Zeis, Yannis (15 Dimitros Street, Ag. Paraskevi, GR-153 42, GR)
Ninolakis, Markos (15 Dimitros Street, Ag. Paraskevi, GR-153 42, GR)
Zeis, Yannis (15 Dimitros Street, Ag. Paraskevi, GR-153 42, GR)
| 1. | Electrochemical method of wet oxidation of polychlorinatedEbiphenyl's, (PCB's), on its own or mixed with other liquids or solids, with controlled voltage and intensity of electric direct current, controlled solution of chloric natrium (NaCI), controlled temperature of electrolysis, controlled pH, method of insertion of PCB's in the electrolytic cell, method of fine grid separation and method of mixing solids that contains PCB's. |
| 2. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the electric voltage of the direct current is between 5V and 600V. |
| 3. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the electric intensity of the direct current during the electrolysis is between 5 to 1800Amp. |
| 4. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the content of chloric natrium in the liquid that the electrolysis take place is 0,5% to 12% of its weight. |
| 5. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the temperature during the electrolysis is bellow 60C°. |
| 6. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the pH during the electrolysis is between 3 to 9,5. |
| 7. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the separation of the PCB's contained in solids is done with aromatic solvents. |
| 8. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the PCB's or the liquids containing PCB's enters the electrolytic cell during the electrolysis by a nebular spray device. |
| 9. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the PCB's or the liquids containing PCB's enters the electrolytic cell during the electrolysis by a fine injection generator. |
| 10. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the liquid oxidants produced by electrolysis are mixed with a mechanical mixer or shaker in a tank apart the electrolytic cell with solids containing PCB's. The solids are hold in the tank by fine grid (screen) made from stainless steel with a hole pass less than 1 mm. AMENDED CLAIMS [Received by the International Bureau on 5 August 2002 (05.08.02): original claims 1 and 4 amended; remaining claims 2,3 and 510 unchanged (1 page)] 1. Electrochemical method of wet oxidation of polychlorinated biphenyl's, (PCB's), on its own or mixed with other liquids or solids, with controlled voltage and intensity of electric direct current, controlled solution of sodium chloride (NaCI), controlled temperature of electrolysis, controlled pH, method of fine grid separation, method of mixing solids that contains PCB's, method of insertion of PCB's in the electrolytic cell where the anode is made by a substrate of titanium covered by electro bonding method of one or two layers where the first one is from tantalum or niobium or zirconium or alloys of theme and the second is made of platinum or rhodium or iridium or ruthenium or palladium or zirconium or alloys of theme where the layers can be applied or separately or in combination and the cathode is made by stainless steel. |
| 11. | 2 Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the electric voltage of the direct current is between 5V and 600V. |
| 12. | 3 Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the electric intensity of the direct current during the electrolysis is between 5 to 1800Amp. |
| 13. | 4 Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the content of sodium chloride in the liquid that the electrolysis take place is 0,5% to 12% of its weight. |
| 14. | 5 Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the temperature during the electrolysis is bellow 60C°. |
| 15. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the pH during the electrolysis is between 3 to 9,5. |
| 16. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the separation of the PCB's contained in solids is done with aromatic solvents. |
| 17. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the PCB's or the liquids containing PCB's enters the electrolytic cell during the electrolysis by a nebular spray device. |
| 18. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the PCB's or the liquids containing PCB's enters the electrolytic cell during the electrolysis by a fine injection generator. |
| 19. | Electrochemical method of wet oxidation for polychlorinated biphenyl's, (PCB's), as claim 1 where the liquid oxidants produced by electrolysis are mixed with a mechanical mixer or shaker in a tank apart the electrolytic cell with solids containing PCB's. The solids are hold in the tank by fine grid (screen) made from stainless steel with a hole pass less than 1 mm. |
LEVEL OF CONVENTIONAL TECHNOLOGY The disposal of materials that include PCB's into the environment has been proved to be very dangerous to the public health internationally. The polychlorinated biphenyls's (PCB's), are counting about two hundred alternatives currently, diluted within solid or liquid solutions are strongly cancer productive. In the past the industry in general, and the electronic industry in particular, the building materials production and the electric devices production, have made an irrational use of PCB's without having the adequate knowledge of their dangerous effects.
Until today, the only way for treating the PCB's is the pyrolysis method in special furnaces, where during the combustion, they produce dioxins to the atmosphere, with out possibility for the filters to hold them. The transfer of PCB's from country to country is forbidden, as a fact that makes difficult to deal with them since there are only few pyrolysis furnaces of PCB's in the world.
THE PATENT'S ADVANTAGES.
The PCB's liquid electrochemical oxidation method solves the treatment problem, because it provides the possibility to treat them on site, the main oxidation resituates are the water and the carbon dioxide (H20 & C02) while the produced gasses during the electrolysis, based on the existing technology, can be controlled environmentally without polluting the atmosphere.
DESCRIPTION The PCB's are located in the environment or in pure solutions, or mixed in liquids or solids, as well in aromatic solvents that have been used to clean parts that includes PCB's.
The invention refers to the method of the wet oxidation of the PCB's by electrolysis on a salt water solution, that contains 0,5% to 12% of its weight of chloric natrium applying simultaneously controlled intensity of electric direct current from 5 to 1800Amp and voltage from 5 to 600V, controlled temperature of electrolytic liquid solution by meaning to keep the increased heat bellow 60Co and controlled pH on each solution mix from 3 to 9,5 units depending of the type of the treated PCB's that overcomes the 200 alternatives.
