WO1998000368A1 - Methods for sanitizing water - Google Patents
Methods for sanitizing water Download PDFInfo
- Publication number
- WO1998000368A1 WO1998000368A1 PCT/US1997/011076 US9711076W WO9800368A1 WO 1998000368 A1 WO1998000368 A1 WO 1998000368A1 US 9711076 W US9711076 W US 9711076W WO 9800368 A1 WO9800368 A1 WO 9800368A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ppm
- water
- peroxyacid
- maintaining
- peracetic acid
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
Definitions
- the present invention relates to methods of using peroxyacids and/or chlorine dioxide to treat swimming pools sanitized with PHMB or other sanitizing agents.
- a method for the "on site” generation of such peroxyacids is also disclosed.
- swimming pool disinfectants such as polyhexamethylene biguanide (“PHMB”), hydrogen peroxide (“H O ”) and polyquatemary ammonium compounds ( “polyquats” ) such as 1 , 6-hexanediamine- N, N,N ' ,N ' -tetramethyl polymer with 1, 6-dichlorohexane (“Q6/6”) have increasingly garnered broad support in the pool & spa water community.
- PHMB polyhexamethylene biguanide
- H O hydrogen peroxide
- polyquats polyquatemary ammonium compounds
- Q6/6 6-dichlorohexane
- swimming pool sanitizers that do not release free chlorine are less prone to bleach swim wear, and are less caustic to equipment used in the swimming pool area.
- One disadvantage of common non-chlorinating sanitizers is that they lack a strong oxidizer (i.e.. chlorine) which is generally necessary to prevent problems such as cloudy water and discoloration of pool surfaces. Accordingly, it is known to the art that pools sanitized with PHMB, polyquats or H_0 2 may periodically require strong oxidation treatments to destroy peroxide resistant organic materials which can hamper system performance, cause cloudy water or produce displeasing odors. Oxidizers can also be used to bleach aesthetically displeasing colors and deposits
- the present invention addresses this need.
- a method of using a peroxyacid such as peracetic acid, to treat the water of a recirculating water system.
- peracetic acid is used in conjunction with PHMB.
- peracetic acid is used in conjunction with Hvisor06-0rom and polyquats.
- peracetic acid is used in conjunction with a polyquatemary ammonium compound, while in a fourth preferred embodiment peracetic acid is used in conjunction with a boron-containing compound.
- the peracetic acid is routinely provided to the water at maintenance levels, while in other preferred embodiments the peracetic acid is used only occasionally to shock treat the water.
- chlorine dioxide is used in conjunction with PHMB, while in another preferred embodiment chlorine dioxide is used with H O- and polyquats.
- chlorine dioxide is used in conjunction with a polyquatemary a monium compound, while in a fourth preferred embodiment chlorine dioxide is used in conjunction with a boron-containing compound.
- the chlorine dioxide is preferably used only occasionally to shock treat the water.
- FIG. 1 is a schematic diagram showing a peroxyacid feeding device according to the present invention.
- FIG. 2 shows a second device for generating peroxyacids on site, accoding to one preferred embodiment of the present invention.
- the present invention relates to methods of using a peroxyacid, such as peracetic acid, or chlorine dioxide to treat the water of a recirculating water system.
- peracetic acid is used in conjunction with PHMB, while in another preferred embodiment peracetic acid is used in conjunction with Hd j O-..
- peracetic acid is used in conjunction with a polyquatemary ammonium compound stabilizer or potentiating adjuvant, while in a fourth preferred embodiment peracetic acid is used in conjunction with a boron-containing compound such as sodium tetraborate, perborates or boric acid, or combinations thereof.
- the peracetic acid is routinely provided to the water at maintenance levels, while in other preferred embodiments the peracetic acid is used only occasionally to shock treat the water.
- chlorine dioxide is used in conjunction with PHMB, while in yet other preferred embodiments chlorine dioxide is used in conjunction with Hd-Od..
- chlorine dioxide is used with a polyquatemary ammonium compound, while in another preferred embodiment chlorine dioxide is used in conjunction with a boron-containing compound.
- the chlorine dioxide is preferably used only occasionally to shock treat the water.
