CN102176830A - Synergistic peroxide based biocidal compositions - Google Patents
Synergistic peroxide based biocidal compositions Download PDFInfo
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- CN102176830A CN102176830A CN2009801382852A CN200980138285A CN102176830A CN 102176830 A CN102176830 A CN 102176830A CN 2009801382852 A CN2009801382852 A CN 2009801382852A CN 200980138285 A CN200980138285 A CN 200980138285A CN 102176830 A CN102176830 A CN 102176830A
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- compound
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- aqueous system
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- 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
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds 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
- A01N59/14—Boron; Compounds thereof
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
Abstract
Disclosed is a method for controlling microbial growth in an aqueous system containing sulfite and/or bisulfite residues by addition of a peroxy compound at a pH of greater than 5. Also disclosed is a method for stabilizing an active halogen biocide in an aqueous system containing peroxide residues by addition of an N-hydrogen compound to the active halogen biocide before combining it with the peroxide containing aqueous system. Further disclosed is an optimized papermaking biocide program consisting of initially treating sulfite bleached pulp with peroxide followed by application of an N-hydrogen-stabilized active halogen compound to the paper producing white waters and an analytical method for determining peroxide concentrations in aqueous systems in the presence of sulfite and/or bisulfite.
Description
Technical field
The present invention relates to the method for controlling microbial growth in the aqueous system that comprises sulphite and/or bisulfite residue (solution or the suspension that obtain after for example using based on the reducing bleach of sulphite).The invention further relates to the method for stabilizing active halogen biocide in containing the peroxide aqueous system.
Background technology
Reducing bleach in papermaking by frequent application.This kind bleaching process adopts bisulfite usually or generates the solution of bisulfite.When strengthening paper brightness, the use of this kind solution also can cause residual in the slurry that is generated the sulphite residue being arranged.The sulphite residue makes slurry preserve and the control of subsequent paper machine deposition becomes more difficult, because many paper slimicides and preservative for example di-bromonitrilopropiona,ide, isothiazolinone, particularly oxidizing biocide become unstable in the presence of sulphite.
Surprisingly, have been found that applying oxidizing biocide in the system that comprises residual sulphite can not only succeed, even collaborative control of microorganisms can be provided at the pH that optimizes.Especially, have been found that after optimizing pH that available hydrogen peroxide even is handled the sulphite bleached pulp effectively synergistically, to strengthen bleaching and control of microorganisms.
Sulphite is well-known to the quick neutralization of hydrogen peroxide in the acid medium (pH＜5), and it is the basis of standard hydrogen peroxide titrimetry method.Have been found that these common inconsistent materials can coexist a period of time under the pH that raises, this time is enough to allow bleaching and control of microorganisms to be used.
Summary of the invention
According to the present invention, the growth of microorganism in the aqueous system that contains sulphite and/or bisulfite residue can be controlled in the following way: pH＞5 are regulated and maintained to aqueous system, preferred pH6-11, more preferably 7.5-10, and interpolation per-compound.PH scope that limits by upper and lower bound among the present invention and any number scope should be understood that also to comprise all subranges that are combined to form by any upper limit and any lower limit.
Preferred per-compound comprises hydrogen peroxide, inorganic peroxy compounds is alkali metal or alkaline earth metal perborate, percarbonate or persulfate for example, organic peroxide acid is peracetic acid or benzylhydroperoxide for example, other organic peroxy compound is urea peroxide for example, and the mixture of aforesaid compound.Term " persulfate " comprises single persulfate (for example, permonosulphuric acid (H simultaneously
2SO
5) salt) and peroxydisulfate (that is peroxy-disulfuric acid (H,
2S
2O
8) salt).
The effectiveness of per-compound can improve by adding bleach-activating such as tetra acetyl ethylene diamine (TAED).
Particularly preferred per-compound is a hydrogen peroxide.
In case of necessity, the pH of aqueous system can for example alkali metal or alkaline earth metal hydroxide, carbonate, heavy carbonate, borate, metasilicate or its mixture be controlled and/or are cushioned by adding alkali or basic salt.
In preferred embodiment, the concentration of this sulphite and/or bisulfite and the per-compound that just the added 1-300ppm that respectively does for oneself, the 5-200ppm that more preferably respectively does for oneself, 10-100ppm most preferably respectively does for oneself.
Can comprise pulping and papermaking, recovery paper pulping and papermaking, slurry or biomass bleaching (biomass bleaching), fabric bleaching and similarly application from the application that sulphite according to the present invention/peroxide compatibleization is benefited.
