Electrolytic process and apparatus for the controlled oxidation of inorganic and organic species in aqueous solutions

• US 5,419,816 A
• Filed: 10/27/1993
• Issued: 05/30/1995
• Est. Priority Date: 10/27/1993
• Status: Expired due to Term

• Current Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Original Assignee: Halox Technologies Incorporated
• Inventors: Sampson, Allison H., Sampson, Richard L.
• Primary Examiner(s): GORGOS, KATHRYN L
• Application Number:
  US08/141,675
• Time in Patent Office: 580 Days
• Field of Search: 204/59 R, 204/103, 204/78, 204/252, 204/263, 204/149, 204/130, 210/748
• US Class Current: 205/556
• CPC Class Codes: B01D 61/48 having one or more compartments filled with ion-exchange material , e.g. electrodeionisation
• CPC Class Codes: B01J 47/08 subjected to a direct electric current
• CPC Class Codes: B01J 49/30 Electrical regeneration
• CPC Class Codes: C02F 1/42 by ion-exchange ion-exchange in general B01J
• CPC Class Codes: C02F 1/46114 Electrodes in particulate form or with conductive and/or non conductive particles between them
• CPC Class Codes: C02F 1/4672 by electrooxydation
• CPC Class Codes: C02F 1/4674 with halogen or compound of halogens, e.g. chlorine, bromine
• CPC Class Codes: C02F 1/4676 by electroreduction
• CPC Class Codes: C02F 1/4695 electrodeionisation
• CPC Class Codes: C02F 2103/023 Water in cooling circuits
• CPC Class Codes: C02F 2103/42 from bathing facilities, e.g. swimming pools
• CPC Class Codes: C02F 2201/46115 Electrolytic cell with membranes or diaphragms
• CPC Class Codes: C02F 2201/46145 Fluid flow
• CPC Class Codes: C02F 2303/04 Disinfection
• CPC Class Codes: C25B 1/00 Electrolytic production of inorganic compounds or non-metals
• CPC Class Codes: C25B 1/24 Halogens or compounds thereof
• CPC Class Codes: C25B 9/40 Cells or assemblies of cells comprising electrodes made of particles; Assemblies of constructional parts thereof

Abstract

An electrolytic process and apparatus is disclosed for oxidizing or reducing inorganic and organic species, especially in dilute aqueous solutions. The electrolytic reactor includes an anode and cathode in contract with a packed bed of particulate ion exchange material which establishes an infinite number of transfer sites in the electrolyte to significantly increase the mobility of the ionic species to be oxidized or reduced toward the anode or cathode, respectively. The ion exchange material is cationic for oxidation and anionic for reduction, or a combination of both for special circumstances. Preferably, the ion exchange material is treated to convert a portion of the transfer sites to semiconductor junctions which act as mini anodes, or cathodes, to significantly increase the capacity of the reactor to oxidize or reduce the species to be treated. Exemplary applications for the disclosed electrolytic process and apparatus are the conversion of halides to halous acids in dilute solutions.

Claims

1. An electrolytic process for oxidizing a species in a dilute aqueous solution, comprising the steps of:

passing an aqueous feed solution containing said species to be oxidized through a monobed of particulate modified cation exchange material interposed between an anode and a cathode, with said bed of modified cation exchange material in direct contact with both said anode and said cathode;

applying a direct current across the anode and cathode;

contacting said aqueous feed solution with said bed for a time to cause at least a portion of said species to be oxidized by said modified cation exchange material so that said aqueous solution contains said species in an oxidized form; and

recovering the aqueous solution containing said oxidized species.

2. A process as defined in claim 1, wherein said modified cation exchange material has active semiconductor junctions formed by a cation species permanently bonded to said cation exchange material.

3. A process as defined in claim 2, wherein at least about 1% of the total ion exchange sites of said cation exchange material are active semiconductor junctions.

4. A process as defined in claim 2, wherein said semiconductor junctions are formed by polyvalent metal cations permanently bonded to said cation exchange material.

5. A process as defined in claim 1, wherein the step of passing said aqueous feed solution through said bed comprises passing said aqueous feed solution through at least two chambers, each of said chambers containing a particulate modified cation exchange material in contact with said anode and said cathode, and said chambers are separated from one another by a cation exchange membrane.

6. An electrolytic process as defined in claim 1, wherein said species to be oxidized is an organic species.

7. An electrolytic process as defined in claim 1, wherein said species to be oxidized is an inorganic species.

8. An electrolytic process for oxidizing an inorganic species as defined in claim 7, wherein said inorganic species to be oxidized is a halide.

9. A process as defined in claim 8, wherein the concentration of said halide in said aqueous feed solution is less than 1,500 mg/l.

10. A process as defined in claim 8, wherein said halide is iodide and the recovered aqueous solution contains hypoiodous acid.

11. A process as defined in claim 8, wherein said halide is bromide and the recovered aqueous solution contains hypobromous acid.

12. A process as defined in claim 8, wherein said halide is chloride and the recovered aqueous solution contains hypochlorous acid.

