CN101058450A - Synergistic biocidal mixtures - Google Patents
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- CN101058450A CN101058450A CNA2007101064265A CN200710106426A CN101058450A CN 101058450 A CN101058450 A CN 101058450A CN A2007101064265 A CNA2007101064265 A CN A2007101064265A CN 200710106426 A CN200710106426 A CN 200710106426A CN 101058450 A CN101058450 A CN 101058450A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Synergistic mixtures of biocides and their use to control the growth of microorganisms in aqueous systems are disclosed. The method of using the synergistic mixtures entails adding an effective amount of a nitrogenous compound activated by an oxidant and at least one non-oxidizing biocide to an aqueous system. The amount of activated nitrogenous compound and non-oxidizing biocide is selected to result in a synergistic biocidal effect.
Description
The application is the denomination of invention submitted on July 11st, 2003 dividing an application for No. 03819956.4 Chinese invention patent application of " Synergistic biocidal mixtures ".
CROSS-REFERENCE TO RELATED APPLICATIONS
The application relates to the 60/405th, No. 235 U.S. Provisional Patent Application of submission on August 22nd, 2002, and requires its right of priority.
Invention field
The synergistic mixt (or combination (combination)) that the present invention relates to biocide with and at the control aqueous system, more specifically be industrial process waters, the most particularly be the application in the microbial growth in paper pulp and the sheet processing system.
Background of invention
The growth that microorganism lacks control can produce serious consequence, as product degraded or damage, product is contaminated and hinder important commercial run on a large scale.Microorganism especially has problem being exposed to the surface growth of water (for example: recirculation system, heat exchanger, DC heating and cooling system, paper pulp and sheet processing system etc.), because the indigenous microorganism population can form microbial film.Decide on environment, microbial film can develop into the thick gel agglomerate that is known as cement (slime).The microorganism that produces cement comprises bacterium, airborne transmission microorganism, sulphate reducing bacteria, filamentous bacterium, product genus bacillus, fungi and algae.
The existence of cement can be disturbed many technologies, system and production, so the generation of cement in full scale plant especially is a problem.For example, the cement settling damages wooden cooling tower and aggravation corrosion when it is deposited into the metallic surface of cooling water system.In addition, the cement settling is easy to stop up or silt up the heat exchange or the cooling efficiency of pipeline, valve and under meter and reduction heat exchange surface.
The generation of cement has disadvantageous effect to paper production.Paper pulp and paper mill systems turn round under the condition that can promote microorganism growth and often cause silting up problem.And, microorganism can form a large amount of can from the system surface removal and with paper bonded cement settling, this causes the scraps of paper to disconnect and the problem of tearing increases.In addition, cement can cause on the finished product generating ugly fault and hole point, and cause quality product to descend or product defective.Make like this and must close paper-making process, thereby cause the loss of production time for cleaning equipment.
The cleaning and the health position of the water system of producing from brew-house, winery, dairy factory and other food and drink industry, cement also is exceptionable.And, sulphate reducing bacteria manufacturing issue in the secondary recovery of the oil of being everlasting or oil drilling water generally speaking.Sulphate reducing bacteria can form the cement settling.Yet the real problem that sulphate reducing bacteria brings is that they can be incorporated in the established microbial film, and produces and to have the very deleterious by product of objectionable odor, and can cause the corrosion of metallic surface by quickening galvanic action.For example, these microorganisms can reduce and be present in vitriol in the injection water, produce hydrogen sulfide.Hydrogen sulfide with stinking smell (being the rotten egg smell) is corrosive, and generates insoluble iron sulfide corrosion products with the metallic surface reaction.
Because exist temperature to raise and the antihygienic situation of environment in many metals processing factory, it is common problem that bacterial pollutant is bred in lubricant and cutting fluid.Because microbial contamination often has to abandon these liquid.
In order to control the problem in the aforesaid various Industrial processes, many biocides (being biocide) have been applied to eliminating, have suppressed or have reduced microbial growth.These biocides are applied to prevent or control the problem that is caused by microorganism growth alone or in combination.
Biocide is divided into oxidation or non-oxide type according to their chemical constitution and binding mode.Oxidation or non-oxide biocide are to use or be used in combination the character that depends on problematic microorganism, adds the medium of biocide separately, and comprise the industrial particular requirement that safety and management aspect are considered.
The oxidation biocide is widely used in industry and has decades, especially in the paper pulp and paper production that use strong oxidizer controlling microbial population.The important aspect that the oxidation biocide is applied to the microbiological manipulation project is that to use the oxidation biocide of sufficient amount residual to keep free oxygenant in technological process.This may go wrong in the water of productive use of the dissolved that contains high density and particulate inorganic and organic substance.Such water of productive use to " demand " of oxygenant higher and variable (be oxygenant can with inorganic and organic substance take place to send out should, and cause it to lose efficacy as biocide).Therefore, the kind of the inorganic and organic substance in the processing stream and quantity will determine the demand of oxygenant.For example, the oxidation biocide is by mineral-type such as ferrous, reductive manganese, sulfide, sulphite etc. and organic compound such as cellulosic fibre and depletion of additive.Therefore, owing to inorganic in these systems and organic substance concentration raise gradually, add disadvantageous physical condition such as temperature and pH, the demand of system will improve.
For the demand that overcomes system and to reach free oxygenant residual, must add the oxygenant of capacity.Although it is simple technically to surpass demand to be fed into a large amount of oxidation biocides, this is also impracticable.Not only adding the ratio rising has increased processing cost, and many bad side effects also can occur in industrial system.These side effects are that system is dependent.
In paper manufacturing systems, as the growth of strong oxidizer through being usually used in controlling microbial of clorox in case the detrimentally affect in the major structure paper technology.Yet, be that machine causes the more problem that overcomes than them through regular meeting as the strong oxidizer of clorox.In paper manufacturing systems, the consumption of especially erosion rate rising of the side effect of strong oxidizer, other valuable slurry chemical product of dye well (for example, rumbling compound, dry strength and wet strength additives and sizing material) raises, and reduce work-ing life.
It is found that, be the effective biocides (U.S.5,976,386) that can be used for industrial use through clorox activatory brometo de amonio.This biocide is effective especially in paper pulp and paper production system.Particularly, the microflora in the brometo de amonio minimizing system effectively (being the set and the bacterium that swims), and help from surface removal cement settling.And different with other common oxygenant project, it does not influence other paper pulp and paper production process and functional additive (for example wetting and dry strength additive, sizing material, dyestuff etc.) when playing this effect.As if consider the benefit of bromination ammonium biocide project, this activity chemistry thing class has and hypochlorite or the different binding mode of other strong oxidizers.Therefore, the significant synergistic discovery between clorox activatory brometo de amonio and other biocide is unexpected.
The manufacture method of the 6th, 222, No. 071 U.S. Patent Publication high-quality chloramines, wherein the binding mixture of clorox and ammonia and ammonium salt reacts at low temperatures.
Summary of the invention
The present invention aims to provide through the synergistic mixt of oxygenant activatory nitrogenous compound and non-oxide biocide (or combination).In addition, thus the present invention also provide by in water system, use significant quantity through oxygenant activatory nitrogenous compound and non-oxide biocide to produce the method that synergy is controlled at the microbial population in the industrial process waters.
The present invention relates to can be used for controlling microorganism in microorganism growth in the water system and the control industrial production system has a problem that the growth of control ground caused some in conjunction with and technology.More specifically, the present invention relates to some mixture (or combination) application in preventing industrial process waters in the microorganism growth and technology or the method that prevents microorganism growth in the industrial process waters.
This model mixture (or combination) and technology (method) contain the present composition, and it demonstrates beat all synergy to microorganism.Particularly, the present invention aims to provide mixture through oxygenant activatory nitrogenous compound and non-oxide biocide (or combination) and uses through oxygenant activatory nitrogenous compound and at least a non-oxide biocide to produce synergistic method to water system.
