DESALINATION

ELSEVIER Desalination 158 (2003) 233-240

www.elsevier.com/locate/desal

Decolorization of wastewater containing direct dye by ozonation

in a batch bubble column reactor
A.H. Konsowa
Chemical Engineering Department, Faculty of Engineering, Alexandria University,Alexandria 21544, Eapt
Tel. +20 (12) 216-2806; Fax +20 (3) 583-1660; email: eccocid@hotmail.com

Received 30 January 2003; accepted 5 February 2003

Abstract
Decolorization of wastewater containing direct dye (Isma Fast Red 8B) by ozonation 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 bubblmg ozone at the bottom of a bubblecolumnreactorcontainingthe dye solution.The effect of
dye concentration,ozone dose, ozone air flow rate and solution pH on the rate of decolorizationwas studied. The
reactionrate was followedby measuringthe dye concentrationat differenttimes of the decolorizationprocess.The rate
of dye oxidationwas found to increasewith increasingozone concentrationin the gas phase (air-ozone) and decreases
with increasingthe dye concentration.The rate of dye oxidationincreaseswith increasinggas flow rate, reaches a
maximumandthen decreaseswitha furtherincreaseinthe gasflowrate.The rate of dye oxidationwas foundto increase
with increasingsolution pH. The decolorizationbreakdownproducts were tested for toxicity and were found to be
nontoxic.

Keywords: Dye decolorization;Ozonation;Bubblecolumnreactor

1. Introduction textile effluents [2]. However, the color of waste-

water from today’s new dyes is much more diffi-
One of the main problems in the treatment of
cult to treat by physical techniques such as
textile dyeing waste water and dye manufacture
adsorption and chemical coagulation to achieve
wastewater is the removal of dye color [ 11.In the
corn-plete decolorization, especially for highly
late 195Os, the trickling filter and activated
soluble dyes. Apart from the physical methods of
sludge processes were shown to be capable of
decolorization, chemical oxidation using oxi-
removing between 84 to 93% of the color in
dants such as ozone, chlorine or hypochlorite,

Presented at the European Conference on Desalination and the Environment: Fresh Waterfor All, Malta, 4-8 May 2003.
European Desalination Society, International WaterAssociation.

001 l-9164/03/$- See front matter Q 2003 Elsevier Science B.V. All rights reserved
PII: SO01 l-9164(03)00458-2
234 A.H. Konsowa /Desalination I58 (2003) 223-240
hydrogen peroxide, potassium permanganate can
be used to destroy the dye to a colorless solution;
the breakdown products can be removed by
conventional biological treatment processes.
A comparison between different oxidants such
as Cl,, H202, KMnO, and 0, was carried out by
Bowers [3], who found that ozone generally
produces nontoxic breakdown products which are
finally converted to CO, and H,O if the con-
ditions are drastic enough, and excess ozone
decomposes after a few minutes to oxygen
without harmful residue, as opposed to other
inorganic oxidants.
In an earlier study [S], the removal of acid dye
(acid fast Red EG) by ozonation was carried out.
The results proved that textile dyeing wastewater
treatment by ozone is a promising technique.
The aim of the present work is to study the
factors affecting the rate of decolorization of a
synthetic waste solution containing a water-
soluble direct dye (Isma fast Red 8 B) by ozone
gas. The study was conducted using a batch
bubble column to take a advantage of the
intensive back-mixing that prevails in bubble
columns. The strong back-mixing reduces the
mixing time between the reactants and accele-
rates the process of decolorization. In addition,
bubble columns are simple in their design and
operation due to the absence of mechanical
moving parts.
2. Materials and methods
The experimental set-up shown in Fig. 1
consists of an air dryer and compressor, ozone
generator, glass bubble column reactor and four
washing bottles. The air dryer consisted of a
column which was filled with a high adsorptive
molecular sieve. Ozone was generated using a
laboratory ozonizer Model 30 1.7 (Erwin Sander);
water was used as the cooling medium. The
reactor had a glass column of 5-cm diameter and
35-cm height with sintered glass at the bottom
through which 0, was introduced to the solution.
The reactor was followed by four washing
bottles, each of them containing 250 ml of acidi-
fied 2% KI solution for determining unreacted
ozone. Before each run the bubble column
reactor was filled with 500 cm3 of the dye solu-
tion. Compressed dry air was allowed to pass
through the ozonizer where ozone formation
takes place. The outlet stream from the ozonizer
containing 0,, 0, and a N, 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 was measured by air flowmeters. The
temperature was fixed at 20°C during all the
experiments.
The unreacted ozone was taken out of the
bubble column reactor through the tygon tubing
and bubbled into the 2% KI solution contained in
the washing bottles where the potassium iodide
solution reacted with the excess ozone according
to the following equation:
0, + KI + H,O - I, + 2KOH+O, (1)
The resulting iodine was titrated using standard
sodium thiosulphate in the presence of starch as
the indicator. The values ofunreacted and reacted
ozone were determined, accordingly [ Ill.
The dye concentration time data during
decolorization was detected using spectropho-
tometry. The dye used in the present work was
water-soluble (Direct fast Red 8B) having the
following structure:
3. Results and discussion
Fig. 2 shows the change of dye concentration
with time during ozonation at different initial dye
 A. H. Konsowa /Desalination 158 (2003) 223-240 235

