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Ozonation of dye in a fixed bed batch bubble column reactor-a case study for the removal of persistent chemicals in waste water by tertiary treatment.
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Industrial activity generates large volume of hazardous effluents. The disposal of dye wastewater is an environmental concern since the associated colour is quite noticeable to the public and some azo dyes may have carcinogenic and/or teratogenic effects on public health. Our study will delineate the concept of tertiary treatment of wastewater taking the concept of ozonation of dye in a bubble column reactor. The main contamination of wastewater by dyes comes from textile industries. 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 colour. The ozone method is known to be effective for decomposing organic chemicals containing carbon-carbon double bonds, olefinic double bonds, acetylenic triple bonds, aromatic compounds, phenols, polycyclic aromatics, heterocyclics, carbon-nitrogen double bonds, carbon-hydrogen bonds, silicon-hydrogen and carbon-metal bonds. Dyes cannot be removed by primary and secondary treatment processes but can be removed by tertiary treatment process. So the need of an advanced oxidation process(AOP). Ozonation is an advanced oxidation process. 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. The present study will describe the reaction kinetics of dye ozonation . The ozonation of dyes was found dominant by


pseudo first-order reaction. The efficacy of the ozonation is explained by the fact that the oxidation potential of ozone(2.07 volts) is 1.52 times higher than that of chlorine. The high oxidation potential allows it to degrade most organic compounds.Our goal will be to study the ozonation of dye in simple batch bubble column and also fixed bed batch bubble column and thus study the ozone kinetics as a strong future understanding of this area. So the vision and objective will be to describe the ozonation in a bubble column reactor which is according to our study the best gas liquid contacting device.


column, ozonation, water treatment , oxidation process, COD,BOD, reactor.

The increasing world population with growing industrial demands has led to a situation where protection of the environment has become a major critical issue and a crucial factor for several industrial processes, which will have to meet the requirements of the sustainable development of modern society. In order to combine industrial activities with preservation of the environment(sustainable development),there is a tendency in most countries to adopt rigid environmental legislation where the well known Green Technology plays a key role. Water pollution is a major issue for modern society. Therefore recycling process water is a growing need for a variety of industries faced with increasing water costs and environmental constraints. Several industrial finishing activities ,such as printed circuit board, the dyeing process and wood-pulp bleaching, generate large volumes of rinse water contaminated with several different inorganic and organic compounds. Wastewater from textile industry is generally characterized by high chemical levels and biological oxygen demand, total suspended solids and strong colour. Neither simple chemical nor biological treatment has proved adequate in de -colorization and sufficient depletion in organic matter so far. Surplus dyes which are not fixed to the fabric throughout the dyeing process-e.g hydrolyzed reactive azo dyes are the main organic components in effluents from textile mills. They are complex organic compounds containing various substituted aromatic nuclei. Their low BOD5/COD(usually less than 0.1) indicate their resistance to conventional biological treatment. Additional oxidative treatment steps-e.g. ozonation –are promising techniques to reduce these recalcitrant wastewater loads. High colour


removal efficiency, enhanced biodegradability, destruction of phenolic compounds as well as considerable reduction in chemical oxygen demand (COD) can be attained by ozonation for textile mill effluents.

Textile plants consume large quantities of water and conventional treatment results in an effluent with high chemical oxygen demand(COD),low biological oxygen demand(BOD) and high colour concentrations. Wastewater containing colour poses a variety of issues to receiving streams including the introduction of toxic or compounds that are recalcitrant to the native microbial consortium. Ozonation is a common treatment for colour containing wastewater as it has been shown to decrease colour, COD and increase the biodegradability(BOD5:COD) of the wastewater. Color reduction in waste water by ozonation can be primarily related to the amount of ozone utilized and it has also been shown to be a function of several additional process variables including initial system pH, temperature, and COD, color and solids concentrations. In our study,a bubble column was used to evaluate the effect of ozonation on the removal of Direct Red 23 from water. Results indicate that ozonation is very effective at removing dye from synthetic textile wastewater. Our study will forecast reaction efficiency of chemicals (such as Red dye) and ozone for various mixing regimes. Ozone oxidation , which can raise the ORP to 2000mV at room temperature offers a model system to study homogeneous oxidation reaction in a fixed bed.

