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
• • 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
  • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
  • C02F2103/023—Water in cooling circuits
• • 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 generally to methods of treating water, and more particularly to a method of treating water with hydrogen peroxide, polyquatemary ammonium compounds and chlorine.
• Biocides traditionally used to control microbial growth include chlorine, bromine, biguanide salts, peroxy compounds, ozone and quaternary ammonium compositions.
• chlorine has long been the dominant disinfectant, although the disadvantages of chlorine have led to a continued search for other disinfecting products.
• chlorine is highly effective it must be applied frequently to maintain its efficacy, and readily forms irritating chloramines and/or trihalomethanes . At high levels, chlorine can harm pool surfaces and equipment.
• peroxides such as hydrogen peroxide are not effective as a stand alone sanitizers except when used at relatively high concentrations (e.g.. 200 ppm or higher) . Unfortunately, as the peroxide concentration increases so does the likelihood of injury or discomfort to swimmers and spa bathers.
• H 2 0_ When regulated waters are treated with H 2 0_, the system can only remain biocidally effective as long as H_0 2 remains available for disinfection. If levels of organic materials accumulate, the half life of peroxide decreases with a corresponding decrease in antimicrobial efficacy.
• a method of treating water by using strong oxidizing agents such as calcium hypochlorite, lithium hypochlorite, activated sodium bromide, sodium dichloroisocyanurate, trichloroisocyanurate, sodium hypochlorite, potassium peroxymonopersulfate, etc. to shock regulated waters treated with hydrogen peroxide (H-,0-) and polyquatemary ammonium compounds (polyquats) .
• H-,0- hydrogen peroxide
• polyquats polyquatemary ammonium compounds
• a method of treating water by adding hydrogen peroxide and a polyquate ary ammonium compound to the water.
• the hydrogen peroxide and the polyquatemary ammonium compound are independently added to the water in amounts effective to maintain in the water a balanced sanitizing solution.
• One object of the invention is to provide a method of enhancing the quality of regulated waters using polyquatemary amonium compounds, hydrogen peroxide and regular shocks with dry or liquid oxidizers.
• Another object of the present invention is to provide an improved method of sanitizing water with dilute hydrogen peroxide. Another object of the present invention is to provide a method of adding flocculant and clarifying properties to dilute hydrogen peroxide solutions.
• Another object of the present invention is to provide a method of reducing the amount of hydrogen peroxide necessary to sanitize recreational waters.
• Another object of the present invention is to provide a method of increasing the half-life of hydrogen peroxide used to sanitize recreational waters.
• FIG. 1 is a graph of the half-life estimations of with and without PDED.
• FIG. 2 is a graph of the half-life estimations of
• strong oxidizing agents such as calcium hypochlorite, lithium hypochlorite, activated sodium bromide, sodium dichloroisocyanurate, trichloroisocyanurate, sodium hypochlorite, potassium peroxymonopersulfate, etc. are used to regenerate regulated waters treated with hydrogen peroxide (H_0 ? ) and polyquatemary ammonium compounds (polyquats) .
• H_0 ? hydrogen peroxide
• polyquats polyquatemary ammonium compounds
• a stable solution of Hun0 flash and a polyquat) or polyquats is added to a body of water to give concentrations of H 2 0 2 ranging from 1-100 ppm and a polyquat concentration ranging from 0.1-30 ppm.
• the H O level ranges from 10-30 ppm and the polyquat level ranges from 1-5 ppm.
• the solution is preferably applied at specified intervals (weekly, bi-weekly or monthly) . At certain intervals (weekly, bi-weekly or monthly), superchlorination or superoxygenating shock treatment is applied prior to adding the H 2 0 2 polyquat solutions. After several hours (if using unstabilized shock treatments), it is preferred to resume the treatment program with another H O polyquat application.
• Unstabilized chlorine products such as calcium hypochlorite, lithium hypochlorite are the preferred shocking agents because the resulting chlorine residuals will quickly be degraded by Ultraviolet radiation from the sun.