dye concentration = Ol
300 ppm
ozone-airflow rate = 100 Uh
dye solution volume = 500 ml

10 15 M 23 30
Ozone concentration g/m3

Fig. 1. Experimental set-up.

50

?? a
II
4
?? 0
+

0 0

??
t 0 a
150
??
?? m 0250
m A350
mm
0450
?? a 0550
P
. * 0 0 OKto

P ?a
.
A
. : = a
a
a 0
m Fig. 2. Concentration time for
??e :
??
* : A A = n different direct dye concentration
?? * ’ 8 o D
?? ’ . “1p” treated with ozone at different
5 10 15 20 15
times.
Time (min)
236 A.H. Konsowa /Desalination
ozmmcamamlmlimr2og/m~
18 dyoK4lu~ml
-WlWMtB=1OOLh
16. pH=7.5
4-
2
- tration on the decolorization time
concentration. The rate of dye removal is high at
the beginning and then decreases with time.
Fig. 3 shows the effect of initial direct dye
concentrations (150 to 600 ppm) on the time
required for the decolorization process. The
decolorization time increases with increasing
initial dye concentration in the waste. The data fit
equation
tD =mc (2)
where to is the dye decolorization time (min), m
a constant, and c the initial dye concentration
(ppm).
Fig. 4 shows the decrease of the dye concen-
tration with time at different ozone concen-
trations. The rate of dye removal increases with
increasing ozone concentration.
Fig. 5 shows the effect of ozone concentration
on the decolorization time; it is obvious that the
decolorization time decreases linearly with an
increasing ozone concentration. For instance,
increasing ozone concentration from 10.156 g/m’
to 25.14 g/m” in the gas phase reduces the decol-
orization of 300 ppm (initial dye concentration)
was reduced by about 54.3%. This result is
consistent with the theories of mass transfer [6].
I58 (2003) 223-240
Fig. 3. Effect of initial dye concen-
eO0 700
of direct dye treated by ozone.
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 increases with a
consequent increase in ozone concentration in the
solution and rate of dye oxidation. Figs. 6 and 7
show the effect of ozone-air flow rate on the
decolorization time. The decolorization time
decreases with increasing gas flow rate until it
reaches a minimum and then increases with a
further increase in the gas flow rate. The initial
decrease in decolorization time with increasing
gas flow rate (Vg) is attributed to the enhance-
ment of the rate of mass transfer of ozone from
air-ozone bubbles to the liquid phase as a result
of (1) eddies generated in the wake of the rising
bubbles, reducing the diffusion layer thickness
that surrounds the bubbles [7]; (2) increase in the
gas hold up (a), according to the equation [8],
(3)
where n ranges from 0.7 to 1.2 in the bubbly
regime which prevails at a relatively low gas flow
rate. The increase in gas holdup increases the
gas-liquid interfacial area with a consequent
increase in the rate of mass transfer of ozone
 A. H. Konsowa /Desalination 158 (2003) 223-240 237

??
Dye~=38oppm
ozoM.dtllmnb-166Lmlr
Dyarolulknvoiumr=SOOmL
a pH= 7.5
0
Ozonr conantnUon (ghn3)
L1 ??

410.15
??
12.57
??
Al5
?? 017.6
a22.0
025

8 10 12 14 16 18 20

Time (min)

Fig. 4. Concentration time data for different ozone concentration for direct dye treatment.

16 -

P 14.
g
5 12

Ii 10 -

% 6-
8-

dyecfxmntm= 3OOppm
4-
ozoneakIkwfate=looUh
2- dyesolsdutbnvolume=5OOml
0 ‘~ _...
__^__...
_._.-l”_.__
__-.___.._._-.__._ .._____..__ ~~.._.~__~~.~~~~.~___~.~_.___-~.__._
_.., Fig. S. Effect of ozone concen-
5 10 15 20 25 30 tration on dye decolorization time.
oixileaJllc&raual~

from the gas bubbles to the solution. The increase
in the decolorization time with gas flow rate after
reaching a minimum value may be attributed to
the transfer of the bubbly regime to the hetero-
geneous regime where large bubbles start to form
as a result of frequent bubble collision and
coalescence [9]. The formation of the large size
bubbles reduces the gas-liquid interfacial area
considerably, with a consequent reduction in the
rate of ozone transfer from the gas phase to the
liquid phase. As a result, the ozone concentration
in the solution decreases, with a consequent
decrease in the rate of dye oxidation. The above
analysis assumes that the liquid phase transfer
coefficient controls the rate of mass transfer of
0, from the gas phase to the liquid phase; this
238 A.H. Konsowa / Desalination 158 (2003) 223-240

