KR20020029081A - Composition and method for controlling biological growth using stabilized sodium hypobromite in synergistic combinations - Google Patents

Abstract

Synergistic compositions and methods for controlling biological growth in industrial fluids are disclosed wherein the compositions are stable hypobromite sodium and coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride At least 7-oxabicyclo [2.2.1] heptan-2,3-di-carboxylic acid and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one Contains one fire.

Description

COMPOSITION AND METHOD FOR CONTROLLING BIOLOGICAL GROWTH USING STABILIZED SODIUM HYPOBROMITE IN SYNERGISTIC COMBINATIONS}

The proliferation of microorganisms and the resulting formation of slime is a common problem in aqueous systems. Problematic slime producing microorganisms can include bacteria, fungi and algae. Slime sediments are typically used in chilled water systems, pulp and paper mill systems, petroleum processes, clay and pigment slurries, recreational water systems, air cleaning systems, decorative water sources, food, beverage, and industrial processing pasteurizers, soft water systems, It occurs in many industrial water systems, including gas scrubber systems, latex systems, industrial lubricants, cutting fluids, and the like.

Proliferation of organic matter such as mussels and shellfish is also a problem in many water systems. The growth of these organics is a serious problem for urban and industrial water systems, such as once-through or recirculating chilled water systems, cooling ponds, receiving pipes, ballast water tanks and ship storage that sucks water from the body that has floated in the water. .

Insecticides and antimicrobials are used to control the growth of microorganisms in many different aqueous media. As used herein, "control" is defined to include both suppression and removal. If left untreated, microorganisms and their biofilms (slimes) may cause deterioration of the cooling tower structure, loss of heat exchange efficiency in the cooling system, aesthetic defects in decorative water sources, increased and accelerated corrosion on metal surfaces, and increased down time. , Or may cause breakage of paper sheets in pulp and paper systems. Bacterial slime is also opposed when they relate to cleanliness and sanitation in breweries, milk processing plants, and other industrial food and beverage processing water systems. Proliferation of microbial contaminants in lubricants and cutting fluids is a common problem due to elevated temperatures and unsanitary conditions found in many metal working plants.

For many types of urban and industrial water systems, the selection of water to receive is often done to prevent the entry of large objects, including mature clams and mussels. However, this selection does not prevent the passage of immature macroinvertebrates. Large invertebrates of these early life stages grow in size and density that attach to and become dirty in water systems. This growth causes severe blockages and damage to the systems they implant, resulting in system downtime and expensive cleaning and repair. As a result of the uncontrolled harmful effects of biological growth and contamination in many industrial processes, various pesticides and antimicrobials have been developed to assist in eliminating and controlling biological growth.

Often, one pesticide is insufficient to control biological growth in an aqueous medium. Insecticides may act in combination, ie synergistically, to obtain better biological performance as opposed to the efficacy obtained when each pesticide is used separately. Pesticides can act on target organics in many different ways to cause cellular stress or death. The mechanism by which the pesticide exerts pesticidal activity depends on many factors including the chemical properties of the pesticide and the biochemical and physical properties of the target organism. Some pesticides target cell membranes or cell walls. Others target critical enzymes or cellular metabolic machinery that lead to cell death or destruction of cell replication.

The combination of two pesticides produces enhanced potency over the cumulative or additional effects of the two pesticides. This probably reflects a synergistic pesticidal effect on some essential component (s) for cells to survive and sustained growth. The combination of two synergistic pesticides allows the addition of smaller amounts of individual pesticides to obtain the desired level of control. This has both beneficial environmental and economic effects. It allows for reduced emissions of potential environmental pollutants and more cost effective control programs for various industrial systems.

It is an object of the present invention to provide novel pesticidal compositions which provide an improved effect in controlling the growth of both microorganisms and macrorooragnsism in industrial fluids. Another object of the present invention is to provide an improved method for controlling microorganisms and macroorganisms in industrial fluids. An advantage of the present invention is that the pesticidal compositions of the present invention reduce the amount of pesticide required to obtain satisfactory biological control.

