WO2004026770A1 - Stabilized bromine and chlorine mixture, method of manufacture and uses thereof for biofouling control - Google Patents
Stabilized bromine and chlorine mixture, method of manufacture and uses thereof for biofouling control Download PDFInfo
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- WO2004026770A1 WO2004026770A1 PCT/US2003/021940 US0321940W WO2004026770A1 WO 2004026770 A1 WO2004026770 A1 WO 2004026770A1 US 0321940 W US0321940 W US 0321940W WO 2004026770 A1 WO2004026770 A1 WO 2004026770A1
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- Prior art keywords
- bromine
- group
- chlorine
- stabilized
- earth metal
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
Definitions
- This invention relates generally to water treatment and, more particularly, to stabilized bromine and chlorine mixtures, method of manufacture and uses thereof for biofouling control.
- Sodium hypochlorite has been widely used in a variety of industrial and recreational water systems to control biofouling. However, unstabilized sodium hypochlorite degrades very quickly in field use conditions. There are several methods known in the art for stabilizing hypochlorite (See, e.g., U.S. Patent Nos. 3,328,294 and
- Bromine is preferred over chlorine for use in water treatment because of its lower volatility and better performance at high pH and amine environments.
- sodium hypobromite is unstable in typical storage conditions, so it is also preferable to provide sodium hypobromite in a stabilized form.
- U.S. Patent No. 6,037,318 discloses a process that first forms stabilized chlorine compounds and then converts them to stabilized bromine compounds.
- this type of process is limiting because only hypochlorite-releasing compounds can be used as the oxidizing source.
- U.S. Patent No. 6,270,722 discloses a method of adding hypochlorite to a mixture of bromide and sulfamate and then adjusting the pH of the mixture.
- a method is disclosed for adding hypochlorite and sulfamate simultaneously to bromide and then adjusting the pH to form a stabilized bromine product.
- the stabilized bromine and chlorine mixtures of the present invention are prepared by simultaneously combining a bromine source, an oxidizer and a stabilizer.
- An alkaline source may optionally be added to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
- the inventive method is economically appealing because it can be carried out as a batch or continuous process and because it can be done at a very high throughput.
- the method of preparation is also flexible because it can be performed at the manufacturing facility or right at the site of the commercial application and the method does not require precise pH control.
- the present invention is directed to a method of making stabilized bromine and chlorine mixtures.
- stabilized bromine and chlorine mixtures means that both the bromine and the chlorine are stabilized in the mixture.
- a bromine source, an oxidizer and a stabilizer are combined simultaneously.
- An alkaline source may be added to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
- the bromine sources which may be used in the practice of the present invention include hydrobromic acid, elemental bromine and alkali or alkaline earth metal bromides, such as sodium bromide, potassium bromide and lithium bromide.
- the preferred bromine source is an alkali or alkaline earth metal bromide.
- the oxidizers which may be used include chlorine gas, hypochlorous acid, hypochlorite salt, chlorite, chlorate, persulfate, permanganate and peracetic acid. Chlorine gas, hypochlorous acid and hypochlorite salt are the most preferred oxidizers. It is believed that other peroxy compounds can also be used in accordance with this invention.
- the stabilizers which may be employed in this invention have the chemical formula R-NH-R 1 , wherein R and R 1 are selected from the group consisting of R 2 CO, R 2 SO 2 , R 2 CF 2 , R 2 CHF, H, OH and PO(OH) 2 , and R 2 is an alkyl group or an aromatic group.
- Suitable stabilizers include saccharin, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid and its alkali or alkaline earth metal salts, organic sulfamates and melamine. Sulfamic acid and its alkali or alkaline earth metal salts are the most preferred stabilizers.
- water treatment chemicals such as tracing compounds, surfactants, corrosion inhibitors and scale inhibitors, can be added to the stabilized bromine and chlorine mixture.
- the molar ratio between the bromine source and the stabilizer be in the range of about 0.2 to 5.
