EXPERIMENTAL STUDIES ON SALINE WASTE WATER TREATMENT USING ELECTROCHEMICAL CATALYTIC REACTORS

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Leather tanning industry is highly polluting as it produces large amount of organic and inorganic pollutants. With high saline content, the wastewater invariably has a rather high conductivity because of the presence of anions and cations in the aqueous solution. Soak liquor was treated through Advanced Oxidation Process, comprising of Electrochemical catalytic oxidation (ECO) and Fentons activated carbon catalytic oxidation system (FACCO). Alum was used to coagulate the suspended particles and the supernatant was sand filtered. It was further treated in ECO reactor consisting of graphite anode, stainless steel cathode and packed with activated carbon catalyst. Electrical current supplied was 13.0A/m2 and potential applied was 8.0V. The percentage removal of COD, TOC, BOD and Protein in ECO reactor of residence time 1 hour was studied. To optimize the reactor, its various parameters such as the hydrogen peroxide concentration, ferrous sulphate concentration, voltage, current and anode to cathode surface area ratio was studied. The ECO reactor designed after optimizing the appropriate operating conditions such as current, potential difference, residence time, chemical dosing of the samples before the oxidation reactions, which can effectively reduce the organic pollutants in the soak liquor. Keywords: Soak liquor- electrochemical catalytic oxidation reactor-chemical oxygen demand-biological oxygen demand

1. INTRODUCTION
Leather tanning industry is highly polluting as it produces large amount of organic and inorganic pollutants. It has a strong potential to cause land and water pollution due to the disposal of untreated effluent. In the tanneries the hides are washed with water to remove the salt and other particles. After washing, a large quantity of water is let out as wastewater. This wastewater consisting 24% sodium chloride, traces of calcium chloride along with bio-particles like blood, flesh, skin and other suspended particles is called soak liquor. The results from the previous investigations revealed that the biological methods may not be a good choice, primarily because of the inhibitory effect of high salinity on the microbial growth. With high saline content, the wastewater invariably has a rather high conductivity because of the presence of anions and cations in the aqueous solution. To take advantage of this characteristic a plausible alternative for dealing with saline wastewater is to use the electro catalytic method. In our study, we conducted the experiments to examine the effects of various operating conditions on the efficiency of the electro catalytic method of treating highly saline wastewater and its followed by Fentons Activated Carbon Catalytic Oxidation (FACCO) for the removal of residual organics from the soak liquor.

2. AIM OF THE STUDY:

To conduct the experiments on the ECO reactor and to optimize its various parameters such as the hydrogen peroxide concentration, ferrous sulphate concentration, voltage, current, anode to cathode surface area ratio, duration. Based on the optimized values, ECO reactor of the following capacities 50m3 per day, 100 m3 per day, 150 m3 per day and 200 m3 per day is to be designed.

3. MATERIALS AND METHODS 3.1 Experimental Procedure

The soak liquor is generated from tanneries; waste pieces of salted hide (trimmings) were soaked in water overnight. 4 liters of water was added for every 1 kg of salted hide. The soak liquor was then cloth filtered to remove sand particles and hair. A part of this filtered soak liquor is collected as the initial sample for analysis.

3.1.1 Primary clarification

The filtered soak liquor is coagulated to settle the suspended particles using a 2% alum solution. After the addition of alum the solution is allowed to stand for two hours. After 2 hours the supernatant is siphoned out. 2

3.1.2 Sand filter

A sand filter was used with diameter of 6 cm and height 30cm. It consisted of 2.5 cm layer of gravel (diameter 3 mm). This was followed by a 10 cm layer of coarse sand ( diameter 1mm). The supernatant liquid was poured into the sand filter through the top and drained at the base through a hole about 2mm in diameter.

3.1.3 Batch studies on electro catalytic oxidation reactor

The coagulated and sand filtered soak liquor was used for electro catalytic oxidation. The oxidation reaction was carried out with initiators H2O2 and FeSO4 and mesoporous activated carbon as the heterogeneous catalyst with a set potential difference and current. The experiment was carried out with different operating conditions. The various operating conditions that had to be studied were H2O2 concentration,FeSO4 concentration, Potential difference, Current, Number of anodes, Distance between electrodes and time

3.2 Electro catalytic reactor

The electro catalytic reactor has a fiber glass body. It has a capacity of 0.006525m3. Dimensions being 0.15mX 0.15mX0.29m. The thickness of the fiber glass being 0.005m. The reactor is packed with pebbles in the bottom (diameter 5mm) for a height of 0.05m followed by gravel (diameter 1.5 to 2mm). It is then packed with activated carbon for a height of 0.15m. The cathode is made of stainless steel and it is placed close to the walls of the reactor on all 4 sides. The anode used is made of graphite. The anode is placed in the center; it has a diameter of 0.025m and a length of 0.21m. Air is supplied using air diffusers placed in the carbon bed and air is sent at a rate of 0.5cfm. An outlet is placed in the bottom its diameter being 0.4mm through which a tube is attached. The working capacity of the reactor is 1250ml. The reactor is used as a batch reactor.

Fig-1: Diagram of electro catalytic reactor

3.3 FACCO reactor

The FACCO reactor is cylindrical with a diameter of 9.5cm with a height of 50cm. The reactor is packed with pebbles in the bottom (diameter 5mm) for a height of 8cm followed by gravel (diameter 1.5 to 2mm) to a height of 2cm. It is then packed with activated carbon for a height of 20cm. The carbon bed is provided with air distributors through which air is sent at a rate of 0.5cfm. On the top the reactor has a revolving distributor through which the sample is sprayed into the reactor. An outlet is placed at a height of 5cm from the base. Before putting the soak liquor which was treated using the electro catalytic reactor into the FACCO reactor the pH is adjusted to 3.5 and 0.1ml of H2O2 per litre and 0.1g of FeSO4 per litre is added and mixed thoroughly. The mixture is fed to the FACCO reactor using a peristaltic pump. The retention time of the soak liquor in the FACCO reactor is 1 hour.

