By Siddharth M. Choksi Guided by Mrs. A.K.Khambete Co guided by Dr.

K D Yadav

 Overview Objectives Phenols and COD from different industries Introduction of Catalytic wet air oxidation (CWAO) Methodology Results Kinetics Conclusion Future scope of study

 Phase one : Literature survey Phase two : To decide the methodology Phase three : Equipment design and selection Phase four : Fabrication of the reactor Phase five : Experiments Phase six : Analysis of results Phase seven : Development of kinetics Phase eight : Cost analysis of the technology Phase nine : Conclusion and suggestions

 To evaluate the catalytic wet air oxidation(CWAO)

technology with the different catalysts for highly concentrated industrial effluents containing Phenols as the main pollutant
To screen the catalysts for optimum economy. To find the removal efficiency of phenols and Chemical

oxygen demand (COD) with different operating parameters. To calculate the capital & operating cost of prototype To develop the kinetics that can be practically implemented.

Raw effluent form different industries

Limits set by MoEF

for Phenols and COD

Phenol : 1 mg/L COD : 250 mg/L
*Source : APHA

 Advance liquid phase oxidation

process for highly polluted industrial waste effluent

Several emerging liquid phase

oxidation methods can be distinguished in terms of the different oxidants, catalysts and operating conditions selected.
Overall efficiency can be increased

with low energy requirements in CWAO compared to WAO.

Currently, there are more than 200

plants operating around the world, for treatment of sewage, industrial effluent and regeneration of the activated carbon.
Typical operating conditions are in the

Suitability of water technologies according to COD contents

* Source : R. Andreozzi, V. Caprio, A. Insola, R. Marotta, Catalysis Today 53 (1999) 51.

range of 100-30 0C and 0.5-20 MPa.

 To prepare the synthetic raw effluent in the laboratory Methods The raw effluent sample will be run through the reactor for the

desired operating parameters

Reactor Operating parameters Possible modifications

The treated effluent will be analyzed in the laboratory for the

final efficiency
IS 3025(part 43):1992 for Phenols IS 3025(part 58):2006 for chemical oxygen demand (COD)

To develop the kinetics through actual results for further

simulation.

 Raw effluent
As per APHA 590 mg/L of Phenols 0.6 gm of solid Phenol crystals are to be dissolved in 1 liter of distilled water (purity : 95 to 99 %) Total 3 liters 51,500 mg/L of COD 0.425 gm of Potassium Acid Phthalate is to be dissolved in 1 liter of distilled water (98 to 100 % recovery expected)

 Pressure : 13 kg/cm2(Up to 20 kg/cm2) Temperature : Up to 160 0C (Gasket and Teflon sheets can take

temperature up to 180 0C) Volume : 3 liters (7 liters) Depth : 15 inch (inside) Dia. : 3 inch (inside) Heating media : glycerin MOC : SS-304 RPM of stirrer : up to 1880 2 No. of temperature sensors Automatic trip system

 IS 3025(part 43):1992 for Phenols IS 3025(part 58):2006 for chemical oxygen demand (COD)

 Conclusion for Phenol

removal

Efficiency A/C-900 : 56.30 % Pure O2 : 64.3 % H2O2 : 75 % Thus it is clear that catalytic power of H2O2 in reducing the Phenols from the effluent is highest among the catalyst used. For purely Phenolic effluent pure O2 can be cheapest solution if high pressure of O2 can be generated by compressor H2O2 can also be proved as an effective catalyst for better efficiency but because of its corrosive nature the material of the reactor should be quite sophisticated (SS316) At high temperature and pressure activated carbon can also be very effective catalyst.

 Conclusion for COD

removal

Efficiency A/C-900 : 57 % Pure O2 : 10.70 % H2O2 : 64.3 % For effluents containing high COD, both activated carbon and H2O2 can be considered as good oxidizing agent but again the nature of H2O2 is corrosive so it can damage the reactor for longer duration Conversion in the case of pure oxygen is not impressive for COD, so in case of highly polluted industrial effluents O2 will be expensive and less effective

 Conclusion
The efficiency of the

Phenol removal increases with temperature and the functionality is linear.

 Conclusion
Like Phenol the efficiency

of the COD removal too increases with temperature and the functionality is also linear. COD removal efficiency increases with temperature more steeply than the Phenol removal

 Conclusion
At low pressure (8 to 10

kg/cm2) the conversion of Phenols were not very prominent, limiting the efficiency as low as 29%. At higher pressure (10 to 13 kg/cm2) the phenol removal efficiency by CWAO follows the exponential form.

 Conclusion
As Phenol removal

efficiency, COD removal also follows the exponential law with pressure at constant temperature and retention time.

 Reaction network model of degradation of Phenol can be

described by the following equations,

Kinetics

 Conclusion
Table shows the activation energy and frequency factor for

Phenol degradation and COD removal from the synthetic effluent by CWAO using A/C-900 grade activated carbon as catalyst with residence time of 2.5 hours and total system pressure of 13 kg/cm2

 Suggestion
We can compare this prototype with the prototype of

incineration having the same capacity. Pre exponential factor can be considered for reconciliation of the actual large scale plant.

 Results show that efficiency increases with high temperature and

pressure. Higher removal efficiency will be achieved by providing more retention time if the sufficient amount of oxygen is present in the reactor. As a catalyst , activated carbon can be very economical and fruitful, though great removal efficiency can be achieved by H2O2 , it can be corrosive and impractical. SS-304 material is not suitable for H2O2 , SS-316 can be a good option. Experiments results show that there is no need of adjusting the initial pH when dealing with the concentrated Phenolic solutions, since reaction products lead to a sufficient drop in the pH for the reaction to proceed.

 Pure oxygen as the catalyst is not very effective for high COD

effluents, it may require higher oxygen pressure for higher removal efficiency. There was almost no conversion of phenols and COD below 100 0 C, so temperature can be considered as the main governing factor for getting good efficiency At high temperature, and on complete oxidation due to presence of excess oxygen, no odor production was detected where as an unpleasant odor was noted when low temperature catalytic oxidation took place.

 A mechanical seal can be useful for stirrer arrangement Bubble type of reactor can be more efficient Continuous reactor can be more practical than the batch

type reactor Better quality is essential in the form of gasket and valves for higher efficiency Instead of boiler we can have electrical heating arrangement in the reactor Reactor should be properly designed for avoiding accidents

 There should be comprehensive comparative studies involving

advance oxidation process prior to biological treatment for reducing the overall treatment cost of highly polluted effluent. Further research should be focused on finding the optimum operating parameters for CWAO to treat wide range of effluents. Further study can be carried out on the sophistication of the reactor and modifications for reducing the operating cost. More deep study on the behavior of different catalyst. Extensive study should be carried on cost analysis of the technology.

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