Embodiment
The present invention aims to provide the novel Synergistic biocidal mixtures (or combination) that is used for water system, and it contains through oxygenant activatory nitrogenous compound and at least a non-oxide biocide.These novel Synergistic biocidal mixtures (or combination) can effectively suppress or control microbial growth in this water system when being used in combination with water system.The present invention also aims to provide by using in water system or add the as described herein less than 1 index of cooperation to produce through at least a non-oxide biocide of oxygenant activatory nitrogenous compound and significant quantity of significant quantity, thereby suppresses or the method for controlling microbial growth.
This unexpectedly provides the biocidal effect stronger than independent composition through oxygenant activatory nitrogenous compound when working in coordination with use with non-oxide biocide in water system.Microbicidel mixture of the present invention (or combination) has can not be by the Acarasiales activity extremely of the height of the known activity precognition of forming this each composition of bonded.The enhanced activity of this mixture (or combination) allows to reduce greatly the total amount of the required biocide of effective treating water system.
The nitrogenous compound that is used for the present invention includes but not limited to ammonium salt.Other nitrogenous compound comprises methylamine; dimethylamine; thanomin; quadrol; diethanolamine; trolamine; the dodecyl thanomin; the hexadecyl thanomin; ethanolamine oleate; Triethylenetetramine (TETA); dibutylamine; Tributylamine; glutamine; dilaurylamine; distearyl amine; butter-methylamine; cocounut oil-methylamine; the N-acetyl glucosamine; pentanoic; the ethanol methylamine; diisopropanolamine (DIPA); methylphenylamine; N-hexyl-N-methylamine; N-heptyl-N-methylamine; N-octyl group-N-methylamine; N-nonyl-N-methylamine; N-decyl-N-methylamine; N-dodecyl-N-methylamine; N-tridecyl-N-methylamine; N-tetradecyl-N-methylamine; N-phenmethyl-N-methylamine; N-styroyl-N-methylamine; N-hydrocinnamyl-N-methylamine; N-alkyl-N-ethamine; N-alkyl-N-aminoethyle alcohol; N-alkyl-N-propylamine; N-propylheptyl-N-methylamine; N-ethylhexyl-N-methylamine; N-ethylhexyl-N-butylamine; N-styroyl-N-methylamine; N-alkyl-N-hydroxyl propylamine; N-alkyl-N-Isopropylamine; N-alkyl-N-butylamine and N-alkyl-N-isobutylamine; N-alkyl-N-hydroxyalkyl amine; hydrazine; urea; guanidine; biguanides; polyamine; primary amine; secondary amine; cyclammonium; Wyovin; low cyclammonium (oligocyclic amine); aliphatic amide; aromatic amine; the polymkeric substance that contains primary and secondary nitrogen; with and the combination.The example of ammonium salt include but not limited to brometo de amonio, volatile salt, ammonium chloride, Neutral ammonium fluoride, ammonium hydroxide, ammonium iodide, ammonium nitrate, ammonium phosphate, Ammonium sulfamate, with and combination.Preferably nitrogenous compound is brometo de amonio and ammonium chloride.
Be used for oxygenant of the present invention comprise but be not limited to chlorine, basic metal and alkaline-earth metal hypochlorite, hypochlorous acid, chlorinated isocyanuric acid ester, bromine, basic metal and alkaline-earth metal hypobromite, hypobromous acid, bromine chloride, halogenated hydantoin, ozone and superoxide such as basic metal and alkaline-earth metal perborate, basic metal and alkaline-earth metal percarbonate, basic metal and alkaline-earth metal persulphate, hydrogen peroxide, percarboxylic acids, peracetic acid, with and combination.
In a particularly preferred embodiment according to the invention, this nitrogenous compound is a brometo de amonio and oxygenant is a clorox.
The example that is used for non-oxide biocide of the present invention includes but not limited to that compound, halohydrocarbon, phenolic aldehyde, acid amides, halogen acid amide, carbamate, the ring structure of aldehyde, release formaldehyde contain the heterogeneous ring compound of nitrogen and sulphur atom, contain the close electroactive substance that activates halogen, nucleophilic active substance and the tensio-active agent with alkyl and at least one leavings group in the alpha-position and/or the vinyl position of electronegativity group.
This compound that contains aldehyde can be straight chain, side chain or fragrance.The example that can be used for aldehyde of the present invention is but is not limited to glutaraldehyde.
The compound of this release formaldehyde is preferably halogenated methylated nitro-hydrocarbon, 2-bromo-2-nitro-the third-1 for example, 3-glycol (bronopol).
This acid amides is preferably halogenated, and for example 2,2-two bromo-3-nitrilo propionic acid amides (DBNPA).
Be used for heterogeneous ring compound of the present invention comprise thiazole, isothiazolinone derivatives, with and combination.Some examples of heterogeneous ring compound include but not limited to 5-chloro-2-methyl-4-isothiazoline-3-ketone (CMIT) and 2-methyl-4-isothiazoline-3-ketone (MIT).
Be used for tensio-active agent of the present invention and comprise washing composition, wetting agent and emulsifying agent.Some examples of tensio-active agent include but not limited to long chain quaternary ammonium compound, aliphatie diamine, guanidine and biguanide compound, with and the combination.
Some close electroactive substances include but not limited to 1,2-two bromo-2,4-dicyanobutane, 2,2-two bromo-3-nitrilo propionic acid amides (DBNPA), two (trichloromethyl) sulfone, 4,5-two chloro-1,2-dithiol-3-ketone, 2-bromo-2-nitrostyrolene, 5-chloro-2-methyl-4-isothiazoline-3-ketone (CMIT), 2-methyl-4-isothiazoline-3-ketone (MIT), with and combination.
This parent's electroactive substance can be as with the compound shown in next and a plurality of structural formulas:
Wherein,
E is-COR ,-SO
2R ,-CN ,-NO
2
X is a halogen.
This nucleophilic active substance can be as with the compound shown in next and a plurality of structural formulas:
Wherein,
R is SCN (thiocyanate ion);
X is a halogen.
Other example that is used for non-oxide biocide of the present invention includes but not limited to 2-methyl-4-isothiazoline-3-ketone (MIT); 5-chloro-2-methyl-4-isothiazoline-3-ketone (CMIT); 2-n-octyl group-4-isothiazoline-3-ketone; 4; 5-two chloro-2-(n-octyl group)-4-isothiazoline-3-ketone; 1; the 2-benzisothiazole-3-ketone; glutaraldehyde; Phthalyldicarboxaldehyde; 2; 2-two bromo-3-nitrilo propionic acid amides (DBNPA); 2-bromo-2-nitrostyrolene; the 2-nitrostyrolene; 2-bromo-4 '-hydroxy acetophenone; methylene radical dithiocyanogen acid esters (MBT); 2-(thiocyanomethylthio) benzothiazole; 3-iodine proyl-N-butyl carbamate; n-alkyl dimethyl phenmethyl ammonium chloride; Timbercote 2000; thiazolinyl dimethyl ethyl ammonium chloride; 4; 5-two chloro-1; 2-dithiol-3-ketone; the last of the ten Heavenly stems sulfenyl ethamine; 2-bromo-2-nitro the third-1; the 3-glycol; hydrochloric acid n-Cyprex; acetate n-Cyprex; chlorination 1-(3-chlorallyl)-3; 5; 7-three azepines-1-nitrogen diamantane; 1; 2-two bromo-2; the 4-dicyanobutane; two (1; the 4-acetyl bromide)-2-butylene; two (1; 2-acetobrom oxygen base) ethane; two (trichloromethyl) sulfone; diiodomethyl p-methylphenyl sulfone; sodium-o-phenyl phenolate; tetrahydrochysene-3; 5-dimethyl-2H-1; 3; 5-hydrazine-2-thioketones; the cationic salts of dithiocarbamate derivative; 4-chloro-3-methylphenol; 2; 4,4 '-three chloro-2 '-hydroxyl-diphenyl ethers and poly-(oxygen ethene (dimethyl iminio) ethylidene (dimethyl iminio) ethylidene perchloride).
