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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Disinfection or sterilisation of materials or objects, in general; Accessories therefor
• • 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
  • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
• • 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
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
• • 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
• • 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
  • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Disinfection or sterilisation of materials or objects, in general; Accessories therefor
  • A61L2/16—Disinfection or sterilisation of materials or objects, in general; Accessories therefor using chemical substances
  • A61L2/18—Liquid substances
• • 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
  • C02F1/72—Treatment of water, waste water, or sewage by oxidation
  • C02F1/722—Oxidation by peroxides
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
  • C02F2103/023—Water in cooling circuits
• • 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
  • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
  • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry

Definitions

• the present invention relates to microbiocidal compositions and to processes of utilizing these microbiocidal compositions for inhibiting the growth of microorganisms in aqueous systems. More particularly, the microbiocidal compositions of this invention comprise a combination of (i) an oxidant, and (ii) a non-oxidizing microbiocide optionally with a surfactant/dispersant, an anti-corrosive material, and/or an anti-scale material.
• Pulp and paper mill systems operate under conditions which encourage the growth of microorganisms and often results in fouling problems. Moreover, microorganisms can form large slime deposits which can become dislodged and show up in the paper product as spots, holes or tears. This necessitates shutting down the paper making process to clean the equipment, and results in lost production time.
• Slime may also be objectionable from the standpoint of cleanliness and sanitation in breweries, wineries, dairies and other industrial food and beverage process water systems.
• sulfate reducing bacteria are often problematic in waters used for the secondary recovery of petroleum or for oil drilling in general. For example, these organisms reduce sulfates present in the injection water to form insoluble iron sulfide deposits and may enhance corrosion of metals by accelerating galvanic action.
• oxidizing biocides have enjoyed widespread use in such applications including chlorine, chlorine dioxide and bromine.
• these oxidizing biocides are not always effective for controlling microbiological growth.
• oxidizing biocides are consumed by inorganic species such as ferrous iron, reduced manganese, sulfides, etc. as well as organic compounds which are commonly found in those systems.
• biocidal compositions permit a reduction in the dosage amount of biocide required to treat nuisance microbiota in industrial waters, and significantly reduces the time required to control microbiological organisms.
• compositions which are used to control or inhibit microbial growth, comprising (i) a microbiocidal effective amount of an oxidant selected from the group of mono- or di- peroxyorganic acids, halogen dioxides, monopersulfates, halogens, halogen releasing compounds, perborates, peroxides, persulfates, permanganates, percarbonates, ozone, and water soluble salts thereof, and mixtures thereof; and (ii) a microbiocidal effective amount of a non-oxidizing microbiocide selected from the group consisting of glutaraldehyde, limonene, bis(trichloromethyl) sulfone, 2-(decylthio)-ethanamine, dodecylguanidine hydrochloride, 2-(2-bromo-2-nitroethyl) furan, poly(oxyethylene (dimethyliminio) ethylene (dimethyliminio)
• Also provided in accordance with the present invention is a method for controlling or inhibiting microbial growth in aqueous systems comprising adding to the system (i) a microbiocidal effective amount of an oxidant selected from the group of mono- or di- peroxyorganic acids, halogen dioxides, monopersulfates, halogens, halogen releasing compounds, perborates, peroxides, persulfates, permanganates, percarbonates, ozone, their water soluble salts, and mixtures thereof; and (ii) a microbiocidal effective amount of a non- oxidizing microbiocide selected from the group consisting of glutaraldehyde, limonene, bis(trichloromethyl) sulfone, 2-(decylthio)-ethanamine, dodecylguanidine hydrochloride, 2-(2-bromo-2-nitroethyl) furan, poly(oxyethylene (dimethyliminio) ethylene (dimethylimini
• the present invention is directed to certain novel biocidal compositions comprising combinations of oxidants and non-oxidizing biocides which are added to an aqueous system in amounts effective to inhibit or control the growth of microorganisms in the aqueous system.
• the biocidal compositions of this invention comprise combinations of (i) an oxidant selected from the group consisting of mono- or di-peroxyorganic acids, halogen dioxides, monopersulfates, halogens, halogen releasing compounds, perborates, peroxides, persulfates, permanganates, percarbonates, ozone, their water soluble salts, and mixtures thereof and (ii) a non-oxidizing microbiocide selected from the group consisting of glutaraldehyde, limonene, bis(trichloromethyl) sulfone, 2-(decylthio)ethanamine, dodecylguanidine hydrochloride, 2-(2-bromo-2-nitroethyl) fur
• Suitable peroxides include inorganic peroxides such as hydrogen peroxide, sodium peroxide, as well as organic peroxides such as benzoyl peroxide and the like.
• Suitable halogen releasing compounds include hydantoins such as 1,3-dichloro-5,5-dimethyl hydantoin, 1,3-dibromo- 5,5-dimethyl hydantoin or 1,3-diiodo-5,5-dimethyl hydantoin.