- the molar ratio between the bromine source and the oxidizer should preferably be in the range of about 0.5 to 2.
- the method of the present invention is maintained at a temperature of less than 120 °F and can be carried out as either a batch or continuous process.
- the stabilized bromine and chlorine mixtures which are prepared in accordance with this invention may be used in a wide variety of commercial applications. These applications include, but are not limited to, the use of the stabilized bromine and chlorine mixture in a method for: (1) controlling biofouling on a hard surface; (2) controlling biofouling occurring on the surfaces of equipment in contact with an industrial water system; (3) controlling biofouling in an aqueous phase of an industrial water system; and (4) controlling microbial growth in an aqueous stream used for transporting or processing food products and on food surfaces and equipment surfaces that come in contact with the aqueous stream.
- the types of industrial water systems in which the stabilized bromine and chlorine mixture may be used to control biofouling include, but are not limited to, cooling water systems, sweetwater systems, gas scrubber systems, air washer systems, evaporative condensers, pasteurizers, produce sanitizer streams, fire protection water systems, pulp and paper systems, heat exchanger tubes and oil field waters.
- the stabilized bromine and chlorine mixture of the present invention can be prepared at the site of the commercial application.
- an alkaline source may be added to the mixture to raise the pH of the stabilized bromine and chlorine mixture to at least 13 to provide thermal stability and shelf life during storage and shipping.
- the alkaline source is preferably an alkali or alkaline earth metal hydroxide.
- Suitable alkaline sources include sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide.
- a stabilized halogen product can be prepared without requiring any particular order of addition of the ingredients.
- a stabilized bromine and chlorine mixture is achieved and can effectively be used to control biofouling.
- the method of making the stabilized bromine and chlorine mixture is economical since it can be conducted as a batch or continuous process and it generates a high yield.
- the inventive method is flexible because it can be performed at the manufacturing facility or right at the site of the commercial application and the method does not require precise pH control.
- a laboratory reactor was set up for preparing a stabilized halogen product from three raw materials: sodium bromide, sodium sulfamate and sodium hypochlorite.
- the sodium sulfamate solution was prepared by mixing an equal molar ratio of sulfamic acid with sodium hydroxide in water.
- a 250 ml solution of sodium hypochlorite (12.0% as available chlorine, pH 12.41)
- a 250 ml solution of sodium sulfamate (20.41%, pH 2.31) were prepared separately.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
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Abstract
Stabilized bromine and chlorine mixtures are prepared by simultaneously combining a bromine source, an oxidizer and a stabilizer. An alkaline source may optionally be added to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
Description
STABILIZED BROMINE AND CHLORINE MIXTURES, METHOD OF IV1ANUFACTURE AND USES THEREOF FOR BIOFOULING CONTROL
FIELD OF THE INVENTION
This invention relates generally to water treatment and, more particularly, to stabilized bromine and chlorine mixtures, method of manufacture and uses thereof for biofouling control.
BACKGROUND OF THE INVENTION
Sodium hypochlorite has been widely used in a variety of industrial and recreational water systems to control biofouling. However, unstabilized sodium hypochlorite degrades very quickly in field use conditions. There are several methods known in the art for stabilizing hypochlorite (See, e.g., U.S. Patent Nos. 3,328,294 and
3,767,586).
Bromine is preferred over chlorine for use in water treatment because of its lower volatility and better performance at high pH and amine environments. However, like sodium hypochlorite, sodium hypobromite is unstable in typical storage conditions, so it is also preferable to provide sodium hypobromite in a stabilized form. U.S. Patent
Nos. 5,683,654 and 5,795,487, as well as the references disclosed therein, teach various methods for stabilizing sodium hypobromite. The '654 and '487 patents disclose batch methods which utilize sodium hypochlorite and sodium bromide as starting materials, followed by the addition of a stabilizer. U.S. Patent No. 6,015,782 similarly discloses a process which includes a hypobromite formation step followed by a bromine stabilization step. However, a disadvantage associated with this technique is that unstabilized hypobromite is formed in a separate step at a high concentration and pH. It
is known that unstabilized hypobromite degrades quickly under such conditions to form bromate, a non-biocidal compound that is very toxic and a suspected carcinogen.