13. A process as defined in claim 1, wherein said oxidized species contained in said recovered aqueous solution is utilized in the oxidation treatment of large volume dilute aqueous solutions used in municipal drinking water supplies, water distributors, cooling towers and swimming pools.

14. A process as defined in claim 1, wherein said oxidized species contained in said recovered aqueous solution is utilized in the controlling of microbiological contamination in large volume dilute aqueous solutions used in municipal drinking water supplies, water distributors, cooling towers and swimming pools.

15. A method for on-site halogen treatment of dilute aqueous solutions used in large volumes in municipal drinking water supplies, water distributors, cooling towers and swimming pools, which comprises adding a halide salt to at least a portion of said aqueous solution, contacting said at least a portion of said aqueous solution containing said halide salt with a monobed of particulate modified cation exchange material interposed between an anode and a cathode of an electrolytic reactor, in which a direct current is applied across the anode and cathode, for a time to cause free radical formation in said modified cation exchange material and oxidation of at least a portion of said halide salt to halous acid by said modified cation exchange material, which halous acid then oxidizes undesirable contaminants in said dilute aqueous solution.

16. A method as defined in claim 15, wherein said electrolytic reactor is placed at an on-site location convenient for treatment of said dilute aqueous solution.

17. A method as defined in claim 15, wherein the undesirable contaminants oxidized in said dilute aqueous solution by said halous acid include inorganic and organic contaminants.

18. A method as defined in claim 15, wherein said halide is iodide and said halous acid is hypoiodous acid.

19. A method as defined in claim 15, wherein said halide is bromide and said halous acid is hypobromous acid.

20. A method as defined in claim 15, wherein said halide is chloride and said halous acid is hypochlorous acid.

21. A method as defined in claim 15, wherein said modified cation exchange material has active semiconductor junctions formed by a cation species permanently bonded to said cation exchange material.

22. A method as defined in claim 21, wherein said semiconductor junctions are formed by polyvalent metal cations permanently bonded to said cation exchange material.

23. A method as defined in claim 15, wherein said dilute aqueous solution to be treated is a municipal drinking water supply.

24. A method as defined in claim 15, wherein said dilute aqueous solution to be treated is a water distributor.

25. A method as defined in claim 15, wherein said dilute aqueous solution to be treated is water for a cooling tower.

26. A method as defined in claim 15, wherein said dilute aqueous solution to be treated is swimming pool water.

27. A method for on-site halogen control of microbiological contamination in dilute aqueous water solutions used in large volumes in municipal drinking water supplies, water distributors, cooling towers and swimming pools, which comprises adding a halide salt to at least a portion of said aqueous solution, contacting said at least a portion of said aqueous solution containing said halide salt with a monobed of particulate modified cation exchange material interposed between an anode and a cathode of an electrolytic reactor, in which a direct current is applied across the anode and cathode, for a time to cause free radical formation in said modified cation exchange material add oxidation of at least a portion of said halide salt to halous acid by said modified cation exchange material, which halous acid then oxidizes undesirable contaminants in said dilute aqueous solution.

28. A method as defined in claim 27, wherein said electrolytic reactor is placed at an on-site location convenient for treatment of said dilute aqueous solution.

29. A method as defined in claim 27, wherein said halide is iodide and said halous acid is hypoiodous acid.

30. A method as defined in claim 27, wherein said halide is bromide and said halous acid is hypobromous acid.

31. A method as defined in claim 27, wherein said halide is chloride and said halous acid is hypochlorous acid.

32. A method as defined in claim 27, wherein said modified cation exchange material has active semiconductor junctions formed by a cation species permanently bonded to said cation exchange material.

33. A method as defined in claim 32, wherein said semiconductor junctions are formed by polyvalent metal cations permanently bonded to said cation exchange material.

34. A system for on-site halogen treatment of dilute aqueous solutions used in large volumes in municipal drinking water supplies, water distributors, cooling towers and swimming pools, which comprises:

means for transferring at least a portion of said aqueous solution from its normal flow to a monobed of particulate modified cation exchange material interposed between and in direct contact with an anode and a cathode of a nearby electrolytic reactor;

electric means for applying a direct current across the anode and cathode;

means for contacting said transferred aqueous solution with said bed to cause at least a portion of halide salt in said aqueous solution to be oxidized to halous acid by said modified cation exchange material; and

means for returning said transferred aqueous solution to its normal flow to oxidize undesirable contaminants or control microbiological contamination in said dilute aqueous solution being treated.

35. A system as defined in claim 34, wherein said halide is iodide and said halous acid is hypoiodous acid.

36. A system as defined in claim 34, wherein said halide is bromide and said halous acid is hypobromous acid.

37. A system as defined in claim 34, wherein said halide is chloride and said halous acid is hypochlorous acid.

38. A system as defined in claim 34, wherein said modified cation exchange material has active semiconductor junctions formed by a cation species permanently bonded to said cation exchange material.

39. A system as defined in claim 38, wherein at least about 1% of the total ion exchange sites of said cation exchange material are active semiconductor junctions.

40. A system as defined in claim 38, wherein said semiconductor junctions are formed by polyvalent metal cations permanently bonded to said cation exchange material.