Australian Journal of Basic and Applied Sciences, 3(4): 4046-4052, 2009

ISSN 1991-8178
© 2009, INSInet Publication

Enhancing of Textil Wastewater Treatment Using Different Catalysts for

Hoda Roushdy Guendy

National Institute of Oceanography and Fisheries, Anfoushy,Egypt.

Abstract: The T extile dyeing industry consumes large quantities of water and produces large values
of wastewater from different steps in the dyeing units is often rich in color. Containing residues of
dyes and chemicals, and requires proper treatment before being released into the environment. The
protection and conservation of natural resources is one of the main priorities of modern society. W ater
is perhaps our most valuable resource, and thus should be recycled. Many of the current recycling
techniques for polluted water only concentrate the pollutant without degrading it or eliminating it. In
this sense, advanced oxidation processes are possibly one of the most effective methods for treatment
of wastewater containing organic products (effluents from chemical and agrochemical industries, the
textile industry, paints, etc.). M ore conventional techniques cannot be used to treat such compounds
because of their high chemical stability and / or low biodegradability. This article describes the ozone
treatment and its application to the treatment of polluted wastewater in presence and in absence of
different catalysts. Ozone oxidation process holds great promise to provide alternative for better
treatment and protection of environment, especially when the process enhances by using different
catalysts as presented in this paper. The presence of some inert inorganic salts such as Zink sulphate
catalyst decreases both the amount of ozone reacted and time of decolourisation. For highly colored
water, color removal will usually be performed by combining several types of treatment. Oxidation
with chlorine and other oxidizing agents can be lead to satisfactory color abatement, but ozone
remains the most efficient oxidizer. The ozonation process degrades refractory, complex and non
biodegradable organic compound into simpler and more easily biodegraded compounds. Most
molecules responsible for colored matter contain one to several aromatic rings and begin to absorb
light at 250 nm. The dyestuffs existed in these wastewater are highly structured organic molecules
which are hardly break down biologically. Decolorisation of two types of azo dyes, Direct Red 4BS
and Direct Pink3B by ozone in aqueous medium was studied in presence and in absence of some salts
as (Zn SO 4 .7H 2 O, AgNO 3 , CuSO 4 .5H 2 O and Cr 2 o 3 ) to see if there is any catalytic effect of such salts
at room temperature. In this study, the effect of ozone on the two groups, the azo and the
–NHCOHN- groups for complete decolorisation. It was found that Zink sulfate catalyses the process
of color removal more than other catalysts. Equations to describe the process and to allow prediction
were developed. In this study, two textile dyes are destroyed by ozone in water solution. These dyes
were selected because of their complex chemical structure and extended application in textile industry.
This research proved its success and would have an impact on wastewater techniques using ozone,
enhancing by different catalysts, so it overcome the problems of textile and other industries wastewater
treatment.

Key words: Textile, wastewater Treatment, Catalytic ozonation, Azo Dyes.

INTRODUCTION

The environmental impact of the textile industry is associated with its high water consumption, as well
as by the color. Variety, and amount of pollutants that are discharged into the wastewater. Nowadays physical-
chemical and biological treatments are mainly applied to these effluents. (Azbar et al., 2004 , Kusvuran et
al.2004, Chan et al. 2008, Al-Ghouti et al.2007, Kara et al. 2007, Qin et al. 2007, Yu-Li et al. 2006).
However these methods concentrate the dye pollutants and necessitate secondary treatment. On the other hand,
degradation involving biological processes is not efficient as the synthetic dyes in the effluent are highly
structured polymers with low biodegradability (Lucas et al. 2008).