Also, U.S. Patent No. 6,037,318 discloses a process that first forms stabilized chlorine compounds and then converts them to stabilized bromine compounds. However, this type of process is limiting because only hypochlorite-releasing compounds can be used as the oxidizing source.
In addition, U.S. Patent No. 6,270,722 discloses a method of adding hypochlorite to a mixture of bromide and sulfamate and then adjusting the pH of the mixture. Alternatively, a method is disclosed for adding hypochlorite and sulfamate simultaneously to bromide and then adjusting the pH to form a stabilized bromine product.
Because the demand for stabilized bromine solutions is expected to increase in the future due to its advantages over chlorine, there is a need for other cost-effective methods of manufacturing stabilized bromine which are flexible and can generate a high throughput. One such method may include preparing a stabilized bromine and chlorine mixture wherein the stabilized chlorine gradually oxidizes the residual bromide in the mixture into stabilized bromine.
Accordingly, it would be desirable to provide a method of making a stabilized bromine and chlorine mixture which can be carried out as a batch or continuous process either at the manufacturing facility or right at the site of the commercial application. It would also be desirable to develop a method of making a stabilized bromine and chlorine mixture which generates a high yield, is flexible and does not require precise pH control.
SUMMARY OF THE INVENTION The stabilized bromine and chlorine mixtures of the present invention are prepared by simultaneously combining a bromine source, an oxidizer and a stabilizer. An alkaline source may optionally be added to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
The inventive method is economically appealing because it can be carried out as a batch or continuous process and because it can be done at a very high throughput. The method of preparation is also flexible because it can be performed at the manufacturing facility or right at the site of the commercial application and the method does not require precise pH control.
DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method of making stabilized bromine and chlorine mixtures. As used herein, "stabilized bromine and chlorine mixtures" means that both the bromine and the chlorine are stabilized in the mixture. In accordance with this invention, a bromine source, an oxidizer and a stabilizer are combined simultaneously. An alkaline source may be added to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
The bromine sources which may be used in the practice of the present invention include hydrobromic acid, elemental bromine and alkali or alkaline earth metal bromides, such as sodium bromide, potassium bromide and lithium bromide. The preferred bromine source is an alkali or alkaline earth metal bromide.
The oxidizers which may be used include chlorine gas, hypochlorous acid, hypochlorite salt, chlorite, chlorate, persulfate, permanganate and peracetic acid.
Chlorine gas, hypochlorous acid and hypochlorite salt are the most preferred oxidizers. It is believed that other peroxy compounds can also be used in accordance with this invention.
The stabilizers which may be employed in this invention have 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.
Suitable stabilizers include saccharin, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid and its alkali or alkaline earth metal salts, organic sulfamates and melamine. Sulfamic acid and its alkali or alkaline earth metal salts are the most preferred stabilizers.
Optionally, other water treatment chemicals, such as tracing compounds, surfactants, corrosion inhibitors and scale inhibitors, can be added to the stabilized bromine and chlorine mixture.
It is preferred that the molar ratio between the bromine source and the stabilizer be in the range of about 0.2 to 5. The molar ratio between the bromine source and the oxidizer should preferably be in the range of about 0.5 to 2.
The method of the present invention is maintained at a temperature of less than 120 °F and can be carried out as either a batch or continuous process.
The stabilized bromine and chlorine mixtures which are prepared in accordance with this invention may be used in a wide variety of commercial applications. These applications include, but are not limited to, the use of the stabilized bromine and chlorine mixture in a method for: (1) controlling biofouling on a hard surface; (2)
controlling biofouling occurring on the surfaces of equipment in contact with an industrial water system; (3) controlling biofouling in an aqueous phase of an industrial water system; and (4) controlling microbial growth in an aqueous stream used for transporting or processing food products and on food surfaces and equipment surfaces that come in contact with the aqueous stream.
