WO1992019553A1 - Divalent silver halide bactericide - Google Patents
Divalent silver halide bactericide Download PDFInfo
- Publication number
- WO1992019553A1 WO1992019553A1 PCT/US1992/003987 US9203987W WO9219553A1 WO 1992019553 A1 WO1992019553 A1 WO 1992019553A1 US 9203987 W US9203987 W US 9203987W WO 9219553 A1 WO9219553 A1 WO 9219553A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- divalent silver
- halides
- divalent
- silver
- water
- Prior art date
Links
Classifications
-
- 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
- C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
Definitions
- the present invention relates to divalent silver (Agll) halide bactericides.
- the bactericidal properties of soluble Ag(II) compounds is the subject of U.S. Patent #5,017,285 of the present inventor.
- the inventor described the preparation of soluble Ag(II) compounds which are effective bactericides in swimming pool and industrial cooling tower waters. These compounds are prepared by dissolving divalent silver oxide, AgO, in certain acids such as phosphoric acid, which form stable Ag(II) complexes. In the course of experimenting with these complexes, it was found that halides precipitated Ag(II) halides from these solutions.
- the primary object of this invention is to provide a source of bactericidally active divalent silver for application to waters utilized for industrial cooling water, swimming pool and hot tub applications which requires 100% kills of a specific standardized bacterium coliform strain within 10 minutes for swimming pools and hot tubs.
- a further object of this invention is to provide for a source of divalent silver ions which will not precipitate silver halide out of water containing halide salts. Summary of the Invention This invention relates to methods for keeping the water in swimming pools, hot tubs and industrial cooling installations free from bacteria. Said methods relate to bactericidal agent additions of divalent silver halides, especially the chloride, bromide or iodide to said waters.
- Divalent silver halides were prepared in the laboratory via various inorganic synthetic routes and were evaluated in the presence of persulfate ion, a known stabilizer for Ag(II) ions, to see whether they were effective at various concentrations in inhibiting bacterial growth.
- the culture that was chosen for evaluation was E. Coli, and a test method based on EPA protocol AOAC 15th 1990:965:13 was utilized, which involves a culture of lOOk/cc and requires 100% kills within 10 minutes for a bacteri ⁇ ide to qualify in swimming pools.
- the evaluations were performed in the presence of 10 L/cc potassium monopersulfate utilizing Oxone which is the registered trademark of said compound manufactured by Dupont Company.
- the silver halides were also added to high salt content water with absolutely no precipitation occurring.
- the silver halides were prepared essentially by three routes: 1) Precipitation from divalent silver nitrate solution with an alkaline metal halide; 2) Direct action of a hydrohalic acid with AgO; 3) Direct action of boiling hot alkaline metal halide solution on AgO.
- Divalent silver nitrate was prepared by dissolving AgO in nitric acid.
Abstract
Divalent silver halides provide a source for divalent bactericidal silver ions in the presence of persulfate. The halides are especially effective when applied to water used in industrial cooling installations, hot tubs and swimming pools and will conform to stringent EPA requirements for waters utilized for bathing as in tubs and pools of 100 % kills of 100 K/cc E. Coli coliforms within 10 minutes, examplary of which are the chloride and bromide which give 100 % kills within 5 minutes. The halides, of course, can be used in salty water since they are solids immune from halide action that would otherwise precipitate soluble divalent silver from solution.
