Separation and Purification Technology 104 (2013) 246–249

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Separation and Purification Technology

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

Coagulation of indigo blue present in dyeing wastewater using a residual bittern

L.F. Albuquerque a,⇑, A.A. Salgueiro a, J.L. de S. Melo b, O. Chiavone-Filho b
a
Science and Technology Center, Universidade Católica de Pernambuco – UNICAP, Brazil
b
Chemical Engineering Department, Universidade Federal do Rio Grande do Norte – UFRN, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: This work presents an experimental study evaluating the reuse of a bittern wastewater (BW) as coagulant
Received 12 August 2011 for clarification of dyeing effluent. Comparison with other coagulants was also considered. The zeta
Received in revised form 30 November 2012 potential and morphology of the flocs were investigated. Despite the importance of magnesium ion
Accepted 3 December 2012
(Mg2+), other ions contained in the BW also contributed to the clarification of the effluent sample. The
Available online 12 December 2012
removals of turbidity and color of the effluent with 200 mg Mg2+/L were higher than 95% and 80%, respec-
tively. The morphology of the flocs in the coagulation with BW was somewhat different in relation to the
Keywords:
flocs obtained with just MgCl2. The adsorption mechanism of particle was observed to be different for
Coagulation
Bittern wastewater
each coagulant. According to the results obtained in the clarification of the dyeing effluent, the bittern
Magnesium ion wastewater can be applied efficiently and economically as a coagulant in the physical–chemical treat-
Dyeing effluent ment of alkaline textile effluent.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction has a large adsorptive surface and a positive surface electrostatic

The indigo blue is the main raw material in the process of denim
dyeing. The chemical characteristic of this dye is the presence of
the ketonic group (C@O), which is water insoluble. But, in the pres-
ence of sodium dithionite in alkaline solution, the dye is converted
to its reduced form (CAOH), a leucoindigo, becoming soluble in
water and exhibiting chemical affinity with cellulose fiber [1].
The wastewater containing indigo is characterized by a dark blue
color due to the presence of the dye not fixed to the fiber during
the dyeing of the fabric [2,3]. Often, an effluent with this character-
istic is treated by physical–chemical process of clarification. This
treatment is effective in removing turbidity and color [4]. In water
and wastewater treatment, hydrolyzing metal salts are commonly
used as coagulant [5]. The coagulant agent commonly used in this
process is aluminum sulfate (Al2(SO4)3) [6], which acts in the range
from pH 5.0 to 8.0 [7]. A prior pH adjustment is required because
effluents from the process of denim dyeing have high pH levels,
between 9.0 and 12.0. Furthermore, some studies showed that
flocs formed with Al2(SO4)3 present a significant irreversibility of
the floc breakage process [8].
Several studies with magnesium chloride (MgCl2) have revealed
an increase in the efficiency of the clarification of alkaline effluents.
The magnesium ion (Mg2+) in the presence of hydroxide alkalinity
forms magnesium hydroxide (Mg(OH)2). This gelatinous precipi-
tate acts as an efficient coagulant to remove color, suspended sol-
ids, organic matter and heavy metals [9]. The Mg(OH)2 precipitate
⇑ Corresponding author. Tel.: +55 81 2119 4168; fax: +55 81 2119 4000.
E-mail address: liana@unicap.br (L.F. Albuquerque).
charge. These characteristics allow removal of the dye through
the neutralization of charges and by the mechanism of adsorptive
coagulation [4]. Another advantage of using this ion is the possibil-
ity of recycling sludge as fertilizer, which cannot occur when using
coagulants containing aluminum or iron due to the limitations of
legislation.
Tan et al. [6] reduced 98% of the color in dyeing wastewater
with MgCl2 at pH between 10.5 and 11.0. The results showed that
MgCl2 is more efficient than the polyaluminium chloride (PAC)
resulting in a lower settling time.
An alternative source of magnesium salts can be the wastewater
from solar sodium chloride (NaCl) manufacturing process.
This wastewater is known as bittern wastewater (BW) with
30,000–60,000 mg Mg2+/L [10,11]. In addition, BW contains other
ions such as sodium, calcium, potassium, chloride and sulfate
[12,13].
The aim of this study was to evaluate the clarification results of
a textile wastewater by Mg2+ as coagulant, applying BW as an
alternative source of this ion.
2. Materials and methods
2.1. Material
Samples of synthetic dye indigo blue as leucoindigo and effluent
collected at the entrance to the equalization tank were used in this
study. The dye and the effluent were donated by a dyeing industry,
located in the Northeastern of Brazil (Extremoz, State of Rio Grande
do Norte). The BW was collected at the outlet of a crystallizer of a

