AU2005201969A1 - Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control - Google Patents

Description

10/05 '05 TUE 15:44 FAX 61299255911 GRIFFITH HACK Q003 0 0 ci 0 1

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): NALCO CHEMICAL COMPANY Invention Title: STABLE OXIDIZING BROMINE FORMULATIONS, METHOD OF MANUFACTURE AND USES THEREOF FOR BIOFOULING CONTROL The following statement is a full description of this invention, including the best method of performing it known to us: COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:44 FAX 61299255911 GRIFFITH HACK S004 o la STABLE OXIDIZING BROMINE FORMULATIONS, METHOD OF MANUFACTURE AND USES THEREOF FOR BIOFOULING CONTROL 2_ FIELD OF THE IIVENTION The present invention relates to formulations used in biofouling control in industrial water systems. More V\ specifically, the present invention relates to methods of 0preparing stable oxidizing bromine formulations and their o use in biofouling control in industrial water systems.

C9 BACKGROUND OF THE INVEiNTION o While elemental liquid bromine is an effective 0 biocide, its low solubility 4g/100g water), low boiling point (54.3C), high vapor pressure (214 mm Hg at and extreme corrosivity limit its use as a biocide in industrial applications. Another oxidizing bromine compound, bromate, has very little antimicrobial activity. Bromate is also very toxic to mammals and is a suspected carcinogen. Nonoxidizing inorganic bromine compounds, such as bromide, have little or no antimicrobial activity.

A mixture of an aqueous bromine solution and a bromine stabilizer has been used to generate stable oxidizing bromine compounds for use as a biocide. An unstabilized aqueous bromine solution is very acidic, unstable and emits very pungent bromine fumes. The concentration of stabilized hypobromite solution that can be made from liquid bromine, however, has been limited due to the low solubility of bromine in water.

It has also been suggested that, in addition to a bromine stabilizer, an oxidizer, such as hypochlorite, be added to activate the bromide to hypobromite. After the completion of the conversion of bromide to hypobromite, the hypobromite is stabilized by the addition of a halogen stabilizer, such as sulfamate. While this is an improved process with a higher level of oxidizing halogen content (around 14%r as Br 2 this process still requires the separate step of synthesizing sodium hypobromite COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:45 FAX 61299255911 GRIFFITH HACK 1@005 C( 2 (NaOBr) as a bromine source. NaOBr is known to be very unstable and will rapidly disproportionate to bromide and bromate, both of which have little or no antimicrobial O activity- In addition, because sodium hypochlorite (NaOCI) is used as an activation agent, the concentration of stabilized product is limited by the available 0" concentration of NaOC1.

O\ Also known are methods of generating bromine for onsite use. Such processes involve electrolytically (C converting bromate into active bromine compounds such as Sbromine, hypobromous acid, hypobromite ion and hydrogen o tribromide under acidic conditions. However, because the above process generates bromine for on-site use, methods or measures for optimizing bromine stabilization are not addressed.

Therefore, methods of generating higher concentrations of stable oxidizing bromine formulations in a safer manner are needed.

SUMMARY OF TE INVENTION The present invention satisfies the aforementioned needs by providing a method of generating a stable oxidizing bromine compound which includes the steps of mixing an alkali or alkaline earth metal bromide and an alkali or alkaline earth metal bromate in water to provide an aqueous solution, cooling the solution to a temperature of less than 25 0 C, preferably less than and more preferably less than 10 0 C, and thereafter adding a halogen stabilizer to the solution, the halogen stabilizer being selected from the group consisting of R- NH,, R-NH-R

R-SO

2

-NH

2

R-SO

2 -NIR R-CO-NWH,

R-CO-NH-R

1 and R-CO-NH-CO-R wherein R is a hydroxy group, an alkyl group or an aromatic group and R' is an alkyl group or an aromatic group. Preferred halogen stabilizers include saccharin, benzenesulfonamide urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, mono or diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:45 FAX 61299255911 GRIFFITH HtACK oo06 WO 00164806 PCIUSn9nin C3 sulfamates and melamine. Sulfamic acid is the most preferred halogen stabilizer.

In an embodiment, the halogen stabilizer is added to o the solution in a molar amount approximately equal to the combined molar amount of alkali or alkaline earth metal bromide and alkali or alkaline earth metal bromate.

In an embodiment, the step of adding the halogen Va stabilizer results in the solution having a pH of less than 2.

(Nq in an embodiment, the method comprises agitating the o solution for a time period of greater than 5 minutes o after the step of adding the halogen stabilizer.

