Desalination 158 (2003) 233–240

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, Egypt
Tel. +20 (12) 216-2806; Fax +20 (3) 583-1660; email:
Received 30 January 2003; accepted 5 February 2003

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 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 gas phase (air–ozone) and decreases
with increasing the dye concentration. The rate of dye oxidation increases with increasing gas flow rate, reaches a
maximum and then decreases with a further increase in the gas flow rate. The rate of dye oxidation was found to
increase with increasing solution pH. The decolorization breakdown products were tested for toxicity and were found
to be nontoxic.
Keywords: Dye decolorization; Ozonation; Bubble column reactor

1. Introduction
One of the main problems in the treatment of
textile dyeing waste water and dye manufacture
wastewater is the removal of dye color [1]. In the
late 1950s, the trickling filter and activated sludge
processes were shown to be capable of removing
between 84 to 93% of the color in textile
effluents [2]. However, the color of waste-water

from today’s new dyes is much more diffi-cult to
treat by physical techniques such as adsorption
and chemical coagulation to achieve com-plete
decolorization, especially for highly soluble dyes.
Apart from the physical methods of
decolorization, chemical oxidation using oxidants such as ozone, chlorine or hypochlorite,
hydrogen peroxide, potassium permanganate can

Presented at the European Conference on Desalination and the Environment: Fresh Water for All, Malta, 4–8 May 2003.
European Desalination Society, International Water Association.
0011-9164/03/$– See front matter © 2003 Elsevier Science B.V. All rights reserved

The dye concentration time data during decolorization was detected using spectrophotometry. who found that ozone generally produces nontoxic breakdown products which are finally converted to CO2 and H2O if the conditions are drastic enough. Results and discussion Fig. A comparison between different oxidants such as Cl2. The temperature was fixed at 20°C during all the experiments.H. The reactor had a glass column of 5-cm diameter and 35-cm height with sintered glass at the bottom through which O3 was introduced to the solution. In an earlier study [5]. Before each run the bubble column reactor was filled with 500 cm3 of the dye solu-tion. O2 and a N2 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. as opposed to other inorganic oxidants.234 A. The air dryer consisted of a column which was filled with a high adsorptive molecular sieve. accordingly [11]. and excess ozone decomposes after a few minutes to oxygen without harmful residue. Materials and methods The experimental set-up shown in Fig. The study was conducted using a batch bubble column to take a advantage of the intensive back-mixing that prevails in bubble columns. 1 consists of an air dryer and compressor. In addition. The aim of the present work is to study the factors affecting the rate of decolorization of a synthetic waste solution containing a watersoluble direct dye (Isma fast Red 8 B) by ozone gas. 2. The dye used in the present work was water-soluble (Direct fast Red 8B) having the following structure: 3. KMnO4 and O3 was carried out by Bowers [3]. the breakdown products can be removed by conventional biological treatment processes. H2O2. water was used as the cooling medium. the removal of acid dye (acid fast Red EG) by ozonation was carried out. ozone generator. 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: O3 + KI + H2O 6 I2 + 2KOH+O2 (1) The resulting iodine was titrated using standard sodium thiosulphate in the presence of starch as the indicator. The strong back-mixing reduces the mixing time between the reactants and accelerates the process of decolorization. Ozone was generated using a laboratory ozonizer Model 301. The outlet stream from the ozonizer containing O3. 2 shows the change of dye concentration with time during ozonation at different initial dye .7 (Erwin Sander). The values of unreacted and reacted ozone were determined. Compressed dry air was allowed to pass through the ozonizer where ozone formation takes place. glass bubble column reactor and four washing bottles. The reactor was followed by four washing bottles. The results proved that textile dyeing wastewater treatment by ozone is a promising technique. Konsowa / Desalination 158 (2003) 223–240 be used to destroy the dye to a colorless solution. each of them containing 250 ml of acidified 2% KI solution for determining unreacted ozone. bubble columns are simple in their design and operation due to the absence of mechanical moving parts.

Fig. Concentration time for different direct dye concentration treated with ozone at different times. .A. Experimental set-up. Konsowa / Desalination 158 (2003) 223–240 235 Fig. 1. 2.H.

