Electrolysis cell for generating chlorine dioxide

• US 7,048,842 B2
• Filed: 09/06/2001
• Issued: 05/23/2006
• Est. Priority Date: 06/22/2001
• Status: Expired due to Term

• Current Assignee: The Procter & Gamble Company
• Original Assignee: The Procter & Gamble Company
• Inventors: Mitchell, Michael D., Nesbitt, Daniel F., Collias, Dimitris I., Tremblay, Mario E., Rasmussen, Craig M.
• Primary Examiner(s): Phasge, Arun S.
• Application Number:
  US09/947,846
• Publication Number:
  US 20030006144A1
• Time in Patent Office: 1,720 Days
• Field of Search: 205/556, 205/499, 204/275.1
• US Class Current: 205/499
• CPC Class Codes: C02F 1/283 using coal, charred products, or inorganic mixtures containing them
• CPC Class Codes: C02F 1/42 by ion-exchange ion-exchange in general B01J
• CPC Class Codes: C02F 1/46104 Devices therefor; Their operating or servicing
• CPC Class Codes: C02F 1/4674 with halogen or compound of halogens, e.g. chlorine, bromine
• CPC Class Codes: C02F 2001/46133 characterised by the material
• CPC Class Codes: C02F 2001/46161 Porous electrodes
• CPC Class Codes: C02F 2101/103 Arsenic compounds
• CPC Class Codes: C02F 2201/4611 Fluid flow
• CPC Class Codes: C02F 2201/46165 Special power supply, e.g. solar energy or batteries
• CPC Class Codes: C02F 2201/4618 Supplying or removing reactants or electrolyte
• CPC Class Codes: C02F 9/00 Multistage treatment of water, waste water or sewage
• CPC Class Codes: Y02W 10/37 using solar energy

Abstract

A method for making chlorine dioxide, by passing an aqueous feed solution comprising sodium chlorite into a non-membrane electrolysis cell comprising an anode and a cathode, adjacent to the anode, while flowing electrical current between the anode and the cathode to electrolyze the aqueous feed solution and convert the halogen dioxide salt to halogen dioxide. The anode is preferably a porous anode through which the aqueous feed solution passes to maximize the conversion of chlorite to chlorine dioxide.

Claims

1. A method for making an aqueous solution comprising halogen dioxide, comprising the steps of:

(1) providing an aqueous feed solution comprising a halogen dioxide salt;

(2) passing the aqueous feed solution into a cell chamber of a non-membrane electrolysis cell comprising an anode and a cathode, and along a passage adjacent to the anode, wherein said cell having said cell chamber does not have an ion permeable membrane that divides the cell into distinct anode and cathode chambers;

(3) flowing an electrical current of less than 1.0 watt between the anode and the cathode, thereby electrolyzing the aqueous feed solution in the passage, whereby a portion of the halogen dioxide salt in the passage is converted to halogen dioxide; and

(4) passing the electrolyzed aqueous solution out of the electrolysis cell, thereby forming an aqueous effluent comprising halogen dioxide

wherein said method results in a production of halogen dioxide at a level of from about 1 ppm to about 200 ppm.

2. The method of claim 1 wherein the anode and the cathode are confronting and co-extensive, with a chamber gap of 0.5 mm or less.

3. The method of claim 1 wherein the anode is a porous anode.

4. The method of claim 3 wherein the porous anode is a porous metallic anode.

5. The method of claim 1 wherein the halogen dioxide comprises a halite salt, and is preferably a chlorite salt, and the halogen dioxide formed is chlorine dioxide.

6. The method of claim 1 wherein the aqueous feed solution comprises the halogen dioxide salt at a concentration of at least 0.1 ppm.

7. The method of claim 1 wherein the aqueous effluent has less than 1.0 ppm, preferably less than 0.1 ppm, free chlorine.

8. The method of claim 1, further comprising the step of passing a portion of the aqueous effluent back into the aqueous feed solution.

9. A method for making an aqueous solution comprising halogen dioxide, comprising the steps of:

(1) providing an aqueous feed solution comprising a halogen dioxide salt;

(2) passing an aqueous feed solution of at least 400 ml per minute into a cell chamber of a non-membrane electrolysis cell comprising an anode, a cathode, and an anode outlet, and along a passage adjacent to the anode, wherein said cell having said cell chamber does not have an ion permeable membrane that divides the cell into distinct anode and cathode chambers;

(3) flowing an electrical current of less than 1.0 watt between the anode and the cathode, thereby electrolyzing the aqueous feed solution in the passage, whereby a portion of the halogen dioxide salt in the passage is convened to halogen dioxide; and

(4) passing the electrolyzed solution adjacent the anode out of the chamber through the anode outlet;

thereby forming an aqueous anode effluent comprising halogen dioxide

wherein said method further comprises the step of returning a remaining cathode effluent back into the aqueous feed solution;

wherein said method results in a production of halogen dioxide at a level of from about 1 ppm to about 200 ppm;

10. The method of claim 9 wherein the halogen dioxide comprises a halite salt, and is preferably chlorite salt, and the halogen dioxide formed is chlorine dioxide.