In'an embodiment, the method comprises adjusting the solution to a pH of greater than 13 through the addition of alkali or alkaline earth metal hydroxide after the step of adding the halogen stabilizer 6 In an embodiment, the step of mixing the alkali or alkaline earth metal bromide and alkali or alkaline earth metal bromate further comprises mixing the alkali or alkaline earth metal bromide and alkali or alkaline earth metal bromate in a molar ratio of alkali or alkaline earth metal bromide:bromate of about 2:1.

In an embodiment, the method of the present invention provides a stable oxidizing bromine compound which includes the steps of mixing about 2 moles of alkali or alkaline earth metal bromide and about 1 mole of alkali or alkaline earth metal bromate in water to provide an aqueous solution, followed by the step of cooling the solution to a temperature of less than followed by the step of adding an acidic halogen stabilizer to the solution to lower the pH of the solution to less than 2, the acidic halogen stabilizer being selected from the group consisting of R-NH 2 R-Nfl-

RSONH

2 R-SOI-NBR1, R-CO-NH 2 R-CO-N14-RI and k-CO-NH- CO-R wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:45 FAX 61299255911 GRIFFITH HACK 007 I WO 00/64806 PCT/US99/29192 S4 group. Preferred halogen stabilizers include urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, mono or di ethanolamine, organic sulfonamides, biuret, o sulfamic acid, organic sulfamates and melamine. The acidic halogen stabilizer is added to the solution in a molar amount approximately equal to a combined molar 0 amount of alkali or alkaline earth metal.bromide and

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0alkali or alkaline earth metal bromate, followed by the Sstep of agitating the solution for a time period of Cl greater than 5 minutes, followed by the step of adding an n alkali or alkaline earth metal hydroxide to the solution o to increase the pH of the solution to a level greater C than 13.

In an embodiment, the method of the present invention provides a method of preparing a stable oxidizing bromine compound which includes the steps of preparing a caustic solution comprising a halogen stabilizer, water and an alkali or alkaline earth metal hydroxide, adding bromine or bromine chloride to the solution while agitating the solution and cooling the solution.

In an embodiment, the halogen stabilizer is selected from the group consisting of R-NH 2

R-NH-R

1 R-SO,-NH, R- SO-NR R-CO-NH 2

R-CO-NH-R

1 and R-CO-NH-CO-R I wherein R is a hydroxy group, an alkyl group or an aromatic group and R' is an alkyl group or an aromatic group. Preferred halogen stabilizers include saccharin, benzenesulfonamide urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, mono or di ethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine.

In an embodiment, the caustic solution has a pH greater than 13 after the addition of the bromine or bromine chloride.

In an embodiment, the step of adding bromine or bromine chloride is further characterized as adding COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TTE 15:46 FAX 61299255911 GRIFFITH HACK o008 iC WO 00/64806 PCT/US9919192 bromine or bromine chloride in a molar amount Sapproximately equal to the molar amount of halogen Sstabilizer and approximately equal to one-half of the o molar amount of alkali or alkaline earth metal hydroxide.

In an embodiment, the solution is cooled to a temperature of less than 25 0

C.

In an embodiment, the step of adding bromine or

VO

Q( bromine chloride is performed without exposing the bromine to air.

Cl In an embodiment, an alkali or alkaline earth metal o n hydroxide is added to the solution after the addition of o bromine or bromine chloride to increase the pH of the solution above 13.

In an embodiment, the method of the present invention provides a method of preparing a stable oxidizing bromine compound in an aqueous solution which includes the steps of dissolving an alkali or alkaline earth metal bromate salt in water to form a solution, followed by the step of adding a halogen stabilizer to the solution, the halogen stabilizer being selected from the group consisting of R-NH 2 R-NH-Rl, R-SO 2 -MH, R-SO,-

NHR

1 R-CO-N,, R-CO-NH-R 1 and R-CO-NH-CO-R' wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic group. Preferred halogen stabilizers include saccharin, benzenesulfonamide urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, mono or di ethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine. Following the addition of the halogen stabilizer, bromine or bromine chloride is added to the solution.

In an embodiment, a step of cooling the solution to a temperature of less than 25°C, preferably less than and more preferably less than 10"C, is performed simultaneously with the step of adding the bromine to the solution.

COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:46 FAX 61299255911 GRIFFITH HACK oo009 WO 0/64806 PCTIUS99/29192 CI 6 In an embodiment, the present invention provides an aqueous biocide solution containing a stable oxidizing Sbromine formulation. The solution comprises at least one o oxidizing bromine compound selected from the group consisting of 'SO 3 NMBr and -SONBr, when sulfamate is used as the bromine stabilizer Sand a base in an amount sufficient to raise the pH of the

VO

solution to a level greater than 13.

