Desalination 242 (2009) 256263

Decolorization of direct dye in textile wastewater by

ozonization in a semi-batch bubble column reactor
Kadir Turhan*, Zuhal Turgut
Yildiz Technical University, Chemistry Department,34220 Esenler, Istanbul,
Turkey
Tel. +90 (212) 4491642; Fax +90 (212) 4491514; email: tu rhankadir@yahoo.com

Received 6 February 2008; accepted revised 2 May 2008

Abstract
Decolorization of wastewater containing direct dye (Sirius Blue SBRR) by ozonization was studied in an
attempt to abate pollution caused by textile dyeing houses and dye-producing plants. The decolorization process
of the direct dye was carried out by bubbling ozone at the bottom of a bubble column reactor containing the dye
solution. The effect of dye concentration, ozone dose, ozone-air flow rate and solution pH on the rate of
decolorization was studied. The reaction rate was followed by measuring the dye concentration at different times
of the decolorization process. The rate of dye oxidation was found to increase with increasing ozone
concentration in the air-ozone and to decrease with increasing the dye concentration. The rate of dye oxidation
increases with increasing the air ozone flow rate and solution pH, reaches a maximum and then decreases with a
further increase in the airozone flow rate. The results with the direct dyestuff wastewater showed that
decolorization was remarkable under the basic condition of pH 12. A large amount of bubbles was formed at a
high ozoneair flow rate. After 26 min of ozone treatment, decolorization was completed. From these results, the
ozone treatment of the dyestuff wastewater in decolorization was excellent.
Keywords: Ozone; Sirius Blue SBRR; Wastewater treatments; Decolorization; Direct Blue 71

1. Introduction
Textile industries consume large amounts of
water and their effluents contain a wide range of
contaminants. Environmentally, these contaminants mean suspended solids, COD, BOD, as
well as high pH and strong color. The removal
of dye
*Corresponding author.

color in the treatment of textile dyeing and dye

manufacture wastewaters is one of the main
prob- lems of textile industry [1]. In the late
1950s, the trickling filter and activated sludge
processes were shown to be capable of todays
new dyes which is much more difficult to be
treated with physical techniques, such as
adsorption and removal 8493% of the color from textile effluents [2].
However, the color of wastewater from chemical co-

0011-9164/09/$ See front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2008.05.005

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257

K. Turhan, Z. Turgut / Desalination 242 (2009) 256263

agulation achieves complete decolorization, especially for highly soluble dyes. Most of the dye
molecules are treated highly efficiently by an
ac- tivated sludge process or any combination of
bio- logical, chemical and structured polymers;
hence it is very difficult to biologically break
them down and therefore they cannot be treated
by physical methods [3]. Although some
treatment processes achieve reduction in COD,
substantial amounts of residual color remain.
Several different meth- ods have been
developed for treatment of textile effluents. The
ozone method is known to be ef- fective for
decomposing organic chemicals con- taining
carboncarbon double bonds, olefinic double
bonds, acetylenic triple bonds, aromatic
compounds, phenols, polycyclic aromatics, heterocyclics, carbonnitrogen double bonds, carbonhydrogen bonds, silicon-hydrogen and carbonmetal bonds [4]. Most of the dyestuffs are
composed of aromatic organic compounds, so
the ozone method is getting more attention with
the prediction that it could decompose various
kinds of dyestuffs. It is reported that ozone is an
effec- tive agent for reducing the color of
dyestuff waste- water [57].

