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WO1993004987A1 - Pastilles donneuses d'ions hypochlorite et d'ions bromure a dissolution lente dans l'eau - Google Patents

Pastilles donneuses d'ions hypochlorite et d'ions bromure a dissolution lente dans l'eau Download PDF

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Publication number
WO1993004987A1
WO1993004987A1 PCT/US1992/006735 US9206735W WO9304987A1 WO 1993004987 A1 WO1993004987 A1 WO 1993004987A1 US 9206735 W US9206735 W US 9206735W WO 9304987 A1 WO9304987 A1 WO 9304987A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
tablet
chlorinated
sodium bromide
tablets
Prior art date
Application number
PCT/US1992/006735
Other languages
English (en)
Inventor
Thomas Charles Kuechler
Lawrence Frederick Rakestraw
Original Assignee
Occidental Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Occidental Chemical Corporation filed Critical Occidental Chemical Corporation
Publication of WO1993004987A1 publication Critical patent/WO1993004987A1/fr

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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
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C02F1/688—Devices in which the water progressively dissolves a solid compound
    • 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
    • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/086—Condensed phosphates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • 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 relates to hypochlorite donor/bromide ion donor tablets for disinfecting recirculating water systems, and more particularly to tablets comprising chlorinated isocyanurates, sodium bromide, and a stabilizer which regulates the rate at which the chlorinated isocyanurate and the sodium bromide are dissolved or dispersed in flowing water.
  • the tablets according to the invention are stable in water, i.e.. the tablets do not disintegrate into fines upon exposure to flowing water, but instead dissolve at relatively uniform and commercially acceptable rates.
  • Tablets prepared according to the invention provide hypobromous acid, which functions as a bromine biocide or disinfectant in recirculating water systems such as cooling towers, swimming pools, spas, etc. BACKGROUND OF THE INVENTION
  • British Pat. No. 1,196,870 discloses dry disinfectant mixtures consisting essentially of the sodium salt of dichloroisocyanuric acid, trichloroisocyanuric acid, or a mixture thereof with an alkali metal bromide and a buffering mixture of sodium carbonate/bicarbonate and optionally including phosphates, polyphosphates, and surface active agents.
  • U.S. Pat. No. 4,557,926, issued to Nelson et. al discloses a tablet for disinfecting toilets comprising an alkali metal salt of dichlorocyanuric acid and either sodium bromide or potassium bromide.
  • solid disinfecting compositions comprising a mixture of 80% -99% by weight trichloro-s-triazinetrione and 1% - 20% by weight potassium bromide.
  • a disinfectant composition be usable in biocide dispensing devices such as erosion feeders, skimmers, and floaters, in order to slowly release the disinfectant into the water system.
  • the preferred disinfectant composition is a mixture of dry solid components that can be compressed into a tablet for use in these devices.
  • hypochlorite ion donor means any compound that will generate hypochlorite species when dissolved in water.
  • chlorinated isocyanurate means dichloroisocyanuric acid, trichloroisocyanuric acid, [mono(trichloro)-tetra(monopotassium dichloro) ]-penta-s- triazinetrione, and [mono(trichloro)-mono(monopotassium dichloro) ]-di-s-triazinetrione, and mixtures thereof.
  • bromide ion donor means any compound that will generate bromide ions when dissolved in water.
  • tablette includes other solid, compressed forms such as sticks and pucks.
  • the present invention relates to hypochlorite donor/bromide ion donor tablets for disinfecting recirculating water systems, and more particularly to tablets comprising chlorinated isocyanurates, sodium bromide, and a stabilizer which regulates the rate at which the chlorinated isocyanurate and the sodium bromide are dissolved or dispersed in flowing water.
  • the tablets according to the invention are stable in water, i.e. , the tablets do not disintegrate into fines upon exposure to flowing water, but instead dissolve at relatively uniform and commercially acceptable rates.
  • the tablets are comprised of the following solid particulate materials: a) chlorinated isocyanurates; and b) sodium bromide; and c) a stabilizer selected from active chlorine stabilizer compounds that are compatible, i.e.. unreactive, • with chlorinated isocyanurates in the solid state, and capable of binding active halogen (chlorine or bromine in the +1 valence state) , and less soluble when fully chlorinated than in the less than fully chlorinated state.
  • active chlorine stabilizer compounds that are compatible, i.e.. unreactive, • with chlorinated isocyanurates in the solid state, and capable of binding active halogen (chlorine or bromine in the +1 valence state) , and less soluble when fully chlorinated than in the less than fully chlorinated state.