To in described aqueous system, form the peroxide or the residue of finite concentration scope owing to handle aqueous system (for example slurry slurries) with per-compound (for example hydrogen peroxide), therefore arbitrarily the follow-up biocide that applies to keep stablizing for peroxide treatment or peroxide residue be very important.Have been found that the solution that comprises hydrogen peroxide, Xi Shi paper making pulp for example, the reactive halogen of available stabilisation is successfully handled.This additional result is unexpected, because well-known active halogen species can be neutralized (because hydrogen peroxide can while as Oxidizing and Reducing Agents) in the presence of peroxide.
Also find to have active halogen species beat all stablizing in the presence of peroxide of the halogen of nitrogen combination especially.According to the present invention, the reactive halogen biocide that contains in the aqueous system of peroxide or peroxide residue can add the N-hydrogen compound to this biocide and carry out stabilisation by before reactive halogen biocide and the aqueous system that contains peroxide merge.Herein and N-hydrogen compound hereinafter be organic or inorganic compound with at least one hydrogen atom that directly is bonded to nitrogen-atoms.
This novel method is suitable for using simultaneously the application of peroxide and reactive halogen most.
The reactive halogen biocide be comprise be in oxidation state 0 or+biocide of 1 halogen (particularly chlorine or bromine, for example element chlorine or bromine and hypochlorite or hypobromite).
In preferred embodiment, the reactive halogen by N-hydrogen compound stabilisation is (with Cl
2Meter) concentration is 0.1-20ppm.Herein and statement hereinafter " with Cl
2Meter " expression is equivalent to the concentration to the elemental chlorine of reactive halogen concentration in the fixed system on the stoichiometry.
Preferred N-hydrogen compound is selected from ammonia, ammonium salt, for example ammonium sulfate and ammonium bromide; other is the nitrogenous compound of carbon containing hydrogen bond not, urea for example, biuret; isocyanuric acid and sulfamic acid, organic N-hydrogen compound, for example para toluene sulfonamide; 5,5-dialkyl group-hydantoins, sulfonyloxy methyl amine; barbiturates, methyl uracil, imidazoline; pyrrolidones, morpholine, antifebrin; acetamide, N-ethyl acetamide, phthalimide; benzamide, succimide, N-monomethylolurea; N-methyl urea, acetyl group urea, uramido methyl formate; methyl carbamate, phthaloyl hydrazine, pyrroles; indoles, formamide, N-methylformamide; dicyandiamide, urethanes, 1; 3-dimethyl biuret, aminomethyl phenyl biuret, 4; 4-dimethyl-2-oxazolidone, 6-methyluracil, 2-imidazolone; ethylidene-urea, 2-pyrimidone, azetidine-2-ketone; 2-Pyrrolidone, caprolactam, phenylsulfinyl imines; phenylsulfinyl imido grpup acid amides, diaryl-or the dialkyl group sulfenimide, isothiazoline-1; the 1-dioxide, hydantoins, glycine; piperidines, piperazine, monoethanolamine; glycine amide, creatine and glycoluril.
Preferred N-hydrogen compound is 5,5-dimethyl hydantoin, urea, ammonia or ammonium salt.
Peroxide in this aqueous system or peroxide residue be hydrogen peroxide, alkali metal or alkaline earth metal percarbonate, perborate or persulfate, organic peroxide acid or aforementioned two or more mixture, most preferably hydrogen peroxide preferably.
The advantageous applications of arbitrary discovery (that is, the synergisticing performance of the sulphite slurry of peroxide treatment and reactive halogen suppress the stability of the degraded that peroxide or peroxide residue cause) is slurry and sheet processing, recovery slurrying and papermaking, deinking, slurry bleaching, biomass bleaching, fabric bleaching or clay slurry bleaching.Preferred aqueous system is slurry and papermaking pulp-liquor and liquid, recovery slurry slurries, slurry thick stock, deinking slush pulp, slurry or biomass bleaching slurries and liquid, fabric bleaching liquid and clay slurry.
Other is preferably used and is water treatment, for example waste water, papermaking liquid and water, pond and thermal water, industrial colling, be exposed to the water of reverse osmosis filter or ion exchange resin, and in the field use that comprises the sterilization of fractionating tank and down-hole application or crust aqueous system.
Other preferably uses the aqueous system that is discovery in food and the crop protection application (comprising fruits and vegetables cleaning, meat and poultry processing, beverage processing, fish culture and aquatic products industry).
Formed the definition of the control of microorganisms scheme of the high performance-price ratio that can be used for papermaking in conjunction with these two kinds discoveries (that is, the synergisticing performance of the sulphite slurry of peroxide treatment and reactive halogen suppress the stability of the degraded that hydrogen peroxide or peroxide residue cause).This scheme comprises with sulphite carries out slurry bleaching, uses peroxide treatment then, in the presence of the reactive halogen biocide of the halogen with nitrogen combination this slurry is converted into paper again.
