WO2004026770A1 - Melange stabilise de brome et de chlore, son procede de fabrication et ses utilisations pour le controle d'encrassement biologique - Google Patents

Melange stabilise de brome et de chlore, son procede de fabrication et ses utilisations pour le controle d'encrassement biologique Download PDF

Info

Publication number
WO2004026770A1
WO2004026770A1 PCT/US2003/021940 US0321940W WO2004026770A1 WO 2004026770 A1 WO2004026770 A1 WO 2004026770A1 US 0321940 W US0321940 W US 0321940W WO 2004026770 A1 WO2004026770 A1 WO 2004026770A1
Authority
WO
WIPO (PCT)
Prior art keywords
bromine
group
chlorine
stabilized
earth metal
Prior art date
Application number
PCT/US2003/021940
Other languages
English (en)
Inventor
Shunong Yang
Original Assignee
Nalco Company
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 Nalco Company filed Critical Nalco Company
Priority to AU2003256524A priority Critical patent/AU2003256524A1/en
Publication of WO2004026770A1 publication Critical patent/WO2004026770A1/fr

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
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • 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
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling

Definitions

  • This invention relates generally to water treatment and, more particularly, to stabilized bromine and chlorine mixtures, method of manufacture and uses thereof for biofouling control.
  • Sodium hypochlorite has been widely used in a variety of industrial and recreational water systems to control biofouling. However, unstabilized sodium hypochlorite degrades very quickly in field use conditions. There are several methods known in the art for stabilizing hypochlorite (See, e.g., U.S. Patent Nos. 3,328,294 and
  • Bromine is preferred over chlorine for use in water treatment because of its lower volatility and better performance at high pH and amine environments.
  • sodium hypobromite is unstable in typical storage conditions, so it is also preferable to provide sodium hypobromite in a stabilized form.
  • U.S. Patent No. 6,037,318 discloses a process that first forms stabilized chlorine compounds and then converts them to stabilized bromine compounds.
  • this type of process is limiting because only hypochlorite-releasing compounds can be used as the oxidizing source.
  • U.S. Patent No. 6,270,722 discloses a method of adding hypochlorite to a mixture of bromide and sulfamate and then adjusting the pH of the mixture.
  • a method is disclosed for adding hypochlorite and sulfamate simultaneously to bromide and then adjusting the pH to form a stabilized bromine product.
  • the stabilized bromine and chlorine mixtures of the present invention are prepared by simultaneously combining a bromine source, an oxidizer and a stabilizer.
  • An alkaline source may optionally be added to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
  • the inventive method is economically appealing because it can be carried out as a batch or continuous process and because it can be done at a very high throughput.
  • the method of preparation is also flexible because it can be performed at the manufacturing facility or right at the site of the commercial application and the method does not require precise pH control.
  • the present invention is directed to a method of making stabilized bromine and chlorine mixtures.
  • stabilized bromine and chlorine mixtures means that both the bromine and the chlorine are stabilized in the mixture.
  • a bromine source, an oxidizer and a stabilizer are combined simultaneously.
  • An alkaline source may be added to the stabilized bromine and chlorine mixture to adjust the pH of the mixture to at least 13.
  • the bromine sources which may be used in the practice of the present invention include hydrobromic acid, elemental bromine and alkali or alkaline earth metal bromides, such as sodium bromide, potassium bromide and lithium bromide.
  • the preferred bromine source is an alkali or alkaline earth metal bromide.
  • the oxidizers which may be used include chlorine gas, hypochlorous acid, hypochlorite salt, chlorite, chlorate, persulfate, permanganate and peracetic acid. Chlorine gas, hypochlorous acid and hypochlorite salt are the most preferred oxidizers. It is believed that other peroxy compounds can also be used in accordance with this invention.
  • the stabilizers which may be employed in this invention have the chemical formula R-NH-R 1 , wherein R and R 1 are selected from the group consisting of R 2 CO, R 2 SO 2 , R 2 CF 2 , R 2 CHF, H, OH and PO(OH) 2 , and R 2 is an alkyl group or an aromatic group.