  • the tablets are comprised of the following solid particulate materials: a) chlorinated isocyanurates; and b) sodium bromide encapsulated with a stabilizer selected from coating agents having a low solubility in aqueous media.
  • the tablets according to the invention are stable in water, i.e. , they do not disintegrate into fines upon exposure to flowing water, but instead dissolve at relatively uniform and commercially acceptable rates.
  • Preferred tablet compositions are those comprising from about 62 wt.% to about 97 wt.% chlorinated isocyanurate, from about 1 wt.% to about 30 wt.% sodium bromide, and from about 2 wt.% to about 8 wt.% stabilizer wherein the stabilizer is an active chlorine stabilizer compound that is compatible with chlorinated isocyanurates in the solid state, and capable of binding active halogen (chlorine or bromine in the +1 valence state) , and less soluble when fully chlorinated than in the less than fully chlorinated state.
  • active chlorine stabilizer compound that is compatible with chlorinated isocyanurates in the solid state, and capable of binding active halogen (chlorine or bromine in the +1 valence state) , and less soluble when fully chlorinated than in the less than fully chlorinated state.
  • the preferred chlorinated isocyanurate is trichloro-s-triazinetrione (also called trichloroisocyanuric acid and trichloroisocyanurate, which is produced and sold by Monsanto Co. under the product name ACL 90 R PLUS.
  • ACL R is a registered trademark of Monsanto Co.
  • the invention permits production of water stable tablets containing up to about 30% by weight sodium bromide.
  • compositions comprising trichloro-s-triazinetrione and sodium bromide. These compositions are merely exemplary of various embodiments of the invention, and should not be viewed as a limitation on any claimed invention.
  • FIGURE 1 illustrates trichloro-s- triazinetrione/sodium bromide tablet structures that provide acceptable water stability properties.
  • FIGURES 2 - 4 illustrate trichloro-s- triazinetrione/sodium bromide tablet structures that are not water stable.
  • FIGURE 5 illustrates an erosion feeder apparatus. DETAILED DESCRIPTION OF THE INVENTION
  • the trichloro-s-triazinetrione/sodium bromide tablet structures illustrated in FIGURE 1 exhibit good water stability properties because the highly soluble sodium bromide particles are distributed throughout a continuous matrix of trichloro-s-triazinetrione particles so that the sodium bromide particles are isolated from each other and form a non-continuous matrix.
  • the sodium bromide particles are considerably smaller than the trichloro-s-triazinetrione particles and occupy the interstices of the trichloro-s-triazinetrione matrix.
  • the sodium bromide and trichloro-s- triazinetrione particles are of similar size and are randomly mixed so that the sodium bromide particles occupy some of the interstices of the trichloro-s- triazinetrione matrix.
  • each sodium bromide particle is completely surrounded by trichloro-s-triazinetrione particles so that the sodium bromide cannot form a continuous matrix.
  • DMH 5,5-dimethylhydantoin
  • DMH, l,3-dichloro-5,5-dimethylhydantoin is less soluble in water and precipitates in the pores of the tablet.
  • the precipitate blocks the pores so water cannot wick into the interior of the tablet and sodium bromide cannot dissolve out.
  • the stabilizer must meet the following criteria:
  • the stabilizer must be compatible, i.e., unreactive, with chlorinated isocyanurates . in the solid state;
  • the stabilizer must be capable of binding active halogen (chlorine or bromine in the +1 valence state) ;
  • the trichloro-s-triazinetrione material used in these tests was Monsanto ACL R 90G and ACL R 90XG, commercial , grades of trichloro-s-triazinetrione that differ only in their particle size distributions.
  • the sodium bromide material used had the particle size distribution described in Table 1.
  • Tablets were prepared using standard well-known procedures. In each experiment, the proper amounts of the desired components were weighed out to produce a total of 100 grams. The components were then thoroughly mixed by tumbling in a closed jar. Six 15 gram tablets were made from the mixture using a Carver Model C hydraulic press and a 1.125 inch I.D. stainless steel die. The area of the punch face was 1.00 square inches.
  • the maximum applied tabletting pressure and the dwell time were set using the controls for the hydraulic drive.
  • the dwell time was held at 2 seconds. Tablets were made at the specified tabletting pressures for a given composition.
  • Tablet water stability was evaluated by visual examination. As the tablets dissolved, they were visually examined for the development of cracks. Tablets were judged to be water stable if the tablets survived for more than eight hours under the standard conditions without cracking through the entire height or width of the tablet, since very minor cracks did not seriously affect the dissolution rate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