The nitrogenous compound that this is activated and the ratio of non-oxide biocide are about 10,000: 1-1: 400, be preferably about 5,000: 1-1: 80.
Biocidal mixtures of the present invention or method are effective with breeding to microbial growth in control and inhibition water system and the adding formula water system (additive aqueous systems).Water system comprises industrial water system such as cooling water system, paper pulp and paper systems, petroleum operation, industrial lubricants and refrigerant, the water of opening a mine, oxidation pond, color lake (lakes) and pond (ponds).Water system comprises adding formula water system.In addition, wherein can use water system of the present invention and include but not limited to that those relate to paint, leather, timber, wood pulp, wood chip, starch, clay, retention aid, sizing material, defoamer, do the system that reaches wet strength additives, pigment slurry (for example precipitated chalk), protein material, timber, animal's leather, plant owse, makeup, cosmetic composition, emulsion, tackiness agent, coating, metal working fluid, swimming pool water, textiles, heat exchanger, pharmaceutical composition, geological drilling lubricant and agrochemical composition.Adding formula water system is to add the water system that maybe will be injected towards in the bigger water system.This water adds the formula system to be included but not limited to retention aid, sizing material, defoamer, does and wet strength additives and pigment slurry.
Effectively use non-oxide biocide required for the present invention and depend on the character of handled water system, microorganism level in the water system and required inhibition degree usually through the dosage of oxygenant activatory nitrogenous compound.Those skilled in the art need not too much test can determine necessary amount.
In weight the weight of handled water system (promptly based on), be per approximately 0.1/1000000th part of (ppm)-100ppm through oxygenant activatory nitrogenous compound based on the effective concentration of activity level, be preferably about 0.5ppm to 50ppm.The selected amount that is used for the collaborative non-oxide biocide of bonded depends on used particular chemicals.Usually, the amount of non-oxide biocide, based on activity level and in the weight of handled water system, for about 0.01ppm to 40ppm.Therefore, the lower limit of required biocide density and the upper limit depend on used specific biocide or biocide combination substantially.
This can add water system through oxygenant activatory nitrogenous compound before non-oxide biocide, perhaps this non-oxide biocide can add before oxygenant activatory nitrogenous compound, and perhaps they can add simultaneously.
In a specific embodiments,, then non-oxide biocide is joined in the water system controllably adding behind oxygenant activatory nitrogenous compound.This non-oxide biocide adds after oxygenant activatory nitrogenous compound adds system at this.Add between nitrogenous compound and the non-oxide biocide the timed interval can for but be not limited to 3 hours or 2 hours or 1.5 hours or 1 hour or 30 minutes or 15 minutes.
In another embodiment, after adding non-oxide biocide, should join in the water system through oxygenant activatory nitrogenous compound.This adds after non-oxide biocide joins system through oxygenant activatory nitrogenous compound.Add between biocide and the nitrogenous compound the timed interval can for but be not limited to 3 hours or 2 hours or 1.5 hours or 1 hour or 30 minutes or 15 minutes.
In another embodiment, this is added in the water system simultaneously through oxygenant activatory nitrogenous compound and non-oxide biocide.
In any specific embodiments, this can knownly arbitrarily can provide the method through oxygenant activatory nitrogenous compound of desired concn to add in water system through oxygenant activatory nitrogenous compound.With similar through the adding of oxygenant activatory nitrogenous compound, in any specific embodiments, this non-oxide biocide can knownly arbitrarily can provide the method through oxygenant activatory nitrogenous compound of desired concn to add in water system.Activated nitrogenous compound and non-oxide biocide each or both can be continuously, be interrupted or alternately be fed in the water system.
These one or more biocides can be used as independent material or combine in the system of being added to other material in the water system that adds the system that handles.For example, these one or more biocides can be with starch, clay, pigment slurry, precipitated chalk, retention aid, sizing material, do and wet strength additives, defoamer or other are used for the additive of the production of paper pulp or sheet paper products.
This biocide can be continuously, be interrupted or alternately add entry and/or add in the formula system.The kind that is fed into the growth that strategy depends on microbial population, problematic microorganism of above-mentioned interpolation biocide and the degree that silt up on the surface in particular system.For example, can non-oxide biocide be added discontinuously being added in the system continuously, or introduce by other feed points (promptly short or long loop, broke storage chest (broke chest), economizer, thick stock, mixing pit, head box (head box)) that adds in formula system handles (being starch makedown solution, retention makedown solution, precipitated chalk slurry etc.) or the water system through oxygenant activatory brometo de amonio.
Embodiment
To claim quantitative through clorox activatory brometo de amonio and claim quantitative non-oxide biocide to add in the bacterial suspension.Whether it grows after measuring the incubation appropriate time, thereby determines this biocide bonded effectiveness.
To claim quantitatively in clorox activatory brometo de amonio adds bacterial suspension, cell suspension by incubation seclected time, is added afterwards and claims quantitative selected non-oxide biocide to this suspension.Render a service by its definite this biocide bonded of whether growing after measuring extra incubation appropriate time.
To claim quantitative selected non-oxide biocide to add in the bacterial suspension and the time that this cell suspension incubation is selected, adding claims quantitative through clorox activatory brometo de amonio in suspension afterwards.Render a service by its definite this biocide bonded of whether growing after measuring extra incubation appropriate time.
Adopt dosage to determine the effect of this active substance and mixture.Its activity is assessment in 5.5 and 8.0 the synthetic plain boiled water (synthetic white water) in the pH value.Artificial bacterial consortium with six kinds of bacterial isolateses containing about equal amount is measured this material.Although strain subject is the representational microorganism that occurs in the paper manufacturing systems, its effect is not limited to these bacteriums.Wherein two kinds of bacterial strains are Klebsiella pneumonia (Klebsiella pneumonia, ATCC 13883) and Pseudomonas aeruginosa (Pseudomonas aeruginosa, ATCC 15442).Four kinds of bacterial strains in addition are to separate from paper manufacturing systems and be accredited as wilting bacillus pumilis (Curtobacteriumflaccumfaciens), onion bulkholderia cepasea (Burkholderia cepacia), Morocco genus bacillus (Bacillus maroccanus) and Pseudomonas glathei (Pseudomonas glathei).All bacterial strains all are incubated overnight under 37 ℃, are suspended in the sterile saline afterwards.Merge then with each bacterial strain of volume with the preparation consortium.With this bacterial consortium with in the presence of the active substance of various concentration, be not dispensed in the hole of microtiter plate.With this microtiter plate at 37 ℃ of following incubations.(t when initial
0) and at 4 hours (t of incubation
4) after read out in optical density(OD) under the 650nm.
Raw data is converted into " bacterial growth inhibition percentage " according to following formula:
% inhibiting rate=[(a-b) ÷ a] * 100
Wherein,
A is (to impinging upon t
nThe time OD)-(to impinging upon t
0The time OD)
B is that (handled thing is at t
nThe time OD)-(handled thing is at t
0The time OD)
Can inhibiting value be mapped by the dosage of each activeconstituents and specific mixture.Can calculate 50% inhibiting rate (I by the dose response curve that is made
50) time dosage.In following embodiment (chart), I
50Value representation is per 1,000,000/umber (ppm) of active substance.
By F.C.Kull, P.C.Eisman, H.D.Sylwestrowicz and R.L.Mayer (1961), Applied Microbiology 9, the described Equation for Calculating index of cooperation of 538-541 (SI).These values are based on reaching the required amount of specific terminal point.The selected terminal point that is used for these researchs is 50% inhibiting rate of bacterial growth.
Index of cooperation (SI)=(QA ÷ Qa)+(QB ÷ Qb)
Wherein:
The quantity of compd A in mixture when QA=reaches terminal point
Independently the work quantity of compd A when reaching terminal point of Qa=
The quantity of compd B in mixture when QB=reaches terminal point
Independently the work quantity of compd B when reaching terminal point of Qb=
If less than 1, then there is synergy in SI; If greater than 1, then there is antagonistic action in SI; If SI equals 1, then there is adduction.