Table 1
Composite textile industry wastewater characteristics [9
23]
Parameters

Values

pH
Biochemical oxygen demand (mg/L)
Chemical oxygen demand (mg/L)
Total suspended solids (mg/L)
Total dissolved solids (mg/L)
Chloride (mg/L)
Total Kjeldahl nitrogen (mg/L)
Color (PtCo)

7.09.0
806000
15012000
158000
29003100
10001600
7080
502500

1.2. Advanced oxidation process (AOP)

The goal of any AOP design is to generate
and use hydroxyl free radical (HO) as strong
oxidant to destroy compounds that cannot be
oxidized by conventional oxidants. Table 2
shows the relative oxidation potentials of several
chemical oxidiz- ers. AOPs are characterized by
production of OH radicals and selectivity of
attack which is a useful attribute for an oxidant.
The versatility of AOP is also enhanced by the
fact that they offer different possible ways for
OH radicals [8].
1.3. Textile dye characteristics

1.1.
Textile
characteristics

wastewater

Composite
textile
wastewater
is
characterized mainly by measurements of
biochemical oxygen demand (BOD), chemical
oxygen demand (COD), suspended solids (SS),
dissolved solids (DS), and color. Typical
characteristics of textile industry wastewater are
presented in Table 1. Results in Table 1 show a
large extent of variation from plant to plant and
sample to sample. As presented in Table 1,
COD values of composite wastewater are
extremely high compared to other parameters.
In most cases BOD/COD ratio of the composite
tex- tile wastewater is around 0.25 which
implies that the wastewater contains large
amounts of non-bio- degradable organic matter
[8].

The chemical industry started in 1856 when

an Englishman William Henry Perkin
accidentally synthesized the first dye, Mauve
(aniline), a bril- liant fuchsia color, while
searching a cure for malaria. In the following
decades a considerable number of new dyes
were synthesized [27]. Nu- merous structures of
dyes exist. All are assigned with a Color Index
classification number. Accord- ing to Shore [28],
most of dyes and pigments in the Color Index
are placed in one of the 25 struc- tural classes
according to their chemical type. Azo dyes, the
largest class, are subdivided into four sections.
Classification of the four sections de- pends on
the number of azo groups within the dye
molecule. The depth of color is related to the
molecular structure of the dyes, which is related

Table 2
Oxidizing potential for conventional oxidizing agents
[2326]

Oxidizing agent
Fluorine
Hydroxyl radical
Oxygen (atomic)
Ozone
Hydrogen peroxide
Hypochlorite
Chlorine
Chlorine dioxide
Oxygen (molecular)

Electrochemical oxidation
potential (EOP), V
3.06
2.80
2.42
2.08
1.78
1.49
1.36
1.27
1.23

to the chromophores (N=N or >C=O)

involved within the structure. In addition,
visible and the UV irradiation electron transfer
effects at vary- ing wavelengths on the dye
structures have been observed, supporting
tautometic capabilities of the dye molecules. An
oscillation between the double and single bonds
occurs along the conjugated molecular chain;
therefore, as the chain becomes longer, the
vibration rate becomes slower result- ing in a
slower kinetic degradation rate. Shore [28] stated
that the reactive dye structures are 95% azo
dyes, except for some bright blues and greens.
Reactive dyes react with a substrate to form a
covalent dyesubstrate bond, where a substance
such as cellulose acts as the substrate [28]:
D CH=CH 2 OH cellulose

D CH 2 CH 2 O cellulose

(1)

where D = reactive dye structure.

Dye fixation onto fibers depends on the dye
property known as fastness, which describes its
ability to bond to the material. Reactive dyes are
very soluble in water and, therefore, are poorly
adsorbed [29]. Any additional chemicals that are
added during the dye application, such as salts
or detergents, will affect the wastewater and
subse- quently the treatment process.

The
ozonation
process
has
been
recommended in recent literature as a potential
alternative for decolorization, and improvement
of the biologi- cal degradation of textile
effluents [30]. Ozone
specifically attacks the conjugated chains that
impart color to the dye molecule. During the
ozonation process, dyes lose their color by the
oxidative cleavage of the chromophores. The
cleavage of CC double bonds and other functional groups will shift the absorption spectra of
the molecules out of the visible region [31].
Slightly more complicated is the process of
ozonation, which can take place in two ways: directly
by ozonolysis,
or induced
hydroxyl
cals formed
as a result
of ozonebydecomposition
radiin water. A part of the physical methods of
decolori- zation, chemical oxidation using
oxidants, such as ozone, chlorine or
hypochlorite, hydrogen per- oxide, and
potassium permanganate, can be used to destroy
the dye to a colorless solution. Then, the
breakdown products can be removed by conventional biological treatment processes [32,33].
The aim of the present work is to study the
factors affecting the rate of decolorization of a
synthetic waste solution containing watersoluble direct dye (Sirius Blue SBRR) by
ozone. The study was conducted using a batchbubble col- umn to take an advantage of the
intensive back- mixing that prevails in bubble
columns. The strong back-mixing reduces the
mixing time between the reactants, and
accelerates the process of decol- orization.