Important applications of the synergistic pesticidal compositions of the invention include microorganisms such as bacteria, fungi and algae in aqueous media and large organisms such as zebra mussels, blue mussels and Asian clams. Controlling growth. The compositions of the present invention have unexpected synergistic activity against microorganisms and macroorganisms.

Stable hypobromite sodium is less volatile and more stable than other halogenated molecules such as sodium hypochlorite and sodium hypobromite. In addition, stable hypobromite sodium is used to obtain higher levels of effective halogen against microbial sterilization than with other halogenated antimicrobials. In addition, stabilized hypobromite sodium has resulted in reduced production of organic halogens (AOX) that can be absorbed in laboratory studies and process waters.

The present invention relates to coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7-oxabicyclo [2.2.1] heptane-2,3-dicarboxylic acid and 4,5- Stable hypobromite sodium is combined with at least one compound selected from the group consisting of dichloro-2-ene-octyl-4-isothiazolin-3-one to provide better biological control. The combination of the two pesticides leads to unexpectedly better results and allows the use of either one of the pesticides in a significantly smaller amount than the amount of each individual insecticide required to achieve the same pesticidal performance. In addition to insecticidal synergism, the use of such insecticide bonds has been shown to include coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7- combined with the reactivity and biofilm removal properties of stable hypobromite sodium Of biomass attached due to the pesticidal persistence of oxabicyclo [2.2.1] heptan-2,3-dicarboxylic acid and 4,5-dichloro-2-ene-octyl-4-isothiazolin-3-one Can result in improved removal. As known in the prior art, stable hypobromite sodium, coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7-oxabicyclo [2.2.1] heptan-2 , 3-dicarboxylic acid and 4,5-dichloro-2-ene-octyl-4-isothiazolin-3-one show pesticidal activity when used alone. However, the prior art does not teach or suggest the performance benefits of the combination or resulting synergistic behavior of the present invention.

The present invention relates generally to pesticides and, more particularly, to compositions and methods for controlling biological growth using stabilized sodium hypobromite in synergistic combinations.

Compositions of the present invention include coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7-oxabicyclo [2.2.1] heptane-2,3-dicarboxylic acid and 4, At least one compound selected from the group consisting of 5-dichloro-2-ene-octyl-4-isothiazolin-3-one and stable hypobromite sodium.

The composition of the present invention effectively controls biological growth in industrial fluids.

The present invention relates to compositions and methods for controlling biological growth in industrial fluids using synergistically bound stable hypobromite sodium. According to the invention, stable hypobromite sodium is added to the industrial fluid in combination with other compounds. Suitable compounds that can be used in combination with stable hypobromite sodium are surfactants such as coco alkyldimethylamine oxide and n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7-oxabicyclo [2.2.1 ] Non-oxidizing insecticides such as heptane-2,3-dicarboxylic acid (also known as endothall) and 4,5-dichloro-2-ene-octyl-4-isothiazolin-3one One is not limited thereto.

Biological growth can be microbiological or macrobiological in nature. Microbiological growth includes bacteria, fungi, algae and their combinations. Large biological growths include zebra mussels ( Dreissena polymorpha, Dreissena bugensis ), pearlfish ( Mytilus edulis ), and Asian clams ( Corbicula fluminea ).

Stable hypobromite sodium may be hypobromite sodium stabilized with sodium sulfamate. Hypobromite sodium can be stabilized with alkali metal sulfamate, such as sodium sulfamate. In addition, hypobromite sodium can also be stabilized with acid amide derivatives selected from the group consisting of carbonic acid, hydrogen cyanide, carboxylic acid, amino acid, sulfuric acid, phosphoric acid and boric acid.

Industrial fluids include in particular cooling water; Food, beverage and industrial process water; Pulp and paper shredder systems; Brewery pasteurizers; Sweetwater systems; Air washing system; Oilfield exploration fluids and muds; Petroleum recovery process; Industrial lubricants; Cutting fluid; Heat transfer system; Gas scrubber system; Latex system; Clay and pigment systems; Ornamental water sources; Water water pipes; Ballast water tanks and ship storage rooms.