Following embodiment is used for illustration the present invention.But these embodiment are intended to limit the present invention or its protection domain absolutely not.These embodiment explanations are with the obtained conspiracy relation of the present composition.
Embodiment
Embodiment 1
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the antagonistic action between the 2-bromo-2-nitrostyrolene (BNS).
| BNS *&AmBr@pH 5.5 | ||||
| ppm BNS | ppm AmBr | Ratio BNS: AmBr | The % inhibiting rate | Index of cooperation |
| 0.76 0.94 0.90 0.93 0.89 0.84 0.34 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 25.00 29.89 | 100∶0 1.2∶1.0 1.0∶1.7 1.0∶3.4 1.0∶7.0 1.0∶14.9 1.0∶73.1 0∶100 | 50 50 50 50 50 50 50 50 | 1.00 1.25 1.23 1.32 1.38 1.51 1.28 1.00 |
| BNS *&AmBr@pH 8.0 | ||||
| ppm BNS | ppm AmBr | Ratio BNS: AmBr | The % inhibiting rate | Index of cooperation |
| 2.48 3.79 5.06 3.93 3.10 4.23 5.64 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 25.00 42.14 | 100∶0 4.8∶1.0 3.2∶1.0 1.3∶1.0 1.0∶2.0 1.0∶3.0 1.0∶4.4 0∶100 | 50 50 50 50 50 50 50 50 | 1.00 1.55 2.08 1.66 1.40 2.01 2.87 1.00 |
* BNS-2-bromo-2-nitrostyrolene
Embodiment 2
Present embodiment explanation is adopted between adding when postponing in 1 hour to be fed into strategy successively, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the synergy between the 2-bromo-2-nitrostyrolene (BNS).By progressively using biocide, the negative interaction between the activeconstituents is minimized and/or is eliminated, and makes biocidal effect improve.
| BNS *&AmBr@pH 5.5 | ||||
| ppm BNS | ppm AmBr | Ratio BNS: AmBr | The % inhibiting rate | Index of cooperation |
| 0.77 0.57 0.62 0.58 0.50 0.17 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 14.67 | 100∶0 1.0∶1.4 1.0∶2.5 1.0∶5.4 1.0∶12.5 1.0∶74.4 0∶100 | 50 50 50 50 50 50 50 | 1.00 0.80 * 0.92 * 0.97 * 1.08 1.07 1.00 |
| BNS *&AmBr@pH 8.0 | ||||
| ppm BNS | ppm AmBr | Ratio BNS: AmBr | The % inhibiting rate | Index of cooperation |
| 2.19 1.78 1.84 1.67 1.03 0.40 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 15.91 | 100∶0 2.3∶1.0 1.2∶1.0 1.0∶1.9 1.0∶6.1 1.0∶31.4 0∶100 | 50 50 50 50 50 50 50 | 1.00 0.86 * 0.94 * 0.96 * 0.86 * 0.97 * 1.00 |
* BNS-2-bromo-2-nitrostyrolene
Embodiment 3
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) and 2-bromo-2-nitro-the third-1 of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0,3-glycol (bronopol, BNPD) synergy between.
| BNPD *&AmBr @pH 5.5 | ||||
| ppm BNPD | ppm AmBr | Ratio BNPD: AmBr | The % inhibiting rate | Index of cooperation |
| 1.16 1.12 1.14 1.11 0.87 0.23 0.00 | 0 0.78 1.56 3.13 6.25 12.50 15.41 | 100∶0 1.4∶1.0 1.0∶1.4 1.0∶2.8 1.0∶7.2 1.0∶55.4 0∶100 | 50 50 50 50 50 50 50 | 1.00 1.01 1.08 1.15 1.15 1.01 1.00 |
| BNPD *&AmBr@pH 8.0 | ||||
| ppm BNPD | ppm AmBr | Ratio BNPD: AmBr | The % inhibiting rate | Index of cooperation |
| 1.34 1.08 1.11 1.03 0.89 0.46 0.00 | 0 0.78 1.56 3.13 6.25 12.50 19.53 | 100∶0 1.4∶1.0 1.0∶1.4 1.0∶3.0 1.0∶7.0 1∶27.0 0∶100 | 50 50 50 50 50 50 50 | 1.00 0.84 * 0.91 * 0.93 * 0.98 * 0.99 * 1.00 |
* BNPD-2-bromo-2-nitro the third-1, the 3-glycol
Embodiment 4
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) and 1 of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0,2-two bromo-2, the synergy between the 4-dicyanobutane (DBDCB).
| DBDCB *&AmBr@pH 5.5 | ||||
| ppm DBDCB | ppm AmBr | Ratio DBDCB: AmBr | The % inhibiting rate | Index of cooperation |
| 2.70 2.81 2.86 2.50 2.19 2.00 1.33 1.25 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 0.78 1.56 2.38 3.13 6.25 12.50 14.37 19.67 21.82 19.88 26.04 22.07 22.99 | 100∶0 3.6∶1.0 1.8∶1.0 1.1∶1.0 1.0∶1.4 1.0∶3.1 1.0∶9.4 1.0∶11.5 1.0∶31.5 1.0∶69.8 1.0∶127.2 1.0∶333.3 1.0∶564.9 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.07 1.13 1.03 0.94 * 1.01 1.04 1.09 1.09 1.07 0.92 * 1.16 0.97 * 1.00 |
| DBDCB *&AmBr@pH 8.0 | ||||
| ppm DBDCB | ppm AmBr | Ratio DBDCB: AmBr | The % inhibiting rate | Index of cooperation |
| 1.85 2.27 1.91 1.42 1.25 1.31 0.96 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 0.78 1.56 3.13 5.65 6.25 12.50 17.78 21.80 23.36 25.93 29.65 30.71 | 100∶0 2.9∶1.0 1.2∶1.0 1.0∶2.2 1.0∶4.5 1.0∶4.8 1.0∶13.0 1.0∶28.5 1.0∶69.8 1.0∶149.5 1.0∶332.0 1.0∶758.9 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.25 1.08 0.87 * 0.86 * 0.91 * 0.93 * 0.92 * 0.88 * 0.85 * 0.89 * 0.99 * 1.00 |
* DBDCB-1,2-two bromo-2,4-dicyanobutane
Embodiment 5
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) and 2 of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0, the synergy between the 2-two bromo-3-nitro propionic acid amides (DBNPA).
| DBNPA & AmBr@pH 5.5 | ||||
| ppm DBNPA | ppm AmBr | Ratio DBNPA: AmBr | The % inhibiting rate | Index of cooperation |
| 3.08 3.50 3.39 3.29 3.35 2.72 2.50 1.25 0.63 0.31 0.16 0.08 0.04 0.02 0.00 | 0 0.78 1.56 3.13 6.25 12.50 13.79 19.16 20.32 19.83 20.56 20.07 19.56 19.49 20.86 | 100∶0 4.5∶1.0 2.2∶1.0 1.1∶1.0 1.0∶1.9 1.0∶4.6 1.0∶5.5 1.0∶15.3 1.0∶32.5 1.0∶63.5 1.0∶131.6 1.0∶256.9 1.0∶500.7 1.0∶997.9 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.18 1.18 1.22 1.39 1.48 1.47 1.33 1.18 1.05 1.04 0.99 * 0.95 * 0.94 * 1.00 |
| DBNPA & AmBr@ pH 8.0 | ||||
| ppm DBNPA | ppm AmBr | Ratio DBNPA: AmBr | The % inhibiting rate | Index of cooperation |
| 2.86 2.99 3.23 3.05 2.94 2.66 2.50 1.25 0.63 0.31 0.16 0.08 0.04 0.02 0.00 | 0 0.78 1.56 3.13 6.25 12.50 14.09 19.22 20.19 20.24 20.78 20.70 20.83 21.24 21.90 | 100∶0 3.8∶1.0 2.1∶1.0 1.0∶1.0 1.0∶2.1 1.0∶4.7 1.0∶5.6 1.0∶15.4 1.0∶32.3 1.0∶64.8 1.0∶133.0 1.0∶265.0 1.0∶533.4 1.0∶1087.2 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.08 1.20 1.21 1.32 1.50 1.52 1.32 1.14 1.03 1.00 0.97 * 0.97 * 0.98 * 1.00 |
* DBNPA-2,2-two bromo-3-nitrilo propionic acid amides
Embodiment 6
When the present embodiment explanation is adopted delay in 1 hour to be fed into strategy successively between adding, act on the activated brometo de amonio (AmBr) and 2 of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0, the synergy between the 2-two bromo-3-nitro propionic acid amides (DBNPA).By progressively using biocide, the negative interaction between the activeconstituents is minimized and/or is eliminated, and obtains the improvement of wider biocidal effect.