2. Materials and methods

Ozone was generated from oxygen (99.9%
purity) by a lab-scale ozone generator, Fischer
502
Model. A schematic diagram of the bench-scale
reactor system is presented in Fig. 1. The reactor
had a glass column of 5 cm in diameter and 110
cm height with sintered glass at the bottom
through which ozone was introduced to the
solution. Oxy- gen gas was allowed to pass
through the ozonizer where ozone formation
took place. The outlet

Fig. 1. Schematic diagram of the bench-scale reactor system.

stream from the ozonizer containing O3 and O2

mixture was allowed to pass through Tygon tubing connected to the bottom of the bubble column. The gas flow rate was controlled by a
needle valve and measured by air flow meters.
The tem- perature was fixed at 201C during
all the ex- periments [34]. The pH of wastewater
was ad- justed to the desired level with Merck
quality ana- lytical grade 0.1 N NaOH and
H2SO4. The unused ozone was taken out of the bubble column
reactor through the Tygon tubing, and bubbled
into 2% KI solution in the washing bottles,
where the potassium iodide solution reacted
with the excess ozone according to the following
equation:
O 3 KI + H 2 O I 2 2KOH +
O2

(2)

The dye concentration time data during

decolorization
were
analyzed
spectrophotometrically. The
dye
named
commercially Sirius Blue SBRR (Direct Blue
71) (C40H23N7Na4O13S4) was purchased from Dystar. It is water-soluble (Mw :
965.94 g/mol) and has the structure as shown in
Fig. 2.
3. Results and discussion
Fig. 3 shows the change of dye concentration
with time during ozonation at different initial
dye concentrations. The rate of dye removal was
high at the beginning and the decreased with
time.
Fig. 4 shows the effect of initial direct dye
concentrations (100800 mg/L) on the time re-

The resulting iodine was titrated using standard sodium thiosulfate, in the presence of
starch as indicator. The values of unused ozone
were de- termined, accordingly [35]. Before
color measurements, treated dye solutions and dye bath effluent samples were filtered by using membrane
fil-

quired for the decolorization process. The decolorization time increases with increasing the initial dye concentration in the waste. The data fit
the equation:

ter paper with a pore size of 0.45 m. The concentrations of dye solutions were determined by
Agilent 8453 model spectrophotometer at its
maximum absorption wavelength of 594 nm for
Sirius Blue SBRR [36].

where tD is the dye decolorization time (min), m

a constant, and c the initial dye concentration (mg/L). In this study, the degradability of
Sirius Blue SBRR in aqueous solutions was investigated using ozone. Additionally, decompo-

tD = m
c

(3)

SO3Na

OH
N N

N N

N N
NaO3S

NH2

SO3Na
SO3Na

Dye concentration (mg/L)

Fig. 2. Structure of Sirius Blue SBRR (Direct Blue 71).

52
48
44
40
36
32
28
24
20
16
12
8
4
0

200

250

300
400

350
450

500
600
700

550
650
750

800

12

16

20

24

28

Ozonization tim e (m in)

Decolorization time (min)

Fig. 3. Concentration time graph for different Sirius Blue SBRR dye concentrations treated with ozone at different times
(ozone conc.: 24 g/m3; dye solution: 2000 mL; ozoneair flow rate: 120 L/h; pH: 8.0).

28
24
20
16
12
8
4
0
0

100

200

300

400

500

600

700

800

Dye conce ntr ation (m

g/L)

Fig. 4. Effect of initial dye concentration on the decolorization time of Sirius Blue SBRR dye treated by ozone (ozone
conc.: 24 g/m3; dye solution: 2000 mL; ozoneair flow rate: 120 L/h; pH: 8.0).