  • Suitable stabilizers include saccharin, urea, thiourea, creatinine, cyanuric acids, alkyl hydantoins, monoethanolamine, diethanolamine, organic sulfonamides, biuret, sulfamic acid and its alkali or alkaline earth metal salts, organic sulfamates and melamine. Sulfamic acid and its alkali or alkaline earth metal salts are the most preferred stabilizers.
  • water treatment chemicals such as tracing compounds, surfactants, corrosion inhibitors and scale inhibitors, can be added to the stabilized bromine and chlorine mixture.
  • the molar ratio between the bromine source and the stabilizer be in the range of about 0.2 to 5.
  • the molar ratio between the bromine source and the oxidizer should preferably be in the range of about 0.5 to 2.
  • the method of the present invention is maintained at a temperature of less than 120 °F and can be carried out as either a batch or continuous process.
  • the stabilized bromine and chlorine mixtures which are prepared in accordance with this invention may be used in a wide variety of commercial applications. These applications include, but are not limited to, the use of the stabilized bromine and chlorine mixture in a method for: (1) controlling biofouling on a hard surface; (2) controlling biofouling occurring on the surfaces of equipment in contact with an industrial water system; (3) controlling biofouling in an aqueous phase of an industrial water system; and (4) controlling microbial growth in an aqueous stream used for transporting or processing food products and on food surfaces and equipment surfaces that come in contact with the aqueous stream.
  • the types of industrial water systems in which the stabilized bromine and chlorine mixture may be used to control biofouling include, but are not limited to, cooling water systems, sweetwater systems, gas scrubber systems, air washer systems, evaporative condensers, pasteurizers, produce sanitizer streams, fire protection water systems, pulp and paper systems, heat exchanger tubes and oil field waters.
  • the stabilized bromine and chlorine mixture of the present invention can be prepared at the site of the commercial application.
  • an alkaline source may be added to the mixture to raise the pH of the stabilized bromine and chlorine mixture to at least 13 to provide thermal stability and shelf life during storage and shipping.
  • the alkaline source is preferably an alkali or alkaline earth metal hydroxide.
  • Suitable alkaline sources include sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide.
  • a stabilized halogen product can be prepared without requiring any particular order of addition of the ingredients.
  • a stabilized bromine and chlorine mixture is achieved and can effectively be used to control biofouling.
  • the method of making the stabilized bromine and chlorine mixture is economical since it can be conducted as a batch or continuous process and it generates a high yield.
  • the inventive method is flexible because it can be performed at the manufacturing facility or right at the site of the commercial application and the method does not require precise pH control.
  • a laboratory reactor was set up for preparing a stabilized halogen product from three raw materials: sodium bromide, sodium sulfamate and sodium hypochlorite.
  • the sodium sulfamate solution was prepared by mixing an equal molar ratio of sulfamic acid with sodium hydroxide in water.
  • a 250 ml solution of sodium hypochlorite (12.0% as available chlorine, pH 12.41)
  • a 250 ml solution of sodium sulfamate (20.41%, pH 2.31) were prepared separately.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention a trait à des mélanges stabilisé de brome et de chlore préparés par la combinaison simultanée d'une source de brome, d'un oxydant et d'un stabilisateur. On peut éventuellement ajouter une source alcaline au mélange stabilisé de brome et de chlore pour ajuster le pH du mélange à une valeur égale ou supérieure à 13.
PCT/US2003/021940 2002-09-19 2003-07-15 Melange stabilise de brome et de chlore, son procede de fabrication et ses utilisations pour le controle d'encrassement biologique WO2004026770A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003256524A AU2003256524A1 (en) 2002-09-19 2003-07-15 Stabilized bromine and chlorine mixture, method of manufacture and uses thereof for biofouling control

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24695502A 2002-09-19 2002-09-19
US10/246,955 2002-09-19

Publications (1)

Publication Number Publication Date
WO2004026770A1 true WO2004026770A1 (fr) 2004-04-01

Family

ID=32028968

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/021940 WO2004026770A1 (fr) 2002-09-19 2003-07-15 Melange stabilise de brome et de chlore, son procede de fabrication et ses utilisations pour le controle d'encrassement biologique

Country Status (2)

