WO2005019111A2 - Composition comprenant un monopersulfate de potassium et un halogene - Google Patents

Composition comprenant un monopersulfate de potassium et un halogene Download PDF

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Publication number
WO2005019111A2
WO2005019111A2 PCT/US2004/024205 US2004024205W WO2005019111A2 WO 2005019111 A2 WO2005019111 A2 WO 2005019111A2 US 2004024205 W US2004024205 W US 2004024205W WO 2005019111 A2 WO2005019111 A2 WO 2005019111A2
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Prior art keywords
component
composition
potassium monopersulfate
water treatment
water
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PCT/US2004/024205
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English (en)
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WO2005019111A3 (fr
Inventor
Perry Martin
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MATERIALS TECHNOLOGY LABORATORIES Inc
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MATERIALS TECHNOLOGY LABORATORIES Inc
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Priority claimed from US10/878,899 external-priority patent/US7255797B2/en
Application filed by MATERIALS TECHNOLOGY LABORATORIES Inc filed Critical MATERIALS TECHNOLOGY LABORATORIES Inc
Publication of WO2005019111A2 publication Critical patent/WO2005019111A2/fr
Anticipated expiration legal-status Critical
Publication of WO2005019111A3 publication Critical patent/WO2005019111A3/fr
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • 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

  • This invention pertains generally to maintenance of aquatic facilities and particularly to sanitizing and/or oxidizing an aquatic facility.
  • BACKGROUND Aquatic facilities such as swimming pools, become contaminated from various components in the environment such as dust, bacteria, and viruses, as well as from waste products produced by the bathers.
  • the pool water is treated to reduce or eliminate chemical oxygen demand (COD) and/or total organic carbon (TOC) in the water.
  • COD chemical oxygen demand
  • TOC total organic carbon
  • chlorine or bromine is used to disinfect the water and prevent viruses and bacteria from being transmitted among the bathers.
  • Halogen donor compounds such as chlorine or bromine are also used to sanitize/oxidize waste products produced by the bathers.
  • the oxidation potential of water must be sustained above a threshold value.
  • the contaminant is any substance that reacts with and consumes the sanitizing/oxidizing agent.
  • contaminants often come in the form of organic compounds. Sanitizing water would be relatively easy if the only type of contaminants were inorganic nitrogen waste products (e.g., ammonia, ammonium), as chlorine can convert the ammonia to inert nitrogen gas using the well known breakpoint chlorination process.
  • the breakpoint chlorination process is significantly impaired. This impairment is at least partly due to the fact that organic nitrogen reacts with the sanitizing agent in a less desirable competing reaction.
  • the competing reaction entails chlorine's reaction with the organic nitrogen to produce a volatile and irritating byproduct known as chloramine (NH 2 C1, NHC1 2 , NCI 3 , R 2 NC1, RHNCl, where R represents organic constituent). Because some of the chlorine is turned into chloramines by the organic nitrogen (instead of being turned into inert nitrogen by the inorganic nitrogen), the ability of chlorine (or other halogen)-based sanitizing/oxidizing agent to rid the water of inorganic nitrogen such as mono- and di- chloroamines is significantly impaired.
  • chloramines In applications such as swimming pool water, where both organic and inorganic nitrogen are present, organic nitrogen that forms chloramines competes for chlorine against inorganic nitrogen that forms inert nitrogen. Chloramines accumulate because chlorine is consumed more readily by the organic byproducts than the already partially oxidized chloramines. Accumulation of chloramines is undesirable for a number of reasons. First, chloramines are less effective as oxidizers than chlorine. Second, incomplete oxidation of the Total Organic Carbon (TOC) by reaction with chlorine produces trihalomethane (THM), which are known carcinogens. Furthermore, chlorammes and THM induce corrosion of metals and impose mild to severe irritation to bathers' eyes, skin, and respiratory systems.
  • TOC Total Organic Carbon
  • THM trihalomethane
  • the organic byproducts must be effectively oxidized independently of chlorine, leaving chlorine free to react with the inorganic nitrogen. This way, the chlorine is free to disinfect the water by converting the inorganic nitrogen to inert nitrogen gas. Also, when the TOC is diminished, the potential for formation of THM by reaction between chlorine and the TOC is reduced. Thus, a method and composition for achieving breakpoint chlorination without accumulation of chloramines and formation of incomplete oxidation products is desired.
  • the invention includes a water treatment product that effectively reduces the amount of organic and inorganic nitrogen by preventing the accumulation of chloramines.
  • the water treatment product contains a much lower level of irritants than most currently available water treatment products, allowing water treatment even while bathers are in the swimmmg pool.
  • the invention is a water treatment composition includes a potassium monopersulfate component, a halogen component including or generating a halogen donor, and a barrier film.
  • the barrier film which allows the potassium monopersulfate component to be combined with the halogen component, includes one or more of an inorganic salt, silicate, borosilicate, and an organic polymer.