Description
DIVALENT SILVER HALIDE BACTERICIDE Background of the Invention The present invention relates to divalent silver (Agll) halide bactericides. The bactericidal properties of soluble Ag(II) compounds is the subject of U.S. Patent #5,017,285 of the present inventor. In said patent the inventor described the preparation of soluble Ag(II) compounds which are effective bactericides in swimming pool and industrial cooling tower waters. These compounds are prepared by dissolving divalent silver oxide, AgO, in certain acids such as phosphoric acid, which form stable Ag(II) complexes. In the course of experimenting with these complexes, it was found that halides precipitated Ag(II) halides from these solutions. It should be noted that the solubility of Ag(II) compounds is totally unrelated to those of Ag(I) in water. For example, Ag(II) sulfate is totally soluble compared to the partially soluble Ag(I) salt. Thus the fact that Ag(II) precipitates halides is not necessarily to be anticipated since the Ag(I) and Ag(II) chemistries are different and distinct despite the fact that they represent dissimilar states of the same element. It was also found that Ag(II) complexes had a greater tolerance for free halide in solution than Ag(I) . Accordingly, water sources containing 100 PPM of dissolved sodium chloride (NaCl) would not precipitate insoluble chloride
from those solutions which are described in my aforementioned patent. However, water with substantially higher halide content precipitated silver halide. It was postulated that for those high halide waters, such as sea water used for swimming pools, brackish waters used in cooling towers, swimming pools maintained with calcium chloride for mineralization or mineralized hot tubs, Ag(II) halides could be useful provided they exhibited bactericidal properties since they are already insoluble and will not be prone to precipitation. This was highly desirable since tests conducted in a swimming pool with a high chloride content produced an aesthetically unacceptable curdy white precipitate of chloride when it was treated with an Ag(II) phosphate complex. Of course, since a divalent silver halide is effective and would by necessity have to be produced from a soluble bactericidally active Ag(II) complex, it would not be the first product of choice for low-salt or salt- free water treatment where said soluble Ag(II) complexes were the preferable product. However, there existed the possibility that direct action of a hydrohalic acid on Ago could yield end product Ag(II) halides even though the latter were insoluble. If this were possible, then said Ag(II) halides would be intrinsically competitive with the soluble Ag(II) complexes. Accordingly, it was found that Ag(II) halides are bactericidally active and
that they could be prepared both directly and indirectly from AgO. Object of the Invention The primary object of this invention is to provide a source of bactericidally active divalent silver for application to waters utilized for industrial cooling water, swimming pool and hot tub applications which requires 100% kills of a specific standardized bacterium coliform strain within 10 minutes for swimming pools and hot tubs. A further object of this invention is to provide for a source of divalent silver ions which will not precipitate silver halide out of water containing halide salts. Summary of the Invention This invention relates to methods for keeping the water in swimming pools, hot tubs and industrial cooling installations free from bacteria. Said methods relate to bactericidal agent additions of divalent silver halides, especially the chloride, bromide or iodide to said waters. Divalent silver halides were prepared in the laboratory via various inorganic synthetic routes and were evaluated in the presence of persulfate ion, a known stabilizer for Ag(II) ions, to see whether they were effective at various concentrations in inhibiting bacterial growth. The culture that was chosen for
evaluation was E. Coli, and a test method based on EPA protocol AOAC 15th 1990:965:13 was utilized, which involves a culture of lOOk/cc and requires 100% kills within 10 minutes for a bacteriσide to qualify in swimming pools. The evaluations were performed in the presence of 10 L/cc potassium monopersulfate utilizing Oxone which is the registered trademark of said compound manufactured by Dupont Company. The silver halides were also added to high salt content water with absolutely no precipitation occurring. The silver halides were prepared essentially by three routes: 1) Precipitation from divalent silver nitrate solution with an alkaline metal halide; 2) Direct action of a hydrohalic acid with AgO; 3) Direct action of boiling hot alkaline metal halide solution on AgO. Divalent silver nitrate was prepared by dissolving AgO in nitric acid. Other objects and features of the present invention will become apparent to those skilled in the art when the present invention is considered in view of the accompanying examples. It should, of course, be recognized that the accompanying examples illustrate preferred embodiments of the present invention and are
not intended as a means of defining the limits and scope of the present invention. Description of the Preferred Embodiments As illustrative of the compositions of this invention are the following: EXAMPLE I Divalent silver nitrate was prepared by dissolving AgO containing 1.0 gram of silver for 5 minutes in 30% volume nitric acid (70% of specific gravity 1.42) . The dissolution proceeded over a 5-minute period at 75-80 degrees C. A yellowish brown solution resulted which was immediately diluted with water. The dissolution of AgO in nitric acid is illustrated by the following reaction: AgO + 2HN03 = Ag(N03)2 + H20 The resulting solution was reacted with an aliquot of sodium bromide. Beautiful crystals of divalent silver bromide precipitated from the solution which upon drying gave a yellow-green solid product. The preparation of divalent silver bromide by this route can be represented as follows: Ag(N03)2 + 2 NaBr = AgBr2 + 2 NaN03 When 5.0 PPM of Ag(II)Br were added to water containing 10 PPM of Oxone which had been adjusted to a pH of 7.5, 100% kills of the aforementioned E. Coli coliforms occurred according to the protocol described in the Summary of my invention after 5 and 10 minutes. This
represented an actual silver concentration of 1.7 PPM which was effective as a swimming pool and hot tub disinfectant according to EPA protocol. EXAMPLE II Two samples of divalent silver chloride were prepared from AgO via alternative routes, the first by reaction of the oxide with a boiling solution of sodium chloride and the second by reaction of the oxide in the cold with concentrated hydrochloric acid. The reactions are respectively: AgO + 2NaCl + H20 = AgCl2 + 2 NaOH and AgO + 2HC1 = AgCl2+ H20 Samples of water containing 10 PPM of Oxone and adjusted to a pH=7.5 were treated with a 5 PPM of divalent silver chloride prepared by both methods. Both samples were submitted to the EPA protocol described in Example I. Both samples gave 100% kills after 5 and 10 minutes. This represented an actual silver concentration of 2.8 PPM which was effective as a swimming pool and hot tub disinfectant. As this invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, the present embodiment is therefore illustrative and not restrictive, since the scope of the invention is defined by the appended claims
rather than by the description preceding them, and all changes that fall within the metes and bounds of the claims or that form their functional as well as conjointly cooperative equivalents, are therefore intended to be embraced by these claims.