| DBNPA & AmBr@pH 5.5 | ||||
| ppm DBNPA | ppm AmBr | Ratio DBNPA: AmBr | The % inhibiting rate | Index of cooperation |
| 3.09 2.50 2.04 1.95 1.69 1.89 1.79 1.25 0.63 0.31 0.16 0.08 0.04 0.02 0.00 | 0 0.24 0.78 1.56 3.13 6.25 12.50 18.32 20.53 22.85 19.30 20.32 19.07 18.86 17.81 | 100∶0 10.4∶1.0 2.6∶1.0 1.2∶1.0 1.0∶1.9 1.0∶3.3 1.0∶7.0 1.0∶14.7 1.0∶32.8 1.0∶73.1 1.0∶123.5 1.0∶260.1 1.0∶488.2 1.0∶965.5 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 0.82 * 0.70 * 0.72 * 0.72 * 0.96 * 1.28 1.43 1.35 1.38 1.13 1.17 1.08 1.06 1.00 |
| DBNPA & AmBr@pH 8.0 | ||||
| ppm DBNPA | ppm AmBr | Ratio DBNPA: AmBr | The % inhibiting rate | Index of cooperation |
| 2.33 1.66 1.59 1.60 1.77 2.17 1.25 0.63 0.31 0.16 0.08 0.04 0.02 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 20.20 21.43 22.07 21.31 21.46 21.86 22.00 22.35 | 100∶0 2.1∶1.0 1.0∶1.0 1.0∶2.0 1.0∶3.5 1.0∶5.8 1.0∶16.2 1.0∶34.3 10∶70.6 1.0∶136.4 1.0∶274.7 1.0∶559.7 1.0∶1126.6 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 0.75 * 0.75 * 0.83 * 1.04 1.49 1.44 1.23 1.12 1.02 0.99 * 0.99 * 0.99 * 1.00 |
* DBNPA-2,2-two bromo-3-nitrilo propionic acid amides
Embodiment 7
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) and 4 of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0,5-two chloro-1, the synergy between 2-dithiol-3-ketone (dithiol).
| Dithiol *& AmBr@pH 5.5 | ||||
| The ppm dithiol | ppm AmBr | Ratio dithiol: AmBr | The % inhibiting rate | Index of cooperation |
| 0.63 0.59 0.41 0.25 0.06 0 | 0 1.56 3.13 6.25 12.50 20.85 | 100∶0 1.0∶2.7 1.0∶7.6 1.0∶25.3 1.0∶197.8 0∶100 | 50 50 50 50 50 50 | 1.00 1.00 0.80 * 0.69 * 0.70 * 1.00 |
| Dithiol *& AmBr@pH 8.0 | ||||
| The ppm dithiol | ppm AmBr | Ratio dithiol: AmBr | The % inhibiting rate | Index of cooperation |
| 0.84 0.51 0.29 0.15 0.04 0 | 0 1.56 3.13 6.25 12.50 20.59 | 100∶0 1∶3.0 1∶10.8 1∶42.7 1∶318.5 0∶100 | 50 50 50 50 50 50 | 1.00 0.69 * 0.50 * 0.48 * 0.65 * 1.00 |
* dithiol-4,5-two chloro-1,2-dithiol-3-ketone
Embodiment 8
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the synergy between the N-Cyprex (DGH).
| DGH *& AmBr@pH 5.5 | ||||
| ppm DGH | ppm AmBr | Ratio DGH: AmBr | The % inhibiting rate | Index of cooperation |
| 3.11 3.13 3.46 3.52 3.63 2.50 2.17 1.25 0.63 0.31 0.16 0.08 0.04 0.02 0.01 0.00 | 0.00 1.25 2.50 5.00 10.00 17.51 20.00 24.48 28.51 29.82 29.29 29.99 27.13 26.61 25.16 25.88 | 100∶0 2.5∶1.0 1.4∶1.0 1.0∶1.4 1.0∶2.8 1.0∶7.0 1.0∶9.2 1.0∶19.6 1.0∶45.6 1.0∶95.4 1.0∶187.5 1.0∶383.8 1.0∶694.5 1.0∶1362.5 1.0∶2576.7 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.05 1.21 1.32 1.55 1.48 1.47 1.35 1.30 1.25 1.18 1.18 1.06 1.03 0.98 * 1.00 |
| DGH *& AmBr@pH 8.0 | ||||
| ppm DGH | ppm AmBr | Ratio DGH: AmBr | The % inhibiting rate | Index of cooperation |
| 1.84 1.82 1.75 1.76 1.63 1.25 1.09 0.63 0.31 0.16 0.08 0.04 0.02 0.01 0.00 | 0.00 1.25 2.50 5.00 10.00 22.05 20.00 26.54 29.99 31.33 30.18 29.26 28.04 28.19 29.42 | 100∶0 1.5∶1.0 1.0∶1.4 1.0∶2.8 1.0∶6.1 1.0∶17.6 1.0∶18.3 1.0∶42.5 1.0∶96.0 1.0∶200.5 1.0∶386.4 1.0∶749.0 1.0∶1435.8 1.0∶2887.2 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.03 1.04 1.13 1.23 1.43 1.28 1.24 1.19 1.15 1.07 1.02 0.96 * 0.96 * 1.00 |
* DGH-hydrochloric acid N-Cyprex
Embodiment 9
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the synergy between N-alkyl (60%C14,30%C16,5%C12,5%C18) the dimethyl benzene ammonio methacrylate (ADBAC).
| ADBAC *& AmBr@pH 5.5 | ||||
| ppm ADBAC | ppm AmBr | Ratio ADBAC: AmBr | The % inhibiting rate | Index of cooperation |
| 3.11 3.14 3.26 3.18 3.24 2.50 1.74 1.25 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 10.00 16.33 20.00 23.85 24.06 24.90 24.80 25.78 24.75 26.45 | 100∶0 2.5∶1.0 1.3∶10 1.0∶1.6 1.0∶3.1 1.0∶6.5 1.0∶11.5 1.0∶19.1 1.0∶38.5 1.0∶79.7 1.0∶158.7 1.0∶330.0 1.0∶633.6 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.06 1.15 1.21 1.42 1.42 1.32 1.30 1.11 1.04 0.99 * 1.00 0.95 * 1.00 |
| ADBAC *& AmBr@pH 8.0 | ||||
| ppm ADBAC | ppm AmBr | Ratio ADBAC: AmBr | The % inhibiting rate | Index of cooperation |
| 2.42 2.85 2.71 2.56 2.50 2.41 1.36 1.25 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 7.69 10.00 20.00 21.03 22.36 22.81 24.43 24.80 24.52 25.12 | 100∶0 2.3∶1.0 1.1∶1.0 1.0∶2.0 1.0∶3.1 1.0∶4.1 1.0∶14.7 1.0∶16.8 1.0∶35.8 1.0∶73.0 1.0∶156.3 1.0∶317.5 1.0∶627.8 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.22 1.22 1.25 1.34 1.39 1.36 1.35 1.15 1.04 1.04 1.02 0.99 * 1.00 |
* ADBAC-N-alkyl (60%C14,30%C16,5%C12,5%C18) dimethyl benzene ammonio methacrylate
Embodiment 10
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the synergy between the Timbercote 2000 (DIDAC).
