WO1999055627A1 - Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control - Google Patents

Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control Download PDF

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Publication number
WO1999055627A1
WO1999055627A1 PCT/US1999/008549 US9908549W WO9955627A1 WO 1999055627 A1 WO1999055627 A1 WO 1999055627A1 US 9908549 W US9908549 W US 9908549W WO 9955627 A1 WO9955627 A1 WO 9955627A1
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WO
WIPO (PCT)
Prior art keywords
solution
group
oxidizer
adjusting
stable oxidizing
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1999/008549
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English (en)
French (fr)
Other versions
WO1999055627A8 (en
WO1999055627A9 (en
Inventor
Shunong Yang
William F. Mccoy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ChampionX LLC
Original Assignee
Nalco Chemical Co
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
Priority to KR1020007011935A priority Critical patent/KR20010034832A/ko
Priority to BR9910011-8A priority patent/BR9910011A/pt
Priority to AU36527/99A priority patent/AU745642B2/en
Priority to NZ507736A priority patent/NZ507736A/xx
Priority to EP19990918668 priority patent/EP1094987A4/en
Priority to CA002329896A priority patent/CA2329896A1/en
Application filed by Nalco Chemical Co filed Critical Nalco Chemical Co
Priority to JP2000545793A priority patent/JP4749544B2/ja
Publication of WO1999055627A1 publication Critical patent/WO1999055627A1/en
Publication of WO1999055627A8 publication Critical patent/WO1999055627A8/en
Publication of WO1999055627A9 publication Critical patent/WO1999055627A9/en
Priority to NO20005421A priority patent/NO20005421L/no
Anticipated expiration legal-status Critical
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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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