On décrit une pastille à dissolution lente dans l'eau pour désinfecter des systèmes d'eau de recyclage contenant de l'isocyanurate chloré, du bromure de sodium et un agent stabilisant régulant la vitesse à laquelle l'isocyanurate chloré et le bromure de sodium se dissolvent et se dispersent dans l'eau courante. L'agent stabilisant peut être un stabilisateur actif du chlore compatible avec des isocyanurates chlorés à l'état solide, capable de fixer l'halogène actif (chlore ou brome à l'état de valence +1), et est moins soluble lorsqu'il est entièrement chloré que lorsqu'il ne l'est pas.
PCT/US1992/006735 1991-08-28 1992-08-12 Pastilles donneuses d'ions hypochlorite et d'ions bromure a dissolution lente dans l'eau WO1993004987A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75057791A 1991-08-28 1991-08-28
US750,577 1991-08-28

Publications (1)

Publication Number Publication Date
WO1993004987A1 true WO1993004987A1 (fr) 1993-03-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/006735 WO1993004987A1 (fr) 1991-08-28 1992-08-12 Pastilles donneuses d'ions hypochlorite et d'ions bromure a dissolution lente dans l'eau

Country Status (4)

Country Link
AU (1) AU2479692A (fr)
IL (1) IL102975A0 (fr)
MX (1) MX9204952A (fr)
WO (1) WO1993004987A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571523A4 (en) * 1991-02-11 1994-06-08 Bio Lab Inc Desinfectant for the treatment of water systems
WO1996036224A1 (fr) * 1995-05-15 1996-11-21 Bio-Lab, Inc. Assainissant et clarificateur multifonction a dissolution lente
EP0723396A4 (fr) * 1993-03-29 1998-05-06 Bio Lab Inc Compositions et procedes inhibant la formation de chloramines et de trihalomethanes en milieu aqueux
US6069142A (en) * 1998-12-23 2000-05-30 Calgon Corporation Synergistic antimicrobial combination of 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one and a mixture of a chlorinated isocyanurate and a bromide compound and methods of using same
WO2000034186A1 (fr) * 1998-12-04 2000-06-15 Stellar Technology Company Compositions solides pour le traitement de l'eau, procedes d'elaboration et d'utilisation
US6303038B1 (en) 1999-06-01 2001-10-16 Albemarle Corporation Solid mixtures of dialkylhydantoins and bromide ion sources for water sanitization
US6749758B2 (en) 2001-12-05 2004-06-15 Albemarle Corporation Methods and systems for uniform-control of bromine concentrations in water
US6787530B1 (en) 1996-08-23 2004-09-07 Monash University Use of pregnane-diones as analgesic agents
US7172782B2 (en) 2001-06-28 2007-02-06 Albemarle Corporation Microbiological control in poultry processing
US7182966B2 (en) 2001-06-28 2007-02-27 Albemarle Corporation Microbiological control in poultry processing
US7579018B2 (en) 2000-01-18 2009-08-25 Albemarle Corporation Microbiological control in aqueous systems
US7901276B2 (en) 2003-06-24 2011-03-08 Albemarle Corporation Microbiocidal control in the processing of meat-producing four-legged animals