Stable hypobromite sodium may range from about 0.05 ppm to about 1000 ppm total residual oxidant (such as chlorine) and coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7- The amount of the compound selected from the group consisting of oxabicyclo [2.2.1] heptane-2,3-dicarboxylic acid and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is about 0.05 ppm to about 1000 ppm of the active ingredient (the amount of the compound in the industrial fluid is called the active ingredient). Here, "total residual oxidant" is defined as hypobromite or hypobromosic acid, expressed in chlorine, and includes chemical bonds of the two compounds with ammonia or organic nitrogen-containing compounds.

As used herein, the term “stabilized hypobromite sodium” refers to NaOBr stabilized with sodium sulfamate. However, NaOBr can be stabilized with other stabilizers including acid amide derivatives of carbonic acid, hydrogen cyanide, carboxylic acids, amino acids, sulfuric acid, phosphoric acid and boric acid. In addition, the stabilizer may be selected from the group of compounds having NH or NH ₂ groups attached to a functional group that desorbs electrons such as C═O, S═O, P═O or B═O.

Stabilization of NaOBr is desirable to prevent imbalances in halates and halides on storage. As a result of stabilization, these pesticides can be stored more safely because less bromate is produced, fewer organic molecules containing halogen are formed, and volatility is reduced. Stable aqueous alkali or alkaline earth metal hypobromite solutions have the following form:

a. Mixing with a chlorine an aqueous solution of an alkaline or alkaline earth metal hypochlorite having from about 5% to about 70% effective halogen with a water soluble bromine ion source;

b. Reacting the bromine ion source with an alkali or alkaline earth metal hypochlorite to form a 0.5 to 70 wt% unstable aqueous alkali or alkaline earth metal hypobromite solution;

c. Adding a constant amount of aqueous alkali metal sulfamate solution to an unstable solution of alkali or alkaline earth metal hypobromite to provide an about 0.5 to about 7 molar ratio of alkali metal sulfamate to alkali or alkaline earth metal hypobromite; And

d. It can be prepared by recovering a stable aqueous alkali or alkaline earth metal hypobromite solution.

Stable hypobromite sodium (STABREX®) used in the present invention is available from Nalco Chemicals, Naperville, Illinois.

The synergistic compositions of the invention may be added separately to industrial fluids or formulated in simple mixtures comprising the essential ingredients thereof.

Stable hypobromite sodium sometimes acts synergistically against microorganisms when combined with other non-oxidizing insecticides or surfactants. The above description is also expected to apply to compositions and methods for controlling the growth of large organisms in industrial fluids that include the combination of stable hypobromite sodium and other non-oxidizing insecticides. Examples of other non-oxidizing insecticides include glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide (DBNPA), 2-bromo-2-nitropropane-1,3 diol, 1-bromo- 1- (bromomethyl) -1,3-propanedicarbonitrile, tetrachloroisophthalonitrile, alkyldimethylbenzylammonium chloride (ADBAC), dimethyl dialkyl ammonium chloride, poly (oxyethylene (dimethylimino) ethylene (die Methyliminooethylene dichloride, methylene bisthiocyanate (MBT), 2-decylthioethanamine (DTEA), tetrakishydroxymethyl phosphonium sulfate (THPS), dithiocarbamate, cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-1-ethanol, 2- (2-bromo-2-nitroethenyl) furan (BNEF), beta-bromo-beta-nitrostyrene (BNS), beta-nitrostyrene (NS), beta-nitrovinyl furan (NVF), 2-bromo-2-bromomethyl-glutaronitrile (BBMGN), bis ( Richloromethyl) sulfone, S- (2-hydroxypropyl) thiomethanesulfonate, tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione, 2- (thiocyanomethyl Thio) benzothiazole (TCTMB), 2-bromo-4'-hydroxyacetophenone, 1,4-bis (bromoacetoxy) -2-butene, bis (tributyltin) oxide (TBTO), copper Sulfate, 2- (t-butylamino) -4-chloro-6- (ethylamino) -s-triazine, dodecylguanidine acetate and dodecylguanadine hydrochloride (DGH).

The following examples are examples of the present invention and are intended to show those skilled in the art how to make and use the invention. This embodiment is not intended to limit the invention or its protection in any way.