Definitions

  • the present invention relates to formulations used in biofouling control in industrial water systems. More specifically, the present invention relates to methods of preparing stable oxidizing bromine formulations and their use in biofouling control in industrial water systems .
  • Ozone is known to be an effective biocide and is used to control biofouling in various industrial water applications.
  • ozone is also very reactive with other water treatment chemicals such as corrosion and scale inhibitors. As a result, it is difficult to maintain a residual ozone concentration in a system thereby substantially reducing the effectiveness of ozone as a biocide.
  • ozone activated hypobromite to increase the biocide residual concentration in the system and to reduce the reaction of ozone with other water treatment chemicals.
  • bromine species such as OBr- , HOBr and Br 2 are produced and are all both unstable and aggressive against water treatment chemicals as well.
  • Methods of generating stabilized hypobromite for use at levels of less than 100 ppm as a secondary disinfectant during water ozonation are also known.
  • the ozonation processes are carried out at a pH of about 8.5.
  • Compounds used to stabilize the hypobromite include 5, 5- dimethylhydantoin and succinamide.
  • bromine compounds such as hypobromite have been used as secondary disinfectants or have been generated for on-site use without concern for stabilization of the bromine
  • the present invention satisfies the aforementioned needs by providing a method of generating a stable oxidizing bromine compound and an aqueous biocide solution containing a stable oxidizing bromine formulation.
  • the method of the present invention can be used to generate stable oxidizing bromine compounds and aqueous solutions containing stable oxidizing bromine compounds for use in biofouling control in industrial water systems .
  • the method of the present invention for generating at least one stable oxidizing bromine compound in an aqueous solution includes the steps of providing a solution comprising an alkali or alkaline earth metal bromide and a halogen stabilizer selected from the group consisting of R-NH 2 , R-NH-R 1 , R- S0 2 -NH 2 , R-CO- NH 2 , R-CO-NH-R 1 and R-CO-NH-CO-R 1 wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic group, followed by the step of adjusting the solution to a pH ranging from 4 to 8 , followed by the step of adding an oxidizer to the solution.
  • a solution comprising an alkali or alkaline earth metal bromide and a halogen stabilizer selected from the group consisting of R-NH 2 , R-NH-R 1 , R- S0 2 -NH 2 , R-CO- NH 2 ,
  • the method further includes the step of adjusting the solution to a temperature ranging from about 0° to about 60 °C, preferably from about 4°C to about 21°C, after the oxidizer is added to the solution.
  • the method of the present invention further includes the step of adjusting the pH ' of the solution to a range of greater than 13 after the oxidizer is added to the solution.
  • the oxidizer is ozone.
  • the alkali or alkaline earth metal bromide is NaBr.
  • the step of adjusting the pH of the solution prior to the addition of the oxidizer further comprises adjusting the pH to a level of about 7.
  • the present invention is a method of treating an industrial water system with a stable oxidizing bromine compound.
  • the method includes the steps of providing a vessel, providing a solution comprising an alkali or alkaline earth metal bromide and a halogen stabilizer selected from the group consisting of R-NH 2 , R-NH-R 1 , R-S0 2 -NH 2 , R-SO ⁇ NHR 1 , R-CO-NH 2 , R-CO-NH- R and R-CO- H-CO-R wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic group, followed by the step of adjusting the pH of the solution to a range from about 4 to about 8, followed by the step of injecting a gaseous oxidizer into the solution to produce stable oxidizing bromine compounds, followed by the step of adding the solution to an industrial water system for biofouling control.
  • a halogen stabilizer selected from the group consisting of R-NH 2
  • the method of the present invention further includes the step of adding gaseous oxidizer to the industrial water system upstream of a point where the stable oxidizing bromine compound is added to the system.
  • the present invention provides a method of treating an industrial water system with a primary biocide and a secondary biocide for biofouling control .
  • the method includes the steps of providing a solution in a first vessel, the solution comprising an alkali or alkaline earth metal bromide and a halogen stabilizer selected from the group consisting of R-NH 2 , R- NH-R 1 , R-S0 2 -NH 2 , R-CO-NH 2 , R-CO-NH-R 1 and R-CO- NH-CO-R 1 wherein R is a hydroxy group, an alkyl group or an aromatic group and R 1 is an alkyl group or an aromatic group, the solution further having a pH ranging from about 4 to about 8, followed by the step of adding a gaseous oxidizer to the solution in the first vessel, at least some of the gaseous oxidizer reacting with the alkali or alkaline earth metal bromide and wherein at least some of the gaseous oxidizer has not
  • the method further comprises the steps of transferring the solution to a second vessel and thereafter increasing the pH of the solution to a level greater than 13 so as to stabilize the hypobromite solution thereby extending its useful life thereby permitting the operator to add the solution to the industrial water system on an "as needed" basis.
  • a method of the present invention provides a method of generating at least one stable oxidizing bromine compound, the method includes the steps of providing a solution comprising an alkali or alkaline earth metal bromide and a halogen stabilizer selected from the group consisting of at least one sulfamate and sulfonamide, followed by the step of adjusting the pH of the solution to a range from 4 to 8 , and followed by the step of adding an oxidizer to the solution selected from the group consisting of ozone, hydrogen peroxide and peracetic acid.
