Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control

• US 6,270,722 B1
• Filed: 03/31/1999
• Issued: 08/07/2001
• Est. Priority Date: 03/31/1999
• Status: Expired due to Term

• Current Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Original Assignee: Nalco Chemical Company (Ecolab, Inc.)
• Inventors: Allain, Eric J., McCoy, William F., Yang, Shunong, Dallmier, Anthony W., Myers, Eric R.
• Primary Examiner(s): MCKANE, ELIZABETH L
• Application Number:
  US09/283,122
• Time in Patent Office: 860 Days
• Field of Search: 422/37, 422/6, 422/14, 810/7, 813/7, 162/1, 162/4, 423/500, 423/504, 252/187.2, 252/380
• US Class Current: 422/37
• CPC Class Codes: A01N 59/00 Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• CPC Class Codes: C01B 7/093 Hydrogen bromide
• CPC Class Codes: C01B 7/096 Bromine
• CPC Class Codes: C01B 7/24 Inter-halogen compounds
• CPC Class Codes: C01D 3/10 Bromides
• CPC Class Codes: C02F 1/50 by addition or application of a germicide or by oligodynamic treatment C02F1/4606, C02F1/467, C02F1/76 take precedence
• CPC Class Codes: C02F 1/766 by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
• CPC Class Codes: C11D 2111/12 Soft surfaces, e.g. textile
• CPC Class Codes: C11D 3/3951 combined with specific additives
• CPC Class Codes: C11D 3/3953 Inorganic bleaching agents C11D3/3951 takes precedence
• CPC Class Codes: C11D 3/3956 Liquid compositions

Abstract

Stabilized bromine solutions are prepared by combining a bromine source and a stabilizer to form a mixture, adding an oxidizer to the mixture, and then adding, an alkaline source to adjust the pH of the mixture to at least 13.

Claims

1. A method of making a stabilized bromine solution comprising the steps of:

a. combining a bromine source and a stabilizer to form a mixture;

b. adding an oxidizer to the mixture; and

c. adding an alkaline source to the mixture to adjust the pH of the mixture to at least 13.

2. The method of claim 1 wherein the bromine source is selected from the group consisting of hydrobromic acid, bromine chloride, elemental bromine, alkali earth metal bromides and alkaline earth metal bromides.

3. The method of claim 1 wherein the stabilizer has the chemical formula R—

NH—

R¹, wherein R and R¹ are selected from the group consisting of R² CO, R² SO₂, R² CF₂, R² CHF, H, OH and PO(OH)₂, and R² is an alkyl group or an aromatic group.

4. The method of claim 1 wherein the stabilizer is selected from the group consisting of saccharin, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine.

5. The method of claim 1 wherein the stabilizer is sulfamic acid.

6. The method of claim 1 wherein the oxidizer is selected from the group consisting of chlorine gas, hypochlorous acid, hypochlorite salt, chlorite, chlorate, elemental bromine, bromine chloride, hydrogen peroxide, persulfate, permanganate and peracetic acid.

7. The method of claim 1 wherein the alkaline source is selected from the group consisting of alkali earth metal hydroxides and alkaline earth metal hydroxides.

8. The method of claim 1 wherein the alkaline source is selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide.

9. The method of claim 1 wherein the molar ratio between the bromine source and the stabilizer is in the range of about 0.2 to 5.

10. The method of claim 1 wherein the molar ratio between the bromine source and the oxidizer is in the range of about 0.5 to 2.

11. The method of claim 1 wherein steps a, b and c are maintained at a temperature of less than 80°

F.

12. The method of claim 1 wherein steps a, b and c are maintained in the temperature range of about 40 to 70°

F.

13. The method of claim 1 wherein step b is maintained at a pH below about 7.

14. A stabilized bromine solution produced by the method of claim 1.

15. In a method for the laundering of soiled garments in which the soiled garments are washed in an aqueous media containing a detergent and a bleaching agent, the improvement comprising using as the bleaching agent the stabilized bromine solution of claim 14.

16. In a method for the manufacture of cellulosic materials in which cellulosic fibers are bleached with an oxidizing agent, the improvement comprising using as the oxidizing agent the stabilized bromine solution of claim 14.

17. In a method for the control of biofouling in a recreational water system in which an oxidizing and biocidal agent is added to control biofouling, the improvement comprising using as the oxidizing and biocidal agent the stabilized bromine solution of claim 14.

18. In a method for the control of biofouling on a hard surface in which an oxidizing and biocidal agent is applied to the surface to control biofouling on the surface, the improvement comprising using as the oxidizing and biocidal agent the stabilized bromine solution of claim 14.

19. In a method for the control of biofouling occurring on the surfaces of equipment in contact with produced oil field waters, the improvement comprising adding to the produced oil field waters an effective biofouling controlling amount of the stabilized bromine solution of claim 14.

20. A method of controlling biofouling in an aqueous system which comprises adding to the aqueous system an effective, biofouling controlling amount of the stabilized bromine solution of claim 14.

21. A method of preventing biofouling on the surfaces of equipment in contact with an industrial water system which comprises adding to the water system an effective biofouling controlling amount of a stabilized bromine solution, said solution having been prepared by the steps of:

a. combining a bromine source and a stabilizer to form a mixture;

b. adding an oxidizer to the mixture; and

c. adding an alkaline source to the mixture to adjust the pH of the mixture to at least 13.

22. The method of claim 21 wherein the industrial water system is selected from the group consisting of a cooling water system, sweetwater system, gas scrubber system, air washer system, evaporative condenser, pasteurizer, produce sanitizer stream, fire protection water system and heat exchanger tube.

23. The method of claim 21 wherein the stabilized bromine solution is added to the industrial water system in an amount of from about 0.1 to about 2000 ppm as available bromine.

24. The method of claim 21 wherein the stabilized bromine solution is added to the industrial water system in an amount of from about 0.5 to about 500 ppm as available bromine.

25. A method of making a stabilized bromine solution comprising the steps of:

a. selecting a bromine source;

b. adding a stabilizer and an oxidizer to the bromine source to form a mixture, wherein the stabilizer and the oxidizer are alternately added to the mixture in an amount sufficient to maintain the pH of the mixture between about 0 and 6.9; and

c. adding an alkaline source to the mixture to adjust the pH of the mixture to at least 13.

26. The method of claim 25 wherein the pH of step b is between about 3 and 6.5.

27. The method of claim 25 wherein the pH of step b is between about 4 and 6.

28. The method of claim 25 wherein the molar ratio between the bromine source and the stabilizer is in the range of about 0.2 to 5.

29. The method of claim 25 wherein the molar ratio between the bromine source and the oxidizer is in the range of about 0.5 to 2.

30. A stabilized bromine solution produced by the method of claim 25.