The types of industrial water systems in which the stabilized bromine and chlorine mixture may be used to control biofouling include, but are not limited to, cooling water systems, sweetwater systems, gas scrubber systems, air washer systems, evaporative condensers, pasteurizers, produce sanitizer streams, fire protection water systems, pulp and paper systems, heat exchanger tubes and oil field waters.
The stabilized bromine and chlorine mixture of the present invention can be prepared at the site of the commercial application. Alternatively, if there is a need to store and transport the stabilized bromine and chlorine mixture, an alkaline source may be added to the mixture to raise the pH of the stabilized bromine and chlorine mixture to at least 13 to provide thermal stability and shelf life during storage and shipping.
The alkaline source is preferably an alkali or alkaline earth metal hydroxide. Suitable alkaline sources include sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide.
The present inventor has discovered that a stabilized halogen product can be prepared without requiring any particular order of addition of the ingredients. By simultaneously combining a bromine source, an oxidizer and a stabilizer, a stabilized bromine and chlorine mixture is achieved and can effectively be used to control biofouling. Moreover, the method of making the stabilized bromine and chlorine mixture is economical since it can be conducted as a batch or continuous process and it
generates a high yield. In addition, the inventive method is flexible because it can be performed at the manufacturing facility or right at the site of the commercial application and the method does not require precise pH control.
EXAMPLE The following example is intended to be illustrative of the present invention and to teach one of ordinary skill how to make and use the invention. This example is not intended to limit the invention or its protection in any way.
A laboratory reactor was set up for preparing a stabilized halogen product from three raw materials: sodium bromide, sodium sulfamate and sodium hypochlorite. The sodium sulfamate solution was prepared by mixing an equal molar ratio of sulfamic acid with sodium hydroxide in water. In order to use one peristaltic pump with multiple pump heads to conduct the experiment, a 250 ml solution of sodium hypochlorite (12.0% as available chlorine, pH 12.41), a 250 ml solution of sodium bromide (17.42%, pH 7.25) and a 250 ml solution of sodium sulfamate (20.41%, pH 2.31) were prepared separately. All three solutions were then pumped at a pump rate of approximately 10 ml/min using PVC tubing to a 1 -liter glass reactor. A motorized HDPE stirrer mixed the solutions in the glass reactor. The temperature of the product was controlled at 68 °F using an ice- water bath. The finished product had a total volume of approximately 750 ml, a pH of 12.40 and a total available chlorine content of 3.79% (product yield is therefore 95% since the theoretical chlorine percentage should be around 4%). Further product characterization using DPD colorimetric technical showed that the product contained 54% bromosulfamate and the remaining 46% as chlorosulfamate on a molar basis.
While the present invention is described above in connection with preferred or illustrative embodiments, these embodiments are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope, as defined by the appended claims.
Claims
1. A method of making a stabilized bromine and chlorine mixture which comprises simultaneously combining a bromine source, an oxidizer and a stabilizer.
2. The method of claim 1 wherein the bromine source is selected from the group consisting of hydrobromic acid, elemental bromine, alkali earth metal bromides and alkaline earth metal bromides.
3. The method of claim 1 wherein the bromine source is selected from the group consisting of alkali earth metal bromides and alkaline earth metal bromides.
4. The method of claim 1 wherein the oxidizer is selected from the group consisting of chlorine gas, hypochlorous acid, hypochlorite salt, chlorite, chlorate, persulfate, permanganate and peracetic acid.
5. The method of claim 1 wherein the oxidizer is selected from the group consisting of chlorine gas, hypochlorous acid and hypochlorite salt.
6. 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.
7. 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 and its alkali or alkaline earth metal salts, organic sulfamates and melamine.
8. The method of claim 1 wherein the stabilizer is selected from the group consisting of sulfamic acid and its alkali or alkaline earth metal salts.
