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Abstract The present study was aimed to treat the dairy wastewater by photocatalytic oxidation methods. The photocatalytic treatment was carried out in a laboratory scale batch reactor with a working volume of 650mL. The main objective of the study is to evaluate the COD reduction of the effluent by varying parameters such as different catalysts (ZnO and TiO2), pH, effluent initial concentrations and light source (UV lamp and Mercury lamp). The photocatalytic oxidation using TiO2 removed higher percentage of COD than ZnO in the dairy effluent. The findings suggest that photo catalytic oxidation would be a promising alternative for the treatment of dairy wastewater. Keywords: photocatalytic; dairy; COD; TiO2
1. Introduction Dairy industries release large quantities of wastewater often the order of thousand cubic meters /day . The dairy wastewater is similar to most other agro-industries wastewaters, characterized by high biological oxygen demand (BOD) and chemical oxygen demand (COD) concentrations representing their high organic content  High concentration of organic matter in dairy wastewater causes pollution problems to surroundings . Aerobic methods tried to treat and dispose dairy wastewater  have been less efficient, mainly due to bulking and excessive growth of biomass . Installation cost of aerobic treatment systems are very high and require considerable input energy for aeration. Anaerobic method for the treatment of dairy wastewater is attracting the attention of researchers because of the presence of high organic content in the waste, low energy requirement of the process, lesser sludge production and generation of fuel in the form of methane . It is reported that the efficiency of high rate anaerobic reactors can be improved by restricting the supporting material to the top 25–30% of the reactor volume . Such a modification would further help to realize the advantages of both fixed film and up flow sludge blanket treatment. This kind of reactor, often called the hybrid anaerobic reactor has been reported to be more stable for the treatment of a series of soluble or partially soluble wastewater . Over the years, hybrid reactors have been used to treat wastewaters from sugar industry, sago, distilleries  and domestic sectors . The elimination of organics present in wastewater has been investigated using chemical and photochemical processes with varying successes . Photocatalysis using semiconductors is a subject of increasing interest which has been extensively performed worldwide to find solutions for wastewater treatment, since the discovery of ‘Honda– Fujishima Effect’ three decades ago. In these processes, the oxidation occurs through an attack of OH_, which has a rate constant billions of times higher than normal rate constants, using air as the oxidant. Among the semiconductors reported so far, outstanding stability and oxidative power makes TiO2, the best semiconductor photocatalyst for environmental remediation and energy conversion processes . The UV radiation required for the photocatalytic processes can be obtained from artificial sources or the sun. There is a significant economic incentive for solar light based
photocatalytic degradations. Recently  successfully reported the treatment of wastewater combining UASB technology and advanced oxidation processes (AOP’s) to treat food processing wastewaters. The solar photocatalytic treatment has the advantage to achieve additional destruction of organics in the wastewater but it is effective only to low strength wastewater . Considering this fact it was employed after the primary anaerobic treatment. The treatment of wastewater using UV radiation holds promise for most part of the Asia . Keeping it in mind, in the present study an attempt has been made for treating dairy wastewater.