1383-5866/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.12.005
 L.F. Albuquerque et al. / Separation and Purification Technology 104 (2013) 246–249
Nomenclature
q2 Density of liquid
q1 Density of particle
dj Diameter of the coagulated particles
BW bittern wastewater
D Diameter of the particles
di Diameter of the particles in suspension
g Acceleration of gravity
uH Hazen unit
saline industry, located in the Northeastern of Brazil (Galinhos,
State of Rio Grande do Norte). The characteristics of the BW
collected are shown in Table 1. The coagulant solutions of
MgCl2R6H2O and Al2(SO4)3 as well as the solutions of NaOH and
H2SO4 for pH adjustment were prepared in the laboratory.
The dye solution was prepared according to the average concen-
tration of the dye contained in the effluent studied. The pH of the
effluent and of the synthetic samples were according to the litera-
ture [6]. The concentration of MgCl2 was first reported in the liter-
ature [6] and subsequently adjusted for the best result for
clarification.
2.2. Coagulation and flocculation tests
The clarification experiments with the colored samples were
performed with the solution of MgCl2 and BW separately to
observe the individual effect of Mg2+. Initially, the determinations
of optimal pH and concentrations of each coagulant were carried
out in the clarification process. The coagulation and flocculation
experiments were conducted in jar test apparatus (218/LDB06,
Nova Ética). After the addition of the sample and of the coagulant,
the speed of the stirrers was adjusted at 150 rpm for 3 min, fol-
lowed by a slow mixing at 48 rpm for 10 min, and then a 30 min
settling time. The analysis of turbidity, true color (after filtration),
zeta potential and particle diameter were performed with the clar-
ified (supernatant). The last two parameters were determined only
with the synthetic samples. The sludge obtained from the clarifica-
tion of the synthetic solution with the solution of MgCl2 and BW
were filtered and dried to analyze the morphologies of the flocs
formed.
2.3. Methods
The concentrations of the ions (Mg2+ and Al3+) in the coagulants
(BW, MgCl2 and Al2(SO4)3) were determined by an atomic absorp-
tion spectroscopy (SpectrAA-10plus, Varian). The pH was mea-
sured by a potentiometer (TEC-3MP, Tecnal) and the turbidity, by
a portable turbidimeter (2100P, Hach). The color analysis was per-
formed by a spectrophotometer (DR2000, Hach). The analysis of
the zeta potential and particle diameter were performed by a zeta
meter (Zetaplus, Brookhaven). The micrographs of the flocs were
performed by a scanning electron microscope (SEM), with the
Table 1
Physicochemical characteristics of the residual bittern.
Parameter Value measured
pH 7.37
Density (20 °C) 1.3010 g/mL
Magnesium (Mg2+) 13,000 mg/L
Calcium (Ca2+) 40 mg/L
Potassium (K+) 4500 mg/L
Chloride (Cl) 235,914 mg/L
247
mV Milivolt
N Number of contacting of the particles
ni Number of particles i
nj Number of particles j
nm Nanometer
NTU Nephelometric Turbidity Units
G Velocity gradient
amplitudes of 1250 and 10,000 (XL30-ESEM, Philips). These
analyses were performed according to APHA [14].
3. Results and discussion
3.1. Zeta potential
Fig. 1 illustrates the results of zeta potential, removal of turbid-
ity and particle diameter obtained in the coagulation and floccula-
tion experiments with the indigo blue dye. All synthetic samples
clarified had negative zeta potential. Therefore, the particles had
an anionic nature even after the addition of the coagulant.
The zeta potential remained negative in all ion concentrations
studied because there are dye particles in the medium that were
not adsorbed and not settled. A mechanism of coagulation by
charge neutralization was observed due to the increase of the zeta
potential. An increment in the concentration of the coagulant from
63 to 126 mg Mg2+/L reduced the zeta potential and did not
improve significantly the clarification (Fig. 1). At this time, the
sweep coagulation mechanism happened in the presence of
Mg(OH)2 precipitate. Gonçalves et al. [15] found that the precipita-
tion with flocs of the hydroxides removed the colloids present in
the medium by capture and the own colloids were used as seeds
for the formation of the precipitate. In this study, the removal of
turbidity was greater than 85% and the zeta potential was at its
lowest level (17.15 mV) when the magnesium ion concentration
was 60 mg Mg2+/L, approximately (Fig. 1). Therefore, this concen-
tration showed to be the most suitable conditions in this study.
The removal of turbidity increased to 92% at the highest concentra-
tion of 126 mg Mg2+/L. The increment of turbidity removal was
negligible compared to the increase concentration of coagulant.
Turbidity Removal (%)
Diameter of Particle (nm)
Zeta Potential (mV)
[Mg2+] (mg/L)
Turbidity removal (%) Zeta Potential (mV) Diam.Particle (nm)
Fig. 1. Zeta potential, removal of turbidity and particle diameter of the synthetic
sample clarified.
248 L.F. Albuquerque et al. / Separation and Purification Technology 104 (2013) 246–249