| DIDAC *& AmBr@pH 5.5 | ||||
| ppm DIDAC | ppm AmBr | Ratio DIDAC: AmBr | The % inhibiting rate | Index of cooperation |
| 1.82 1.82 1.65 1.66 1.75 1.25 1.01 0.63 0.31 0.15 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 10.00 20.09 20.00 21.43 23.48 23.41 21.23 23.74 23.91 | 100∶0 1.5∶1.0 1.0∶1.5 1.0∶3.0 1.0∶5.7 1.0∶16.1 1.0∶19.7 1.0∶34.3 1.0∶75.1 1.0∶149.8 1.0∶271.8 1.0∶607.8 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.05 1.01 1.12 1.38 1.53 1.39 1.24 1.15 1.07 0.93 * 1.01 1.00 |
| DIDAC *& AmBr@pH 8.0 | ||||
| ppm DIDAC | ppm AmBr | Ratio DIDAC: AmBr | The % inhibiting rate | Index of cooperation |
| 1.62 1.53 1.50 1.38 1.28 1.25 0.91 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 10.00 16.27 20.00 21.90 22.95 21.26 24.58 25.58 26.87 | 100∶0 1.2∶1.0 1.0∶1.7 1.0∶3.6 1.0∶7.8 1.0∶13.0 1.0∶21.9 1.0∶35.0 1.0∶73.5 1.0∶136.1 1.0∶314.6 1.0∶654.9 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 0.99 * 1.02 1.04 1.16 1.38 1.31 1.20 1.05 0.89 * 0.96 * 0.98 * 1.00 |
* DIDAC-Timbercote 2000
Embodiment 11
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the synergy between the glutaraldehyde (Glut).
| Glut *& AmBr@pH 5.5 | ||||
| ppm Glut | ppm AmBr | Ratio Glut: AmBr | The % inhibiting rate | Index of cooperation |
| 2.06 1.64 1.76 1.76 1.64 1.21 0.46 0.00 | 0.00 0.47 0.94 1.88 3.75 7.50 15.00 19.31 | 100∶0 3.5∶1.0 1.9∶1.0 1.0∶1.1 1.0∶2.3 1.0∶6.2 1.0∶32.4 0∶100 | 50 50 50 50 50 50 50 50 | 1.00 0.82 * 0.90 * 0.95 * 0.99 * 0.98 * 1.00 1.00 |
| Glut *& AmBr@pH 8.0 | ||||
| ppm Glut | ppm AmBr | Ratio Glut: AmBr | The % inhibiting rate | Index of cooperation |
| 6.68 5.73 5.64 5.59 4.98 3.95 1.05 0.00 | 0 0.47 0.94 1.88 3.75 7.50 15.00 22.31 | 100∶0 12.2∶1.0 6.0∶1.0 3.0∶1.0 1.3∶1.0 1.0∶1.9 1.0∶14.3 0∶100 | 50 50 50 50 50 50 50 50 | 1.00 0.88 * 0.89 * 0.92 * 0.91 * 0.93 * 0.83 * 1.00 |
* Glut-glutaraldehyde
Embodiment 12
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) and 1 of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0, the synergy between the 2-benzisothiazole-3-ketone (BIT).
| BIT *& AmBr@pH 5.5 | ||||
| ppm BIT | ppm AmBr | Ratio BIT: AmBr | The % inhibiting rate | Index of cooperation |
| 1.62 3.11 4.64 7.25 13.49 20.00 10.00 5.00 2.50 1.25 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 10.00 34.14 28.36 29.53 30.48 29.80 27.99 28.35 26.70 26.82 26.60 28.34 | 100∶0 2.5∶1.0 1.9∶1.0 1.5∶1.0 1.3∶1.0 1.0∶1.7 1.0∶2.8 1.0∶5.9 1.0∶12.2 1.0∶23.8 1.0∶44.8 1.0∶90.7 1.0∶170.9 1.0∶343.3 1.0∶680.9 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.97 2.95 4.66 8.69 13.57 7.18 4.12 2.62 1.82 1.37 1.19 1.04 1.00 0.96 * 1.00 |
| BIT *& AmBr@pH 8.0 | ||||
| ppm BIT | ppm AmBr | Ratio BIT: AmBr | The % inhibiting rate | Index of cooperation |
| 3.59 6.12 7.29 13.09 17.65 20.00 10.00 5.00 2.50 1.25 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 10.00 53.51 46.91 40.07 39.69 37.03 35.86 36.32 34.26 33.78 33.49 35.90 | 100∶0 4.9∶1.0 2.9∶1.0 2.6∶1.0 1.8∶1.0 1.0∶2.7 1.0∶4.7 1.0∶8.0 1.0∶15.9 1.0∶29.6 1.0∶57.4 1.0∶116.2 1.0∶219.3 1.0∶432.4 1.0∶857.3 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.74 2.10 3.78 5.19 7.06 4.09 2.51 1.80 1.38 1.17 1.10 1.00 0.96 * 0.94 * 1.00 |
* BIT-1, the 2-benzisothiazole-3-ketone
Embodiment 13
The present embodiment explanation is fed into strategy down simultaneously, act on the activated brometo de amonio (AmBr) and 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone (isothiazolinone, ISO) synergy between of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0.
| iso *& AmBr@pH 5.5 | ||||
| ppm Iso | ppm AmBr | Ratio Iso: AmBr | The % inhibiting rate | Index of cooperation |
| 0.14 0.13 0.12 0.11 0.09 0.07 0.02 0.00 | 0.00 0.39 0.78 1.56 3.13 6.25 12.50 18.98 | 100∶0 1.0∶2.9 1.0∶6.4 1.0∶14.4 1.0∶34.8 1.0∶87.6 1.0∶647.9 0∶100 | 50 50 50 50 50 50 50 50 | 1.00 0.94 * 0.88 * 0.84 * 0.79 * 0.82 * 0.79 * 1.00 |
| Iso *& AmBr@pH 8.0 | ||||
| ppm Iso | ppm AmBr | Ratio Iso: AmBr | The % inhibiting rate | Index of cooperation |
| 0.15 0.15 0.13 0.12 0.10 0.08 0.03 0.00 | 0.00 0.39 0.78 1.56 3.13 6.25 12.50 23.28 | 100∶0 1.0∶2.5 1.0∶5.9 1.0∶13.5 1.0∶31.0 1.0∶81.6 1.0∶394.2 0∶100 | 50 50 50 50 50 50 50 50 | 1.00 1.08 0.95 * 0.87 * 0.83 * 0.80 * 0.76 * 1.00 |
* Iso-isothiazolinone-5-chloro-2-methyl-4-isothiazoline-3-Tong ﹠amp; The mixture of 2-methyl-4-isothiazoline-3-ketone
Embodiment 14
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) and 4 of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0,5-two chloro-2-just-synergy between octyl group-3 (2H)-isothiazolinone.
| DCOI *& AmBr@pH 5.5 | ||||
| ppm DCOI | ppm AmBr | Ratio DCOI: AmBr | The % inhibiting rate | Index of cooperation |
| 0.39 0.43 0.42 0.34 0.31 0.37 0.25 0.16 0.08 0.04 0.02 0.01 0.00 | 0.00 1.25 2.50 5.00 7.73 10.00 20.00 27.76 30.11 29.64 28.69 29.22 28.13 | 100∶0 1.0∶2.9 1.0∶5.9 1.0∶14.8 1.0∶24.7 1.0∶27.3 1.0∶79.2 1.0∶177.7 1.0∶385.4 1.0∶758.9 1.0∶1469.1 1.0∶2991.7 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.14 1.17 1.05 1.08 1.30 1.36 1.39 1.27 1.15 1.07 1.06 1.00 |
| DCOI *& AmBr@pH 8.0 | ||||
| ppm DCOI | ppm AmBr | Ratio DCOI: AmBr | The % inhibiting rate | Index of cooperation |
| 1.49 1.43 1.44 1.36 1.25 1.17 0.79 0.63 0.31 0.16 0.08 0.04 0.02 0.01 0.00 | 0.00 1.25 2.50 5.00 8.61 10.00 20.00 26.55 29.28 32.48 34.33 34.40 32.89 33.04 34.50 | 100∶0 1.1∶1.0 1.0∶1.7 1.0∶3.7 1.0∶6.9 1.0∶8.5 1.0∶25.5 1.0∶42.5 1.0∶93.7 1.0∶207.8 1.0∶439.4 1.0∶880.7 1.0∶1684.0 1.0∶3383.6 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.00 1.04 1.06 1.09 1.08 1.11 1.19 1.06 1.05 1.05 1.02 0.97 * 0.96 * 1.00 |
* DCOI-4,5-two chloro-2-n-octyl group-3 (2H)-isothiazolinone
Embodiment 15
Present embodiment explanation is fed into strategy down simultaneously, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the synergy between methylene radical two thiocyanic ester (MBTC).