  • Another advantage of the present invention is that it provides stable oxidizing bromine compound in a high concentration without a direct use of a concentrated form of unstabilized bromine.
  • Still another advantage of the present invention is that it provides a method for generating stable oxidizing bromine compounds without unwanted by-products such as high levels of bromate .
  • Still another advantage of the present invention is that the method of the present invention does not generate chloride and therefore the method of the present invention provides stable oxidizing bromine formulations that are less corrosive.
  • Yet another advantage of the present invention is that it provides stable oxidizing bromine compounds that are safer to transport .
  • Still another advantage of the present invention is that it generates very little bromate.
  • Yet another advantage of the present invention is that it generates stable oxidizing bromine compounds for biofouling control that are more compatible with other water treatment chemicals.
  • the stable oxidizing bromine compound provided can be used as either sole biofouling control agents or as secondary biofouling control agents.
  • Another advantage of the present invention is that it provides an improved method of microbiofouling control in pulp and paper processing systems.
  • Another advantage of the present invention is that it provides an improved method of microbiofouling control in a food processing system. Yet another advantage of the present invention is that it provides improved microbiofouling control in a beverage processing system.
  • Still another advantage of the present invention is that it provides improved microbiofouling control in a recreational water system.
  • Another advantage of the present invention is that it provides an improved method of disinfecting a hard surface .
  • Figure 1 illustrates schematically an apparatus for generating stable oxidizing bromine compounds for use in an industrial water system.
  • the present invention provides a plurality of formulations and methods for generating a wide concentration of stable oxidizing bromine compounds that can be used as primary or secondary biofouling control agents in cooling water and other industrial systems . While ozone is discussed as an example oxidizer for the methods described herein, it will be noted that other oxidizers such as peroxides, peracetic acid and other peroxygen compounds can also be used as an oxidizer or primary oxidizer.
  • the stable oxidizing bromine compound products are formed by directly ozonating a mixture solution of a sodium bromide and a sodium sulfamate (or other primary or secondary amines, or amides which are stable in an ozone environment) at an optimal pH range.
  • ozone serves as the oxidizer, bromide salt as the bromine . source, and sulfamate as the oxidizing bromine stabilizer.
  • bromide and sulfamate are added in equal molar amounts .
  • the pH of the solution is adjusted by the addition of caustic (sodium hydroxide) or acid.
  • the optimal solution pH for the process ranges from 4 to 8.
  • reaction mechanism is believed to be the following sequential chemical reactions:
  • the second reaction starts as soon as trace amounts of hypobromite are generated in the first reaction. It is known that unstabilized hypobromite is very corrosive and more volatile than stabilized hypobromite.
  • the in- si tu stabilization process described herein minimizes the loss of hypobromite by chemical decomposition and physical evaporation.
  • one of the major decomposition by-products of hypobromite is bromate. It has been confirmed that methods practices in accordance with the present invention produce no detectable bromate (or less than 50 ppm of bromate in 5.2% stabilized hypobromite product) .
  • a direct field of process for on- site generation of stable oxidizing bromine compounds is used as an oxidant because it is used extensively in field operations.
  • Ozonators like that shown at 11 in Figure 1 are found at many application sites .
  • Ozone is supplied from the generator 11 through the reactor 12 and is injected in the system stream 13 through the conduit 14 as the primary biocide.
  • the reaction vessel 12 already includes a solution of alkali or alkaline earth metal bromide, a halogen stabilizer which may be sulfamate and a pH ranging from 4 to 8. Ozone may be recycled back into the reactor 12 through the return line 15.
  • the ozonation time required for complete conversion can be predetermined or measured with a color wheel since the available halogen concentration linearly correlates with light absorption from 400 to 600 nm, preferably measured at 460 nm.
  • the stable oxidizing bromine compounds may then be transferred from the reactor 12 to the storage vessel 16 where it can be added to the water stream 13 through the valve 17 on an "as- needed" basis.
  • Example I By way of example, a synthesis of stabilized oxidizing bromine compound can be carried out as follows.
  • the pH of the solution is about 7.0.
  • Ozonation is carried out by bubbling ozone gas through a fritted glass extended to the bottom of the cylinder.
  • Example III By way of another example, using the apparatus illustrated in Figure 1 for a 100,000 gallon cooling water system, a 1814 grams/day ozonator is utilized.
  • Ozone generated from the ozonator is introduced into the bottom of the reactor 12 through a diffuser (not shown) .
  • the 5 liter reactor 12 is filled with a mixture of 389 grams of NaBr, 440 grams of sulfamic acid, 302 grams of
  • the method of the present invention can be used to provide improved microbiofouling control in pulp and paper processing systems, food and beverage processing systems, recreational water systems and, the method of the present invention can be used as a method of disinfecting a hard surface.
  • Food processing includes, but is not limited to, adding the present invention to an aqueous media used to transport food through various processing steps and also disinfecting process equipment and waste water streams.