For better oxidation of the PCB's, their entrance to the electrolytic cell is made by a nebular nozzle device or by injection in purpose to increase the contact surface with the electrolysis produced oxidants.
In case that the PCB's are mixed with solids their treatment with the produced oxidants is made through a fine mechanical grid (screen), of lmm pass that does not aloud the re-circulation of the fine solid parts trough the cell, but only the generated liquid part. The full contact of the oxidants with the solid parts is helped with a mechanical mixer.
EXAMPLE 1 (drawing 1) A mix of oil and PCB's, specially the PCB 52, of a weight of 100gr is placed in a storage tank (b) for farther treatment. From the storage tank is pumped through pump (3), and a nebular device nozzle (2) to the electrolytic cell (a) where the anode (h) is made from noble and strategic metals and the cathode (u) of stainless steel 316 L. The dimensions of the electrolytic cell are for the anode 300mm long and 19mm rod massif special covert metal and for the cathode a tube 450mm long, 80mm of diameter with 2mm thickness. The polychlorinated biphenyl's enters in the electrolytic cell through the nebular device (2). The internal space of the electrolytic cell is filled up with water containing 5% chloric natrium (NaCI). The electrolytic cell is fed with continuous electric current from a feeder (e) with adjusted voltage from 0,1 to 48V and adjusted intensity from 0,5 to 500Amp. The feeder is powered from an electric board (d) who provides the necessary power to all electric devices and motors (1), (2), (3), (4), (5). The system disposes alternating temperature generator (i) surrounding the electrolytic cell and keeps the temperature bellow 60 Co and especially to the 36 Co The loss of excess heat is achieved with a cooling device (c). Furthermore the electrolytic cell disposes exhaust (1) with filter (s) for the released gasses. The salt water in the electrolytic cell is electrolyzed for 30 min with a voltage of 15V and an intensity of 100Amp in order to produce strong oxidants such as H2, Cl2, Cl03, 03, 02, H202, [OH], [CIOH], [0]. After 30min the pH is corrected with HCI to 4 from the tank (k), which is the ideal value for this mix. Through the nebular device (2) we start the controlled spraying of the oil-PCB 52 mix from the top of electrolytic cell through the injection nozzles (6) with a rate of 2000mgr/min.
In the bottom of the electrolytic cell is placed a magnetic shaker (4) with the purpose of steering and lifting the solution of the oil-PCB52 because this mix is heavier than the salt water, so any volume of mix that is not been oxidized during their entrance and are lead to the bottom, they are lifted to the cell's active volume for a better oxidation. After the entrance of the oil-PCB52 mix in the cell the electrolysis is continued for 30min. The oxidation of the oil-PCB52 mix is fulfilled.
The released gasses are collected through a gas exhaust (1) and lead to a filter (s).
EXAMPLE 2 (drawing 2) Mud from a seabed of 25kg that contains PCB's is placed in a closed tank (b) of 1001it volume that disposes a gas exhaust device (1) and gas filter (s). A volume of 501it of water is added containing 3,1% of its weight of chloric natrium. In the tank there is fitted a mixer (9) for the mechanical mixing of the mud and the liquid. In the middle of the tank height is fixed also a fine grid (screen) (10) of 0,25mm pass in order to keep the solids on the bottom. A submersible pump (3) re-circulates the liquid part over the fine grid, through the electrolytic cell (a). The return from the electrolytic cell discharges in the part of the tank that contains the mud (8) in purpose to diffuse the oxidants within its body. We correct the pH to 9 by adding caustic soda (NaOH) from the tank (k) through the dosing pump (11) and we start the electrolysis with a voltage of 24V and an intensity of 200Amp from the direct current transformer (e). The feeder is powered from an electric board (d) who provides the necessary power to all electric devices and motors (1), (3), (5), (7), (11). The system disposes alternating temperature generator (i) surrounding the electrolytic cell and keeps the temperature bellow 60C° and especially to the 30C°.
The electrolysis take place for three hours and the PCB's oxidation is fulfilled.
EXAMPLE 3 Oil transformer containing PCB's and oils is evacuated and its liquids are collected in a tank. The internal oil circulation tubes are cleaned with toluene that remains in the tubes for 24 hours. Both the originally emptied liquids and the results after the toluene cleaning are gathered into the tank. The system disposes alternating temperature generator (i) surrounding the electrolytic cell and keeps the temperature bellow 60 Co and especially to the 36 Co The electrolytic cell contains water with dissolved chloric natrium (NaCI) in a relation of 10% per its weight and we start electrolysis with a voltage of 12V and an intensity of 240Amp. After 30min we correct the pH to 4, which is ideal for the present mix of oil-PCB's-toluene.
From the concentration tank we take Hit of the mix and with the controlled injection device we spray within the electrolytic cell through four nozzles in a rate of 10.000mgr/min. In the base of the electrolytic cell is fitted a magnetic mixer for the steering up and the lifting of the solution. This mix is heavier than the water, so that any mix quantities that have not been oxidized during the entrance to the electrolytic cell and have been leaded to the bottom are lifted to the active volume of the cell. After the total entrance of the mix oil-PCB's-toluene we continue the electrolysis for 60min. The oxidation of the mix is now fulfilled. The produced gasses are collected through an exhaust and leaded to a filter.
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