  • thei nvention is a method of preparing a water treatment composition by providing a potassium monopersulfate component and combining the potassium monopersulfate component with a halogen donor and a barrier film.
  • the invention is a method of treating water by obtaining a solid product containing potassium monopersulfate and a halogen donor, and periodically adding the mixture to a body of water.
  • the invention is also a method of combining potassium monopersulfate and a halogen donor into a stable product. Potassium monopersulfate and halogen donor(s) were previously not combined because of their incompatibility.
  • the invention includes coating either the potassium monopersulfate with one or more of inorganic salt, silicate, borosilicate, and organic polymer to overcome this incompatibility. After the coating, the halogen donor is added to the coated potassium monopersulfate to form a PMPS- halogen product.
  • Embodiments of the invention are described herein in the context of a swimming pool, and particularly in the context of disinfecting the swimming pool water. However, it is to be understood that the embodiments provided herein are just preferred embodiments, and the scope of the invention is not limited to the applications or the embodiments disclosed herein. Due to the above-mentioned disadvantages of using a halogen to treat water that contains both organic and inorganic contaminants, potassium monopersulfate (KHSO 5 , herein referred to as PMPS) is sometimes used with halogen. PMPS is effective at removing TOC and prevents the accumulation of chloramines by allowing them to be oxidized via breakpoint chlorination.
  • KHSO 5 potassium monopersulfate
  • PMPS does not produce THMs.
  • PMPS has its disadvantages as well.
  • PMPS is usually accompanied by an irritating byproduct, K 2 S 2 O 8 (potassium oxodisulfate). Since bathers can tolerate only a low level of K 2 S 2 O8, there is naturally a limit to how much PMPS can be added to a body of water.
  • K 2 S 2 O 8 potassium oxodisulfate
  • bathers can tolerate only a low level of K 2 S 2 O8
  • PMPS is added as part of a shock treatment whereby an entire dosage is spread across the surface of the pool at once. The dosage is limited to 1 ⁇ 2 lb/10,000 gallons per week, depending on the manufacturer.
  • PMPS in conjunction with a sanitizing agent, such as a halogen donor.
  • a sanitizing agent such as a halogen donor.
  • PMPS-and- halogen-based water treatment a problem with PMPS-and- halogen-based water treatment is that PMPS is not compatible with some of the chlorine/bromine donor products that are most commonly used today (e.g., calcium hypochlorite, dichloro isocyanurate, trichloro-isocyanurate, bromo-chloro- dimethylhydantoin (BCDMH), dibromo-dimethylhydantoin (DBDMH).
  • the invention includes a PMPS-halogen product including PMPS and one or more halogen donors.
  • the product overcomes the incompatibility problem between the PMPS and halogen donors by implementing a barrier film between the PMPS and halogen donor(s) which allows the PMPS and the halogen donor to be combined into a stable composition.
  • the product uses a PMPS that is substantially free of K 2 S 2 O 8 so that more of the product can be used without posing a health hazard to the bathers.
  • the PMPS-halogen product frees up the halogen to react with inorganic wastes by having PMPS remove organic wastes.
  • the halogen-PMPS composition contains 1) a halogen component that includes or produces a halogen donor, 2) a PMPS component having the formula (KHSO 5 ) ⁇ (KHSO 4 ) y (K.
  • halogen-PMPS composition enhances disinfection rates by sustaining higher oxidation-reduction potential (ORP) values in water that is being treated.
  • this halogen-PMPS composition promotes breakpoint chlorination of organic nitrogen and of inorganic nitrogen in the presence of organic chemical oxygen demand (COD).
  • the process for preparing this PMPS component is described in U.S. Provisional Patent Application Serial No. 60/505,466, which is incorporated by reference herein in its entirety.
  • the PMPS component of the PMPS-halogen product is made of about 43 to about 76 wt. % KHSO 5 , less than about 0.5 wt. % (and preferably less than about 0.2 wt.
  • the alkali magnesium salt comprises one or more of Mg(OH) 2 , MgCO 3 , Mg(HCO 3 ) 2 , MgO, (MgCO 3 ) 4 -Mg(OH) 2 -5H 2 O, CaMg(CO 3 ) 2 , MgO-CaO, Ca(OH) 2 -MgO or combinations thereof.
  • the halogen component is a substance that includes or generates a halogen donor, such as one or more of calcium hypochlorite, trichloroisocyanurate, dichloroisocyanurate, lithium hypochlorite, dibromo-dimethylhydantoin, bromo-chloro- dimethylhydantoin, sodium bromide, and sodium chloride.
  • a halogen donor such as one or more of calcium hypochlorite, trichloroisocyanurate, dichloroisocyanurate, lithium hypochlorite, dibromo-dimethylhydantoin, bromo-chloro- dimethylhydantoin, sodium bromide, and sodium chloride.
  • the barrier film which may be an inorganic salt, silicate, borosilicate, an organic polymer, or any combination thereof, allows the halogen donor and the PMPS composition to be combined.
  • the inorganic salt may be one or more of sodium, potassium, magnesium, calcium, or a combination thereof, combined with one or more of carbonate, bicarbonate, hydroxide, oxide, silicate, borate, or combinations thereof.
  • the silicate may be sodium, potassium, lithium, silicate, borosilicate, or a combination thereof.
  • the organic polymer comprises chitin, chitosan, polymaleic acid, phosphinocarboxylic acid, carboxylate-sulfonate copolymer, a carboxylate-sulfonate terpolymer, or a combination thereof.