| MBT *& AmBr@pH 5.5 | ||||
| ppm MBT | ppm AmBr | Ratio MBT: AmBr | The % inhibiting rate | Index of cooperation |
| 0.36 0.39 0.38 0.37 0.31 0.21 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 19.98 | 100∶0 1.0∶2.0 1.0∶4.1 1.0∶8.5 1.0∶20.3 1.0∶60.3 0∶100 | 50 50 50 50 50 50 50 | 1.00 1.14 1.14 1.20 1.18 1.21 1.00 |
| MBT *& AmBr@pH 8.0 | ||||
| ppm MBT | ppm AmBr | Ratio MBT: AmBr | The % inhibiting rate | Index of cooperation |
| 0.71 0.65 0.63 0.53 0.47 0.34 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 27.80 | 100∶0 1.0∶1.2 1.0∶2.5 1.0∶5.9 1.0∶13.2 1.0∶36.6 0∶100 | 50 50 50 50 50 50 50 | 1.00 0.95 * 0.95 * 0.87 * 0.90 * 0.93 * 1.00 |
* MBTC-methylene diisocyanate
Embodiment 16
Present embodiment explanation is adopted between adding when postponing in 1 hour to be fed into strategy successively, acts on the activated brometo de amonio (AmBr) of the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and the synergy between methylene radical two thiocyanic ester (MBTC).By progressively using biocide, the negative interaction between the activeconstituents is minimized and/or is eliminated, and obtains the improvement of wider biocidal effect.
| MBT& AmBr@pH 5.5 | ||||
| ppm MBT | ppm AmBr | Ratio MBT: AmBr | The % inhibiting rate | Index of cooperation |
| 0.38 0.46 0.39 0.36 0.31 0.25 0.16 0.08 0.04 0.04 0.02 0.01 0.00 | 0.00 0.78 1.56 3.13 3.73 6.25 9.43 11.08 12.50 12.52 13.08 13.64 13.82 | 100∶0 1.0∶1.7 1.0∶4.0 1.0∶8.7 1.0∶11.9 1.0∶25.4 1.0∶60.4 1.0∶141.8 1.0∶307.9 1.0∶320.5 1.0∶669.8 10∶1396.3 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.26 1.15 1.17 1.09 1.10 1.09 1.01 1.01 1.01 1.00 1.01 1.00 |
| MBTC& AmBr@pH 8.0 | ||||
| ppm MBT | ppm AmBr | Ratio MBT: AmBr | The % inhibiting rate | Index of cooperation |
| 0.73 0.85 0.68 0.63 0.48 0.33 0.31 0.16 0.12 0.08 0.04 0.02 0.01 0.00 | 0.00 0.78 1.56 1.65 3.13 6.25 7.04 10.54 12.50 13.10 13.23 14.67 14.59 15.19 | 100∶0 1.1∶1.0 1.0∶2.3 1.0∶2.6 1.0∶6.5 1.0∶18.7 1.0∶22.5 1.0∶67.5 1.0∶101.1 1.0∶167.6 1.0∶338.6 1.0∶751.3 1.0∶1494.0 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.21 1.03 0.96 * 0.86 * 0.87 * 0.89 * 0.91 * 0.91 * 0.97 * 0.92 * 0.99 * 0.97 * 1.00 |
* MBT-methylene diisocyanate
Embodiment 17
Present embodiment explanation is fed into strategy down simultaneously, the synergy between the activated brometo de amonio (AmBr) that acts on the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and pair (trichloromethyl) sulfone (sulfone).
| Sulfone *& AmBr@pH 5.5 | ||||
| The ppm sulfone | ppm AmBr | Ratio sulfone: AmBr | The % inhibiting rate | Index of cooperation |
| 1.87 1.68 1.27 1.40 1.25 1.12 0.63 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 6.69 10.00 18.16 20.00 23.72 25.58 27.38 26.79 27.44 | 100∶0 1.3∶1.0 1.0∶2.0 1.0∶3.6 1.0∶5.3 1.0∶9.0 1.0∶29.1 1.0∶31.9 1.0∶75.9 1.0∶163.7 1.0∶350.5 1.0∶685.8 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 0.95 * 0.77 * 0.93 * 0.91 * 0.96 * 1.00 * 1.06 1.03 1.02 1.04 1.00 1.00 |
| Sulfone *& AmBr@pH 8.0 | ||||
| The ppm sulfone | ppm AmBr | Ratio sulfone: AmBr | The % inhibiting rate | Index of cooperation |
| 8.42 8.38 8.57 8.18 7.59 5.00 3.62 2.50 1.25 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 1.25 2.50 5.00 10.00 16.93 20.00 23.75 29.92 32.44 33.68 32.56 32.32 32.17 33.80 | 100∶0 6.7∶1.0 3.4∶1.0 1.6∶1.0 1.0∶1.3 1.0∶3.4 1.0∶5.5 1.0∶9.5 1.0∶23.9 10∶51.9 1.0∶107.8 1.0∶208.4 1.0∶413.7 1.0∶823.6 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.03 1.09 1.12 1.20 1.09 1.02 1.00 1.03 1.03 1.03 0.98 * 0.97 * 0.96 * 1.00 |
* sulfone-two (trichloromethyl) sulfone
Embodiment 18
Present embodiment explanation is adopted between adding when postponing in 1 hour to be fed into strategy successively, the synergy between the activated brometo de amonio (AmBr) that acts on the artificial bacterial consortium in the synthetic plain boiled water of pH5.5 and 8.0 and pair (trichloromethyl) sulfone (sulfone).By progressively using biocide, the negative interaction between the activeconstituents is minimized and/or is eliminated, and obtains the improvement of wider biocidal effect.
| Sulfone *& AmBr@pH 5.5 | ||||
| The ppm sulfone | ppm AmBr | Ratio sulfone: AmBr | The % inhibiting rate | Index of cooperation |
| 4.44 6.48 6.93 5.97 4.99 5.80 5.00 2.50 1.25 0.63 0.31 0.16 0.08 0.04 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 21.02 23.78 25.91 28.44 29.87 24.86 30.32 29.59 39.23 | 100∶0 8.3∶1.0 4.4∶1.0 1.9∶1.0 1.0∶1.3 1.0∶2.2 1.0∶4.2 1.0∶9.5 1.0∶20.7 1.0∶45.5 1.0∶95.6 1.0∶159.1 1.0∶388.0 1.0∶757.5 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.48 1.60 1.42 1.28 1.62 1.66 1.17 0.94 * 0.87 * 0.83 * 0.67 * 0.79 * 0.76 * 1.00 |
| Sulfone *& AmBr@pH 8.0 | ||||
| The ppm sulfone | ppm AmBr | Ratio sulfone: AmBr | The % inhibiting rate | Index of cooperation |
| 10.25 10.04 11.61 11.64 7.28 6.11 5.00 2.50 1.25 0.63 0.31 0.16 0.08 0.00 | 0.00 0.78 1.56 3.13 6.25 12.50 12.92 17.51 17.81 18.84 20.29 17.83 18.46 32.19 | 100∶0 12.8∶1.0 7.4∶1.0 3.7∶1.0 1.2∶1.0 1.0∶2.0 1.0∶2.6 1.0∶7.0 1.0∶14.2 1.0∶30.1 1.0∶64.9 1.0∶114.1 1.0∶236.3 0∶100 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 | 1.00 1.00 1.18 1.23 0.90 * 0.98 * 0.89 * 0.79 * 0.68 * 0.65 * 0.66 * 0.57 * 0.58 * 1.00 |
* sulfone-two (trichloromethyl) sulfone
Although described the present invention with regard to its specific specific embodiments, obviously, many other forms of the present invention and change it will be apparent to those skilled in the art that.Appended claims and the present invention should be considered to contain all this tangible form and changes that belong within the spirit and scope of the invention usually.