In an embodiment, the.base in the solution is an C alkali or alkaline earth metal hydroxide.

L

r o It is therefore an advantage of the present O invention to generate a stable oxidizing bromine

C

containing solution using liquid bromine or bromine chloride in a safe and efficient manner whereby no bromine fumes are generated.

It is another advantage of the present invention to generate a higher concentration of stabilized hypobromite without the need for a separate step for hypobromite generation.

Another advantage of the present invention is that it provides a method for generating water soluble solid stable oxidizing bromine compounds.

Still another advantage of the present invention is that it provides a method for generating stable oxidizing bromine compounds without unwanted by-products such as high levels of bromate.

Still another advantage of the present invention is that the method of the present invention does not generate chloride and therefore the method of the present invention provides stable oxidizing bromine formulations that are less corrosive.

Yet another advantage of the present invention is that it provides stable oxidizing bromine compounds that are safer to transport and that are non-acidic.

Yet another advantage of the present invention is that it generates stable oxidizing bromine compounds for COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:46 FAX 61299255911 GRIFFITH HACK o010 SWO 00/64806 PCTUS99129192 CRN 7 biofouling control in industrial water systems that are more compatible with other water treatment chemicals than unstabilized oxidizing bromine compounds.

o The industrial water systems include cooling water systems, cooling ponds, reservoirs, sweetwater applications, decorative fountains, pasteurizers, evaporative condensers, hydrostatic sterilizers and

VO

Sretorts, gas scrubber systems and air washer systems.

Another advantage of the present invention is that Cl it provides an improved method of biofouling control in o pulp and paper processing systems.

o Another advantage of the present invention-is that Cl it provides an improved method of biofouling control occurring on the surfaces of equipment in contact with produced oil field waters.

Another advantage of the present invention is that it provides an improved method of biofouling control in a food processing system.

Yet another advantage of the present invention is that it provides improved biofouling control in a beverage processing system.

Still another advantage of the present invention is that it provides improved biofouling control in a recreational water system.

Another advantage of the present invention is that it provides an improved method of disinfecting a hard surface.

Another advantage of the present invention is that it provides an improved bleaching method for the laundering of soiled garments and for the manufacture of cellulosic materials.

And, another advantage of the present invention is that it provides an improved method of washing food items, such as fruit and other food items.

COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TLTE 15:47 FAX 61299255911 GRIFFITH HACK o011 WO 0064806 PCT/US9/29192 (N8 Other objects and advantages of the present invention will be apparent upon a review of the following detailed description and appended claims.

0 DETAILED DESCRIPTION OF THEINVENTION The present invention provides a plurality of V\ formulations and methods for generating a wide 0' concentration of stable oxidizing bromine compounds for o biofouling control in cooling water and other industrial systems.

o In an embodiment, the strategy employed by the 0 present invention utilizes a mixture of alkali or alkaline earth metal bromide and alkali or alkaline earth metal bromate in water as the bromine source. Bromate also serves as an oxidizing agent. The molar ratio of bromide to bromate is optimally 2:1. The solution is then cooled to a temperature preferably of less than and even more preferably of less than 10°C. An acidic stabilizer or acidic stabilizing solution, such as sulfamic acid, is then added to the solution to lower the pH of the solution to less than 2. Additional stabilizer is then added to achieve equal molar amounts relative to bromine for optimal stabilization. Without being limited by theory, the following reactions are believed to occur: HO-SO,-NH, H -O-SO,-NH2 (1) 2Br" BrO r 3H 3HBrO (2) HBrO "O-SO 2

-NH

2 -O-SOz-NH-Br, "O-S0 2 -NBrg, and other stable oxidizing bromine compounds (3) Since bromide, bromate and sulfamate co-exist in the resulting solution, reaction to reaction occurs sequentially with respect to each other. Without being limited by theory, the existence of an oxidizing bromine stabilizer and correct bromide to bromate ratio are believed to prevent the formation of bromine according to the following reaction: NaBrO 3 6H 3Br, GNa 4 3 HRO (4) COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TLTE 15:47 FAX 61299255911GRFIHAC j01 GRIFFITH HACK Z012 oWO 00/64806 P~U9/99 C~1 9 if reaction were to happen instead of reactioni half of the raw bromine source would convert back to non-biocidal and non-oxidizing bromide according to 0 reaction Br: 2

I{

2 0 HBrO H~r However, an analysis of products prepared in accordance with the present invention confirms that the reaction yield is higher than so%. In fact, more than o 80% of the bromine source was converted to oxidized CA bromine forms. Accordingly, the reaction yield of at o least 80% was achieved, o The reaction time for reactions 1-3 a: a pH of less than 2 ranges from 5 to 10 minutes with good agitation.