Dye concen_Wppm
Dye aohaion volum~SOOml
ozoneJ-~20~
pti= 7.5

0
Ozone-air flow rate (Uh)
b
*a0
0140
Aa0
0
0400

()i __r 4

0 1 2 3 4 5 6 7 0 9 10
Time (mir)

Fig. 6. Concentration time data for different ozone-air flow rates.

A
A
A
A
A A A A

100 200 300 400 500 600

Ozone-air flow rate, Uh

Fig. 7. Effect of ozone-air flow rate on decolorization time.

assumption is justified by the low solubility of O3
in aqueous solutions [IO].
Figs. 8 and 9 show the effect of different
initial dye solution pH on the dye decolorzation
efficiency and dye decolorzation time. It is seen
that the decolorization time deceases with
increasing initial solution pH. According to
Elovitz et al. [ 1I], the pH affects the ozonation
process by affecting the rate of ozone decom-
position and ozonation kinetics. The rate of
ozone decomposition is favored by the formation
of hydroxyl radicals at higher pH values. This
 A.H. Konsowa / Desalination 158 (2003) 223-240 239
4s-

??
40. II A

0 PH
Q
??
2
A5
II10
?? ? ?
011
0
012

B
10 *

s-

0 .~_..^____~_.__.__.___~____._..__~.._._~_.~_ ___...__
*
t
_._____...~_
?? ii&,____ __.._-.-~___f_._...,_._..~.._._..,

0 1 2 3 4 S 6 7 S 8 10

Time (min)

Fig. 8. Dye concentration vs. time at different solution pH.

Fig. 9. Effect of initial solution pH

on decolorizationtime.

explains the reduction in the dye decolorization down products of the direct dye to determine the
time by about 32% when the pH value changed presence of toxic breakdown products which
from 2 to 12. Finally, the decolorization break- might adversely affect subsequent biological
down products were subjected to toxicity and a treatment. It was found that the oxidation
biodegradability test. An algae toxicity test was products are nontoxic to algae and have a high
carried on the decolorization (ozonation) break- tendency for biodegradation.
240 A.H. Konsowa /Desalination 158 (2003) 223-240
4. Conclusions
The decolorization of direct dye (Isma fast red
8B) by ozone in a batch bubble column reactor
was found to be an efficient technique for textile
dyeing wastewater treatment. Dye concentration,
ozone concentration, ozone-air flow rate and pH
were found to have a considerable effect on the
rate of dye oxidation by ozone. Toxicity tests
performed on the dye decolorization breakdown
products revealed that these breakdown products
are nontoxic, i.e., the waste solution is amenable
to further treatment by biological techniques in
order to reduce the BOD of the solution.
rw V. Caprio et al., A new attempt for the evaluation of
References
[l] E.H. Sinider and J.J. Porter, American Dyestuff
Cl11 Elavitz and U. Gunten, Ozone. Sci. Eng., 21(3)
Reporters, (1974) 36-48.
[2] I. Rizzuti, V. Augugu Liar0 and G. Marrucci, Chem
Eng. Sci., 3 1 (1976) 877-880.
r31 A.R. Bowers et al., Chemical oxidation of aromatic
compounds: Comparison of H,O,, KMn04 and for
toxicity, Departmentof Civil Engineering,Vanderbilt
University, USA, 1990. 1
PI A.H Konsowa, M.Sc Thesis, Alexandria University,
1996.
[51 V.K. Patil and M.M. Shorma, Chem. Eng. Res. Des.,
61 (1983) 21.
Fl E.L. Cussler, Mass Transfer in Fluid Systems, Cam-
bridge University Press, Cambridge, UK, 1984.
171C.H. Kuo, Mass transfer in ozone absorption,
Environ. Progress, l(3) (1982) 189-195.
PI Y.T. Shah, B.G. Kelkar, S.P Godbole and W.D
Deckwer, AICHE J., 28 (1982) 353.
PI T.Marugama,S. Yoshidaand T. Mizushina,J. Chem.
Eng. Japan, 14 (1981) 352.
the absorption constant of ozone in water, Chem.
Eng. Sci, 37(1) (1982) 122.
M.
(1999) 239-260.