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4557926A (en) * 1983-09-06 1985-12-10 Monsanto Company Method and tablet for sanitizing toilets
US4698165A (en) * 1985-10-18 1987-10-06 Glyco Inc. Shock treatment of aqueous systems
EP0403465A1 (fr) * 1989-06-16 1990-12-19 University Of Houston Procédés biocides pour circuits aqueux
EP0427517A1 (fr) * 1989-11-06 1991-05-15 Bio-Lab, Inc Composition oxydante N-halogénée et oxydant N-halogéné qui contient un pigment bleu stable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4557926A (en) * 1983-09-06 1985-12-10 Monsanto Company Method and tablet for sanitizing toilets
US4698165A (en) * 1985-10-18 1987-10-06 Glyco Inc. Shock treatment of aqueous systems
EP0403465A1 (fr) * 1989-06-16 1990-12-19 University Of Houston Procédés biocides pour circuits aqueux
EP0427517A1 (fr) * 1989-11-06 1991-05-15 Bio-Lab, Inc Composition oxydante N-halogénée et oxydant N-halogéné qui contient un pigment bleu stable

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571523A4 (en) * 1991-02-11 1994-06-08 Bio Lab Inc Desinfectant for the treatment of water systems
EP0723396A4 (fr) * 1993-03-29 1998-05-06 Bio Lab Inc Compositions et procedes inhibant la formation de chloramines et de trihalomethanes en milieu aqueux
WO1996036224A1 (fr) * 1995-05-15 1996-11-21 Bio-Lab, Inc. Assainissant et clarificateur multifonction a dissolution lente
US5648314A (en) * 1995-05-15 1997-07-15 Bio-Lab, Inc. Slow-dissolving multi-functional sanitizer and clarifier
AU706731B2 (en) * 1995-05-15 1999-06-24 Bio-Lab, Inc. Slow-dissolving multi-functional sanitizer and clarifier
US6787530B1 (en) 1996-08-23 2004-09-07 Monash University Use of pregnane-diones as analgesic agents
US6447722B1 (en) 1998-12-04 2002-09-10 Stellar Technology Company Solid water treatment composition and methods of preparation and use
WO2000034186A1 (fr) * 1998-12-04 2000-06-15 Stellar Technology Company Compositions solides pour le traitement de l'eau, procedes d'elaboration et d'utilisation
US6069142A (en) * 1998-12-23 2000-05-30 Calgon Corporation Synergistic antimicrobial combination of 4,5-dichloro-2-N-octyl-4-isothiazolin-3-one and a mixture of a chlorinated isocyanurate and a bromide compound and methods of using same
US6303038B1 (en) 1999-06-01 2001-10-16 Albemarle Corporation Solid mixtures of dialkylhydantoins and bromide ion sources for water sanitization
US7579018B2 (en) 2000-01-18 2009-08-25 Albemarle Corporation Microbiological control in aqueous systems
US7985413B2 (en) 2000-01-18 2011-07-26 Albemarle Corporation Microbiological control in aqueous systems
US7172782B2 (en) 2001-06-28 2007-02-06 Albemarle Corporation Microbiological control in poultry processing
US7182966B2 (en) 2001-06-28 2007-02-27 Albemarle Corporation Microbiological control in poultry processing
US6749758B2 (en) 2001-12-05 2004-06-15 Albemarle Corporation Methods and systems for uniform-control of bromine concentrations in water
US7901276B2 (en) 2003-06-24 2011-03-08 Albemarle Corporation Microbiocidal control in the processing of meat-producing four-legged animals

Also Published As

Publication number Publication date
IL102975A0 (en) 1993-01-31
AU2479692A (en) 1993-04-05
MX9204952A (es) 1993-03-01

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