- poly- (iminoimidocarbonyl-iminoimidocarbonyliminohexamethylene) chloride also called polyhexamethylene biguanide or PHMB
- That compound is well known to the art and can be obtained from commercial sources.
- Hydrogen peroxide is also well known, and can be obtained from known commercial sources.
- the pool is routinely treated with polyquatemary ammonium compounds (polyquats) such as 1 , 6-hexanediamine-N,N,N ' ,N ' -tetramethyl polymer with 1 , 6-dichlorohexane (Q6/6, also identified as polyhexamethylenedimethyl ammonium chloride) and two of its homologs (Q6/12 and Q6/4).
- polyquats polyquatemary ammonium compounds
- Q6/6 also identified as polyhexamethylenedimethyl ammonium chloride
- Q6/12 and Q6/4 two of its homologs
- the water is routinely treated with boron-containing compounds such as sodium tetraborate, boric acid, sodium perborate or some combinations thereof.
- boron-containing compounds such as sodium tetraborate, boric acid, sodium perborate or some combinations thereof.
- the secondary treatment chemical may be either a peroxyacid, such as peracetic acid (“PAA”), or chlorine dioxide.
- PAA peracetic acid
- An effective PAA treatment can be provided by a ready made solution or by a solution prepared on site by the end user or service technician.
- PAA is preferably prepared by mixing an equimolar mixture of acetic acid and peroxide. Two percent H,,S0. (in acetic acid) serves as the acidified catalyst.
- PAA is less stable than H-O.- and occasionally requires special shipping and handling precautions, it may be advantageous to generate PAA on site.
- the individual components H--0 2 and acid catalyst
- the individual components could be mixed prior to use, ensuring the full potency of the PAA.
- the amount of PAA formed would be dependent upon the starting H-.0 2 concentration.
- One preferred embodiment uses 27.5-40% H 2 0 2 with an equimolar mount of acetic acid with 2% sulfuric acid.
- a solution containing 30% H 2 0 2 with an equimolar quantity of acidified catalyst could be expected to form about 10% PAA within a few hours (13).
- the chlorine dioxide is produced on site to avoid transportation and handling issues.
- water sanitized with PHMB preferably has 0.1 ppm to 100 ppm residual PHMB in the water. Preferred concentrations are 0.5 ppm to 10 ppm PHMB.
- Water sanitized with H.O. and polyquats preferably has 0.05 ppm to 200 ppm residual Hdon0,. in the water. Preferred concentrations are 10 ppm to 50 ppm H ? 0 2 .
- Water sanitized with polyquats preferably has 0.05 ppm to 75 ppm residual polyquat in the water. Preferred concentrations are 2 ppm to 10 ppm polyquat.
- Water sanitized with boron-containing compounds preferably has 1 ppm to 200 ppm residual boron-containing compound in the water. Preferred concentrations are 25 ppm to 50 ppm boron-containing compound.
- maintenance levels of PAA are preferably between about 0.1 ppm and 200 ppm PAA. More preferred concentrations are 5 ppm to 20 ppm PAA.
- Shock treatment levels of PAA are preferably between about 0.1 ppm and 300 ppm PAA. More preferred shock treatment concentrations are 10 ppm to 50 ppm PAA.
- Shock treatment levels of chlorine dioxide are preferably between about 0.1 ppm and 500 ppm chlorine dioxide. More preferred shock treatment concentrations are 1 ppm to 10 ppm chlorine dioxide.
- the methods of use comprise providing sanitizers and the novel PHMB compatible oxidizers to the water in amounts appropriate to provide the desired levels.
- both the sanitizers and the PHMB compatible oxidizers are maintained in the water routinely, while with the shock treatment methods the oxidizer is added only periodically, as needed to provide effective control.
- a 5,000 gallon pool treated with PHMB had developed green and brown deposits on the pool's surfaces.
- PAA was generated in situ by mixing one gallon of H ? 0 2 with one-half gallon of acidified catalyst and allowing the mixture to sit for 4.5 hours prior to application.
- green algae and brown deposits had been effectively decolorized.
- There was no resulting loss of PHMB as would be expected with a strong oxidizer.
- chlorine is used to oxidize the plumbing of PHMB pools. However, the chlorine is backwashed out and none of it is allowed to enter the pool.
- PAA is less stable than H_0d.