Our delineation of ozonation will start with its inherent mechanism.The oxidation potential of ozone(2.07 volts) is 1.52 times higher than that of chlorine. The high oxidation potential allows it to degrade most organic compounds The oxidizing ability of ozone is derived from the third, or nascent oxygen atom. Oxygen and hydroxyl radicals(OH’) generated in the aqueous solution are able to open the aromatic rings. Theoretically, ozone is able to oxidise inorganic and organics to their highest oxidation states, depending on the molecular selectivity and decay rates. The decomposition rate of ozone is affected by pH, temperature and ozone concentration. Ozone reacts with organic compounds dissolved in water through either direct attack or indirect free radical attack. The hydroxyl radicals are generated by ozone decomposition in aqueous solutions and especially


catalysed by hydroxide ions(i.e. higher pH) or intermediate products of ozonation with decomposition-promoted properties such as formic acids. During the ozonation process, dyes lose their colour by the oxidative cleavage of the chromophores. The direct reactions of ozone are very suitable for opening aromatic rings by means of ozone cycloaddition, while the indirect attacks are very suitable for mineralization of the total organic carbon(TOC).

The reaction kinetics of ozonation can be determined after the Osat is reached, and the resistance of the ozone transfer from gas phase to liquid phase becomes insignificant where the concentrations of ozone are uniform in the liquid. In this view,the ozone consumption rate is determined solely by the rate of chemical reaction in the bulk. The reaction kinetics of dye ozonation, therefore ,was studied under this circumstance, and the rate constants of dye decay were determined at various initial dye concentrations and pHs. The ozonation at different pH s have showed that the reaction followed a pseudo first-order reaction. Since the oxidising ability of ozone comes from either molecular ozone or hydroxyl free radicals, the rate of dye disappearance can be formulated as follows:

d [ D] = K 0 [ D ][ O3 ] + K OH [ D ][ OH ' ]......... .......( 1) dt

H where [D ] is the concentration of dye in the solution, [O3 ] and [O ' ] are

the concentrations of ozone and hydroxyl radicals, and K 0 and K OH are the respective kinetic rate constants. In this study, since the ozone was offered in excess, the hydroxyl free radicals and ozone concentration in the solution are presumably close to constants(i.e. at steady state).Therefore, equation(1) can be rearranged to the pseudo first-order equation in equation(2) where the K is the overall pseudo first – order rate constant.

d [ D] = −( K 0 [O3 ] + K OH [OH ' ])[ D ] = −K [ D ]......... ..( 2) dt

Treatment of industrial or domestic wastewater by ozone takes place in diffusion ozone contactors or mechanically agitated reactors. Therefore, the ozonation process not only depends on the kinetic reactions but also on the


mass transfer between phases. On the one hand , the kinetic reaction is a complex mechanism, the consumption of ozone by water depends on the water quality parameters such as temperature, pH, alkalinity and organic matter content. On the other hand, the efficiency of ozone mass transfer depends on the hydrodynamic behaviour of the fluid, solubility ratio and mass transfer coefficient. Ozone can react with organic compounds through molecular or radical reactions. Electrophillic attack by molecular ozone is very selective and usually occurs with atoms that have a negative charge density(eg. N,P,O) and nucleophillic carbons,and with multiply bonded constituents such as carbon-carbon and nitrogen-nitrogen. Ozone can react also through the hydroxyl radical(HO’) generated during its decomposition. HO’ generation is usually promoted at high pH, with the addition of hydrogen peroxide, UV irradiation or by reaction with the organic compound itself. The hydroxyl radical is very powerful(E0=2.80V) , and a non -selective oxidant, which can be used to enhance the decay rate of organic compounds. However, various studies have shown that the partial oxidation of the azo dye(i.e. colour removal)is performed by molecular action of ozone without a significant reduction in total organic carbon(TOC).

Our aim and objective is to unfold the hidden secrets of the kinetics of ozonation or oxidation of dye. Vision and objectivity of scientific research is massive and untold. The preliminary understanding is given below. Most commercial dyes used today are mixtures of dye pigments and other auxillaries. The purified dye were tested by spectrophotometer to ensure that the samples obeyed Beer’s law. In our research, all experiments were carried out in a 30l cylindrical contact tower. The ozone output in an ozonator (ENALY-OZU-300U)is 200-300mg/hr. First degradation of dye solutions in simple bubble column are aimed. Then dye degradation with gravels in the bubble column(fixed bed) are investigated. The dye taken is Direct Red 23,a dye used in textile industries.