11. A method of making an aqueous solution comprising halogen dioxide, comprising the steps of:

(1) providing an aqueous supply solution comprising halogen dioxide salt;

(2) passing a portion of the aqueous supply solution into a cell chamber of a non-membrane electrolysis cell comprising an anode and a cathode, and along a passage adjacent to the anode, wherein said cell having said cell chamber does not have an ion permeable membrane that divides the cell into distinct anode and cathode chambers;

(3) flowing an electrical current of less than 1.0 watt between the anode and the cathode, thereby electrolyzing the aqueous feed solution in the passage, whereby a portion of the halogen dioxide salt is converted to halogen dioxide, and forming an aqueous effluent comprising halogen dioxide;

(4) oxidizing an oxidizable material with the converted halogen dioxide in the aqueous effluent, whereby the halogen dioxide reverts back to a halogen dioxide salt; and

(5) returning the used effluent solution comprising the reverted halogen dioxide salt back to the aqueous supply solution

wherein said method results in a production of halogen dioxide at a level of from about 1 ppm to about 200 ppm.

12. The method of claim 11 wherein the halogen dioxide is a chlorite salt.

13. A halogen dioxide generating system, comprising:

a) a source of an aqueous feed solution comprising a halogen dioxide salt;

b) a non-membrane electrolysis cell comprising an anode and a cathode spaced apart from said anode, said anode and said cathode being separated by a non-conducting porous flow barrier in contact with each of said anode and said cathode, and having a cell chamber with an inlet and an outlet, wherein said chamber does not have an ion permeable membrane that divides the cell into distinct anode and cathode chambers;

c) a means for passing the aqueous feed solution into the chamber and along a passage through said porous flow barrier adjacent to the anode, and out of the outlet; and

d) an electric current supply to flow a current through the aqueous feed solution in the passage, to convert a portion of the halogen dioxide salt to halogen dioxide, and thereby form an aqueous effluent comprising halogen dioxide

wherein said system produces from about 1 ppm to about 200 ppm of halogen dioxide.

14. The halogen dioxide generating system of claim 13 wherein the anode and the cathode are confronting and co-extensive, with a chamber gap of 0.5 mm or less.

15. The halogen dioxide generating system of claim 13 wherein the anode is a metallic porous anode.

16. A halogen dioxide generating and re-circulating system, comprising:

a) a source of an aqueous feed solution comprising a halogen dioxide salt;

b) a non-membrane electrolysis cell comprising an anode and a cathode spaced apart from said anode, said anode and said cathode being separated by a non-conducting porous flow barrier in contact with each of said anode and said cathode, and having a cell chamber with an inlet and an outlet, wherein said chamber does not have an ion permeable membrane that divides the cell into distinct anode and cathode chambers;

c) a means for passing the aqueous feed solution into the chamber, and along a passage through said porous flow barrier adjacent to the anode, and out of the outlet;

d) an electric current supply to flow a current through the aqueous solution between the anode and the cathode, to convert at least a portion of the halogen dioxide salt in the passage to halogen dioxide, and thereby form an aqueous effluent comprising halogen dioxide;

e) a means for delivering the aqueous effluent into contact with a halogen dioxide depletion target, whereby a portion of the halogen dioxide in the aqueous effluent oxidizes the depletion target and reverts back to a halogen dioxide salt; and

f) a means for returning the depleted effluent comprising the reverted halogen dioxide salt back to the source

wherein said system produces from about 1 ppm to about 200 ppm of halogen dioxide.

17. A battery-powered electrolysis device for use to make on demand an aqueous solution comprising chlorine dioxide, comprising:

a) an electrolysis cell comprising an anode and a cathode and a non-conducting porous flow barrier disposed between the anode and the cathode and in contacting relationship therewith, and having a cell chamber,

b) a pump for providing an aqueous feed solution comprising a halogen dioxide salt into the cell chamber and along a passage through said porous barrier adjacent to the anode,

c) a battery for flowing electrical current between the anode and the cathode when the aqueous feed solution flows within the chamber and along the passage, whereby a portion of the halogen dioxide salt is converted to halogen dioxide

wherein said electrolysis cell further comprises a single outlet in fluid communication with the cell chamber

further wherein said device requires less than about 8.5 watts of power.

18. The battery-powered electrolysis device according to claim 17, wherein the device is a solution spray bottle, wherein the pumping means comprises a electrically-driven pump that pumps solution from the bottle to the electrolysis cell, and wherein the electrolysis cell comprises an anode and a confronting, co-extensive cathode, having a cell chamber gap of 0.5 mm or less.

19. An electrolysis cell for electrolyzing an aqueous solution, comprising:

a porous anode,

a cathode spaced apart from said anode to provide a flow path therebetween, said flow path further comprising a non-conducting porous flow barrier disposed therein,

a cell chamber positioned between the porous anode and the cathode, the cell chamber having said non-conducting porous flow barrier;

whereby each of the porous anode and the flow barrier exert a resistance to the flow of the aqueous solution through the electrolysis cell

wherein said electrolysis cell further comprises a partition in said cell chamber, said partition separating effluent exiting the cell chamber adjacent the anode from effluent exiting the cell chamber adjacent the cathode.

20. The electrolysis cell of claim 19, wherein the porous anode is a metallic porous anode.

21. The electrolysis cell of claim 19, wherein the flow barrier comprises a porous plastic.

22. The electrolysis cell of claim 19, wherein the aqueous solution comprises a halogen dioxide salt.