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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)
  • Paper (AREA)
PCT/US1999/008549 1998-04-29 1999-04-26 Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control Ceased WO1999055627A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
KR1020007011935A KR20010034832A (ko) 1998-04-29 1999-04-19 안정한 산화브롬 조성물 및 그 제조방법과 이를 사용한생오염 억제
AU36527/99A AU745642B2 (en) 1998-04-29 1999-04-26 Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control
NZ507736A NZ507736A (en) 1998-04-29 1999-04-26 Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control
EP19990918668 EP1094987A4 (en) 1998-04-29 1999-04-26 STABLE OXIDIZING BROMINE COMPOUND, METHOD FOR PRODUCING THE SAME AND USE FOR PREVENTING BIOLOGICAL DEPOSITS
CA002329896A CA2329896A1 (en) 1998-04-29 1999-04-26 Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control
BR9910011-8A BR9910011A (pt) 1998-04-29 1999-04-26 Processo para geração de pelo menos um composto de bromo oxidante estável e para tratamento de um sistema de água industrial, composto de bromo oxidante estável, e, processos para controle de microbioincrustação e para desinfecção de uma superfìcie dura
JP2000545793A JP4749544B2 (ja) 1998-04-29 1999-04-26 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
NO20005421A NO20005421L (no) 1998-04-29 2000-10-27 Stabile oksiderende brom formuleringer, fremgangsmåter ved fremstilling derav og fremgangsmåter ved anvendelse for mikrobiologisk vekst kontroll