• periodic superchlorination may be necessary for the system to maintain optimal performance, active chlorine will actually be present for relatively brief periods of time.
• activated sodium bromine Bromine (as sodium bromide) can be activated by hypochlorous acid generated from bleach or dry oxidizers in water. Maintaining excellent water quality with such infrequent use of a halogen shock treatment is surprising.
• Stabilized chlorinating agents using a cyanuric acid carrier would be as effective as unstabilized chlorine, but oxidizing chlorine would remain active for longer periods of time. Residual levels of chlorine might cause irritation to swimmers or might degrade H 2 0_. Potassium onoperioxytsulfate is a non-chlorine alternative for persons desiring to avoid the use of halogens.
• Another aspect of the present invention uses dilute hydrogen peroxide as a sanitizer along with a polyquatemary ammonium stabilizer for treating regulated waters.
• the stabilizer allows H 2 0 2 to remain biocidally active for longer periods of time and enhances its overall efficacy.
• the sanitizer and stabilizer can be added separately or blended together for a single, slug application.
• the ideal dose would comprise 1-2 gallons of the active ingredients (blended or separate) to maintain 20,000 gallons of regulated water every two weeks.
• the ability to effectively treat such a large volume of water without mechanical feeders and with such an infrequent dosing schedule is an unexpected advantage of the invention.
• polyquatemary ammonium compounds may be used in the various aspects of the present invention, including poly(hexamethylammoniu ) chloride ("Q6/6"), pol [oxyethylene-(dimethylimino) ethylene-(dimethylimino) ethylene dichloride] (“PDED”), dodecamethylenedimethylimino chloride ("Q6/12") and 1,3-diazo-2, -cyclopentadiene with l-chloro-2, 3-epoxypro ⁇ ane (“IPCP”).
• Q6/6 poly(hexamethylammoniu ) chloride
• PDED pol [oxyethylene-(dimethylimino) ethylene-(dimethylimino) ethylene dichloride]
• IPCP 3-epoxypro ⁇ ane
• the hydrogen peroxide and the polyquatemary ammonium compound are added independently so that appropriate concentrations of each composition may be maintained in the water. Appropriate concentrations are generally determined by testing the treated water. Then, the appropriate amount of either composition may be added. This technique provides the additional benefit of allowing the two components to be stored and handled separately.
• the water should contain between 5 and 40 ppm H_0_ and a polyquatemary ammonium stabilizer concentration between 1 and 20 ppm.
• a concentrated, blended product should contain between 10% and 80% H 2 0 2 and 2% to 40% polyquat per' >ne gallon container. When applied as separate products, the relative concentrations of H 2 0_ and polyquat should remain the same, using either gallon or half gallon containers.
• the various aspects of the present invention provide simple, albeit novel, improvements to the existing art.
• the invention precludes the need to purchase a mechanical device to apply the products. The cost of equipment and upkeep is thereby eliminated.
• the invention is flexible in that the ingredients can be packaged as a shelf stable blend or in separate containers.
• the schedule of product additions can be tailored to meet the needs of individual pool owners. For example, more or less stabilizer may be required in certain cases and can be added without adding unnecessary quantities of the other composition.
• abandoning the mechanical device will make the technology more practical for consumers treating regulated waters.
• this system melds the antimicrobial and aesthetic benefits of monomeric and polymeric quaternary ammonium compounds. That is, a biocidally efficacious system that produces only small amounts of foam, if any.
• the invention is superior to the polybiguanide system in that the components can be blended in one container.
• the polyquatemary ammonium compounds act as flocculants.
• Flocculants are chemicals that are used to aggregate suspended solids from liquids, thereby facilitating their separation via precipitation or filtration. Consistent with this ability, polyquats are capable of cell adhesion and aggregation. Studies performed in pools with swimmers have shown that polyquats such as Q6/6 are unable to sanitize water when used alone. In such cases bacterial densities were as high
• Table 1 displays a brief excerpt from the in-use pool study.