If the product is not going to be used immediately, a strong base, such as NaQE, is added to raise the product pH to a level greater than 13 making the product thermally stable. During the pH adjustment, temperature control is important because the temperature increase by the heat generated from the acid-base reaction can cause the product to decompose. Accordingly, cooling may be necessary.

The product made with the above process has good thermostability and a high total available halogen concentration, as high as 34k as Br..

EXAMPLES

The following examples are intended to be illustrative of the present invention and to teach one of ordinary skill how to make and use the invention. These examples are not intended to limit the invention or its protection in any way.

Examl By way of an example, synthesis of a stable oxidizing bromine product in accordance with the abovedescribed method is carried out by mixing 21.2 grams of NaBrO 3 32.8 grams of NaBr and 100 grams of water, cooling the solution to 3 0 C, adding 48 grams of sulfamic acid to COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:47 FAX 61299255911 GRlFFITH HACK Z013 WO 0016489 PCrs991 0 the solution and agitating the solution for 10 minutes.

Then, 48 grams of 50% aqueous NaOH is added slowly to the solution while controlling the solution temperature to a 0 range between 4C and 140C. The resulting product was a golden yellow solution with a pH of 13.77 and available halogen concentration of 25.1% as Br 2 In this example, 0the theoretical Br 2 is 29.9 if all of the bromine sources Va (bromide and bromate) were to convert to stable oxidizing obromines. Therefore, the yield is about 84%.

Cl Example II By way of another example, synthesis of stable ooxidizing bromine formulations in accordance with the Cl "above-described method is carried out by mixing 21.2 grams of NaBrO 3 32.8 grams of NaBr and 100 grams of water in a reactor, cooling the solution to 3 0 C, adding 44 grams of sulfamic acid to the solution and agitating the solution for 10 minutes, slowly adding 43 grams of 501 aqueous NaOH while controlling the reactor temperature between 3 0 C and 140C. The resulting product was a golden yellow solution with a pH of 14.11 and available halogen concentration of 27.7% as Br 2 In this example, the theoretical Br 2 is 31.2 if all of the bromine sources (bromide and bromate) are converted into stable oxidizing bromines. Therefore, the product yield is about 88.6%.

In another embodiment, liquid bromine is used as both oxidizer and bromine source. Sulfamate or other nitrogen base compounds are used as stabilizers. In addition, an adequate amount of alkali or alkaline earth metal hydroxide is required to maintain product pH.

Formulation temperature is also extremely critical in insuring the formation of stable oxidizing bromines.

Without adequate pH and temperature control, the heat generated by the exothermic reaction will cause rapid .4ecomposition of the oxidizing species.

The process of making high concentration stable oxidizing bromine formulations consists of two steps. In COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TIE 15:47 FAX 61299255911 GRIFFITH HACK o14 WO 0064806 PC /LS99f29192 the first step, a caustic stabilizing solution is prepared by mixing sulfamic acid, water and alkali or alkaline metal hydroxides (preferably NaON, Mg(OH) 2 or o other hydroxides). The p of the alkali or alkaline earth metal sulfamate solution is higher than 14. Excess hydroxides are purposely added to neutralize the acids generated by the subsequent bromination step and to Va maintain a high p (preferably greater than 13) in the finished product. The preferred molar ratio of sulfamate (Nq to liquid bromine is 1:1. The preferred molar ratio of o hydroxide to liquid bromine is 2.2:1. The stabilizer o solution can also be obtained by dissolving alkali or (Nq alkaline metal sulfamate in water and adding an appropriate amount of hydroxide.

The process is normally carried out in a jacketed glass reactor equipped with a proper mixing device. A cooling system for the reactor should be set up so that the reactor temperature can be controlled at an optimal range. An excessively high reaction temperature during the bromination step will accelerate sulfamate hydrolysis and cause decomposition of the desired product.

The second step of the process is to slowly add liquid bromine into the stabilizer solution under good agitation. Bromine is preferably added directly into the stabilizer solution through a Teflone tube to prevent elemental bromine exposure to air. The addition rate is controlled so that the reaction temperature is preferably below 25 0 C. The higher the reaction temperature, the lower the product yield. If the reaction temperature gets over 350C, sulfamate will start hydrolyzing into sulfate and ammonium- The resulting ammonium will react with and consume hypobromite and produce nitrogen gas which can be observed as vigorous foaming. With proper addition rates of liquid bromine, the liquid bromine will react instantaneously and will be stabilized- The process does not produce detectable bromine fumes.

COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:48 FAX 61299255911 GRIFFITH HACK 015 SWO 00164806 PCT/US991992 0 N 12 The product made with the above-described process was found to include no detectable bromate (less than ppm with ion chromatography analysis); no detectable 0 product concentration change was observed during a 2 month storage period at room temperature. For a 16.2% (as Br 2 product, the product has a half life of 74.5 days at 57QC.

\O

SExample

III

SBy way of an example, synthesis of a stable C(l oxidizing bromine product using the above-described V) method is achieved by mixing 52.16 grams of sulfamic Sacid, 42.0 grams of water and 128.0 grams of 50% aqueous cl NaOH in a 500 ml three-neck glass reactor. The mixture is cooled to a temperature of about 30C under constant agitation and refrigerated in a water bath. 82.5 grams of liquid bromine (99.8% Br 2 is slowly added to the solution and the reaction temperature is controlled and maintained below 10 0 C. The resulting solution has a pH of 12.5. The solution pH was increased to a level greater than 13 by adding 3.0 grams of 501 NaOH. The bromine content in the resulting solution was 26.2% as Br 2 while a theoretical content if 100% conversion is achieved is 27.0% as Br 2 After overnight storage at room temperature (21C), the formation of large amounts of crystals was observed in the solution. Using a 0.45 pm filter to separate the crystal from the liquid, followed by dehydration of the crystals under vacuum overnight, 46.8% as Br, was detected in the solid product while 18.7% of bromine content as Br 2 remained in the liquid. The solid product was found to be extremely water soluble. Accordingly, the present invention provides a solid stable oxidizing bromine product which is water soluble.

The solid product obtained in the above example has a very high concentration of stable oxidizing bromine COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:48 FAX 61299255911 GRIFFITH HACK 016 InWO 00/64806 ra111899/29192 Cl 13 compounds. The remaining content is believed to be water, excess NaOH and NaBr.

Other hybrid methods can be used to generate stable o oxidizing bromine compounds. One such method consists of using bromate salt as an oxidizer and bromine source, liquid bromine as an oxidizer, bromine source and acidic compound and sulfamate or another suitable halogen

IN

stabilizer as the bromine stabilizer. The reaction mechanism would be as follows: Cl Br 2

H

2 0 2H+ Br- OBr (6) o BrO,- 2Br- 14 30Br- (7) OBr- Stabilizer Stable oxidizing bromines (8) Cl The process can be carried out by dissolving bromate salt and water, adding sulfamate or other stabilizer to the solution, slowly adding liquid bromine, adjusting the pH to a level greater than 13 by adding NaOH, if the resulting product is to be stored for a long period of time. The process should be conducted at a temperature less than 250C, especially during the addition of liquid brominein an embodiment, the stable oxidizing bromine compound of the present invention can be used to provide improved biofouling control in industrial water systems, pulp and paper processing systems, food and beverage processing systems and recreational water systems. The stable oxidizing bromine compound of the present invention can also be used as a bleaching agent and to disinfect a hard surface. By way of example only, the present invention may be added to an aqueous media used to transport food through various processing systems and also to disinfect process equipment and waste water streams.

It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:48 FAX 61299255911 GRIFFITH HACK 017 WO 00/64806 PCTS99/29192 0 0 14 Sdeparting from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes 0 and modifications be covered by the appended claims.

VO

oD COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10

Claims (41)

1. A method of generating a stable oxidizing bromine compound, the method comprising the following steps: mixing an alkali or alkaline earth metal bromide and an alkali or alkaline earth metal bromate in water to 4\ provide an aqueous solution, 1 cooling the solution to a temperature less than o 25*C, and C adding a halogen stabilizer to the solution, the o halogen stabilizer being selected from the group Sconsisting of R-NH,, R-NH-R 1 R-SO 2 -NH, R-SO2-NRR 1 R-CO- NH,, R-CO-NH-R I and R-CO-NR-CO-R wherein R is a hydroxy group, an alkyl group or an aromatic group and R is an alkyl group or an aromatic group.

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

3. The method of claim 1 wherein the halogen stabilizer is added in a molar amount approximately equal to a combined molar amount of alkali or alkaline earth metal bromide and alkali or alkaline earth metal bromate.