Claims
1. A method for controlling the growth of bacteria in the water of swimming pools, hot tubs and industrial cooling towers which comprises adding a divalent silver halide in the presence of an oxidizing agent so s to provide a source of divalent silver ions.
2. A method as claimed in claim 1 where the oxidizing agent is a persulfate. .
3. A method according to claim 1 which can be utilized in salt water without causing any precipitation of bactericidally active divalent silver ions.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/697,783 US5078902A (en) | 1991-05-09 | 1991-05-09 | Divalent silver halide bactericide |
US697,783 | 1991-05-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992019553A1 true WO1992019553A1 (en) | 1992-11-12 |
Family
ID=24802520
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/003987 WO1992019553A1 (en) | 1991-05-09 | 1992-05-07 | Divalent silver halide bactericide |
Country Status (3)
Country | Link |
---|---|
US (1) | US5078902A (en) |
AU (1) | AU2028492A (en) |
WO (1) | WO1992019553A1 (en) |
Families Citing this family (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5073382A (en) * | 1991-05-09 | 1991-12-17 | N. Jonas & Co., Inc. | Divalent silver alkaline bactericide compositions |
US5098582A (en) * | 1991-05-09 | 1992-03-24 | N. Jonas & Co., Inc. | Divalent silver oxide bactericides |
US5336499A (en) * | 1992-01-10 | 1994-08-09 | Antelman Technologies, Ltd. | Molecular crystal device for pharmaceuticals |
US5211855A (en) * | 1992-01-24 | 1993-05-18 | N. Jonas & Co., Inc. | Method of treating water employing tetrasilver tetroxide crystals |
US5223149A (en) * | 1992-05-18 | 1993-06-29 | N. Jonas & Co., Inc. | Trivalent silver water treatment compositions |
US5681575A (en) | 1992-05-19 | 1997-10-28 | Westaim Technologies Inc. | Anti-microbial coating for medical devices |
GEP20002074B (en) * | 1992-05-19 | 2000-05-10 | Westaim Tech Inc Ca | Modified Material and Method for its Production |
US5676977A (en) * | 1994-09-22 | 1997-10-14 | Antelman Technologies Ltd. | Method of curing AIDS with tetrasilver tetroxide molecular crystal devices |
US6210566B1 (en) * | 1996-09-25 | 2001-04-03 | Joseph A. King | Nestable containers and improved water treatment materials |
EP1041879B2 (en) * | 1997-10-10 | 2012-03-21 | Pure Bioscience | Disinfectant and method of making |
US6726936B1 (en) | 1998-06-19 | 2004-04-27 | Sumitomo Metal Mining Co., Ltd. | Antimicrobial agents |
GB2385790B (en) * | 1998-06-19 | 2003-10-22 | Sumitomo Metal Mining Co | Antimicrobial agents |
JP4558934B2 (en) * | 1998-10-29 | 2010-10-06 | 住友金属鉱山株式会社 | Antibacterial agent |
US6565893B1 (en) | 1999-02-17 | 2003-05-20 | Worldwide Pure Water, Inc. | Process for preparing a disinfectant containing suspended metals |
US6224779B1 (en) * | 1999-04-01 | 2001-05-01 | Marshall L. Spector | Inhibition of algae in swimming pools |
US7261905B2 (en) * | 1999-04-07 | 2007-08-28 | Pure Bioscience | Disinfectant and method of making |
US6258385B1 (en) | 1999-04-22 | 2001-07-10 | Marantech Holding, Llc | Tetrasilver tetroxide treatment for skin conditions |
FR2792500B1 (en) * | 1999-04-23 | 2004-05-21 | Internat Redox Dev | AQUEOUS COMPOSITION, IN PARTICULAR IN THE FORM OF GEL, BASED ON HO2F, ACIDS AND METAL IONS, PREPARATION METHOD, PARTICULARLY WHEN THE SAID IONS ARE AG2 + AND USE IN THE FIELD OF DISINFECTION AND / OR SURFACE TREATMENT |
US6214299B1 (en) | 1999-06-01 | 2001-04-10 | Robert J. Holladay | Apparatus and method for producing antimicrobial silver solution |
US6383273B1 (en) | 1999-08-12 | 2002-05-07 | Apyron Technologies, Incorporated | Compositions containing a biocidal compound or an adsorbent and/or catalyst compound and methods of making and using therefor |
US6645531B1 (en) | 2000-01-06 | 2003-11-11 | Marantech Holding Llc | Multivalent electron active compositions and methods of making and using same |