Figure1:Structure of Direct Red 23 dye
Different purified dye concentrations(100 mg/l,110mg/l,121 mg/l,134.5mg/l,200mg/l and 300mg/l) and saturated ozone concentrations in excess(by adjusting air flow rate)were applied to investigate the reaction kinetics of dye ozonation. After that ozonation was tested for initial dye concentrations of 60mg/l,70mg/l,80mg/l and 100mg/l with gravels. Samples were collected from the bubble column reactor at times of 5,10,15,20,25,30 minutes, then the residual dyes were analysed by UV spectrophotometer(UNICAM made) for measurement of absorbances. Some preliminary results of our research are shown below. Absorbances are found out from the samples taken. The relation between absorbance and concentration is y=0.0302 x + 0.4135[y=Absorbance, x=concentration(mg/l)] R2=0.9655,R=regression coefficient. The rate constant( k ) and order of reaction( n ) was found out by the following process:

dC A n = kC A dt dC A )=log( k )+ n log( C A ),Y=a + b X dt dC A ),a=log( k ),b= n ,X=log( C A ) dt

log( −

Y=log( −

The constants a and b can be found out by the following equations;


∑y=a n +b ∑x, ∑x y=a∑x+b∑x2 The order of reaction ( n ) is found to be in accordance to Konsowa et al(2003) .The value lies between 0.7 to 1.2.

Fig2: Concentration vs Time-without media


Fig3:Concentration vs Time-without media

Fig4: Concentration vs Time-with media

Fig 5: Conversion vs Time-without media


Fig 6:Conversion vs Time-without media

Fig 7: Conversion vs Time-with media


EXPERIMENTAL ANALYSIS OF THE DATA OBTAINED: Trends seen from the experiment:
• More or less 80% degradation can be obtained for 60mg/l,70mg/l,80mg/l and 100mg/l for dye degradation in presence of gravels Within 30 minutes the degradation conversion reaches 80% for these initial concentrations The following are the final degradation (with gravels)  60mg/l-96%-30minutes  70mg/l-91%-25minutes  80mg/l-75%-30minutes  100mg/l-70%-30minutes

• •

Some other trends(without gravels):
 134.5mg/l,98% conversion,30min,order-0.74  121mg/l,97% conversion,20min,order-0.255  200mg/l,70% conversion,30min,order-0.875  100mg/l,72% conversion,40min,order-0.61

• It can be seen that the degradation rate is higher for bubble column reactor with gravels or media. This shows that fixed bed bubble column reactor is effective. High mass transfer rate and high contact surface area being helpful in dye degradation High volumetric mass transfer coefficient in fixed bed reactor.

• •


Difference in different types of order due to the different types of parallel, series and multiple reactions of the breakage of the azo or anthraquinone dyes.

The differences observed in the rate constant and the order of reaction is due to the breakage of the double bonds of azo or anthraquinone dyes and different products are obtained. Decolorization was complete within a few minutes of ozonation possibly due to the cleavage of chromophore groups. It was observed that its structural destruction occurs predominantly at higher pH’s. The results obtained by the experimental study confirm that a definite step of a combined treatment concept is a potential technique for decolorization and biodegradability enhancement of wastewater containing reactive azo dyes. It could be applied as a selective measure for the treatment of segregated line streams and is a promising tool for highly flexible wastewater treatment avenues

Ozonation of dye is a vast avenue to deal with in today’s scientific era. Man’s research endeavours are intense,vast and versatile. Our study projected a minor and a minute portion of a giant chemical application. Textile dye effluents are a persistent environmental problem. It is a major health and environmental hazard. So the hazard can only be effectively solved by this advanced oxidation process-ozonation. Ozonation through its strong research background hope to be an effective avenue and intense alternative. Thus this procedure can bring in more research thoughts and vision widening the path of learning of other persistent chemicals in tertiary treatment. The message is clear. Ozonation of dye in a fixed bed bubble column reactor is pathbreaking and absolutely inspiring. It can unfold and unveil many unknown problems of dye ozonation. Environmental pollution due to dye effluents will be a major research area and its abatement will not be a distant dream in future.



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