Fig. increasing ozone concentration from 10. (2) increase in the gas hold up (g).7 to 1. reducing the diffusion layer thickness that surrounds the bubbles [7]. 3 shows the effect of initial direct dye concentrations (150 to 600 ppm) on the time required for the decolorization process. and c the initial dye concentration (ppm).156 g/m3 to 25. The rate of dye removal increases with increasing ozone concentration.2 in the bubbly regime which prevails at a relatively low gas flow rate. Fig. as the ozone concentration increases in the air bubbles (carrier of ozone). Effect of initial dye concentration on the decolorization time of direct dye treated by ozone. (3) where n ranges from 0. 4 shows the decrease of the dye concentration with time at different ozone concentrations. The rate of dye removal is high at the beginning and then decreases with time. 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. According to these theories. For instance. 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. This result is consistent with the theories of mass transfer [6]. 3. 5 shows the effect of ozone concentration on the decolorization time. The decolorization time increases with increasing initial dye concentration in the waste.H. Figs. according to the equation [8].14 g/m3 in the gas phase reduces the decolorization of 300 ppm (initial dye concentration) was reduced by about 54. Fig. concentration.236 A. it is obvious that the decolorization time decreases linearly with an increasing ozone concentration.3%. The data fit equation tD = mc (2) where tD is the dye decolorization time (min). Konsowa / Desalination 158 (2003) 223–240 Fig. The initial decrease in decolorization time with increasing gas flow rate (Vg) is attributed to the enhancement 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. The increase in gas holdup increases the gas–liquid interfacial area with a consequent increase in the rate of mass transfer of ozone . 6 and 7 show the effect of ozone–air flow rate on the decolorization time. m a constant.

Konsowa / Desalination 158 (2003) 223–240 237 Fig. Concentration time data for different ozone concentration for direct dye treatment. 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 heterogeneous regime where large bubbles start to form as a result of frequent bubble collision and coalescence [9]. Fig. The above analysis assumes that the liquid phase transfer coefficient controls the rate of mass transfer of O3 from the gas phase to the liquid phase. with a consequent decrease in the rate of dye oxidation. this . The formation of the large size bubbles reduces the gas–liquid interfacial area considerably.A.H. Effect of ozone concentration on dye decolorization time. with a consequent reduction in the rate of ozone transfer from the gas phase to the liquid phase. the ozone concentration in the solution decreases. 4. 5. As a result. from the gas bubbles to the solution.

This . the pH affects the ozonation process by affecting the rate of ozone decomposition and ozonation kinetics. Figs. assumption is justified by the low solubility of O3 in aqueous solutions [10]. 6. 7. Konsowa / Desalination 158 (2003) 223–240 Fig.238 A. It is seen that the decolorization time deceases with increasing initial solution pH. The rate of ozone decomposition is favored by the formation of hydroxyl radicals at higher pH values. Concentration time data for different ozone–air flow rates. Effect of ozone–air flow rate on decolorization time. 8 and 9 show the effect of different initial dye solution pH on the dye decolorzation efficiency and dye decolorzation time. Fig. [11].H. According to Elovitz et al.

Fig. 8. time at different solution pH.H. It was found that the oxidation products are nontoxic to algae and have a high tendency for biodegradation. .A. explains the reduction in the dye decolorization time by about 32% when the pH value changed from 2 to 12. An algae toxicity test was carried on the decolorization (ozonation) break- down products of the direct dye to determine the presence of toxic breakdown products which might adversely affect subsequent biological treatment. Effect of initial solution pH on decolorization time. 9. Dye concentration vs. Konsowa / Desalination 158 (2003) 223–240 239 Fig. Finally. the decolorization breakdown products were subjected to toxicity and a biodegradability test.

Department of Civil Engineering.D Deckwer.P Godbole and W. Shah. [2] I. Sci.H. . Mizushina. Cambridge. Sci. Eng. Bowers et al.. References [1] E. B. A new attempt for the evaluation of the absorption constant of ozone in water.K. Kelkar. J. 21(3) (1999) 239–260. Alexandria University.Marugama. Eng. Kuo. UK. Augugu Liaro and G. Cambridge University Press. S. Chem.J. 37(1) (1982) 122. [10] V. (1974) 36–48... [3] A.M. 1984. Sinider and J. S.H Konsowa. [4] A. Vanderbilt University. Environ. i..e. Chem Eng. Chem. 1990. Japan. 61 (1983) 21. Konsowa / Desalination 158 (2003) 223–240 4.H. Mass transfer in ozone absorption. KMnO4 and for toxicity .. [11] M. Eng. American Dyestuff Reporters. Caprio et al. ozone concentration.T. Cussler.. [5] V. Des. Toxicity tests performed on the dye decolorization breakdown products revealed that these breakdown products are nontoxic. Porter.L.240 A. M.H. Mass Transfer in Fluid Systems. Patil and M. 1996. USA. Dye concentration. Rizzuti. Progress. 14 (1981) 352. 31 (1976) 877–880..R. Res. ozone–air flow rate and pH were found to have a considerable effect on the rate of dye oxidation by ozone. Yoshida and T. the waste solution is amenable to further treatment by biological techniques in order to reduce the BOD of the solution. [7] C.G. [8] Y. Gunten. 1(3) (1982) 189–195. 28 (1982) 353. Shorma. Elavitz and U. Ozone. AICHE J. V. [9] T. Marrucci. Chemical oxidation of aromatic compounds: Comparison of H2O2.Sc Thesis. Sci. 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. [6] E. Chem. Eng.