US6669966B1 (en) | 2000-01-06 | 2003-12-30 | Marantech Holding Llc | Compositions for facilitating skin growth and methods and articles using same |
US20060105057A1 (en) * | 2000-01-06 | 2006-05-18 | Marantech Holding, Llc | Compositions using tetrasilver tetroxide and methods for management of skin conditions using same |
US6485755B1 (en) | 2000-01-06 | 2002-11-26 | Marantech Holding | Methods of using electron active compounds for managing cancer |
US20040022868A1 (en) * | 2000-01-06 | 2004-02-05 | Marantech Holding Llc | Compositions using tetrasilver tetroxide and methods for management of skin conditions using same |
US6346201B1 (en) | 2000-04-05 | 2002-02-12 | Icf Technologies, Inc. | Ozonated solutions of tetrasilver tetroxide |
US6890953B2 (en) * | 2000-04-06 | 2005-05-10 | Innovative Medical Services | Process for treating water |
US20040044073A1 (en) * | 2002-08-31 | 2004-03-04 | Innovative Medical Services | Composition and process for treating acne |
WO2005030028A2 (en) * | 2003-04-28 | 2005-04-07 | Aidance Medical Diagnostics, Llc | Methods for detecting presence of cellular constituents |
US7435438B1 (en) | 2003-05-16 | 2008-10-14 | Pure Bioscience | Disinfectant and method of use |
CA2526150C (en) * | 2003-06-03 | 2014-05-06 | American Biotech Labs | Treatment of humans with colloidal silver composition |
AU2004267997B2 (en) * | 2003-08-28 | 2010-06-03 | Pure Bioscience | Silver dihydrogen citrate compositions comprising a second antimicrobial agent |
US7582594B2 (en) * | 2003-10-17 | 2009-09-01 | Applied Research Associates, Inc. | Dioxirane formulations for decontamination |
US7560033B2 (en) * | 2004-10-13 | 2009-07-14 | E.I. Dupont De Nemours And Company | Multi-functional oxidizing composition |
US20050211612A1 (en) * | 2004-03-25 | 2005-09-29 | Mattson Roy W Jr | Water suction purification device |
US20060051430A1 (en) * | 2004-09-07 | 2006-03-09 | Arata Andrew B | Silver dihydrogen citrate compositions |
US7799234B2 (en) * | 2007-04-09 | 2010-09-21 | Innovation Services, Inc. | In-line waste disinfection method |
US7794606B2 (en) * | 2007-04-09 | 2010-09-14 | Innovation Services, Inc. | Modular flameless waste treatment method |
US9045718B2 (en) | 2007-04-09 | 2015-06-02 | Innovation Services, Inc. | Residue cleaning composition and method |
US8399028B2 (en) * | 2008-08-14 | 2013-03-19 | Exciton Technologies Inc. | Antimicrobial silver solutions |
WO2017034871A1 (en) | 2015-08-21 | 2017-03-02 | G&P Holding, Inc. | Silver and copper itaconates and poly itaconates |
Citations (2)
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---|---|---|---|---|
US4055655A (en) * | 1975-07-21 | 1977-10-25 | National Research Laboratories | Complexes of heavy metal ions and polyfunctional organic ligands used as antimicrobial agents |
US4092245A (en) * | 1977-04-07 | 1978-05-30 | Goetz, Trustee Sylvia | Liquid purification method |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5017295A (en) * | 1990-05-01 | 1991-05-21 | N. Jonas & Co., Inc. | Divalent silver bactericide for water treatment |
-
1991
- 1991-05-09 US US07/697,783 patent/US5078902A/en not_active Expired - Lifetime
-
1992
- 1992-05-07 WO PCT/US1992/003987 patent/WO1992019553A1/en active Application Filing
- 1992-05-07 AU AU20284/92A patent/AU2028492A/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4055655A (en) * | 1975-07-21 | 1977-10-25 | National Research Laboratories | Complexes of heavy metal ions and polyfunctional organic ligands used as antimicrobial agents |
US4092245A (en) * | 1977-04-07 | 1978-05-30 | Goetz, Trustee Sylvia | Liquid purification method |
Also Published As
Publication number | Publication date |
---|---|
AU2028492A (en) | 1992-12-21 |
US5078902A (en) | 1992-01-07 |
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