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/069,653 US6007726A (en) 1998-04-29 1998-04-29 Stable oxidizing bromine formulations, methods of manufacture thereof and methods of use for microbiofouling control
US09/069,653 1998-04-29

Publications (3)

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WO1999055627A1 true WO1999055627A1 (en) 1999-11-04
WO1999055627A8 WO1999055627A8 (en) 2000-01-27
WO1999055627A9 WO1999055627A9 (en) 2000-03-02

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Country Link
US (1) US6007726A (https=)
EP (1) EP1094987A4 (https=)
JP (1) JP4749544B2 (https=)
KR (1) KR20010034832A (https=)
CN (1) CN1298370A (https=)
AR (1) AR016240A1 (https=)
AU (1) AU745642B2 (https=)
BR (1) BR9910011A (https=)
CA (1) CA2329896A1 (https=)
CO (1) CO5050388A1 (https=)
ID (1) ID27578A (https=)
NO (1) NO20005421L (https=)
NZ (1) NZ507736A (https=)
WO (1) WO1999055627A1 (https=)
ZA (1) ZA200005916B (https=)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6299909B1 (en) 1998-06-01 2001-10-09 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US6306441B1 (en) 1998-06-01 2001-10-23 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US6348219B1 (en) 1998-06-01 2002-02-19 Albemarle Corporation Processes for preparing concentrated aqueous liquid biocidal compositions
US6352725B1 (en) 1998-06-01 2002-03-05 Albemarle Corporation Continuous processes for preparing concentrated aqueous liquid biocidal composition
US6375991B1 (en) 2000-09-08 2002-04-23 Albemarle Corporation Production of concentrated biocidal solutions
KR100339129B1 (ko) * 1999-12-13 2002-05-31 심상희 알칼리 금속 또는 알칼리 토금속의 차아브롬산염을 이용한미생물 오염제어방법 및 이에 사용되는 오염제어시스템
US6506418B1 (en) 1999-09-24 2003-01-14 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US6652889B2 (en) 1998-06-01 2003-11-25 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation and use
EP1194371A4 (en) * 1999-04-21 2004-03-31 Nalco Chemical Co STABLE OXIDIZING BROMIC COMPOUND, METHOD FOR PRODUCING THE SAME AND USE FOR PREVENTING BIOLOGICAL DEPOSIT
US6986910B2 (en) 2001-06-28 2006-01-17 Albemarle Corporation Microbiological control in poultry processing
US7182966B2 (en) 2001-06-28 2007-02-27 Albemarle Corporation Microbiological control in poultry processing
US7223719B1 (en) 2004-03-16 2007-05-29 Albemarle Corporation Breaker composition and process
US7371397B2 (en) 2000-01-18 2008-05-13 Albemarle Corporation Methods for microbiological control in aqueous systems
US7578968B1 (en) 2002-05-03 2009-08-25 Albemarle Corporation Microbiological control in oil or gas field operations
US7901276B2 (en) 2003-06-24 2011-03-08 Albemarle Corporation Microbiocidal control in the processing of meat-producing four-legged animals
US8293795B1 (en) 1998-06-01 2012-10-23 Albemarle Corporation Preparation of concentrated aqueous bromine solutions and biocidal applications thereof
US8496830B2 (en) 2007-06-29 2013-07-30 Christ Water Technology Ag Treatment of water with hypobromite solution
WO2014020601A1 (en) 2012-07-31 2014-02-06 Bromine Compounds Ltd. Method for preparing bromine based biocidal aqueous compositions
US8679548B2 (en) 1998-06-01 2014-03-25 Albemarle Corporation Active bromine containing biocidal compositions and their preparation
US9005671B2 (en) 2004-09-07 2015-04-14 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US9452229B2 (en) 2005-06-10 2016-09-27 Albemarle Corporation Highly concentrated, biocidally active compositions and aqueous mixtures and methods of making the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6511682B1 (en) 1998-06-01 2003-01-28 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US7087251B2 (en) 1998-06-01 2006-08-08 Albemarle Corporation Control of biofilm
US6287473B1 (en) * 1998-06-29 2001-09-11 Nalco Chemical Company Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control
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US6669904B1 (en) * 1999-03-31 2003-12-30 Ondeo Nalco Company Stabilized bromine solutions, method of making and uses thereof for biofouling 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
JP2001104971A (ja) * 1999-10-07 2001-04-17 Nec Corp 廃水処理方法および装置
US6620441B1 (en) 2001-06-28 2003-09-16 Albemarle Corporation Stabilized active bromine biocidal solutions
JP2003142445A (ja) * 2001-11-08 2003-05-16 Mitsubishi Electric Corp 洗浄装置及び洗浄方法
KR100465046B1 (ko) * 2001-11-23 2005-01-13 애큐랩주식회사 알칼리금속 또는 알칼리토금속의 차아할로겐산염을 함유한미생물 성장억제 조성물 및 이를 이용한 미생물 제어방법
US6749758B2 (en) * 2001-12-05 2004-06-15 Albemarle Corporation Methods and systems for uniform-control of bromine concentrations in water
US7407592B2 (en) * 2002-04-17 2008-08-05 Nutech 03, Inc. Ozone retention method and system
AU2003256524A1 (en) * 2002-09-19 2004-04-08 Nalco Company Stabilized bromine and chlorine mixture, method of manufacture and uses thereof for biofouling control
US20040074847A1 (en) * 2002-10-16 2004-04-22 Jaquess Percy A. Stable N-bromo-2-pyrrolidone and methods to make the same
US20040120853A1 (en) * 2002-12-20 2004-06-24 Carpenter Joel F. Biocidal control in recovery of oil by water injection
EP1638394A4 (en) * 2003-06-27 2009-11-11 Enviro Tech Chemical Services HIGHLY CONCENTRATED BROMA COMPOSITIONS AND METHOD FOR THE PRODUCTION THEREOF
US7455859B2 (en) * 2003-06-27 2008-11-25 Enviro Tech Chemical Services, Inc. Highly concentrated bromine compositions and methods of preparation
US7883622B1 (en) * 2003-09-23 2011-02-08 Barnes Ronald L Water treatment methods and systems using combinations of ozone and chlorine generators
US7309503B2 (en) * 2004-05-10 2007-12-18 Enviro Tech Chemical Services, Inc. Methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids
WO2006022694A2 (en) * 2004-08-06 2006-03-02 Enviro Tech Chemical Services, Inc. Methods of preparing highly concentrated aqueous bromine solutions
US20060029680A1 (en) * 2004-08-06 2006-02-09 Harvey Michael S Methods of preparing highly concentrated aqueous bromine solutions
BRPI0620851B1 (pt) 2005-12-01 2016-08-23 Albemarle Corp método para controle microbiano no processo de produção de carne de animais quadrúpedes
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US11286183B2 (en) 2015-11-19 2022-03-29 Envirosystems Inc. System and method for treatment of spent caustic wastewater
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US11085010B2 (en) 2017-08-18 2021-08-10 Ecolab Usa Inc. Method for off-line cleaning of cooling towers
TWI690496B (zh) * 2019-02-01 2020-04-11 兆聯實業股份有限公司 水處理系統