• Suitable mono- or di-peroxyorganic acids include, but are not limited to, peracetic acid, perbenzoic acid, peroxypropionic acid, hexane diperoxoic acid, dodecanediperoxoic acid.
• Suitable halogen dioxides include chlorine dioxide, bromine dioxide and iodine dioxide.
• Suitable oxidants include sodium perborate, sodium percarbonate, potassium permanganate, sodium persulfate, potassium persulfate, ammonium persulfate, chlorine, bromine, iodine and chlorine, bromine, iodine releasing compounds, sodium monopersulfate, potassium monopersulfate, and ammonium monopercarbonate.
• Potassium monopersulfate is a preferred oxidant and is commercially available from DuPont as OXONE.
• the enhanced activity of the mixture permits a significant reduction in the total quantity of the biocide required for an effective treatment of an aqueous system.
• the enhanced biocidal effectiveness of the compositions of the present invention was particularly surprising since not all oxidants provide enhanced biocidal activity when used in combination with non-oxidizing biocides. In fact, some oxidants are actually antagonistic when used in combination with non-oxidizing biocides, and result in less biocidal effectiveness than the use of either component alone.
• biocidal combinations of this invention are effective for controlling and inhibiting the growth and reproduction of microorganisms in cooling water systems, pulp and paper mill systems, petroleum operations (e.g. oil well applications) , industrial lubricants and coolants, lagoons, lakes and ponds, etc.
• the particular type of microorganisms present in these areas vary from location to location, and even at a given location over a period of time.
• an aqueous system is treated to inhibit the growth of the microorganisms by adding to the aqueous system at least one oxidant and at least one non-oxidizing microbiocide. These components are present in the system at the same time. While it is possible to combine the oxidant and the non-oxidizing biocide, it is generally preferred not to combine the microbiocide with the oxidant too far in advance of being added to the aqueous system because these materials may adversely react when they are brought into direct contact with each other in their concentrated forms.
• the dosage amounts of oxidant and non-oxidizing biocide which are added to an aqueous system may vary widely depending upon the nature of the aqueous system being treated, the level of organisms present in the aqueous system and the level of inhibition desired.
• An important consideration when dosing the oxidants of the present invention are the levels of ferrous iron, reduced manganese, sulfide, ammonia, organic constituents, and the like, which may react with and thereby consume the oxidants of the present invention.
• Oxidant Demand refers to the difference between the oxidant dosage amount and the residual oxidant concentration after a prescribed contact time and at a given pH and temperature.
• Oxidant Requirement refers to the oxidant dosage amount required to achieve a given residual oxidant concentration at a prescribed contact time, pH and temperature. Since the levels of ferrous iron, reduced manganese, sulfide, etc. can vary widely from system to system, the oxidant demand should be determined for the aqueous system being treated in accordance with the method of this invention.
• the dosage amount of oxidant which is added to an aqueous system i.e., a biocidally effective amount, refers to the residual oxidant concentration in an aqueous system. Residual oxidant concentration can readily be determined by one skilled in the art by conventional means. In general, the dosage amount of oxidant may be from
• 0.1 ppm to 100 ppm preferably from about 0.5 ppm to about 45 ppm.
• the dosage amount of microbiocide in the system may be from 0.1 ppm to 125 ppm, preferably about 0.5 ppm to about 45 ppm.
• the resulting combination possesses a higher degree of effectiveness against microorganisms than the individual components comprising the combination. While larger quantities of the microbiocides or oxidant may be used with no detrimental effect, such large quantities increase the cost of treatment and generally provide little additional benefit.
• the biocidal compositions of the present invention may optionally be used in combination with one or more surfactants/dispersants to disperse biomass and to enhance the dispersibility and stability of these microbiocidal formulations.
• Suitable surfactants/ dispersants include, but are not limited to, cationic, nonionic, anionic, or amphoteric surfactants and polymers such as fluorinated surfactants, alkylaryl polyether alcohols, polyether alcohols, sodium dodecyl sulfate, sodium nonylbenzene sulfonate, sodium dioctyl sulfosuccinate, octylphenoxypolyethoxyethanol, ethylene and/or propylene oxide condensates with long chained alcohols, mercaptans, amines, carboxylic acids, sodium sulfonate of condensated naphthalene-formaldehyde and lignin sulfonate, alkyl benzene
• FC-99 is an anionic surfactant which is a 25% active solution of amine-perfluoroalkyl sulfonates in water.
• FC-100 is an amphoteric surfactant which is a 28% active solution of fluorosurfactant solids in glycol/water.
• FC-129 is an anionic surfactant which is a 50% solution of potassium fluorinated alkyl carboxylates in water, butyl cellosolve and ethanol.
• the dosage amount of surfactant/dispersant in the aqueous system is not critical, per se, provided of course that it is added in an amount effective to disperse the bi ass or stabilize a particular microbiocidal formulationa These dosage amounts are typically from 0.5 to 500 ppm.