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 the stabilized bromine and chlorine mixture is made at a temperature of less than 120 °F.
12. A stabilized bromine and chlorine mixture produced by the method of claim 1.
13. A method of controlling biofouling on a hard surface which comprises applying to the hard surface an effective, biofouling controlling amount of the stabilized bromine and chlorine mixture of claim 12.
14. A method of controlling biofouling occurring on the surfaces of equipment in contact with an industrial water system which comprises adding to the industrial water system an effective, biofouling controlling amount of the stabilized bromine and chlorine mixture of claim 12.
15. The method of claim 14 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, pulp and paper system, heat exchanger tube and oil field waters.
16. A method of controlling biofouling in an aqueous phase of an industrial water system which comprises adding to the aqueous phase an effective, biofouling controlling amount of the stabilized bromine and chlorine mixture of claim 12.
17. The method of claim 16 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, pulp and paper system, heat exchanger tube and oil field waters.
18. A method of controlling microbial growth in an aqueous stream used for transporting or processing food products and on food surfaces and equipment surfaces that come in contact with the aqueous stream which comprises adding to the aqueous stream an effective, microbial growth controlling amount of the stabilized bromine and chlorine mixture of claim 12.
19. The method of claim 1 further comprising the step of adding an alkaline source to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
20. The method of claim 19 wherein the alkaline source is selected from the group consisting of alkali earth metal hydroxides and alkaline earth metal hydroxides.
21. The method of claim 19 wherein the alkaline source is selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide.
22. A stabilized bromine and chlorine mixture produced by the method of claim 19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003256524A AU2003256524A1 (en) | 2002-09-19 | 2003-07-15 | Stabilized bromine and chlorine mixture, method of manufacture and uses thereof for biofouling control |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24695502A | 2002-09-19 | 2002-09-19 | |
| US10/246,955 | 2002-09-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004026770A1 true WO2004026770A1 (en) | 2004-04-01 |
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ID=32028968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2003/021940 Ceased WO2004026770A1 (en) | 2002-09-19 | 2003-07-15 | Stabilized bromine and chlorine mixture, method of manufacture and uses thereof for biofouling control |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU2003256524A1 (en) |
| WO (1) | WO2004026770A1 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008056025A2 (en) | 2006-11-09 | 2008-05-15 | Kemira Oyj | Method for preventing growth of microorganisms, and a combination for the prevention of microbial growth |
| EP1871429A4 (en) * | 2005-03-31 | 2008-12-03 | Ashland Licensing & Intellectu | Process for inhibiting biofilm formation on and/or removing biofilm from an enhanced tube |
| US7776363B2 (en) * | 2006-01-27 | 2010-08-17 | Nalco Company | Suppressing microbial growth in pulp and paper |
| EP2236034A3 (en) * | 2004-05-10 | 2011-12-21 | Enviro Tech Chemical Services Inc. | Method of preparing a bromide- and chloride-containing liquid |
| US20130280349A1 (en) * | 2012-04-23 | 2013-10-24 | Lonza, Inc. | Active halogen antimicrobial composition and method of use |
| US8574605B2 (en) | 2004-05-10 | 2013-11-05 | Enviro Tech Chemical Services, Inc. | Methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids |
| WO2014020601A1 (en) * | 2012-07-31 | 2014-02-06 | Bromine Compounds Ltd. | Method for preparing bromine based biocidal aqueous compositions |
| US9161543B2 (en) | 2011-10-21 | 2015-10-20 | Nalco Company | Biocontrol through the use of chlorine-stabilizer blends |
| US10850999B2 (en) | 2015-04-24 | 2020-12-01 | Ecolab Usa Inc. | Submergible biocide reactor and method |