Country Link
AU (1) AU2003256524A1 (fr)
WO (1) WO2004026770A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1871429A1 (fr) * 2005-03-31 2008-01-02 Ashland Licensing and Intellectual Property LLC Procede pour empecher la formation de biofilm sur un tube ameliore et/ou pour eliminer un biofilm d'un tube ameliore
WO2008056025A2 (fr) 2006-11-09 2008-05-15 Kemira Oyj Procédé servant à empêcher le développement de microorganismes et combinaison d'agents servant à empêcher le développement microbien
US7776363B2 (en) * 2006-01-27 2010-08-17 Nalco Company Suppressing microbial growth in pulp and paper
EP2236034A3 (fr) * 2004-05-10 2011-12-21 Enviro Tech Chemical Services Inc. Procédé de préparation de liquide contenant du bromure et de chlorure
US20130280349A1 (en) * 2012-04-23 2013-10-24 Lonza, Inc. Active halogen antimicrobial composition and method of use
US8574605B2 (en) 2004-05-10 2013-11-05 Enviro Tech Chemical Services, Inc. Methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids
WO2014020601A1 (fr) * 2012-07-31 2014-02-06 Bromine Compounds Ltd. Procédé de préparation de compositions aqueuses biocides à base de brome
US9161543B2 (en) 2011-10-21 2015-10-20 Nalco Company Biocontrol through the use of chlorine-stabilizer blends
US10850999B2 (en) 2015-04-24 2020-12-01 Ecolab Usa Inc. Submergible biocide reactor and method
WO2021092048A1 (fr) 2019-11-06 2021-05-14 De Nora Holdings Us, Inc. Production contrôlée de solutions aqueuses d'halogène présentant des compositions variables
WO2022070451A1 (fr) * 2020-09-30 2022-04-07 オルガノ株式会社 Composition pour le traitement de l'eau, procédé de traitement de l'eau, procédé de fabrication d'une composition pour le traitement de l'eau et procédé de traitement d'un circuit d'eau de refroidissement
US11905498B2 (en) 2020-02-12 2024-02-20 Ecolab Usa Inc. Use of urea or a urea/chelator combination to chemically stabilize peroxycarboxylic acid and peroxide formulations

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5662940A (en) * 1989-06-16 1997-09-02 University Of Houston Biocidal methods and compositions for recirculating water systems
US6007726A (en) * 1998-04-29 1999-12-28 Nalco Chemical Company Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control
US6110387A (en) * 1999-04-22 2000-08-29 Albemarle Corporation Sulfamate stabilization of a bromine biocide in water
US6270722B1 (en) * 1999-03-31 2001-08-07 Nalco Chemical Company Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control
US6478972B1 (en) * 1999-12-13 2002-11-12 Acculab Co., Ltd. Method of controlling microbial fouling

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5662940A (en) * 1989-06-16 1997-09-02 University Of Houston Biocidal methods and compositions for recirculating water systems
US6007726A (en) * 1998-04-29 1999-12-28 Nalco Chemical Company Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control
US6270722B1 (en) * 1999-03-31 2001-08-07 Nalco Chemical Company Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control
US6110387A (en) * 1999-04-22 2000-08-29 Albemarle Corporation Sulfamate stabilization of a bromine biocide in water
US6478972B1 (en) * 1999-12-13 2002-11-12 Acculab Co., Ltd. Method of controlling microbial fouling