Decolorization time (min)

sition kinetics of Sirius Blue SBRR in the presence of ozone was calculated using maximum
rate constants, from graphics of concentration vs.
time.
Fig. 5 shows the effect of ozone
concentration on the decolorization time; it is
very clear that the decolorization time decreases
linearly with in- creasing ozone concentration.
For example, in- creasing ozone concentration
from 4.21 g/m3 to
24.03 g/m3 in the gas phase reduces decolorization of 400 mg/L (initial dye concentration) by
about 90.58%. This result is consistent with the
theories of mass transfer [37]. According to
these theories, as the ozone concentration
increases in the air bubbles (carrier of ozone),
the driving force for the transfer of ozone to the
dye solution in- creases with a consequent
increase in ozone con-

centration in the solution and rate of dye oxidation.

Fig. 6 shows the effect of different initial dye
solution pHs on the dye decolorization time. It
is seen that the decolorization time decreases
with increasing the initial solution pH.
According to Elovitz and von Gunten [30], pH
affects the ozo- nization process by affecting the
rate of ozone de- composition and ozonization
kinetics [30]. The rate of ozone decomposition is
favored by the for- mation of hydroxyl radicals
at higher pH values. This explains the reduction
in the dye decoloriza- tion time by 55.71% when
the pH value changed from 2 to 12.
The color of the dyestuff is mainly due to the
aromatic covalent bonding. Ozone is an
excellent

24
20
16
12
8
4
0
0

12

16

20

24

Ozone conce ntr ation (g/m

3
)

Fig. 5. Effect of ozone concentration on dye decolorization time (dye conc.: 400 mg/L; dye solution: 2000 mL; ozone
air flow rate: 120 L/h; pH: 8.0).

Decolorization time

28
24
20
16
12
8
4
0
0

pH

10

12

14

Fig. 6. Effect of initial solution pH on decolorization time (dye conc.: 400 mg/L; dye solution: 2000 mL; ozoneair
flow rate: 120 L/h; ozone conc.: 24 g/m3).

agent in the decomposition of aromatic covalent

compounds, and it is good for the decolorization
of the dyestuff wastewater [6,38].
Raw dyestuff wastewater samples had dark
blue color before the treatment. Direct dyestuff
wastewater was remarkably decolorized with
ozone treatment. Transparent yellow color was
observed after about 14 min of the reaction. Decolorization was completed in about 26 min.
The change of the absorbance of the direct
dyestuff wastewater with time at 594 nm is
given in Table 3. The reduction of the
absorbance of the direct dyestuff wastewater
was 97.4% after 26 min of the reaction.
4. Conclusions
The decolorization of direct dye (Sirius Blue
SBRR) by ozone in a batch bubble column reactor was found to be an efficient technique for
tex- tile dyeing wastewater treatment. Dye
concentra- tion, ozone concentration and pH
were found to have a considerable effect on the
rate of dye oxi- dation by ozone. Toxicity tests
performed on the dye decolorization breakdown
products revealed that these breakdown
products are nontoxic, i.e., the waste solution is
responsible to further treat- ment by biological
techniques in order to reduce the BOD of the
solution.
The results with the direct dyestuff wastewater showed that decolorization were remarkable
under the basic condition of pH 12. A large
amount of bubble was formed at high inlet gas
flow rate. After 26 min of ozone treatment,
decolorization was completed. From these
results, the ozone treatment of the dyestuff
wastewater in decolori- zation was excellent.

Table 3
Absorbance reduction of direct dyestuff wastewater
(wavelength 594 nm)
Time (min)

Absorbance

Raw wastewater
4
6
8
10
12
14
16
18
20
22
24
26

5.8
2.5
2.1
1.8
1.4
1.0
0.81
0.63
0.51
0.43
0.34
0.25
0.15

[3]
[4]

[5]

[6]

[7]
[8]

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