2. Materials and methods. The effluent is collected from avin milk dairy, Karaikudi. The organics concentration in the dairy wastewater was adjusted to the desired level by diluting the feed water using distilled water. The characteristics of collected effluent is shown table.1 2.1 UV lamp setup: The lab scale photo catalytic reactor is constructed from stainless steel. The maximum loading capacity of the reactor is 500ml. A PVC frame was mounted on top of the reactor. The PVC frame had provisions for inserting the UV lamp. The exposed surface of the UV lamp was housed in PVC tube. 2.2 Mercury lamp set up:
The lab scale set up for photo catalytic oxidation is a chamber fitted with 16 watt mercury lamp. The chamber has four reflecting surfaces. 400 ml of effluent was taken in a glass beaker and placed over a magnetic stirrer inside the chamber. The chamber was covered with a wooden board. Provisions were made for collection of samples. 2.3 Analysis of COD This test is highly useful to find out the pollution strength of industrial effluents and sewage. Chemical oxygen as the name implies is the oxygen requirement of a sample for oxidation of organic and inorganic matter. COD is generally considered as the oxygen equivalent of the amount of organic matter utilizable by potassium dichromate(K2Cr2O7). The organic matter of the sample is oxidized to water, carbon di-oxide and ammonia by reflux ion with a known excess of potassium di chromate in a 50% sulphuric acid solution. The excess dichromate is titrated with a standard solution of ferrous ammonium sulphate solution 3. Results and discussion 3.1 Effect of pH and initial concentration. Solution pH is an important variable in the evaluation of aqueous-phase mediated photocatalytic reactions. It influences adsorption and dissociation of the substrate, catalyst surface charge, oxidation potential of the valence band and other physicochemical properties of the system. Hence experiments were conducted to study the impact of pH on the rate of photocatalytic degradation by keeping the catalysts TiO2 and ZnO constant (300 mg/L) and varying the pH of the anaerobically treated dairy wastewater 4.5 and 7.5. From the results we found that higher COD removal achieved at the pH of 7.5. 3.2 Effect of catalysts. In this study two types of catalysts TiO2 and ZnO were used for the photocatalytic degradation of dairy effluent. Titanium dioxide in the anatase form appears to be the most photo-active and the most practical of the semiconductors for widespread environmental application such as water purification, wastewater treatment, hazardous waste control, air purification, and water disinfection. ZnO appears to be a suitable alternative to TiO2; however ZnO is unstable with respect to incongruous dissolution to yield Zn(OH)2 on the ZnO particle surfaces and thus leading to catalyst inactivation over time and good results
have been obtained but their applications remain limited only by pH. From the results it was found that TiO2 shows better COD removal than ZnO. 3.3 Photocatalytic degradation of dairy effluent Photocatalytic oxidation utilizes ultraviolet or near-ultraviolet radiation to promote electrons from the valence band into the conduction band of a titanium dioxide semiconductor. Destruction of organic compounds takes place through reactions with molecular oxygen or through reactions with hydroxyl radicals and super-oxide ions formed after the initial production of highly reactive electron and hole pairs. As the electrons move form valence band to conduction band TiO2 generates electron hole-pairs to produces hydroxyl radicals. The hydroxyl radicals react with organic compounds to produce water and a reactive organic radical. This organic radical combines with oxygen to form peroxides which are released into the atmosphere. Figures 1 & 2 shows clearly the photocatalytic degradation of dairy effluent. From this figure we found that 76.6% and 66.6 percentage of cod reduction was obtained by TiO2 and ZnO respectively. During photocatalytic oxidation all the pollutants were converted to CO2.
Fig.1. Photo degradation using TiO2 (COD reduction: 76.6%)
Fig.2. Photo degradation using ZnO (COD reduction: 66.6%) Conclusions. The photocatalytic treatment was carried out in a laboratory scale batch reactor evaluated the COD reduction of the dairy effluent by varying parameters such as different catalysts (ZnO and TiO2), effluent initial concentrations and light source (UV lamp and Mercury lamp). The working pH and catalyst loading for the photochemical oxidation were 7.5 and 5gpL, respectively. The photocatalytic oxidation using TiO2 showed higher percentage remival of COD than ZnO in the dairy effluent. The findings suggest that photo catalytic oxidation would be a promising alternative for the treatment of dairy wastewater. From the results it was found that Photo catalytic oxidation with UV lamp gave a maximum COD removal of 77% at a pH of 7.5 in 4 hrs. Acknowledgement Authors thank Ministry of Environment and Forests for the financial support to carry out the work under Project No. GAP 23/07 and the General Manager, Aavin milk processing company, Karaikudi, Tamilnadu for providing the dairy effluent. References  Wheatley, A.D., Johnson, K.A., Winstanley, C.I., 1991. The reliability of anaerobic digestion for the treatment of food processing effluent. In: Proeedings of 5th Symposium on Anaerobic Digestion, Bolonga, pp. 135–146.  Orhon, D., Gorgon, E., Grimly, G., Rattan, N., 1993. Biological treatability of dairy wastewaters. Water Res. 27, 625–633.
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