4. The method of claim 1 wherein the halogen stabilizer is sulfamic acid. The method of claim 1 wherein the step of adding the halogen stabilizer results in the solution having a pH of less than 2.

6. The method of claim 1 further comprising the following step after the step of adding the halogen stabilizer: agitating the solution for a time period greater than 5 minutes. COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:49 FAX 61299255911 GRIFFITH HACK 1019 WO 00/64806 PCTUS9929192 C] 16

7. The method of claim 1 further comprising the following step after the step of adding the halogen stabilizer: o adjusting the solution to a pH of greater than 13.

8. The method of claim 1 wherein the step of mixing the alkali or alkaline earth metal bromide and 0' alkali or alkaline earth metal bromate further comprising VO mixing the alkali or alkaline earth metal bromide and the alkali or alkaline earth metal bromate in a molar ratio C'q of alkali or alkaline earth metal bromide:bromate of o about 2:1. o 9, A stable oxidizing bromine compound prepared by c' the following steps: mixing an alkali or alkaline earth metal bromide and an alkali or alkaline earth metal bromate in water to provide an aqueous solution, cooling the solution to a temperature less than and adding a halogen stabilizer to the solution, the halogen stabilizer being selected from the group consisting of R-NHB, R-NH-R R-SO 2 -NH2, R-SO 2 NHR, R-CO- NH,, R-CO-NH-R' and R-CO-NH-CO-R wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic group. The stable oxidizing bromine compound of claim 9 wherein the halogen stabilizer is selected from the group consisting of saccharin, benzenesulfonamide, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine.

11. In a method for the control of biofouling in an industrial water system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 9. COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TIE 15:49 FAX 61299255911 GRIFFITH HACK 020 in WO 06/64806 PCTUS99129192 (C 17

12. In a method for the control of biofouling in a pulp and paper processing system in which an oxidizing Sagent is added to control the biofouling, the method 0 comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 9.

13. In a method for the control of biofouling 0 occurring on the surfaces of equipment in contact with VO produced oil field waters in which an oxidizing agent is added to control the biofouling, the method comprising 0 using as the oxidizing agent the stable oxidizing bromine o compound of claim 9. S14. In a method for the control of biofouling in a C food processing system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 9. In a method for the control of biofouling in a beverage processing system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 9.

16. In a method for the control of biofouling in a recreational water system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 9.

17. In a method of disinfecting a hard surface in which an oxidizing agent is added to disinfect the hard surface, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 9.

18. In a method of washing food items in which an oxidizing agent is added to disinfect the food items, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 9.

19. In a method of laundering soiled garments and manufacturing cellulosic materials in which an oxidizing COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TLTE 15:49 FAX 61299255911 GRIFFITH HACK U021 SWO00/64806 PCT/US99129192 0 0 Cl| 18 >agent is used as a bleaching agent, the method comprising -using as the oxidizing agent the stable oxidizing bromine Scompound of claim 9. o 20. A method of generating a stable oxidizing bromine compound, the method comprising the following steps: 0 mixing about 2 moles of alkali or alkaline earth Va (metal bromide and about 1 mole of alkali or alkaline earth metal bromate in water to provide an aqueous Cl| solution, o cooling the solution to a temperature of less than 0 o c l adding an acidic halogen stabilizer to the solution to lower the pH of the solution to less than 2, the acidic halogen stabilizer being selected from the group consisting of saccharin, benzenesulfonamide, urea, thiourea, creatinine. cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine, the acidic halogen stabilizer being added in a molar amount approximately equal to a combined molar amount of alkali or alkaline earth metal bromide and alkali or alkaline earth metal bromate, agitating the solution for a time period greater than 5 minutes, and adding an alkali or alkaline earth metal hydroxide to the solution to increase the pH of the solution to greater than 13.

21. A stable oxidizing bromine compound prepared by the following steps: mixing about 2 moles of alkali or alkaline earth metal bromide and about 1 mole of alkali or alkaline earth metal bromate in water to provide an aqueous solution, cooling the solution to a temperature of less than 106C, COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:50 FAX 61299255911 GRIFFITH HACK @022 SWO 0064806 PCT/US9929192 19 adding an acidic halogen stabilizer to the solution to lower the pH of the solution to less than 2, the acidic halogen stabilizer being selected from the group 0 consisting of saccharin, benzenesulfonamide, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine, 0 the acidic halogen stabilizer being added in a molar amount approximately equal to a combined molar amount of Cl alkali or alkaline earth metal bromide and alkali or o alkaline earth metal bromate, o agitating the solution for a time period greater than 5 minutes, and adding an alkali or alkaline earth metal hydroxide to the solution to increase the pH of the solution to greater than 13.