| WO2021092048A1 (en) | 2019-11-06 | 2021-05-14 | De Nora Holdings Us, Inc. | Controlled production of aqueous halogen solutions with varying compositions |
| WO2022070451A1 (en) * | 2020-09-30 | 2022-04-07 | オルガノ株式会社 | Composition for treating water, water treatment method, method for manufacturing composition for treating water, and cooling water system treatment method |
| US11905498B2 (en) | 2020-02-12 | 2024-02-20 | Ecolab Usa Inc. | Use of urea or a urea/chelator combination to chemically stabilize peroxycarboxylic acid and peroxide formulations |
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| US6007726A (en) * | 1998-04-29 | 1999-12-28 | Nalco Chemical Company | Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control |
| US6110387A (en) * | 1999-04-22 | 2000-08-29 | Albemarle Corporation | Sulfamate stabilization of a bromine biocide in water |
| US6270722B1 (en) * | 1999-03-31 | 2001-08-07 | Nalco Chemical Company | Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control |
| US6478972B1 (en) * | 1999-12-13 | 2002-11-12 | Acculab Co., Ltd. | Method of controlling microbial fouling |
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2003
- 2003-07-15 WO PCT/US2003/021940 patent/WO2004026770A1/en not_active Ceased
- 2003-07-15 AU AU2003256524A patent/AU2003256524A1/en not_active Abandoned
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| US5662940A (en) * | 1989-06-16 | 1997-09-02 | University Of Houston | Biocidal methods and compositions for recirculating water systems |
| US6007726A (en) * | 1998-04-29 | 1999-12-28 | Nalco Chemical Company | Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control |
| US6270722B1 (en) * | 1999-03-31 | 2001-08-07 | Nalco Chemical Company | Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control |
| US6110387A (en) * | 1999-04-22 | 2000-08-29 | Albemarle Corporation | Sulfamate stabilization of a bromine biocide in water |
| US6478972B1 (en) * | 1999-12-13 | 2002-11-12 | Acculab Co., Ltd. | Method of controlling microbial fouling |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2236034A3 (en) * | 2004-05-10 | 2011-12-21 | Enviro Tech Chemical Services Inc. | Method of preparing a bromide- and chloride-containing liquid |
| US8574605B2 (en) | 2004-05-10 | 2013-11-05 | Enviro Tech Chemical Services, Inc. | Methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids |
| EP1871429A4 (en) * | 2005-03-31 | 2008-12-03 | Ashland Licensing & Intellectu | Process for inhibiting biofilm formation on and/or removing biofilm from an enhanced tube |
| US7581874B2 (en) | 2005-03-31 | 2009-09-01 | Hays George F | Apparatuses and systems for monitoring fouling of aqueous systems including enhanced heat exchanger tubes |
| US7594430B2 (en) | 2005-03-31 | 2009-09-29 | Beardwood Edward S | Methods for monitoring fouling of aqueous systems including enhanced heat exchanger tubes |
| US7776363B2 (en) * | 2006-01-27 | 2010-08-17 | Nalco Company | Suppressing microbial growth in pulp and paper |
| WO2008056025A2 (en) | 2006-11-09 | 2008-05-15 | Kemira Oyj | Method for preventing growth of microorganisms, and a combination for the prevention of microbial growth |
| WO2008056025A3 (en) * | 2006-11-09 | 2008-11-27 | Kemira Oyj | Method for preventing growth of microorganisms, and a combination for the prevention of microbial growth |
| US9272927B2 (en) | 2006-11-09 | 2016-03-01 | Kemira, Oyj | Method for preventing growth of microorganisms, and a combination for the prevention of microbial growth |
| US9161543B2 (en) | 2011-10-21 | 2015-10-20 | Nalco Company | Biocontrol through the use of chlorine-stabilizer blends |
| US9265259B2 (en) | 2011-10-21 | 2016-02-23 | Nalco Company | Use of sulfamic acid or its salts as stabilizers especially in combination with ammonium salt and/or ammine for bleach or other halogen containing biocides in the paper area |
| US9220272B2 (en) * | 2012-04-23 | 2015-12-29 | Lonza, Inc | Active halogen antimicrobial composition and method of use |
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| AU2003256524A1 (en) | 2004-04-08 |
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