  • the carboxylate component of the carboxylate- sulfonate copolymer or the carboxylate-sulfonate terpolymer is derived from either polyacrylic acid, polymethacrylic acid or polymaleic acid, and the sulfonate portion of the carboxylate-sulfonate copolymer or the carboxylate-sulfonate terpolymer is derived from an aliphatic or aromatic compound.
  • the aliphatic compound comprises methacrylamido methyl propane sulfonic acid, and the aromatic compound comprises styrene sulfonic acid.
  • the terpolymer incorporates a nonionic component such as (meth)acrylamide, substituted (meth)acrylamide, vinyl alcohol, allyl alcohol, vinyl esters, an ester of vinyl or allyl alcohol, styrene, isobutylene or diisobutylene.
  • the barrier film may be coated onto either the halogen donor or the PMPS composition.
  • the barrier film may be coated by covering the composition with the barrier film material while mechanically mixing the barrier film material in a screw auger or a rotary drum.
  • the barrier film may be applied by using a fluidized driver. If the barrier film material is an inorganic salt, it may be applied before, during, or after the drying of the composition.
  • the barrier film material is silicate, borosilicate, and/or organic polymer, on the other hand, it is preferably applied to the composition either while the composition is drying or after the composition is dried.
  • the coating is then applied in the fo ⁇ n of a foam or atomized spray to maximize distribution, and further dried by using a suitable conventional drier including but not limited to a rotary drier or a fluidized drier.
  • a halogen-PMPS product containing the PMPS composition and one or more of the halogen donors can effectively control the chloramine, COD, and TOC levels in the treated water and reduce or even eliminate the problems associated with the accumulation of these undesirable products. Further, the halogen-PMPS composition reduces or eliminates any byproducts resulting from incomplete oxidation of the waste.
  • This composition may be in powder form, granular form, or in the shape of a pellet, nugget, tablet, sphere, briquette, puck, etc.
  • the halogen component functioning as the halogen oxidizer may be calcium hypochlorite, trichloroisocyanurate, dichloroisocyanurate, lithium hypochlorite, dibromo-dimethylhydantoin, bromo-chloro-dimethylhydantoin, sodium bromide, sodium chloride, or a combination thereof.
  • the PMPS compound used for the PMPS-halogen product has a K 2 S 2 O 8 byproduct concentration below 0.5 wt. % and preferably below 0.2 wt. %.
  • the low K 2 S 2 O 8 concentration allows the PMPS-halogen product to be used at a higher dosage than what is currently allowed. In fact, the PMPS-halogen product may be used continually while the pool is being used.
  • the composition can then be shaped into a useful solid form by using established processing techniques. If the composition is granular, it may be produced using rotary mixers and/or rotary driers. Alternatively, a spray graining technique may be used with a fluidized drier. If the composition is a tablet, a nugget, a briquette, a sphere, a puck or a solid object of a different shape, it may be produced by combining and mixing the components of the composition and applying pressure to a mold or extruding the objects of the desired shape.
  • a well-known binding agent may be used to enhance the cohesiveness of the particles.
  • the pressure level that is applied during extrusion may be adjusted according to the desired hardness of the end product.
  • the shaped composition e.g., a tablet
  • the PMPS-halogen product is preferably released in a controlled manner.
  • some exemplary shapes for the PMPS-halogen product include powder, granules, nugget, briquette, pucks, etc. - anything deemed suitable by a person skilled in the art.
  • the disclosed stable composition can then be employed in water treatment applications as an improved disinfectant.
  • the PMPS-halogen product may be used in a liquid form.
  • the solid form of PMPS-halogen product is dissolved in water using any number of dry product feed devices.
  • a tank with a mixer and a pump may be used.
  • a chemical feeder which contains the PMPS composition may be used to dissolve some or all of the composition before using the solution.
  • the composition may be applied by periodically using a timer, or by manually or automatically activating the feed system. The method allows for frequent incremental feed or continuous feed of the composition even when bathers are present, without concern of causing irritation.
  • “Frequent incremental feed” refers to a feed of at least one cycle per day.
  • the concentration of chloramines and other undesirable byproducts is sustained at much lower levels than when the components of the composition are used separately. Furthermore, when the pool water is "shock" treated by addition of the powder or granular composition across the surface of the pool, the combined level of chlorine and other undesirable contaminants is reduced to a level much lower than that achieved using current methods of shock treatment or breakpoint chlorination. Also, with the halogen- PMPS composition of the invention, there is no need for an oxidation reduction potential (ORP) control device of the type disclosed in U.S. Patent No. 6,620,315.
  • ORP oxidation reduction potential
  • halogen-PMPS composition may be included in the halogen-PMPS composition without deviating from the scope of this invention.
  • pH buffering agents e.g., coagulants; clarifiers, algae control agents (e.g., boron or lanthanum based additives)
  • clarifiers e.g., boron or lanthanum based additives
  • algae control agents e.g., boron or lanthanum based additives