22. In a method for the control of biofouling in an industrial water system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 21.

23. A method of generating a stable oxidizing bromine compound, the method comprising the following steps: preparing a caustic solution comprising a halogen stabilizer, water and an alkali or alkaline earth metal hydroxide, the halogen stabilizer being selected from the group consisting of R-NH a R-NH-R 1 R-SO-NH 2 R-SO-NHR R-CO-NH,, R-CO-NH-R' and R-CO-NH-CO- l R wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic group, adding a compound selected from bromine or bromine chloride to the solution while mixing the solution, and cooling the solution.

24. The method of claim 23 wherein the halogen stabilizer is selected from the group consisting of COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:50 FAX 61299255911 GRIFFITH HACK [a 023 WO 0/64806 PCT/US99/29192 02 0 (N saccharin, benzenesulfonamide, urea, thiourea, c creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, o biuret, sulfamic acid, organic sulfamates and melamine. The method of claim 23 wherein the caustic solution has a pH after the addition of bromine of 0 greater than 13. Va

26. The method of claim 23 wherein the step of o adding the bromine compound is further characterized as Cl| adding said compound in a molar amount approximately o equal to a molar amount of halogen stabilizer and o approximately one-half of a molar amount of alkali or c l alkaline earth metal hydroxide.

27. The method of claim 23 wherein the cooling step is further characterized as cooling the solution to a temperature of less than

28. The method of claim 23 wherein the step of adding the bromine containing compound is performed without exposing the compound to air.

29. The method of claim 23 further comprising the following step after the addition of the bromine or bromine chloride: adding an alkali or alkaline earth metal hydroxide to the solution to increase the pH of the solution above 13. A stable oxidizing bromine compound prepared by the following stepst preparing a caustic solution comprising a halogen stabilizer, water and an alkali or alkaline earth metal hydroxide, the halogen stabilizer being selected from the group consisting of R-NH2,, R-NH-R, R-SO-N 2 R-SO 2 -NHR 1 R-CO-NH 2 R-CO-NH-R' and R-CO-NE-CO-R' wherein R is a hydroxy group, an alkyl group or an aromatic group an R" is an alkyl group or an aromatic group, adding a compound selected from bromine or bromine chloride to the solution while mixing the solution, and COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:50 FAX 61299255911 GRIFFITH HACK @024 WO00 PCT/S99/29192 WO 00164806 (N1 21 cooling the solution.

31. The stable oxidizing bromine compound of claim wherein the halogen stabilizer is selected from the 0 group consisting of saccharin, benzenesulfonamide, urea, thiourea, creatinine. cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine.

32. In a method for the control of biofouling in an o industrial water system in which an oxidizing agent is C added to control the biofouling, the method comprising Susing as the oxidizing agent the stable oxidizing bromine O compound of claim

33. In-a method for the control of biofouling in a pulp and paper processing system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim

34. In a method for the control of biofouling occurring on the surfaces of equipment in contact with produced oil field waters in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim In a method for the control of biofouling in a food processing system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim

36. In a method for the control of biofouling in a beverage processing system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim

37. In a method for the control of biofouling in a recreational water system in which an oxidizing agent is added to control the biofouling, the method comprising COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:51 FAX 61299255911 GRIFFITH HACK @025 of WO 00/64806 PCT/US/29192 (N 22 using as the oxidizing agent the stable oxidizing bromine compound of claim

38. In a method of disinfecting a hard surface in o which an oxidizing agent is added to disinfect the hard surface, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 0" 39. In a method of washing food items in which an VO Soxidizing agent is added to disinfect the food items, the o method comprising using as the oxidizing agent the stable Cl oxidizing bromine compound of claim In a method of laundering soiled garments and o manufacturing cellulosic materials in which an oxidizing Cl agent is used as a bleaching agent, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim

41. A method of generating a stable oxidizing bromine compound, the method comprising the following steps; preparing a caustic solution comprising a halogen stabilizer, water and an alkali or alkaline earth metal hydroxide, the halogen stabilizer being selected from the group consisting of saccharin, benzenesulfonamide, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine, adding a compound selected from bromine or bromine chloride to the solution in a molar amount approximately equal to a molar amount of halogen stabilizer and approximately one-half of a molar amount of alkali or alkaline earth metal hydroxide and without exposing the bromine to air, mixing the solution, the solution having a pH after the mixing step of greater than 13, cooling the solution to a temperature of less than and COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:51 FAX 61299255911 GRIFFITH HACK o1026 WO 0064806 PCTIUS99129192 123 adding an alkali or alkaline earth metal hydroxide to the solution to increase the pH of the solution above 13. S42. A stable oxidizing bromine compound prepared by the following steps: preparing a caustic solution comprising a halogen IN stabilizer, water and an alkali or alkaline earth metal Shydroxide, the halogen stabilizer being selected from the o group consisting of saccharin, benzenesulfonamide, urea, (C thiourea, creatinine, cyanuric acids, alkyl hydantoins, o monoethanolamine, diethanolamine, organic sulfonamides, Sbiuret, sulfamic acid, organic sulfamates and melamine, adding a compound selected from bromine or bromine chloride to the solution in a molar amount approximately equal to a molar amount of halogen stabilizer and approximately one-half of a molar amount of alkali or alkaline earth metal hydroxide and without exposing the bromine to air, mixing the solution, the solution having a pH after the mixing step of greater than 13, cooling the solution to a temperature of less than and adding an alkali or alkaline earth metal hydroxide to the solution to increase the pH of the solution above 13.

43. In a method for the control of biofouling in an industrial water system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 42.

44. A method of generating a stable oxidizing bromine compound in an aqueous solution, the method comprising the following steps: dissolving an alkali or alkaline earth metal bromate salt in water to form a solution, COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:51 FAX 61299255911 GRIFFITH HACK M027 SWO 00/64806 PCTUS99/29192 C24 >adding a halogen stabilizer to the solution, the halogen stabilizer being selected from the group consisting of R-NH 2 R-NH-R, R-SO--NH 2 R-SOa-NHR, R-CO- 0 NH,, R-CO-NH-R and R-CO-NH-CO-R 1 wherein R is a hydroxy group, an alkyl group or an aromatic group and RI is an alkyl group or an aromatic group, and 0" adding bromine to the solution. The method of claim 44 wherein the halogen Sstabilizer is selected from the group consisting of Cl saccharin, benzenesulfonamide, urea, thiourea, o creatinine, cyanuric acids, alkyl hydantoins, Smonoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine.

46. The method of claim 44 further comprising the following step performed simultaneously with the step of adding bromine: cooling the solution to a temperature of less than

47. A stable oxidizing bromine compound prepared by the following steps: dissolving an alkali or alkaline earth metal bromate salt in water to form a solution, adding a halogen stabilizer to the solution, the halogen stabilizer being selected from the group consisting of R-NH 2 R-NH-R 1 R-SOa-NH 2 R-SO,-NMHR, R-CO- NH,, R-CO-NH-R 1 and R-CO-NH-CO-R wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic group, and adding bromine to the solution.

48. The stable oxidizing bromine compound of claim 47 wherein the halogen stabilizer is selected from the group consisting of saccharin, benzenesulfonamide, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid, organic sulfamates and melamine. COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:52 FAX 61299255911 GRIFFITH HACK o28 0 WO 00/64806 PCTI99192

49. In a method for the control of biofouling in an industrial water system in which an oxidizing agent is added to control the biofouling, the method comprising 0 using as the oxidizing agent the stable oxidizing bromine compound of claim 47. In a method for the control of biofouling in a 0" pulp and paper processing system in which an oxidizing agent is added to control the biofouling, the method ocomprising using as the oxidizing agent the stable ci oxidizing bromine compound of claim 47. o.51. In a method for the control of biofouling ooccurring on the surfaces of equipment in contact with produced oil field waters in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 47.

52. In a method for the control of biofouling in a food processing system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 47.

53. In a method for the control of biofouling in a beverage processing system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 47.

54. In a method for the control of biofouling in a recreational water system in which an oxidizing agent is added to control the biofouling, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 47. In a method of disinfecting a hard surface in which an oxidizing agent is added to disinfect the hard surface, the method comprising using as the oxidizing agent the stable oxidizing bromine compound of claim 47. COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10 10/05 '05 TUE 15:52 FAX 61299255911 GRIFFITH HACK @029 n WO 00164806 PCT/US99/29192 S26

56. In a method of washing food items in which an oxidizing agent is added to disinfect the food items, the method comprising using as the oxidizing agent the stable 0 oxidizing bromine compound of claim 47.

57. In a method of laundering soiled garments and manufacturing cellulosic materials in which an oxidizing agent is used as a bleaching agent, the method comprising 0" using as the oxidizing agent the stable oxidizing bromine 0 compound of claim 47. (N o o (N COMS ID No: SBMI-01239139 Received by IP Australia: Time 15:54 Date 2005-05-10