The highest diameter of the particle in the sample clarified in

the studied conditions, was determined at the concentration of
40 mg Mg2+/L (Fig. 1). Despite the flocs reach the size limit, the tur-
bidity removal was higher than 80%, even with the most flocs set-
tled. However, the increase in the coagulant concentration led to a
better decantation, as confirmed by the reduction of the particle
diameter (Fig. 1). The diameter became similar to the initial sample
at a concentration of 126 mg Mg2+/L. The flocs settled during the
coagulation and flocculation, and the remaining particles are actu-
ally residual dyes that are in suspension due to its low concentra-
tion. This was observed when the particle diameter was compared
to the turbidity removal and the zeta potential was similar to the
dye in the initial sample.
Therefore, the formation of flocs and its settlement are directly
dependent on the concentration and particle diameter, as seen in
the Camp and Stein correlation (Eq. (1)) and in the law of Stokes
Fig. 3. SEM of flocs obtained with MgCl2 (10,000).
(Eq. (2)) [16].

1
N¼ ni nj Gðdi þ dj Þ ð1Þ color of a textile effluent happened at pH greater than 11.0 and pH
6 around 7.0 in the presence of Mg2+ and Al3+, respectively. Table 2
2 shows the physicochemical characteristics of the untreated indus-
V ¼ gd ðq1  q2 Þ=18g ð2Þ trial effluent. The pH of the industrial effluent had coincidently the
recommended value for coagulation with magnesium. Therefore, it
was not necessary to adjust the pH to the application of this
3.2. Morphology of flocs
coagulant. However, for the application of the aqueous solution
of Al2(SO4)3 it was necessary to adjust previously the pH. The
The morphologies of the flocs decanted in the clarification with
results of clarification are illustrated in Figs. 4 and 5 for the three
MgCl2 and BW showed to be different. These results indicated that
coagulant systems.
the coagulation mechanism was unique for each coagulant. In
Figs. 4 and 5 illustrate the turbidity removal and the color
addition, the involvement of other ions in coagulation with BW
removal with BW, respectively. The removal results became con-
was confirmed. The flocs formed with BW were compact with a
stant from 100 mg Mg2+/L. The similarity of the turbidity removal
homogeneous microstructure and smooth. The hydrophobic flocs
with MgCl2 and BW indicated that the Mg2+ contained in the BW
were characterized to have a more defined morphology (Fig. 2).
was the main responsible species agent in the coagulation process.
However, the floc formed with MgCl2 presented as clusters of
In addition, the other ions in this wastewater contributed to the
spikes, as illustrated in Fig. 3. Morphological characteristics indi-
color removal. The concentration of Mg2+ in the BW was deter-
cated flocs hydrophilic feature due to the empty spaces before
mined to be 13,000 mg/L. Then, the concentration of 100 mg
filled with the liquid. The hydrophilic flocs absorbed much more
Mg2+/L corresponded to approximately, 7.0 L of BW/m3 of the
water and they swelled. Hence, they had greater resistance to the