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5264136A (en) * 1992-10-30 1993-11-23 Great Lakes Chemical Corporation Methods for generating residual disinfectants during the ozonization of water
US5603840A (en) * 1995-05-15 1997-02-18 Nalco Chemical Company Method of achieving microbiological control in open recirculating cooling water
US5683654A (en) * 1996-03-22 1997-11-04 Nalco Chemical Co Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3222276A (en) * 1963-02-06 1965-12-07 Great Lakes Chemical Corp Bromination process
US3328294A (en) * 1966-09-19 1967-06-27 Mead Corp Process for control of micro-organisms in process streams
US3493654A (en) * 1967-01-19 1970-02-03 Dow Chemical Co Stabilized aqueous bromine compositions
US3558503A (en) * 1968-07-22 1971-01-26 Dow Chemical Co Stable bromo-sulfamate composition
US4613332A (en) * 1984-07-11 1986-09-23 The Clorox Company Controlled generation hypochlorite compositions and method
US4792407A (en) * 1986-11-25 1988-12-20 Ultrox International Oxidation of organic compounds in water
US4759852A (en) * 1987-10-15 1988-07-26 Nalco Chemical Company Use of sulfamic acid to inhibit phosphonate decomposition by chlorine-bromine mixtures
US4992209A (en) * 1989-10-26 1991-02-12 Nalco Chemical Company Method for inhibiting corrosion in cooling systems and compositions therefor, containing a nitrite corrosion inhibitor and bromosulfamate
US5888428A (en) * 1992-10-30 1999-03-30 Great Lakes Chemical Corporation Methods for generating residual disinfectants during the ozonization of water
EP0700366A1 (de) * 1993-05-17 1996-03-13 SCHMIDDING-WERKE Wilhelm Schmidding GmbH & Co. Verfahren zur behandlung bromidhaltiger wässer durch ozon
US5565109B1 (en) * 1994-10-14 1999-11-23 Lonza Ag Hydantoin-enhanced halogen efficacy in pulp and paper applications
JPH10509141A (ja) * 1994-11-04 1998-09-08 ベッツディアボーン・インコーポレイテッド 相乗的な殺生物組合せ物
US5589106A (en) * 1995-02-14 1996-12-31 Nalco Chemical Company Carbon steel corrosion inhibitors
ZA962117B (en) * 1995-03-27 1996-09-26 Electrocatalytic Inc Process and apparatus for generating bromine
CA2239586C (en) * 1995-12-07 2005-07-26 The Procter & Gamble Company Process for manufacturing bleaching compositions
BR9702226A (pt) * 1996-03-22 1999-02-23 Nalco Chemical Co Processos para preparar uma solução de hipobromito de metal alcalino ou alcalino-teroso para lavar roupas sujas para fabricar materiais celulósicos e para controlar e evitar microbioincrustação solução aquosa estabilizada de um hipobromito de metal alcalino ou alcalino-terroso e sistema de água industrial
WO1997043392A1 (en) * 1996-05-15 1997-11-20 The Procter & Gamble Company Process for manufacturing bleaching compositions comprising chlorine and bromine sources and product thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5264136A (en) * 1992-10-30 1993-11-23 Great Lakes Chemical Corporation Methods for generating residual disinfectants during the ozonization of water
US5603840A (en) * 1995-05-15 1997-02-18 Nalco Chemical Company Method of achieving microbiological control in open recirculating cooling water
US5683654A (en) * 1996-03-22 1997-11-04 Nalco Chemical Co Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1094987A4 *