Corresponding Author: Hoda Roushdy Guendy, National Institute of Oceanography and Fisheries, Anfoushy,Egypt.
E-mail: [email protected]
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The amount of discharged effluents into the environment can be reduced reusing the textile wastewater
once it has been treated. It can also produce savings in water consumption, chemicals and energy. In the same
way, the quantity of treated wastewater can be improved if conventional treatments are combined with more
advanced processes as reasnable option for efficient removal of color pollutants from contaminated water.
(Bandala et al.2008, Ibhadon et al. 2008, Gemeay et al. 2008, Mounir et al. 2007).
Advanced oxidation, activated carbon adsorption, ionic exchange, membrane techniques, etc. (Giardelli
et.al. 2001). Chemical oxidation degrades organic compounds and it does not produce any additional waste.
In this kind of oxidation, the most common oxidants are ozone, H 2 O 2 and their combination with UV radiation.
Ozone is a very powerful oxidant for water and wastewater treatment. Once dissolved in the water, ozone
reacts with high number of organic compounds in two different ways: by direct oxidation, as molecular ozone,
or by indirect reaction, through the formation of secondary oxidants such as free radicals, particularly hydroxyl
radical. By means of organic matter ozonation, it is expected to achieve color and COD elimination, and an
increase of the biodegradable organic carbon for later biological stages (Bes-Pia et al.2004, Ciardelli et al.2001,
Bertanza et al.2001, Sevimli, and Kinaci, 2002, and Kweon et al.2004). Physical- chemical treatment allows
reducing dissolved, suspended colloidal and non settable matter as well as color from dyes. Depending on
the wastewater characteristics, COD of textile effluent can be reduced between 50- 70% (Bes-Pia et al. 2003,
Bes-Pia et al. 2002).
Oxidation using ozone, H 2 O 2 , and UV was reported to decolorize the wastewater, reduce its COD, and
enhanced the biodegradability of its toxic chemicals (Ledakowicz et al.2001, Arslan and Balcioglu 2001,
Dogruel et al. 2002, Lin and Lai 2000, Ciardelli et al. 2001 and Bertanza et al. 2001).
Under acid conditions ozone can mainly react directly with organic compounds, while under alkaline conditions
ozone can mainly decompose to OH radical, which reacts with the target compound (Von Gunten, 2003 and
Koch, 2002).
Catalytic ozonation is one such example of the AOPs that can fulfill the listed criteria because it is easy
to operate and the apparatus needed is simple. The presence of some heterogeneous catalyst, which could
improve the ozone capability for the degradation of refractory organic pollutant Literature review, showed that
the application of ozone in presence of catalyst in the form of metal oxide such as TiO 2 and M nO 2 can
increase the generation of hydroxyl radical. (Beltran et al.2002), or salt such as Mn + 2 , Mn + 4 and Fe + 2 (Sauleda
and Brillas.2001), has increased the ozonation rate of organic compounds as compared to ozonation alone.

M ATERIAL AND M ETHODS

The experimental set up is shown in Fig (1). It is consisted of an ozone generator, a reactor and washing
bottles. The ozone generator is cooled with water, and is supplied by a constant flow rate of oxygen or dry
air, which is led through a flow meter that indicates the rate of gas flow; it can be adjusted with a needle
valve. If the rate of gas flow is increased, the amount of ozone liberated is increased, but its concentration is
decreased, and vice versa. The azonated oxygen stream passes traveled through Tygon tubing into a reactor
stirred with magnetic stirrer. The reactor holds the dye solution under investigation, and ozonated gas stream
is dispersed into the solution to very small bubbles by means of a sintered glass dispersion stone. The
unreacted ozone passes out of the reaction vessel through Tygon tubing through two washing bottles contained
a known volume of an acidified 2% K I solution. Finally the excess gas is vented to a hood (it contains no
ozone).

Fig. 1: Schematic Representation of the Ozonation Set- Up

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The potassium iodide solution reacts with the excess ozone according to the equation:

O 3 +2KI +H 2 O ====è I 2 + 2KOH + O 2 (1)

The resulted iodine is then titrated using standard sodium thiosulfate with starch as indicator.

I 2 + 2S 2 O -2 3 ===è 2I - +S 4 O 6 -2 (2)

A standard calibration curve for the ozone generated at different oxygen flow rate and different periods
of time, without any solution in the reactor is established. From this calibration curve, the ozone input to the
reactor could be determined. The unreacted ozone is calculated from the titration .The reacted ozone at any
specified conditions can be easily calculated by material balance. Two direct dyes were used in this
investigation. The first was direct fast scarlet 4BS and the second was direct pink 3B. Both of them are water
soluble used in dying cotton, viscose, wool and natural silk. The chemical structures of the two dyes are:

Direct Scarlet 4BS (C.I. Direct Red 4BS)

Direct pink 3B (CI Direct Red 31)

For each dye the wave length of the maximum absorbance (ë m ax ) and the calibration curves at ë max of
the dye were determined .The absorbance curve was carried out at different concentration (5-40 mg/L). The
temperature was kept constant 25 C 0 and the dye solution value was 700 mL.
The ozoniser apparatus is laboratory organizer type: 301.7. A product of Erwin sander is supplied with
compressed air from air dryer the dried air is subjected to the effect of high voltage for the ozone generation,
water is used as cooling medium in the ozoniser.
Specifications:
Operation gas: oxygen, or dry air
Capacity: 5-10 g ozone/h
Concentration: 20 g ozone /m 3 ,
Maximum concentration: 40-90 g/m 3
The quantity of ozone generated is to be determined by calibration of the performance of the apparatus.
It depends on: Flow rate, current and time. It is to be noted that potassium iodide solution should be kept
neutral (using a buffer mixture), otherwise oxygen, whether unconverted to ozone or resulting from ozone
consumption according to equation 1, reacts with HI as follows:

O 2 + 4 HI ====è 2 H 2 O + 2 I 2 . (3)

And a false indication of the quantity of ozone generated is obtained.

RESULTS AND DISCUSSION

The calibration curve for the total ozone generated in gm from the ozone generator as a function of time
of ozonation in minutes is shown in Fig.(2). For this calibration curve, conditions were: Oxygen flow rate =
100 L/h and oxygen pressure = 20p.s.i. The curve is not a straight line for the entire time span; it is rather
a straight line for a short period of time up to 20 minutes then production rate increases slowly. This will
affect results in some published literature when one considers the amount of ozone produced for example after
60 minutes equals 4 times that after 15 minutes. For a correct material balance and to calculate the exact
amount of actual ozone reacted in a given system after a specified period of time, knowledge of the actual
amount of ozone generated must be correctly known.

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Fig. 2: Calibration Curve of Total Ozone Generated at Oxygen Flow Rate 100 L/h, Oxygen Pressure 20 PSI

Figure (3) shows the minimum time of decolorizaton of both dyes using ozone. It is clear that the
minimum time of decolorization for such direct dyes with ozone is a linear function in the initial dye
concentration. This mans that:
t = m c
W here:
t= minimum decolorization time by ozone
c=initial dye concentration
m=constant, varies only from dye to another.

Fig. 3: Relation between Time of Decolorization and Different Dyes Concentrations

Information gained from such graph is important since by carrying only one experiment for decolorization
at certain initial concentration, one can predict the required time for any unknown concentration. Fig. (3)
Shows that as the initial concentration of the solute (dye) in water increases, the time of decolorization
increases. If one investigates the chemical structure of the two dyes, one can scientifically guess that the scarlet
one should take more time to decolorize than the direct pink. Although both have two azo groups –N=N-, the
scarlet has one more group –NHCOHN--. In the decolorization by ozone, the azo groups are attacked first
resulting in a complete decolorization of the pink dye, where as more time is needed for the ozone to do the
job for the scarlet dye, since ozone has to work on the remaining –NHCOHN- group, the temperature was kept
constant (room temperature).

Figure (4) shows that amount of ozone reacted increases with increasing the initial dye concentration. A
relationship between those two variables is developed to be as follows:

b
Z = a C
W here:
Z = amount of ozone reacted to cause decolorization
C = initial dye concentration
a, b = constants

This means that “Z” is a logarithmic function in “C”. On a log— log paper this relation could be easily
verified. Approximately 0.17 gm of ozone is required to decolorize one gm of dye, if the initial dye
concentration in solution is 1.0g/L.

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Figure (5) shows the effect of adding different catalysts in different concentration on the amount of ozone
reacted for a 100mg/L scarlet dye sample. It is clear that some salts are better than others. In this respect zinc
sulphate was found to give the best results.
In Figure (6) the effect of these catalysts is shown. The % reduction in time of decolorization increased
as the catalyst concentration increased. Zinc sulfate was chosen as the best catalyst that enhances dye
decolorization.

Fig. 4: Effect of Initial Dye Concentration on Amount of O zone Reacted for D ecoiorization of Direct Red
4BS without Catalyst

Fig. 5: Effect of Different Catalysts Concentration on Reacted Ozone for Decolorization (Initial Dye
Concentration= 100mg/L)

Fig. 6: Effect of Different Catalysts Concentrations on % T ime Reduction for Decolorization of Direct Red
4BS by Ozone

Conclusion:
Decolorization of direct dyes by ozone can be carried out successfully and could be quantitatively
predicted. In the decolorization process, increasing the initial dye concentration results in an increase in both
the time needed for decolorization and the absolute amount of ozone reacted. Equation (1) and (2) describe
the behavior of the process. Calibration curve for total ozone generated over the full span of ozonation time
must be determined to insure correct results. The presence of some inert inorganic salts such as zinc sulfate
catalyzes the process of decolorization i.e. decrease both the amount of ozone reacted and the time of
decolorization.

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ACKNOW LEDGEM ENT

The author would like to express her deep gratitude and thanks to the one who gave her the opportunity
to learn and work in this interesting field of textile wastewater treatment, the memory of Prof. Dr. Mohamed
Safwat El Mahdy.

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