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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)
  • Paints Or Removers (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un produit comprenant un monopersulfate de potassium et un halogène. Ce produit convient pour le traitement d'installations aquatiques telles que des piscines. Bien qu'on sache qu'une combinaison de monopersulfate de potassium et d'halogène soit efficace pour épurer l'eau, un produit comprenant ces deux composants ne pouvaient être fabriqué à cause de l'incompatibilité existant entre ces deux composants. Ce produit surmonte cette incompatibilité en utilisant un film barrière entre les deux composants. Ce film barrière qui comprend un ou plusieurs sels inorganiques, du silicate, du borosilicate et un polymère organique est revêtu sur l'un des composants avant que ce dernier soit combiné avec le second. Ce produit peut être extrudé et moulé en une forme souhaitée et ajouté à l'eau à traiter, comme il se doit.
PCT/US2004/024205 2003-08-14 2004-07-26 Composition comprenant un monopersulfate de potassium et un halogene Ceased WO2005019111A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US49536703P 2003-08-14 2003-08-14
US60/495,367 2003-08-14
US10/878,899 2004-06-28
US10/878,899 US7255797B2 (en) 2003-08-13 2004-06-28 Composition including potassium monopersulfate and a halogen

Publications (2)

Publication Number Publication Date
WO2005019111A2 true WO2005019111A2 (fr) 2005-03-03
WO2005019111A3 WO2005019111A3 (fr) 2009-04-16

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2004292538B2 (en) * 2003-11-21 2009-10-29 Lanxess Corporation Multi-functional oxidizing composition
CN101935096A (zh) * 2010-08-17 2011-01-05 海安县中丽化工材料有限公司 降cod脱色絮凝剂的生产方法
CN103755653A (zh) * 2014-01-26 2014-04-30 菏泽华意化工有限公司 一种利用二氯异氰尿酸和碳酸钙生产三氯异氰尿酸的方法
CN105540772A (zh) * 2015-12-25 2016-05-04 武汉回盛生物科技有限公司 一种水产养殖用底质改良片剂及其制备方法
CN108585135A (zh) * 2018-05-18 2018-09-28 济南雨露生物科技有限公司 一种安全环保的高效水处理消毒净化剂

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1170122A (en) * 1967-02-21 1969-11-12 Richardson Merrell Ltd Sterilizing Composition.
US4880547A (en) * 1975-06-30 1989-11-14 Kenji Etani Methods for water treatment

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2004292538B2 (en) * 2003-11-21 2009-10-29 Lanxess Corporation Multi-functional oxidizing composition
CN101935096A (zh) * 2010-08-17 2011-01-05 海安县中丽化工材料有限公司 降cod脱色絮凝剂的生产方法
CN103755653A (zh) * 2014-01-26 2014-04-30 菏泽华意化工有限公司 一种利用二氯异氰尿酸和碳酸钙生产三氯异氰尿酸的方法
CN103755653B (zh) * 2014-01-26 2015-11-18 菏泽华意化工有限公司 一种利用二氯异氰尿酸和碳酸钙生产三氯异氰尿酸的方法
CN105540772A (zh) * 2015-12-25 2016-05-04 武汉回盛生物科技有限公司 一种水产养殖用底质改良片剂及其制备方法
CN108585135A (zh) * 2018-05-18 2018-09-28 济南雨露生物科技有限公司 一种安全环保的高效水处理消毒净化剂

Also Published As

Publication number Publication date
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