Synergy is determined by the equation for the calculation of the synergy index determined by: Cool, F.C., Iceman, P.C., Sylwestrowix, H.D. And industrially accepted methods as described by Mayer, R. L. Applied Microbiology, 9: 538-541 (1961).

Q _a / Q _A + Q _b / Q _B = synergy index (SI)

Where

Q _A = concentration (ppm) of Compound A acting alone, indicating an endpoint;

Q _a = concentration of Compound A in the mixture, in ppm, representing the endpoint;

Q _B = concentration of Compound B acting alone indicating the endpoint (ppm);

Q _b = concentration of Compound B in the mixture representing the endpoint, in ppm.

Antagonism occurs when the sum of Q _a / Q _A and Q _b / Q _B is greater than 1.0. When the sum is 1.0, additivity appears, and when the sum is 1.0 or less, synergy is demonstrated.

Example 1

Chlorella sorokiniana green algae were allowed to grow in Proteose medium for 3 weeks, harvested by centrifuge and resuspended in synthetic cooling water (pH 8.2). For evaluation, 96-well tissue culture microplates (FALCON® 3075) wells were prepared with 200 μl of the indicated pesticide in synthetic coolant. 100 μl of Chlorella sorokiniana cell suspension (10 colony forming units per ml (CFU)) was injected into each microplate well providing a total of 300 μl volume. The microplates were covered with the provided lids and incubated at 25 ° C. for 6 days with a 16 hour / 8 hour light / dark cycle (cool-white fluorescent lamp, 1255 lux). After incubation, the suspension was removed by aspiration from each microplate well and chlorophyll was extracted from the remaining cells using dimethyl sulfoxide (DMSO). Reduction of algal cell chlorophyll content due to algal activity was measured using optical density at 650 nm (Beckman Biomec® plate reader) of each extract. As shown in Table 1 below, synergy was observed.

Pesticide Insecticide amount (ppm) Optical Density (OD _{650 nm} ) Synergy index ¹ radish radish 0.412 A 16 0.097 A 8 0.293 A 4 0.356 A 2 0.373 A One 0.396 A 0.5 0.412 A 0.25 0.390 B 16 0.057 B 8 0.085 B 4 0.192 B 2 0.196 B One 0.251 B 0.5 0.279 B 0.25 0.369 A / B 8 / 0.5 0.122 0.750 A / B 1/1 0.216 0.563 A / B 0.5 / 1 0.243 0.531 A / B 0.25 / 1 0.210 0.516

A = STABREX® stabilized hypobromite sodium, available from Nahlko Chemical, Naperville, Illinois, and pesticides were measured in total residual oxidant (ppm).

B = 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, available from Rohm and Haas Corporation, Philadelphia. Pesticides were measured in terms of active ingredient (ppm).

The ¹ endpoint used for the synergy index calculation was OD ₆₅₀ = 0.250.

Example 2

The experimental protocol described above in Example 1 was used. However, the experimental inoculum for this example was 100 μl of Scenedesmus obliquus green algae (10 ⁶ CFU / ml). As shown in Table 2, synergy was observed.

Pesticide Insecticide amount (ppm) Optical Density (OD _{650 nm} ) Synergy index ¹ radish radish 0.164 A 32 0.051 A 16 0.095 A 8 0.108 A 4 0.134 A 2 0.161 A One 0.149 A 0.5 0.156 C 256 0.044 C 128 0.046 C 64 0.048 C 32 0.063 C 16 0.092 C 8 0.105 C 4 0.118 A / C 16/4 0.071 0.625 A / C 16/8 0.066 0.750 A / C 8/8 0.075 0.500 A / C 8/16 0.066 0.750 A / C 4/16 0.063 0.625

A = STABREX® stabilized hypobromite sodium, available from Nahlko Chemical, Naperville, Illinois, and pesticides were measured in total residual oxidant (ppm).

C = coco alkyldimethylamine oxide measured in ppm as active ingredient.

The ¹ endpoint used to calculate the synergy index was OD ₆₅₀ = 0.080.

