comparatively examined at dose of 4.5 and 6.5 mg/L as Al

184

C. Wu et al. / Separation and Purication Technology 95 (2012) 180187

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

Floc Growth Rate, 10

-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

C. Wu et al. / Separation and Purication Technology 95 (2012) 180187

(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

1000 1200 1400 1600 1800 2000

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

Floc formation and breakage were greatly affected by stirring


rate and the responses to increasing shear were different for AS
and ASSA coagulant. For AS coagulant, when the stirring rate increased to 50 rpm, ocs size decreased slightly. When the stirring
rate increased to 100 rpm and above, a signicant drop in ocs size
could be observed, and then a gradual decline followed. The ocs
began to re-grow again when the shear was reduced. However,
the ocs could not re-grow to their previous sizes at the steady
phase. This is consistent with the ndings of previous studies
[34]. However, when the stirring rate increased from 50 rpm to
400 rpm, ocs size decreased slightly at the ASSA coagulant. Flocs
formed by ASSA were almost not destroyed even at the low stir-

1000 1200 1400 1600 1800 2000

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

C. Wu et al. / Separation and Purication Technology 95 (2012) 180187

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

The effect of coagulant aid SA on coagulation performance and


oc characteristics with AS in D.Y. RGFL synthetic water treatment
was evaluated in this study. The following conclusions were
obtained:

AS
AS-SA

50

40

30
10

20

30

40

50

60

70

Dosage, mg/L
100

COD removal effciency,%

90

(b)

80
70

1. When SA was used in combination with AS, the color removal


was improved to varying degrees depending on the doses of
SA and AS, and the color removal was more enhanced by SA
at lower AS dose than at higher one.
2. The growth rate and average size of ocs formed by ASSA were
larger than those by AS in steady-state after oc growth phase,
and the distribution of oc size had a wider range.
3. For both AS and ASSA, the oc strength and recovery ability
decreased with increasing shear rates. However, both oc
strength and recovery ability were greatly improved with SA
addition.

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.

It can be explained as follows: the strength and re-growth of


ocs were partly controlled by coagulation mechanisms of different coagulants. As mentioned in Section 3.1, for AS, charge neutralization was not the mechanism involved in color removal, physical
entrapment of colloids within coagulant precipitates and adsorption might play an important role. It has been reported that the
ocs formed by charge neutralization have total recoverability
[35], while sweep and adsorption ocs have poor re-growth after
breakage [36,37]. So, the ocs formed by AS showed less ability
to resist shear and worse re-growth after breakage. For ASSA,
the oc strength factors and recovery factors were signicantly improved compared to AS regardless of the shear rate applied. It was
suspected that the microocs formed by AS were tightly connected
by SA molecules after SA addition, which resulted in the increase of
oc strength. It is only a hypothesis and needs further investigation. It has been reported that recoverability of ocs gives some
indication of the oc internal bonding structure [34]. After the ocs
were broken, the SA with the electrostatic attraction and Van der
Waals on newly exposed microocs surface may bond the oc fragments together, resulting in the good recoverability of the ocs
formed by ASSA.
3.4. Treatment of the actual textile wastewater
In this study, the color removal efciency and COD removal efciency of ASSA were compared with that of the traditional coag-

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.

C. Wu et al. / Separation and Purication Technology 95 (2012) 180187


[14] Q. Kang, B.Y. Gao, Q.Y. Yue, W.Z. Zhou, D.Z. Shen, Residual color
prolesofreactive dyes mixture during a chemical occulation process,
Colloids Surf. A: Physicochem. Eng. Asp. 299 (2007) 4553.
[15] P. Jarvis, B. Jefferson, S.A. Parsons, Floc structural characteristics using
conventional coagulant for a high doc, low alkalinity surface water source,
Water Res. 40 (2006) 27272737.
[16] Nurudeen.A. Oladoja, Yekini.D. Aliu, Snail shell as coagulant aid in the alum
precipitation of malachite green from aqua system, J. Hazard. Mater. 164
(2009) 14961502.
[17] K. Kaneko, K. Kanada, M. Miyagi, N. Saito, T. Ozeki, H. Yuasa, Formation of
water insoluble gel in dry coated tablets for the controlled release of the
ophylline, Chem. Pharmac. Bull. 46 (1998) 728729.
[18] E.L. Sharp, P. Jarvis, S.A. Parsons, B. Jefferson, The impact of zeta potential on
the physical properties of ferric-NOM ocs, Environ. Sci. Technol. 40 (2006)
39343940.
[19] J. Gregory, Turbidity uctuations in owing suspension, J. Colloid Interf. Sci.
105 (1985) 357371.
[20] S.S. Chou, S.C. Lin, C.P. Huang, Application of optical monitor to evaluate the
coagulation of pulp wastewater, Water Sci. Technol. 37 (1998) 111119.
[21] J.C. Wei, B.Y. Gao, Q.Y. Yue, Y. Wang, Effect of dosing method on color removal
performance and occulation dynamics of polyferricorganic polymer dualcoagulant in synthetic dyeing solution, Chem. Eng. J. 151 (2009) 176182.
[22] Y. Wang, B. Gao, Q. Yue, W. Zhou, Y. Chu, On-line optical determination of oc
size of Fe(III) coagulants, J. Environ. Sci. 17 (2005) 921925.
[23] T. Li, Z. Zhu, D. Wang, C. Yao, H. Tang, The strength and fractal dimension
characteristics of alum-kaolin ocs, Int. J. Miner. Process. 82 (1) (2007) 2329.
[24] M.A. Yukselen, J. Gregory, Int. J. Miner. Process. 73 (2004) 251.
[25] A. Nurudeen Oladoja, D. Yekini Aliu, Snail shell as coagulant aid in the alum
precipitation of malachite green from aqua system, J. Hazard. Mater. 164
(2009) 14961502.
[26] A. Vilg-Ritter, J. Rose, A. Masion, J.-Y. Bottero, J.-M. Lain, Chemistry and
structure of aggregates formed with Fe-salts and natural organic matter,
Colloids Surf. A. 147 (1999) 297308.

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.

Оценить