Claims (26)
1. method of controlling microorganism growth in the water system, it comprise in water system add significant quantity through oxygenant activatory ammonium salt and at least a non-oxide biocide, the amount of described activated ammonium salt and non-oxide biocide is through selecting the index of cooperation to be less than 1, and described non-oxide biocide is selected from following group: aldehyde, the compound of release formaldehyde, halohydrocarbon, phenolic aldehyde, acid amides, carbamate, ring structure contains the heterogeneous ring compound of nitrogen and sulphur atom, the close electroactive substance that activates halogen is contained in alpha-position and/or vinyl position at the electronegativity group, nucleophilic active substance with alkyl and at least one leavings group, aliphatie diamine, guanidine, biguanides, n-alkyl dimethyl phenmethyl ammonium chloride, Timbercote 2000.
2. the method for claim 1, wherein said ammonium salt comprises brometo de amonio or ammonium chloride.
3. the method for claim 1, wherein said oxygenant is to be selected from following group: chlorine, basic metal and alkaline-earth metal hypochlorite, hypochlorous acid, chlorinated isocyanuric acid ester, bromine, basic metal and alkaline-earth metal hypobromite, hypobromous acid, bromine chloride, halogenated hydantoin, ozone, superoxide with and combination.
4. method as claimed in claim 3, wherein said superoxide be selected from basic metal and alkaline-earth metal perborate, basic metal and alkaline-earth metal percarbonate, basic metal and alkaline-earth metal persulphate, hydrogen peroxide, percarboxylic acids, peracetic acid with and combination.
5. the method for claim 1, wherein said oxygenant comprises hypochlorous acid or basic metal and alkaline-earth metal hypochlorite.
6. the method for claim 1, wherein said close electroactive substance comprises a member in the compound that is selected from shown in one or more following structural:
Wherein
E is-COR ,-SO
2R ,-CN ,-NO
2
X is a halogen.
7. the method for claim 1, wherein said nucleophilic active substance comprises a member in the compound that is selected from shown in one or more following structural:
Wherein
R is SCN;
X is a halogen.
8. the method for claim 1, wherein said at least a non-oxide biocide comprises 2,2-two bromo-3-nitrilo propionic acid amides.
9. the method for claim 1, wherein said at least a non-oxide biocide comprises glutaraldehyde.
10. the method for claim 1, wherein said at least a non-oxide biocide is to be selected from following group: thiazole derivative, isothiazolinone derivatives with and combination.
11. the method for claim 1, wherein said at least a non-oxide biocide be selected from 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone with and combination.
12. the method for claim 1, wherein said at least a non-oxide biocide comprises 2-bromo-2-nitro-propane-1,3-glycol.
13. the method for claim 1, wherein said at least a non-oxide biocide is a hydrochloric acid dodecyl guanidine.
14. the method for claim 1, wherein said close electroactive substance is to be selected from following group: 1,2-two bromo-2,4-dicyanobutane, 2,2-two bromo-3-nitrilo propionic acid amides, two (trichloromethyl) sulfone, 4,5-two chloro-1,2-dithiol-3-ketone, 2-bromo-2-nitrostyrolene, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone with and combination.
15. the method for claim 1, wherein said at least a non-oxide biocide comprises methylene radical two thiocyanate-s.
16. the method for claim 1, the wherein activated ammonium salt and the ratio of non-oxide biocide are 10,000: 1 to 1: 400.
17. method as claimed in claim 16, the wherein activated ammonium salt and the ratio of non-oxide biocide are 5,000: 1 to 1: 80.
18. the method for claim 1, wherein and by weight based on the weight of handled water system based on activity level, the content of described activated ammonium salt is 0.1-100ppm, based on activity level and based on the weight of handled water system by weight, the content of described non-oxide biocide is 0.01-40ppm.
19. method as claimed in claim 18, wherein based on activity level by weight, the content of activated ammonium salt is 0.5 to 50ppm, based on activity level by weight the content of non-oxide biocide be 0.01 to 40ppm.
20. the method for claim 1, wherein said through oxygenant activatory ammonium salt and at least a non-oxide biocide by continuously, be interrupted or alternately be added in the water system.
21. the method for claim 1, wherein said activated ammonium salt and non-oxide biocide are added in the water system simultaneously.
22. the method for claim 1, wherein said activated ammonium salt joined in the water system before described at least a non-oxide biocide adds.
23. the method for claim 1, wherein said at least a non-oxide biocide joined in the water system before activated ammonium salt adds.
24. the method for claim 1, wherein said water system comprises industrial water system.
25. the method for claim 1, wherein said industrial water system are to be selected from following group: paper pulp and paper making water system, cooling water system and the water of opening a mine.
26. a synergistic mixt that contains through oxygenant activatory ammonium salt, non-oxide biocide and water system, wherein said non-oxide biocide such as claim 1 definition.
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| US40523502P | 2002-08-22 | 2002-08-22 | |
| US60/405,235 | 2002-08-22 | ||
| US10/266,509 | 2002-10-08 |
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| CNB038199564A Division CN1325388C (en) | 2002-08-22 | 2003-07-11 | Synergistic biocidal mixtures |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103391917A (en) * | 2010-09-21 | 2013-11-13 | 溴品有限公司 | Method for preparing bromourea |
| CN103636671A (en) * | 2009-09-29 | 2014-03-19 | 陶氏环球技术有限责任公司 | Synergistic microbicidal compositions comprising 2,2-dibromomalonamide and an oxidizing biocide |
| CN111432637A (en) * | 2017-10-18 | 2020-07-17 | 索理思科技公司 | Compositions exhibiting synergistic effects in biofilm control |
| CN112119040A (en) * | 2018-06-13 | 2020-12-22 | Ay实验室有限公司 | System and method for monitoring biocide treated process water by oxygen sensor |
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2003
- 2003-07-11 CN CNA2007101064265A patent/CN101058450A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103636671A (en) * | 2009-09-29 | 2014-03-19 | 陶氏环球技术有限责任公司 | Synergistic microbicidal compositions comprising 2,2-dibromomalonamide and an oxidizing biocide |
| CN103636671B (en) * | 2009-09-29 | 2016-01-06 | 陶氏环球技术有限责任公司 | Comprise the synergistic microbicidal compositions of 2,2-dibromo malonamide and Oxidizing biocides |
| CN103391917A (en) * | 2010-09-21 | 2013-11-13 | 溴品有限公司 | Method for preparing bromourea |
| CN103391917B (en) * | 2010-09-21 | 2016-08-17 | 溴品有限公司 | A kind of method for preparing bromourea |
| CN111432637A (en) * | 2017-10-18 | 2020-07-17 | 索理思科技公司 | Compositions exhibiting synergistic effects in biofilm control |
| CN111432637B (en) * | 2017-10-18 | 2022-10-25 | 索理思科技公司 | Compositions exhibiting synergistic effects in biofilm control |
| CN112119040A (en) * | 2018-06-13 | 2020-12-22 | Ay实验室有限公司 | System and method for monitoring biocide treated process water by oxygen sensor |
| US11427482B2 (en) | 2018-06-13 | 2022-08-30 | A.Y. Laboratories Ltd. | System and method for monitoring process water treated with a biocide using an oxygen sensor |
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