Fig-2: Diagram of FACCO reactor

3.4 Analysis of soak liquor

The various factors that must be analyzed in the soak liquor are chemical oxygen demand, total organic carbon, protein estimated by Lowrys method, microbial activity, biological oxygen demand, total solids and dissolved salts.

4. RESULTS AND DISCUSSION 4.1 Effect of H2O2

In the study of the effect of H2O2 concentration, the potential difference was maintained at 8V and current maintained at 0.8A, with the concentration of FeSO4 being 100mg/L. One anode was used and the distance between the electrodes is 0.065m. The residence time was one hour. And the different amounts of H2O2 concentrations used were 0.025; 0.05; 0.075 and 0.1ml/L.It is observed that the maximum percentage reduction occurs when a concentration of 0.1ml/L of hydrogen peroxide is used. 0.1ml It is clearly seen that better degradation of the parameters studied occurs when a concentration /L of hydrogen peroxide is used. Thus hydrogen peroxide is optimized to 0.1ml/L.

4.2 Effect of FESO4

For the study of the effect of FeSO4 concentration, the potential difference was maintained at 8V and current maintained at 0.8A, with the concentration of H2O2 being 0.1ml/L. One anode was used and the distance between the electrodes is 0.065m. The residence time was one hour. And the different amounts of FeSO4 concentrations used were 0; 25; 50; 75 and 100mg/L.The optimum 5

concentration of Ferrous sulphate has been fixed at 75 mg/L since there is no considerable change in the degradation COD, TOC and BOD when 75 mg/L or 100 mg/L of ferrous sulphate is used.

4.3 Effect of Potential Difference

For the study of the effect of potential difference, the current is maintained at 0.8A, with the concentration of H2O2 being 0.1ml/L and concentration of FeSO4 being 100mg/L. One anode is used and the distance between the electrodes is 0.065m. The residence time is one hour. And the potential difference is maintained varied using a rectifier as 2V, 4V, 6V and 8V. It has been observed that the organic depletion was maximum when the potential difference in the electro catalytic oxidation reactor is maintained at 8 V and it was noted that the further increase in the potential didnt affect the values considerably.

4.4 Effect of current

For the study of the effect of current, the potential difference was maintained at 8V, with the concentration of H2O2 being 0.1ml/L and concentration of FeSO4 being 100mg/L. One anode was used and the distance between the electrodes is 0.065m. The residence time was one hour. And the current was maintained at different values, which are 0.5A, 0.6A, 0.7A and 0.8A.

4.5 Effect of Anode/Cathode surface area ratio

For the study of the effect of number of anode/cathode surface area ratio, the potential difference was maintained at 8V and current maintained at 0.8A, with the concentration of H2O2 being 0.1ml/L and that of FeSO4 being 100mg/L. Distance between the electrodes was 0.065m. The residence time was one hour. The experiment was carried out by first running the reactor with one anode and then with two and finally with three anodes. It was observed that the more the anode to cathode surface area better was the oxidation of the organics in the soak liquor though there was some loss in the net effective anodic surface area. From the observation, the surface area of the anode increases the oxidation of the organics also increase considerably.

4.6 Effect of distance between electrodes

Long gap between the electrodes may prove to be ineffective for the actual design the electrodes are spaced out at a distance of approximately 0.142 m. The following tables and graphs provide a better insight.

4.7 Effect of Duration

It was observed that as the residence time increases, there is increased oxidation of the organics in the soak liquor due to increased generation of hydroxyl radicals and hence improved reduction in the physico-chemical characteristics. It is noticed that the best results were obtained as the residence time was increased but since there was no considerable increase in reduction of the organics the residence time was optimized at 1 hr.

5. UV SPECTROSCOPY FOR THE SAMPLE:

Further a UV absorption spectroscopy was conducted to verify the degradation of the complex organic molecules to simpler organic structures. The following graphs were obtained.

Fig-3: UV absorption spectra for initial

Fig-4: UV absorption spectra for sample treated by ECO reactor.

. Fig-5: UV absorption spectra for sample treated by FACCO react

6. CONCLUSION
An ECO reactor was designed after optimizing the appropriate operating conditions such as current, potential difference, residence time, chemical dosing of the samples before the oxidation reactions which can effectively reduce the organic pollutants in the

soak liquor which is one of the main effluents discharged from the leather industries evidently observed by the reduction of COD, BOD, Protein, TOC values. Moreover, the quality of the dissolved salts, after comparing the color and the odor of the dissolved salts obtained after treating the ECO treated soak liquor sample in the FACCO reactor met the standards for reuse. No sludge is generated after treating the sample in the ECO and hence poses no problem of sludge disposal. Hence the ECO reactor can be concluded as a feasible technology for treatment of saline waste water with high organic load and especially for leather industries.

REFERENCE
[1] [2] [3] [4] [5] Marcel Dekker (1989) Chemistry and physics of carbon, vol. 21, pp.147 386 Butterworth (1989) Introduction to carbon science vol19, pp.107-51 Bio resource Technology (2002), vol. 81, pp 45-52. Chemosphere 45, (2001), pp85-90. Ellis Harwood (1987) Chemical Processes in wastewater treatment, pp185-215