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2236034A3 (fr) * 2004-05-10 2011-12-21 Enviro Tech Chemical Services Inc. Procédé de préparation de liquide contenant du bromure et de chlorure
US8574605B2 (en) 2004-05-10 2013-11-05 Enviro Tech Chemical Services, Inc. Methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids
EP1871429A4 (fr) * 2005-03-31 2008-12-03 Ashland Licensing & Intellectu Procede pour empecher la formation de biofilm sur un tube ameliore et/ou pour eliminer un biofilm d'un tube ameliore
US7581874B2 (en) 2005-03-31 2009-09-01 Hays George F Apparatuses and systems for monitoring fouling of aqueous systems including enhanced heat exchanger tubes
US7594430B2 (en) 2005-03-31 2009-09-29 Beardwood Edward S Methods for monitoring fouling of aqueous systems including enhanced heat exchanger tubes
EP1871429A1 (fr) * 2005-03-31 2008-01-02 Ashland Licensing and Intellectual Property LLC Procede pour empecher la formation de biofilm sur un tube ameliore et/ou pour eliminer un biofilm d'un tube ameliore
US7776363B2 (en) * 2006-01-27 2010-08-17 Nalco Company Suppressing microbial growth in pulp and paper
US9272927B2 (en) 2006-11-09 2016-03-01 Kemira, Oyj Method for preventing growth of microorganisms, and a combination for the prevention of microbial growth
WO2008056025A3 (fr) * 2006-11-09 2008-11-27 Kemira Oyj Procédé servant à empêcher le développement de microorganismes et combinaison d'agents servant à empêcher le développement microbien
WO2008056025A2 (fr) 2006-11-09 2008-05-15 Kemira Oyj Procédé servant à empêcher le développement de microorganismes et combinaison d'agents servant à empêcher le développement microbien
US9161543B2 (en) 2011-10-21 2015-10-20 Nalco Company Biocontrol through the use of chlorine-stabilizer blends
US9265259B2 (en) 2011-10-21 2016-02-23 Nalco Company Use of sulfamic acid or its salts as stabilizers especially in combination with ammonium salt and/or ammine for bleach or other halogen containing biocides in the paper area
US20130280349A1 (en) * 2012-04-23 2013-10-24 Lonza, Inc. Active halogen antimicrobial composition and method of use
US9220272B2 (en) * 2012-04-23 2015-12-29 Lonza, Inc Active halogen antimicrobial composition and method of use
WO2014020601A1 (fr) * 2012-07-31 2014-02-06 Bromine Compounds Ltd. Procédé de préparation de compositions aqueuses biocides à base de brome
US10850999B2 (en) 2015-04-24 2020-12-01 Ecolab Usa Inc. Submergible biocide reactor and method
WO2021092048A1 (fr) 2019-11-06 2021-05-14 De Nora Holdings Us, Inc. Production contrôlée de solutions aqueuses d'halogène présentant des compositions variables
EP4054338A4 (fr) * 2019-11-06 2023-12-06 De Nora Holdings US, Inc. Production contrôlée de solutions aqueuses d'halogène présentant des compositions variables
US11905498B2 (en) 2020-02-12 2024-02-20 Ecolab Usa Inc. Use of urea or a urea/chelator combination to chemically stabilize peroxycarboxylic acid and peroxide formulations
WO2022070451A1 (fr) * 2020-09-30 2022-04-07 オルガノ株式会社 Composition pour le traitement de l'eau, procédé de traitement de l'eau, procédé de fabrication d'une composition pour le traitement de l'eau et procédé de traitement d'un circuit d'eau de refroidissement

Also Published As

Publication number Publication date
AU2003256524A1 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
AU766029B2 (en) Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control
EP1411995B1 (fr) Traitement des eaux pour controle des biosalissures au moyens de solutions de brome stabilisees
AU2002322449A1 (en) Stabilized bromine solutions, method of making and uses thereof for biofouling control
JP5334886B2 (ja) 安定した酸化臭素調合物、生物付着制御のためのその製造方法および使用
US6423267B1 (en) Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control
US6287473B1 (en) Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control
WO2006004643A1 (fr) Composition oxydante stable de brome, procédé pour la fabrication et l’utilisation de celle-ci pour le contrôle de l’encrassement biologique
JP2002512885A (ja) 安定な酸化性の臭素製剤、その製造方法および微生物汚損の制御のために使用する方法
WO2003073848A1 (fr) Procede de preparation d'un biocide contenant un hypochlorite stabilise et d'une source d'ions de bromure et procede de regulation d'un encrassement microbien a l'aide de cette source
WO2001042145A1 (fr) Procede de lutte contre les salissures microbiennes et systeme de lutte associe
WO2004026770A1 (fr) Melange stabilise de brome et de chlore, son procede de fabrication et ses utilisations pour le controle d'encrassement biologique
MXPA04010987A (es) Proceso par la preparacion de soluciones concentradas de hipobromuros estabilizados.
US20100221361A1 (en) Stable oxidizing bromine composition, method of manufacture and use thereof for biofouling control
MXPA01009211A (en) Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control
AU2005201969A1 (en) Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP