WO2013059074A1 - Improved biocontrol through the use of chlorine-stabilizer blends - Google Patents
Improved biocontrol through the use of chlorine-stabilizer blends Download PDFInfo
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- WO2013059074A1 WO2013059074A1 PCT/US2012/059846 US2012059846W WO2013059074A1 WO 2013059074 A1 WO2013059074 A1 WO 2013059074A1 US 2012059846 W US2012059846 W US 2012059846W WO 2013059074 A1 WO2013059074 A1 WO 2013059074A1
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- halogen
- process stream
- urea
- stabilizer
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/11—Halides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
Definitions
- At least one invention pertains to compositions and methods for reducing biological activity in process streams, e.g. water based process streams.
- Biological activity in process streams is problematic for a variety of reasons, including, but not limited to sanitation problems, process equipment efficiency problems, and product quality problems.
- high biological activity levels have a deleterious effect on equipment operation.
- the problems associated with manufacturing certain paper types, e.g. tissue/recycled products are more pronounced, because high fungal levels present the quandary of providing a biocide program that stabilizes the biocide well enough so that it is not readily consumed (good persistence) and providing a biocide at sufficient levels to combat periodic spikes in biological activity - a need for less stabilization/decreased persistence.
- bleaching/processing of recycled fiber presents the additional quandary for papermakers because papermakers are balancing the addition of sulfite post bleaching/processing of recycled fibers, which quenches a halogen, e.g. chlorine, with the need to maintain chlorine in the system, more specifically, a persistent level of chlorine in the papermaking system without having to add more
- a halogen e.g. chlorine
- At least one invention relates to methods and compositions effective at stabilizing oxidant biocides.
- Oxidant biocides such as peroxide acid and halogen chemicals like sodium hypochlorite have been widely used in the pulp and paper industry. These oxidant biocides are highly effective at immediately killing large numbers of microorganisms.
- Oxidant biocides are not naturally stable and they tend to oxidize rapidly and over time lose their effectiveness.
- In environments with very high populations of microorganisms such as in process water which is rich in organic and inorganic material on which the microorganisms can feast, sufficient numbers of microorganisms can survive until after the oxidant biocides have lost effectiveness.
- N-hydrogen sources have also been used to stabilize oxidant biocides but they too have been unsatisfactory because they are volatile and too rigid in their dosage requirements. This rigidity prevents the kind of flexible molar ratio adjustments that are often required to suit the specific conditions of the particular water system they are used to treat.
- biocide blends typically include an oxidant halogen which provides an initial large kill of the organisms and another longer lasting but less effective biocide which provides more long term microorganism suppression.
- biocide blends typically include an oxidant halogen which provides an initial large kill of the organisms and another longer lasting but less effective biocide which provides more long term microorganism suppression.
- biocides are themselves incompatible with other biocides and the use of multiple biocides, each having their own preparation and introduction issues, requires an inordinate investment in complex application equipment.
- biocide feeding machines be installed at various points along a
- At least one embodiment of the invention is directed to a composition
- a composition comprising: a halogen source, urea, and an additional halogen stabilizer excluding urea, optionally an alkali in a concentration sufficient to provide said composition with a pH of greater than 10.
- the composition excludes a stabilized bromine compound.
- the stabilizer may comprise one item from the list consisting of: an N-hydrogen compound, ammonia, ammonium salts, ammonium sulfamate, ammonium sulfate, sulfamic acid, sodium sulfamate, cyanuric acid, succinimide, urea, glycouril, glycine, amino acids, and any combination thereof.
- the stabilizer may comprise at least two compositions of matter each of which function as a halogen stabilizer.
- the halogen source may be selected from the group consisting of at least one of the following: a chlorine source, an alkaline hypohalite, Cl 2 gas, NaOCl, Ca(OCl) 2 , and electrically generated chlorine.
- the composition may contain: an alkaline hypohalite, urea, and ammonium sulfamate.
- the urea and additional halogen stabilizer may be in a ratio of 50:50 with one another.
- At least one embodiment of the invention is directed to a method for reducing biological activity in a process stream comprising providing the composition to a process stream.
- the composition may be added to the process stream by the following mode of addition: forming a mixture of at least an alkali in a concentration sufficient to maintain a pH of greater than 10 in the final composition and an alkaline hypohalite, and secondarily mixing said mixture with a second mixture containing urea and said additional stabilizer, wherein said secondary mixing is optionally done with a T-mixer.
- the process stream may be a papermaking process stream.
- the papermaking process may be a process selected from the group consisting of: tissue and/or towel, board; packaging; pulping; and recycled pulping.
- the process stream may contain fungus.
- the process stream may have a sulfite concentration of between 2 ppm to 50 ppm.
- the method may further comprise monitoring the biological activity in the process stream prior to and subsequent to the addition of said composition.
- the biological activity may be monitored by taking a sample of said process stream and plating said sample on a Petri dish or similar apparatus or by measuring ATP levels of a sample from the process stream or by taking a sample of said process stream and monitoring dissolved oxygen and optionally the oxidation reduction potential of said sample and optionally responding by adding or reducing the amount of one or more chemistries which are added to said process stream, wherein said chemistries include said composition.
- the method may further comprise adding a second composition to said process stream that contains a halogen, urea, and excludes an additional N-hydrogen compound.
- At least one embodiment of the invention is directed to a method of preventing the growth of microorganisms in a process water stream.
- the method includes the step of:
- the composition comprises: a halogen source, a halogen stabilizer containing a mixture of a sulfur bearing species with urea and/or ammonium sulfate at any ratio, and optionally an alkali.
- the sulfur bearing species includes sulfamic acid or its salt equivalent.
- the molar ratio of sulfamic acid to halogen atoms in the halogen source is more than 2: 1.
- the sulfur bearing species may further comprises a nitrogen stabilizer.
- the nitrogen stabilizer may be one item selected from the group consisting of ammonium sulfate, sodium sulfamate, and any combination thereof.
- the molar ratio of halogen to all of the sulfur in the sulfur bearing species may be more than 2: 1.
- the alkali may be sodium hydroxide.
- the halogen may be chlorine, sodium hypochlorite, 1,3,5-Trichloroisocyanuric acid (TCCA), 1- bromo-3-chloro-5,5-dimethyl-2,4-imidazolidedione (BCDMH) and l,3-dichloro-5,5-dimethyl- 2,4-imidazolidedione (DCDMH).
- the method may further comprise the steps of first adding to the sulfamic acid an alkali and then the adding urea and/ or sodium sulfate.
- the process water stream may be so rich in food for microorgasnisms that a single halogen oxidant biocide is not effective at exterminating the microorganisms population but the composition is.
- the process water stream may be one selected from the list consisting of a cooling tower water stream, and papermaking process water stream.
- the ratio of sulfamic acid or its salt to nitrogen stabilizer may be optimized at any ratio between the concerns of biocidal efficacy and impact on chemical additive present in the process water stream.
- the ratio of sulfamic acid or its salt to nitrogen stabilizer may be optimized at any ratio between the concerns of biocidal efficacy and corrosion on equipment present in the process water stream.
- the composition when used in a papermaking process might not reduce the effectiveness of OBA and DYE additives on paper made from that process.
- the salt may be sodium sulfamate.
- FIG. 1 is a flowchart illustrating one method of combining constituents of the biocide composition.
- FIG. 2 is a second flowchart illustrating one method of combining constituents of the biocide composition.
- FIG. 3 is a third flowchart illustrating one method of combining constituents of the biocide composition.
- FIG. 4 is a graph displaying data which demonstrates the effectiveness of the invention.
- Alkali means a composition of matter that functions as a pH altering chemical base.
- Dyes means one or more compositions used in the papermaking industry to alter the optical properties of a substrate. Dyes often contain chromophoric groups and auxochrome and have good affinity to fiber and compatibility to other additive in paper industry.
- Neitrogen stabilizer means a stabilizer which contains at least one nitrogen atom.
- OPA optical brightening agent
- Dyes or pigments that absorb ultraviolet radiation and reemit it at a higher frequency in the visible spectrum (blue), thereby effecting a white, bright appearance.
- Porture means a solid material used in a papermaking process to alter the optical properties of a substrate.
- Halogen Source means a halogen atom by itself or a halogen atom associated with a cationic counterpart.
- Halogen Stabilizer means a halogen based material whose presence in proximity to a composition of matter functioning as an oxidizing biocide increases the amount of time that the composition remains in a sufficient chemical state to continue functioning as a biocide, this includes but is not limited to materials which preserve (or slow down the rate of loss of) the oxidizing capability of the biocide composition.
- Stabilizer means a composition of matter that increases the length of time that oxidizing halogen ions retain oxidant capacity and are capable of releasing free ions slowly thereby remaining an effective biocidal agent in a liquid environment.
- Substrate means a sheet of paper, a sheet of paper precursor, a mass of fibers, or any other cellulose based or synthetic fibrous material that can be coverted into a sheet of paper by a papermaking process.
- the present invention provides for a composition and a method of use for said composition, which reduces biological activity in a process stream by providing a more efficient application of a biocide.
- the biocide is more efficiently utilized, e.g.
- biocide in the system when needed, which can provide an environmental benefit because a process operator can use less biocide to combat various types of microorganisms and bacteria that pervade process streams, e.g. including water based systems, wherein one water based system example is a papermaking system.
- the composition contains at least the following components: halogen, urea, and an additional halogen stabilizer excluding urea.
- Stabilizers can be blended with chlorine or bromine to yield a milder oxidant.
- Benefits of halogen-stabilization include increased persistence of the halogen residual for improved control of microbial growth in biofilm or surface deposits and in systems with long residence times and high halogen demand.
- Halogen-stabilization can also improve compatibility of the halogen with sensitive process additives, including dyes, optical brightening agents, polymers, and corrosion control products.
- sensitive process additives including dyes, optical brightening agents, polymers, and corrosion control products.
- the halogen becomes too persistent when it is blended with stabilizers, for example urea.
- the program may not adequately control fungi and several types of bacteria, including sphingomonads and spore- forming bacteria.
- Some forms of stabilized-halogen are more volatile, reducing the halogen residual available in the water-phase and contributing to vapor-phase corrosion.
- an alkali in a concentration sufficient to provide a pH of greater than 10.
- the pH is greater than 12.
- the pH range is from 12 to about 13.5.
- An alkali can include one or more of the following chemistries: sodium hydroxide and potassium hydroxide.
- an additional component excluding a stabilized bromine compound from said composition.
- the halogen is selected from at least one of the following: a chlorine source, alkaline hypohalite, Cl 2 gas (e.g. added to H 2 0 stream prior to blending), NaOCl, Ca(OCl) 2 , and electrically generated chlorine.
- the composition comprises urea in combination with additional stabilizer, including ammonium Sulfamate, to stabilize halogens for biocontrol
- the stabilizer is an N-hydrogen compound.
- the N-hydrogen compound is ammonium sulfamate.
- the N-hydrogen compound excludes ammonium sulfate.
- the composition contains: an alkaline hypohalite, urea, and ammonium sulfamate.
- the ratios between urea and an additional stabilizer can vary depending upon system conditions, e.g. levels of fungus. For example, one could take into account chemical kinetics between: (a) urea with halogen; b) additional stabilizer with halogen; and (c) blend of urea and additional stabilizer with halogen.
- the stabilizer blend between urea and the additional stabilizer is 50:50.
- a method for reducing biological activity in a process stream is also disclosed, e.g. process stream contained in a water system.
- the method comprises: providing a composition to a process stream, wherein said composition contains: a halogen, urea, and an additional stabilizer excluding urea, optionally an alkali in a concentration sufficient to provide said composition with a pH of greater than 10; and optionally excluding a stabilized bromine compound from said composition.
- the composition is added to the process stream by the following mode of addition: forming a mixture of at least an alkali in a concentration sufficient to provide a pH of greater than 10 and an alkaline hypohalite, and secondarily mixing said mixture with a second mixture containing urea and said additional stabilizer, wherein said secondary mixing is optionally done with a T-mixer.
- the method comprises: adding a second composition to said process stream that contains a halogen, urea, and excludes an additional N-hydrogen compound.
- the composition is added to the process stream by the following mode of addition: forming a mixture of at least an alkali in a concentration sufficient to provide a pH of greater than 10, preferably 12 to 13.5, and an alkaline hypohalite, and secondarily mixing said mixture with a second mixture containing urea and an additional stabilizer.
- a mixture of at least an alkali in a concentration sufficient to provide a pH of greater than 10, preferably 12 to 13.5, and an alkaline hypohalite and secondarily mixing said mixture with a second mixture containing urea and an additional stabilizer.
- One of ordinary skill in the art could mix the first mixture and second mixture via a variety of techniques, e.g. apparatuses.
- the first mixture and second mixture are mixed together with a T-mixer.
- a T-mixer One of ordinary skill the art would understand what a T-mixer is.
- one of ordinary skill in the art can utilize a mixing chamber, such as the one disclosed in U.S. Patent No. 7,550,060, herein incorporated by reference, to carry out a mixing protocol of the chemistries.
- the methodology of the present invention is applicable to a variety of process streams or aqueous based systems or water based systems or industrial based systems or a combination thereof.
- the process stream is a papermaking process stream.
- the papermaking process is a process selected from the group consisting of: tissue and/or towel, board; packaging; pulping; and recycled pulping.
- the process stream contains fungus. In at least one embodiment, the process stream has a sulfite concentration of between 2 ppm to 50 ppm.
- the efficacy of the composition for reducing biological activity can be measured by a variety of analytical techniques and controls schemes.
- the process stream further comprises monitoring said biological activity in said process stream prior to and subsequent to the addition of said composition.
- the biological activity is monitored by taking a sample of said process stream and plating said sample on a Petri dish or similar apparatus.
- the biological activity is monitored by measuring ATP (adenosine triphosphate) levels of a sample from said process stream.
- ATP adenosine triphosphate
- the biological activity is monitored by taking a sample of said process stream and monitoring dissolved oxygen and optionally the oxidation reduction potential of said sample and optionally responding to said biological activity by adding or reducing the amount of one or more chemistries which are added to said process stream, wherein said chemistries include said composition.
- compositions by themselves or compositions utilized to treat a process stream can be made outside of the process stream or within the process stream (in situ) or a combination thereof.
- a composition comprising a halogen, a halogen stabilizer, and optionally an alkali are provided for inhibiting the growth of microorganisms in a papermaking environment.
- the stabilizer is a composition comprising sulfur.
- the sulfur bearing species includes sulfamic acid (or its salt equivalent such as sodium sulfamate).
- the molar ratio of the halogen to the sulfamic acid is more than 2: 1.
- the stabilizer is a composition comprising a mixture of sulfur bearing species with urea.
- the halogen is mixed with sulfamic acid at molar ratio of Nitrogen to Chlorine of more than 2: 1.
- the stabilizer is a composition comprising a mixture of sulfur bearing species with ammonium sulfate.
- the sulfur bearing species further comprises a nitrogen stabilizer.
- the nitrogen stabilizer is one item selected from the group consisting of ammonium sulfate, sodium sulfamate, or any combination thereof.
- the molar ratio of halogen to all of the sulfur in the sulfur bearing species is more than 2: 1.
- the alkali is sodium hydroxide.
- the halogen are chlorine, sodium hypochlorite, 1,3,5- Trichloroisocyanuric acid (TCCA), l-bromo-3-chloro-5,5-dimethyl-2,4-imidazolidedione (BCDMH) and l,3-dichloro-5,5-dimethyl-2,4-imidazolidedione (DCDMH).
- TCCA 1,3,5- Trichloroisocyanuric acid
- BCDMH l-bromo-3-chloro-5,5-dimethyl-2,4-imidazolidedione
- DCDMH l,3-dichloro-5,5-dimethyl-2,4-imidazolidedione
- the sulfamic acid is first amended with alkali and then the urea/ammonium sulfate is added. Sodium hypochlorite is added to above mixture.
- hypochlorite first at molar ratio more than 2: 1 nitrogen to chlorine and then is added to urea or ammonium sulfate.
- the urea or ammonium sulfate combined sodium hypochlorite first then is added to sulfur baring nitrogen at different ratio.
- the order is significant because different stabilized halogen species are generated at different rates due to differing equilibrium constants. These differences can be accounted for by dosing the halogens in different amounts and in different orders. Also chlorine is able to transfer from stabilized chlorine to other nitrogen species so the order of combinations can compensate for that.
- composition contains no buffer.
- the composition contains no alkali.
- composition can be formulated on site by mixing the components together before mixing with halogen oxidant.
- composition can be formulated on site by mixing the components as illustrated in any one of FIGs 1, 2, and/or 3.
- microorganisms killed by the biocide are sessile. In at least one embodiment the microorganisms killed by the biocide are planktonic.
- the sulfamic acid and the nitrogen stabilizer readily combine so when mixing the two a high product yield is achieved with little waste.
- the mixture of sulfamic acid and nitrogen stabilizer functions at many different ratio amounts.
- the relative amounts of sulfamic acid or nitrogen stabilizer can be appropriately increased or decreased depending on the particular environment it is to be used in. For example in cases where nitrogen stabilizer may interfere with particular paper additives such as OBA or DYE, the relative amount of sulfamic acid will be increased. In contrasts in contexts where the sulfamic acid has compatibility issues, the amount of nitrogen stabilizer can be increased.
- the details of the formulation is targeted towards the nature of the biological infestation.
- a formulation containing relatively equal amounts of sulfamic acid and the nitrogen stabilizer is used because it is optimized to causes low impact on additives and low degrees of corrosion which is more desirable than a highly effective biocide when the infestation is weak.
- effectiveness of the biocide is more important than the one time effects on additives or corrosion and a therefore a formulation containing more sulfamic acid relative to the molar amount of nitrogen stabilizer is used.
- a formulation having only two variables a number of condition specific ratios can be provided which requires a simple input system yet is capable of dynamically responding to different conditions over the life cycle of the industrial facility.
- the composition is used as a biocidal agent in a cooling tower.
- the composition is used to reduce biofilm on a surface.
- Biofilm is the accumulation of sessile organisms on the surfaces of equipment.
- the composition is used to treat microorganisms in a membrane system.
- Membrane systems are often prone to biofilm colonization as
- the membrane system is a water permeable membrane. In at least one embodiment the membrane is a part of a water treatment system.
- the composition has a particular pH before it is introduced into the system.
- the pH is greater than 5 and less than 12, and is most preferably between 8 and 10.
- the ratio of the contents of the composition are balanced to optimize the composition's effectiveness and utility.
- chlorosulfamate was used in a ratio of 1 : 1 with chlorine. This resulted in stronger than desired bonding of the chlorine and as a result it reduced the rate of releasing sulfamate from sulfate thereby reducing the effectiveness of the composition.
- the ratio is different and as a result the composition is more effective.
- the ratio of sulfamate to stabilizer within the composition is between (less than 4): 1 and (more than 1): 1.
- FIG. 4 illustrates that 12% Sulfamic Acid and 3% ammonium sulfate showed more active on bioactivity inhibition than other combinations of stabilizers.
- chloronitrogen species that is effective as a biocide.
- the dosing sequence of the composition is calibrated to make optimal use of the relative equilibrium rates of the various chemical reactions.
- Each of the chemical reactions occurs at different rates and as a result CI species are constantly passing back and forth between molecules and have different availabilities at different times.
- the reagents required for the lower occurring reactions are added to the composition first and are allowed to react somewhat or completely before the reagents required for the faster reactions are added. This avoids the faster reactions competing with the slower reactions.
- the reagents required to allow the chlorosulfamate species to react with the amine to form chloramine and ammonia is only added to the composition after chloroamine has been partially or completely formed.
- the composition is diluted to produce a more mild (and less violent, reactive, or destructive) biocide effect.
- the methods of diluting biocides disclosed in US Patents 6, 132,628 and 7,067,063 are employed.
- the composition is diluted so the species exists within the range of 100 ppm to 150,000 ppm.
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Abstract
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ620835A NZ620835B2 (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
KR1020147007838A KR102095212B1 (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
PL12842036T PL2768538T3 (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
CA2844833A CA2844833C (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
ES12842036.1T ES2635119T3 (en) | 2011-10-21 | 2012-10-12 | Enhanced biocontrol through the use of bleach stabilizer combinations |
EP12842036.1A EP2768538B1 (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
MYPI2014001112A MY185106A (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
JP2014537126A JP6110392B2 (en) | 2011-10-21 | 2012-10-12 | Improvement of ecological control by using chlorine stabilizer mixture |
AU2012326500A AU2012326500B2 (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
BR112014007142-0A BR112014007142B1 (en) | 2011-10-21 | 2012-10-12 | COMPOSITION AND METHOD FOR REDUCING BIOLOGICAL ACTIVITY IN A PROCESS CURRENT |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011103285841A CN103053613A (en) | 2011-10-21 | 2011-10-21 | Improved biological control by using chlorine-stabilizing agent mixture |
CN2011103285841 | 2011-10-21 | ||
US13/289,547 | 2011-11-04 | ||
US13/289,547 US9161543B2 (en) | 2011-10-21 | 2011-11-04 | Biocontrol through the use of chlorine-stabilizer blends |
Publications (1)
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WO2013059074A1 true WO2013059074A1 (en) | 2013-04-25 |
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PCT/US2012/059846 WO2013059074A1 (en) | 2011-10-21 | 2012-10-12 | Improved biocontrol through the use of chlorine-stabilizer blends |
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Country | Link |
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EP (1) | EP2768538B1 (en) |
JP (1) | JP6110392B2 (en) |
KR (1) | KR102095212B1 (en) |
CN (2) | CN109303064A (en) |
AR (1) | AR088373A1 (en) |
AU (1) | AU2012326500B2 (en) |
BR (1) | BR112014007142B1 (en) |
CA (1) | CA2844833C (en) |
ES (1) | ES2635119T3 (en) |
MY (1) | MY185106A (en) |
PL (1) | PL2768538T3 (en) |
TW (1) | TWI546262B (en) |
WO (1) | WO2013059074A1 (en) |
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JP5990717B1 (en) * | 2016-03-11 | 2016-09-14 | 株式会社片山化学工業研究所 | Cyanogen-containing wastewater treatment agent and cyanide-containing wastewater treatment method using the same |
JP6578561B2 (en) * | 2016-08-25 | 2019-09-25 | 株式会社片山化学工業研究所 | Cyanogen-containing wastewater treatment agent and cyanide-containing wastewater treatment method using the same |
CN112119040B (en) | 2018-06-13 | 2022-12-30 | Ay实验室有限公司 | System and method for monitoring biocide treated process water by oxygen sensor |
AU2020300849A1 (en) * | 2019-07-01 | 2021-12-23 | A.Y. Laboratories Ltd. | Method for producing a biocide |
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AU2012326500A1 (en) | 2014-02-27 |
AR088373A1 (en) | 2014-05-28 |
AU2012326500B2 (en) | 2015-09-10 |
CA2844833A1 (en) | 2013-04-25 |
NZ620835A (en) | 2015-07-31 |
EP2768538B1 (en) | 2017-05-17 |
TWI546262B (en) | 2016-08-21 |
CA2844833C (en) | 2019-06-18 |
JP2015501307A (en) | 2015-01-15 |
PL2768538T3 (en) | 2017-10-31 |
CN109303064A (en) | 2019-02-05 |
MY185106A (en) | 2021-04-30 |
BR112014007142A2 (en) | 2017-04-04 |
JP6110392B2 (en) | 2017-04-05 |
KR102095212B1 (en) | 2020-03-31 |
TW201323349A (en) | 2013-06-16 |
ES2635119T3 (en) | 2017-10-02 |
KR20140079767A (en) | 2014-06-27 |
EP2768538A4 (en) | 2015-05-20 |
EP2768538A1 (en) | 2014-08-27 |
BR112014007142B1 (en) | 2019-08-06 |
CN103053613A (en) | 2013-04-24 |
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