Example 3

Green algae isolated from a cooling tower in Malaysia were grown for several days in Bold's Basal Medium, then collected by centrifugation and resuspended in synthetic cooling water (pH 8.2). For evaluation, 12-well tissue culture microplates (FALCON®) wells were prepared in 4 ml algal suspension (OD = 0.15) and the indicated pesticides were taken. Plates were incubated at 25 ° C. for 24 hours with constant illumination. After incubation, 1 ml samples were removed from each microplate well and the chlorophyll in each sample was extracted using 90% acetone and standard tricolor spectrophotometric procedures (Standard Method for Investigating Water and Wastewater, 19th Edition (1995)). Measured. The results are shown in Table 3 below, and the percentage reduction in chlorophyll was recorded for untreated control cultures. Synergy was shown.

Pesticide Insecticide amount (ppm) Percent reduction in chlorophyll Synergy index ¹ radish radish 0 A 32 68.74 A 16 34.12 A 8 26.98 A 4 0 A 2 0 A One 0 A 0.5 0 D 16 100 D 12 86.52 D 8 66.27 D 4 37.47 D 2 19.12 D One 7.91 A / D 2/2 51.20 0.310 A / D 4/2 46.61 0.380 A / D 8/2 42.83 0.500 A / D 1/4 54.94 0.530 A / D 2/4 61.82 0.560 A / D 4/4 64.54 0.630

A = STABREX® stabilized hypobromite sodium, available from Nahlko Chemical, Naperville, Illinois, and pesticides were measured in total residual oxidant (ppm).

D = Tetra-alkyl phosphonium chloride available as Bellaside® 350 from NJ, Princeton, FMC and pesticides were measured in ppm active ingredient.

^One endpoint used for the synergy index calculation was ≧ 40% chlorophyll reduction.

While the invention has been described above in connection with preferred or exemplary embodiments, these embodiments are not intended to be exhaustive or limited to the invention. Rather, the present invention is intended to embrace all alternatives, modifications and equivalents falling within its spirit and scope as defined in the appended claims.

Claims (19)