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495169B1 (en) 1998-06-01 2002-12-17 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US6652889B2 (en) 1998-06-01 2003-11-25 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation and use
US6348219B1 (en) 1998-06-01 2002-02-19 Albemarle Corporation Processes for preparing concentrated aqueous liquid biocidal compositions
US6352725B1 (en) 1998-06-01 2002-03-05 Albemarle Corporation Continuous processes for preparing concentrated aqueous liquid biocidal composition
US8293795B1 (en) 1998-06-01 2012-10-23 Albemarle Corporation Preparation of concentrated aqueous bromine solutions and biocidal applications thereof
US8679548B2 (en) 1998-06-01 2014-03-25 Albemarle Corporation Active bromine containing biocidal compositions and their preparation
US6306441B1 (en) 1998-06-01 2001-10-23 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US6299909B1 (en) 1998-06-01 2001-10-09 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
EP1194371A4 (en) * 1999-04-21 2004-03-31 Nalco Chemical Co STABLE OXIDIZING BROMIC COMPOUND, METHOD FOR PRODUCING THE SAME AND USE FOR PREVENTING BIOLOGICAL DEPOSIT
US6506418B1 (en) 1999-09-24 2003-01-14 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
KR100339129B1 (ko) * 1999-12-13 2002-05-31 심상희 알칼리 금속 또는 알칼리 토금속의 차아브롬산염을 이용한미생물 오염제어방법 및 이에 사용되는 오염제어시스템
US7371397B2 (en) 2000-01-18 2008-05-13 Albemarle Corporation Methods for microbiological control in aqueous systems
US6551624B2 (en) 2000-09-08 2003-04-22 Albemarle Corporation Production of concentrated biocidal solutions
US6869620B2 (en) 2000-09-08 2005-03-22 Albemarle Corporation Production of concentrated biocidal solutions
US6375991B1 (en) 2000-09-08 2002-04-23 Albemarle Corporation Production of concentrated biocidal solutions
US6986910B2 (en) 2001-06-28 2006-01-17 Albemarle Corporation Microbiological control in poultry processing
US7182966B2 (en) 2001-06-28 2007-02-27 Albemarle Corporation Microbiological control in poultry processing
US7172782B2 (en) 2001-06-28 2007-02-06 Albemarle Corporation Microbiological control in poultry processing
US7578968B1 (en) 2002-05-03 2009-08-25 Albemarle Corporation Microbiological control in oil or gas field operations
US7901276B2 (en) 2003-06-24 2011-03-08 Albemarle Corporation Microbiocidal control in the processing of meat-producing four-legged animals
US7223719B1 (en) 2004-03-16 2007-05-29 Albemarle Corporation Breaker composition and process
US7576041B2 (en) 2004-03-16 2009-08-18 Albemarle Corporation Bromine-based sulfamate stabilized breaker composition and process
US9005671B2 (en) 2004-09-07 2015-04-14 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US9452229B2 (en) 2005-06-10 2016-09-27 Albemarle Corporation Highly concentrated, biocidally active compositions and aqueous mixtures and methods of making the same
US8496830B2 (en) 2007-06-29 2013-07-30 Christ Water Technology Ag Treatment of water with hypobromite solution
WO2014020601A1 (en) 2012-07-31 2014-02-06 Bromine Compounds Ltd. Method for preparing bromine based biocidal aqueous compositions
EP2879491A4 (en) * 2012-07-31 2016-01-20 Bromine Compounds Ltd METHOD FOR PRODUCING BIOCIDES AQUEOUS BROMBASIS COMPOSITIONS

Also Published As

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JP4749544B2 (ja) 2011-08-17
NO20005421D0 (no) 2000-10-27
CO5050388A1 (es) 2001-06-27
ZA200005916B (en) 2001-05-22
NO20005421L (no) 2000-12-19
WO1999055627A8 (en) 2000-01-27
US6007726A (en) 1999-12-28
AR016240A1 (es) 2001-06-20
AU745642B2 (en) 2002-03-28
CN1298370A (zh) 2001-06-06
NZ507736A (en) 2002-11-26
JP2002512885A (ja) 2002-05-08
BR9910011A (pt) 2001-01-09
ID27578A (id) 2001-04-12
WO1999055627A9 (en) 2000-03-02
EP1094987A1 (en) 2001-05-02
EP1094987A4 (en) 2002-11-04
CA2329896A1 (en) 1999-11-04
KR20010034832A (ko) 2001-04-25
AU3652799A (en) 1999-11-16

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