- the use of in situ generated PAA may be of significant commercial value for treating regulated waters. However, this will require - l i ⁇
- FIG. 1 a schematic of a prototypical device for a pool has been outlined in FIG. 1.
- the pool operator would remove the lid to add the components (peroxide and acid catalyst) .
- the chemicals could be added to a sealed device through filling ports.
- the pool operator would switch the on/off valve to the "on" (open) position and the in situ generated PAA would enter the pool through the plumbing (FIG. 1. ) .
- EXAMPLE 7 In some cases, pool owners may not wish to adapt their existing plumbing to accommodate a device such as is described in Example 6. For these c-md users, a similar device which fits directly over the skimmer may be of value. It is described in FIG. 2.
- a consumer with a chlorine pool (20,000 gallons) was experiencing persistent cloudiness although her chlorine levels were being maintained at greater than 5 ppm.
- a pool is treated with a boron-containing compound to achieve and optimal level of boon between 25-50 ppm.
- the boron acts to stabilize PAA in addition to helping to maintain clear water.
- Peracetic acid (ca. 10-20 ppm) is added weekly in order to oxidize and sanitize water. Should problems occur in such a system (e.q., cloudy water, malodors, algae, etc.), a consumer would have the option of using an additional dose of PAA or shock chlorination .
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU35786/97A AU726566B2 (en) | 1996-07-03 | 1997-06-25 | Methods for sanitizing water |
EP97932290A EP0912448A4 (en) | 1996-07-03 | 1997-06-25 | Methods for sanitizing water |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/675,042 US5779914A (en) | 1996-07-03 | 1996-07-03 | Methods for sanitizing water |
US08/675,042 | 1996-07-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1998000368A1 true WO1998000368A1 (en) | 1998-01-08 |
WO1998000368A9 WO1998000368A9 (en) | 1998-06-11 |
Family
ID=24708836
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/011076 WO1998000368A1 (en) | 1996-07-03 | 1997-06-25 | Methods for sanitizing water |
Country Status (6)
Country | Link |
---|---|
US (1) | US5779914A (en) |
EP (1) | EP0912448A4 (en) |
AU (1) | AU726566B2 (en) |
CA (1) | CA2259382A1 (en) |
WO (1) | WO1998000368A1 (en) |
ZA (1) | ZA975822B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2808016A1 (en) * | 2000-04-21 | 2001-10-26 | Atofina | Aqueous composition for purification of, e.g., urban waste water, comprises a compound capable of releasing chlorine dioxide, an organic peracid, and a source of water |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19856198A1 (en) * | 1998-12-05 | 2000-06-08 | Degussa | Swimming pool water treatment process |
AU5864401A (en) * | 2000-06-02 | 2001-12-17 | Avecia Inc | Treatment of circulating water systems |
ES2189649B1 (en) * | 2001-06-15 | 2004-09-16 | Oftrai S.L. | NEW DISINFECTANT AND ANTISEPTIC COMPOSITION. |
ITMI20020568A1 (en) * | 2002-03-18 | 2003-09-18 | Caffaro Spa Ind Chim | PROCEDURE AND EQUIPMENT FOR WATER DISINFECTION |
US8668779B2 (en) * | 2002-04-30 | 2014-03-11 | Nalco Company | Method of simultaneously cleaning and disinfecting industrial water systems |
US7252096B2 (en) * | 2003-04-08 | 2007-08-07 | Nalco Company | Methods of simultaneously cleaning and disinfecting industrial water systems |
US7449119B2 (en) | 2005-07-28 | 2008-11-11 | Chemtura Corporation | Methods for controlling Mycobacterium chelonae and removing bacterial cell membrane fragments from turbulent waters |
US20110024367A1 (en) * | 2009-07-29 | 2011-02-03 | Martin Roy W | Cyclic process for in-situ generation of chlorine dioxide in biguanide treated aquatic facilities |
US9238587B2 (en) | 2013-03-15 | 2016-01-19 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of water and fluids with chlorine dioxide |
US10442711B2 (en) * | 2013-03-15 | 2019-10-15 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse |
JP5711846B1 (en) * | 2014-10-21 | 2015-05-07 | 助川化学株式会社 | Water mold control method in aquaculture water |
CA3077382A1 (en) | 2017-10-03 | 2019-04-11 | Italmatch Chemicals Gb Limited | Treatment of circulating water systems including well treatment fluids for oil and gas applications |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US4253971A (en) * | 1977-06-14 | 1981-03-03 | Macleod Norman A | Water treatment |
US5368749A (en) * | 1994-05-16 | 1994-11-29 | Nalco Chemical Company | Synergistic activity of glutaraldehyde in the presence of oxidants |
US5393781A (en) * | 1993-07-08 | 1995-02-28 | Fmc Corporation | Method for controlling zebra mussels |
US5478482A (en) * | 1994-05-16 | 1995-12-26 | Bio-Lab, Inc. | Method and compositions for treating recirculating water systems |
US5501802A (en) * | 1993-04-22 | 1996-03-26 | Fmc Corporation | Method for treating water using an organic sanitizer and a persulfate |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3386915A (en) * | 1964-03-18 | 1968-06-04 | Solvay | Process for the manufacturing of chlorine dioxide in solution and the use of the solution thus obtained |
FR2636239B1 (en) * | 1988-09-09 | 1992-09-18 | Produits Ind Cie Fse | DISINFECTANT COMPOSITION FOR THE PREVENTION OF SUBCLINIC MAMMITIS IN RUMINANTS |
DE3840103C2 (en) * | 1988-11-28 | 1994-10-06 | Bayrol Chem Fab Gmbh | Method for sterilizing and de-aerating water |
ZA905554B (en) * | 1989-09-27 | 1991-04-24 | Buckman Labor Inc | Synergistic combinations of ionenes with hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine in controlling fungal and bacterial growth in synthetic metalworking fluid |
IL102627A (en) * | 1992-07-23 | 1996-05-14 | Abic Ltd | Solid composition releasing chlorine dioxide |
US5449658A (en) * | 1993-12-07 | 1995-09-12 | Zeneca, Inc. | Biocidal compositions comprising polyhexamethylene biguanide and EDTA, and methods for treating commercial and recreational water |
-
1996
- 1996-07-03 US US08/675,042 patent/US5779914A/en not_active Expired - Lifetime
-
1997
- 1997-06-25 WO PCT/US1997/011076 patent/WO1998000368A1/en not_active Application Discontinuation
- 1997-06-25 CA CA002259382A patent/CA2259382A1/en not_active Abandoned
- 1997-06-25 EP EP97932290A patent/EP0912448A4/en not_active Withdrawn
- 1997-06-25 AU AU35786/97A patent/AU726566B2/en not_active Ceased
- 1997-06-30 ZA ZA975822A patent/ZA975822B/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4253971A (en) * | 1977-06-14 | 1981-03-03 | Macleod Norman A | Water treatment |
US5501802A (en) * | 1993-04-22 | 1996-03-26 | Fmc Corporation | Method for treating water using an organic sanitizer and a persulfate |
US5393781A (en) * | 1993-07-08 | 1995-02-28 | Fmc Corporation | Method for controlling zebra mussels |
US5368749A (en) * | 1994-05-16 | 1994-11-29 | Nalco Chemical Company | Synergistic activity of glutaraldehyde in the presence of oxidants |
US5478482A (en) * | 1994-05-16 | 1995-12-26 | Bio-Lab, Inc. | Method and compositions for treating recirculating water systems |
Non-Patent Citations (1)
Title |
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See also references of EP0912448A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2808016A1 (en) * | 2000-04-21 | 2001-10-26 | Atofina | Aqueous composition for purification of, e.g., urban waste water, comprises a compound capable of releasing chlorine dioxide, an organic peracid, and a source of water |
WO2001081251A1 (en) * | 2000-04-21 | 2001-11-01 | Atofina | Aqueous composition based on chlorine dioxide |
Also Published As
Publication number | Publication date |
---|---|
AU726566B2 (en) | 2000-11-09 |
CA2259382A1 (en) | 1998-01-08 |
ZA975822B (en) | 1998-09-01 |
EP0912448A1 (en) | 1999-05-06 |
US5779914A (en) | 1998-07-14 |
EP0912448A4 (en) | 2000-07-12 |
AU3578697A (en) | 1998-01-21 |
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