Stabilized hypobromite sodium and coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7-oxabicyclo [2.2.1] heptane-2,3-dicarboxylic acid and 4 A composition for controlling biological growth in industrial fluid, comprising an effective amount of at least one compound selected from the group consisting of, 5-dichloro-2-n-octyl-4-isothiazolin-3-one. The composition of claim 1, wherein said biological growth is microbiological growth. The composition of claim 2, wherein the microbiological growth is selected from the group consisting of bacteria, fungi, algae and combinations thereof. The composition of claim 1, wherein said biological growth is a large biological growth. 5. The composition of claim 4, wherein said large biological growth is selected from the group consisting of zebra mussels, pearl mussels and Asian clams. The composition of claim 1, wherein said stabilized hypobromite sodium is hypobromite sodium stabilized with sodium sulfamate. 7. The composition of claim 6 wherein the hypobromite sodium is stabilized with alkali metal sulfamate. 7. The composition of claim 6, wherein the hypobromite sodium is stabilized with an acid amide derivative selected from the group consisting of carbonic acid, hydrogen cyanide, carboxylic acid, amino acid, sulfuric acid, phosphoric acid and boric acid. The method of claim 1, wherein the industrial fluid is coolant; Food, beverage and industrial process water; Pulp and paper shredder systems; Brewery pasteurizers; Soft water system; Air washing system; Oilfield exploration fluids and muds; Petroleum recovery process; Industrial lubricants; Cutting fluid; Heat transfer system; Gas scrubber system; Latex system; Clay and pigment systems; Ornamental water sources; Water water pipes; A composition comprising a ballast water tank and a vessel storage compartment. The method of claim 1 wherein the amount of stabilized hypobromite is from about 0.05 ppm to about 1000 ppm total residual oxidant, coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7-oxa The amount of compound selected from the group consisting of bicyclo [2.2.1] heptane-2,3-dicarboxylic acid and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is about 0.05 ppm To about 1000 ppm of the active ingredient. As a method for controlling biological growth in industrial fluids, stable hypobromite sodium and coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7-oxabicyclo [2.2.1] To control the effective biological growth control amount of at least one compound selected from the group consisting of heptane-2,3-dicarboxylic acid and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one Adding to the process. 12. The method of claim 11, wherein said biological growth is microbiological growth. 13. The method of claim 12, wherein said microbiological growth is selected from the group consisting of bacteria, fungi, algae and combinations thereof. 12. The method of claim 11, wherein said biological growth is large biological growth. 15. The method of claim 14, wherein said large biological growth is selected from the group consisting of zebra mussels, pearl mussels, and Asian clams. 12. The system of claim 11, wherein the industrial fluid is coolant; Food, beverage and industrial process water; Pulp and paper shredder systems; Brewery pasteurizers; Soft water system; Air washing system; Oilfield exploration fluids and muds; Petroleum recovery process; Industrial lubricants; Cutting fluid; Heat transfer system; Gas scrubber system; Latex system; Clay and pigment systems; Ornamental water sources; Water water pipes; And a ballast water tank and a vessel storage compartment. 12. The method of claim 11, wherein the amount of stabilized hypobromite sodium is from about 0.05 ppm to about 1000 ppm total residual oxidant, and said coco alkyldimethylamine oxide, n-coco alkyltrimethylenediamine, tetra-alkyl phosphonium chloride, 7 The amount of the compound selected from the group consisting of -oxabicyclo [2.2.1] heptane-2,3-dicarboxylic acid and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is about 0.05 ppm to about 1000 ppm active ingredient. Compositions for controlling large biological growth in industrial fluids, such as glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol, 1- Bromo-1- (bromomethyl) -1,3-propanedicarbonitrile, tetrachloroisophthalonitrile, alkyldimethylbenzylammonium chloride, dimethyl dialkyl ammonium chloride, poly (oxyethylene (dimethyliminoo) ethylene (die Methylimino) ethylene dichloride, methylene bisthiocyanate, 2-decylthioethanamine, tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate, cyanodithioimidocarbonate, 2-methyl-5-nitro Imidazole-1-ethanol, 2- (2-bromo-2-nitroethenyl) furan, beta-bromo-beta-nitrostyrene, beta-nitrostyrene, beta-nitrovinyl furan, 2-bromo-2 Bromomethyl Glutaronitrile, Bis (Trickle) Rhomethyl) sulfone, S- (2-hydroxypropyl) thiomethanesulfonate, tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione, 2- (thiocyanomethylthio ) Benzothiazole, 2-bromo-4'-hydroxyacetophenone, 1,4-bis (bromoacetoxy) -2-butene, bis (tributyltin) oxide, copper sulfate, (2-t- Butylamino) -4-chloro-6- (ethylamino) -s-triazine, dodecylgluanidine acetate, and dodecylgluanidine hydrochloride comprising a combination of stable hypobromite sodium with a compound selected from the group consisting of A composition, characterized in that. Methods for controlling large biological growth in industrial fluids include stable hypobromite sodium and glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1, 3 diol, 1-bromo-1- (bromomethyl) -1,3-propanedicarbonitrile, tetrachloroisophthalonitrile, alkyldimethylbenzylammonium chloride, dimethyl dialkyl ammonium chloride, poly (oxyethylene (dimethylimi) Nio) ethylene (dimethylimino) ethylene dichloride, methylene bisthiocyanate, 2-decylthioethanamine, tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate, cyanodithioimidocarbonate, 2-methyl-5 Nitroimidazole-1-ethanol, 2- (2-bromo-2-nitroethenyl) furan, beta-bromo-beta-nitrostyrene, beta-nitrostyrene, beta-nitrovinyl furan, 2-bromo 2-bromomethyl article Rutaronitrile, bis (trichloromethyl) sulfone, S- (2-hydroxypropyl) thiomethanesulfonate, tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione, 2 -(Thiocyanomethylthio) benzothiazole, 2-bromo-4'-hydroxyacetophenone, 1,4-bis (bromoacetoxy) -2-butene, bis (tributyltin) oxide, copper Effective antimicrobial binding of compounds selected from the group consisting of sulfate, 2- (t-butylamino) -4-chloro-6- (ethylamino) -s-triazine, dodecylguanidine acetate and dodecylguanidine hydrochloride Adding to the industrial fluid.