• Table 1. Bacterial Densities Versus Water Clarity.
• Q Q suspension (about 10 to 10 organisms) containing £. aeruginosa. E. coli . and £. aureus . These are some of the major bacteria which can be recovered from recreational and industrial waters. Peroxide and polyquat concentrations were monitored after about 24 hours and recorded in Tables 2-6. Moreover, samples were removed 30 minutes after inoculation, treated with a neutralizer and plated onto nutrient agar to determine the number of viable bacteria.
• Table 7 demonstrates the inability of H 2 0 2 to control bacterial growth, even at high concentrations.
• previous research has demonstrated that PDED like H O , is not an effective sanitizer when used alone (data not shown) .
• Table 8 demonstrates the ability of polyquats to enhance H_0 , rendering it more efficacious. While PDED has demonstrated antimicrobial synergy with oxidizers, these data indicate that polyquats can also stabilize and extend peroxide half life in the use dilutions.
• Example 3 The experiment summarized in Example 3 is identical to Example 2, except that Q6/6 was substituted for PDED (Tables io and 11) . Q6/6 alone is not an effective sanitizer in regulated waters (data not shown) . As was the case with PDED, Q6/6 stabilized and enhanced the efficacy of H_0_ . Hydrogen peroxide alone had a shorter half life and was not an effective bactericide even at the highest levels tested.
• FIG. 2 graphically shows the difference in half life. Based on the regression, we can extrapolate that H 2 0 2 alone would have lasted for about 9 days, but would have lasted for almost 16 days when stabilized with Q6/6.
• the method disclosed precludes the use of mechanized feeders, it offers tenable benefits for individuals involved in treating regulated waters. This method allows for a substantial cost savings, the elimination of feeder problems and maintenance and improved efficacy due to the inherent flexibility of applying bottled products.
• Table 13 shows the surprising effect that a chlorine shock has on peroxide half life.
• a 5,000 above ground pool was maintained on 10 ppm H ? 0 consult and 5 ppm of a polyquat (Q6/12) weekly.
• the pool was challenged daily with an artificial insult containing synthetic sweat and a bacterial inoculum consisting of P. aeruginosa (10 9-10 cells).
• the pool received natural inoculations from the environment. In some cases, H 2 0 2 was not measured due to intervening weekends.
• EXAMPLE 5 In another experiment, a 5,000 gallon, above ground pool was treated with 27.5 ppm H 2 0 2 and 10 ppm of a polyquat (Q6/6) on a weekly basis. Neither synthetic insult nor prepared bacterial inocula were added since human swimmers contributed natural flora and secretions whenever they were in the pool. These swimmers (4) averaged between 2-4 hr per person per week in this particular pool.
• H_0 applications resulted in theoretical (or near theoretical) levels of H 2 0 2 in the pool (6/28-7/9). As the trial progressed, subsequent H Guide0 ? applications were substantially less productive (7/9-7/13). In order to restore H 2 0 2 half life to its original length, 6 gallons of H 2 0 2 were needed within a four day period even though the maintenance application rate was only 1.5 gallons per seven days.

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• 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)
• Physical Water Treatments (AREA)

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• 1997
  • 1997-03-17 ZA ZA9702298A patent/ZA972298B/xx unknown
  • 1997-03-18 EP EP97916788A patent/EP0888250A4/fr not_active Withdrawn
  • 1997-03-18 BR BR9708098A patent/BR9708098A/pt active Search and Examination
  • 1997-03-18 NZ NZ331893A patent/NZ331893A/en unknown
  • 1997-03-18 CA CA002249701A patent/CA2249701A1/fr not_active Abandoned
  • 1997-03-18 WO PCT/US1997/004200 patent/WO1997034835A1/fr not_active Application Discontinuation
  • 1997-03-18 AR ARP970101076A patent/AR009944A1/es not_active Application Discontinuation
  • 1997-03-18 AU AU25319/97A patent/AU2531997A/en not_active Abandoned

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