• the biocidal compositions of the present invention may also be used in combination with an anti-corrosive material. Suitable anti-corrosive materials include, but are not limited to, phosphates such as sodium tripolyphosphate or tetrapotassium pyrophosphate, phosphonates, carboxylates, etc.
• the anti-corrosive material may be blended with the oxidant before being added to the system or may be added separately.
• the anti-corrosive material is generally added to the system in a dosage amount of from 0.5 to 50% based on the total amount of oxidant and anti- corrosive material in the mixture. More preferably, the amount of the anti-corrosive material is at least 1% of the total amount of oxidant and anti-corrosive material in the mixture.
• biocidal compositions of this invention may also be used in combination with other biocides which further enhance the synergistic effectiveness.
• preferred biocidal combinations include glutaraldehyde with isothiazolone.
• the ratio of these biocidal combinations can range from 1:10 to 10:1 on a weight basis.
• a preferred isothiazolone is a mixture of 5- chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4- isothiazolin-3-one.
• the biocidal compositions of the present invention may also be used in combination with an anti-scale material.
• Suitable anti-scale materials include, but are not limited to, polyacrylates such as sodium polyacrylate, phosphonates such as hydroxyethylidene diphosphonic acid, etc.
• the anti-scale material is generally added to the system in a dosage amount of from 0.5 to 50% based on the total amount of oxidant and anti- scale material in the mixture.
• the oxidants of this invention may be in solid or liquid form and may be diluted with a solid or liquid carrier. Powders may be prepared with a finely divided solid carriers including talc, clay, pyrophyllite, diatomaceous earth, hydrated silica, calcium silicate, or magnesium carbonate.
• Powders may typically contain 1 to 15 percent of the microbiocides of this invention, while a wettable powder may be obtained by increasing the proportion of microbiocide to about 50 percent or more.
• a typical formulation of a wettable powder comprises 20 percent to 50 percent of the suitable compounds of this invention, 45 percent to 75 percent of one or more finely divided solids, one percent to five percent of a wetting agent, and one percent to five percent of a dispersing agent.
• oxidants of this invention may also be used in the form of liquid concentrates. These are prepared by diluting or dissolving the oxidants and/or microbiocides of this invention in a solvent together with one or more surface active agents.
• the synergism of the two-component microbiocidal combinations of the present invention was demonstrated by testing a wide range of concentrations and ratios of compounds, generated by two-fold serial dilutions in a liquid.
• the liquid medium is composed of deionized water supplemented with inorganic constituents to simulate an industrial water.
• Work was performed with the bacterium Enterobacter aerogenes or a mixed bacteria culture consisting of Enterobacter aerogenes, Escherichia coli, Pseudomonas aeruginosa, and Bacillus subtilis ; the fungus Aspergillus niger; and for the algae, Chlorella vulgaris, or Scenedesmus quadracauda . All organisms were representative of those typically found in industrial waters.
• Each table in the examples is organized to show synergy by illustrating (1) the concentration of each test material acting alone required to produce a given end-point of growth prevention or colony-forming-unit inhibition as compared to untreated controls; and (2) the lower required concentrations of the combined test materials.
• This example shows synergies between glutaraldehyde and H 2 0 2 using the bacterium Enterobacter aerogenes and a mixed bacteria culture.
• This example demonstrates synergies between glutaraldehyde and H 2 0 2 using the green algae Chlorella vulgaris and Scenedesmus quadracauda .
• the data (Table 5) indicate hydrogen peroxide as synergist with a combination of glutaraldehyde and Kathon 886F(4:1 active) using the green algae Chlorella vulgaris .
• Kathon 886F is a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
• This example demonstrates synergies between limonene and oxidizing biocides using a mixture of four bacteria species.
• This example demonstrates synergies between tetradecyl dimethyl benzyl ammonium chloride and the oxidizing biocide hydrogen peroxide.
• This example shows synergy between tributyltetradecyl phosphonium chloride and hydrogen peroxide (Table 12) .
• This example shows synergies between glutaraldehyde and sodium hypochlorite.

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• 1995
  • 1995-10-31 WO PCT/US1995/013947 patent/WO1996014092A1/en not_active Ceased
  • 1995-10-31 BR BR9509598A patent/BR9509598A/pt not_active Application Discontinuation
  • 1995-10-31 EP EP95938952A patent/EP0789595A4/de not_active Withdrawn
  • 1995-10-31 KR KR1019970702893A patent/KR970706850A/ko not_active Withdrawn
  • 1995-10-31 NZ NZ296363A patent/NZ296363A/en unknown
  • 1995-10-31 CA CA 2204279 patent/CA2204279A1/en not_active Abandoned
  • 1995-10-31 FI FI971852A patent/FI971852A7/fi unknown
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  • 1995-10-31 JP JP51536696A patent/JPH10509141A/ja not_active Ceased
  • 1995-10-31 CZ CZ971354A patent/CZ135497A3/cs unknown
• 1997
  • 1997-04-30 NO NO972002A patent/NO972002L/no not_active Application Discontinuation

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