untreated dyeing wastewater.
medium during the settling, reducing its speed. In addition, they
In the effluent clarification with the solution of Al2(SO4)3, the
could be easily broken.
concentration of 200 mg Al3+/L was required in order to get similar

3.3. Clarification efficiency with industrial wastewater

Table 2
After studies of coagulation and flocculation by the coagulants Physicochemical characteristics of untreated industrial effluent.
BW and MgCl2 with synthetic samples, experiments with real Parameter Unity Results
industrial wastewater containing the same dye (indigo blue) were
pH – 11.4–12.3
performed to evaluate the efficiency of the clarification. According
Turbidity NTU 1665–2484
to Albuquerque [17], the best removal efficiencies of turbidity and Color uH 1180–1576
Turbidity removal (%)

BW

MgCl2

Al2(SO4)3

[cation] (mg/L)

Fig. 2. SEM of flocs obtained with BW (10,000). Fig. 4. Turbidity removal in industrial wastewater with various coagulants.
 L.F. Albuquerque et al. / Separation and Purification Technology 104 (2013) 246–249
Color removal (%)
BW
MgCl2
Al2(SO4)3
[cation] (mg/L)
Fig. 5. Color removal in industrial wastewater with various coagulants.
removal (turbidity and color) when BW was applied as coagulant
(Figs. 4 and 5). The need for higher concentrations of coagulant
indicated a predominance of the coagulation mechanism by scan-
ning. The disadvantages of the application of Al2(SO4)3, compared
to BW or MgCl2 in alkaline and colorful effluents were:
 higher concentrations of the reagents or inputs;
 prior adjustment of pH with acid, because this increase the
costs and complexity of the process and;
 generation of sludge or residue with aluminum, due to the alu-
minum concentration in solid waste is limited by Brazilian
agency [18], being allowed up to 0.01 mg/L
An empirical evaluation about the sludge was carried out. It was
verified a settling fast (<5 min) and a small amount of the sludge
generated (<50% v/v).
4. Conclusions
Different morphologies of the flocs in the clarification of the
synthetic sample with indigo blue dye by the BW and MgCl2 solu-
tion indicate that the adsorption mechanism of particles with these
coagulants probably occurs in different ways. However, the simi-
larities of the turbidity removal results demonstrate the impor-
tance relevant of the Mg2+ in the clarification process of the
wastewater.
The coagulation mechanism of Mg2+ occurs mainly by charge
neutralization due to the approach of the zeta potential to zero fol-
lowed by a reduction with the increase of coagulant concentration.
249
The wastewater of saline industry, an unused effluent, may be
applied efficient and economically, as a coagulant in physical–
chemical treatment of alkaline textile effluent, containing indigo
blue dye.
Acknowledgments
This work was supported by CAPES (Coordenação de Aper-
feiçoamento de Pessoal de Nível Superior), CNPq (Conselho Nacion-
al de Desenvolvimento Científico e Tecnológico) and INCT
(Instituto Nacional de Ciência e Tecnologia).
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