In preferred embodiment, this aqueous system that comprises peroxide can be by comprising the composition acquisition of at least a per-compound greater than 5 described aqueous system interpolation to pH.
In the application of preferred merging method, this aqueous system is selected from the slurries of pulping and papermaking, the slurries that reclaim slurry, slurry thick stock, deinking slush pulp, slurry or biomass bleaching slurries and liquid, fabric liquid lime chloride and clay slurry.
According to the present invention, can apply sulphite and per-compound (alternatively in conjunction with activator such as tetraacetyl ethylene diamine) by uniting, unite to apply per-compound and reactive halogen or unite to apply sulphite and per-compound and unite subsequently and apply or generate per-compound and active halogen is usually optimized cost performance.This unite apply at present by these materials fast mutually neutralization be under an embargo.The present invention has confirmed associating even the collaborative method of using the compound of these types.
Another target of the present invention is to determine the analytical method of peroxide concentrations in the aqueous system that contains sulphite and/or bisulfite.This method comprises the steps:
(i) the excessive N-stabilized hydrogen active chlorine compound that adds the amount of determining stays a certain amount of unreacted N-stabilized hydrogen active chlorine compound simultaneously to destroy this sulphite and/or bisulfite immediately,
(ii) measure the amount of unreacted N-stabilized hydrogen active chlorine compound, thereby determine sulphite and/or bisulfite concentration, and
(iii) determine peroxide concentrations.
Step (ii) in the amount of unreacted N-stabilized hydrogen active chlorine compound can measure by any methods known in the art, particularly measure by known DPD method according to ISO 7393-2.The amount of the unreacted N-stabilized hydrogen active chlorine compound that sulphite and/or bisulfite concentration record in (ii) corresponding to the amount of the N-stabilized hydrogen active chlorine compound that adds in step (i) and step poor.
The (iii) middle peroxide concentrations of step can be definite by one of methods known in the art, for example can be by adopting thiosulfatimetry to determine with potassium iodide as indicator.
The preferred N-stabilized hydrogen active chlorine compound that adopts in above-mentioned analytical method is a 1-chloro-5,5-dimethyl hydantoin (MCDMH).
Following non-limiting example purpose is more specifically to set forth the present invention.
Embodiment
Common (decimal system) logarithm of the colony forming single-digit amount of statement " 1g cfu/mL " expression in every milliliter, be term " minimizings " in conjunction with the time represent to handle before in every milliliter the colony forming single-digit amount and handle after the common logarithm of the ratio of colony forming single-digit amount in every milliliter.Unless indicate separately, all percentages or ppm concentration are the concentration based on weight.
Embodiment 1
The aqueous solution that will comprise sodium sulphite and hydrogen peroxide obtains sulphite content (with SO 21 ℃ of mixing
3 2-Meter) be that 20.0ppm and pH are 6.7 solution for 40ppm, content of hydrogen peroxide.Solution temperature is maintained 21 ℃, after mixing, measured residual sulphite and peroxide content in 15,30 and 60 minutes.This step comprises the 1-chloro-5 that adds the known quantity excessive with respect to the residual sulphite content of estimating to sample, 5-dimethyl hydantoin (MCDMH).Measure residue MCDMH concentration by the total halogen method of standard DPD then.Since sulphite under all pH rapidly in and MCDMH, the concentration of sulphite is the concentration that records that the interpolation concentration of MCDMH deducts MCDMH, equation 1 vide infra.This step is at H
2O
2Leaving is effectively, because H
2O
2Not with the MCMDH reaction, and do not disturb gross activity halogen method, because this method is approximately being carried out under the neutral pH.
(1) [sulphite]=[MCDMH
Add]-[MCDMH
Record]
H
2O
2Concentration can be by writing down the H that adopts acid thiosulfatimetry to record with the KI indicator
2O
2Concentration determine (HACH HYP-1 hydrogen peroxide test kit-Hach Co., Loveland, CO).Because this titration is carried out under acid pH, this method can obtain the H excessive with respect to sulfite concentration in the sample
2O
2Concentration.Because sulfite concentration can obtain H by MCMDH analysis and equation 1
2O
2Concentration can calculate by following equation 2:
(2) [H
2O
2]=[H
2O
2 record]+[sulphite
Calculate]
The evaluated error of this method is ± 1ppm.
This results are shown in table 1, has wherein shown even the obvious residual concentration of observed two kinds of materials after 30 minutes.
Table 1
Embodiment 2
Repeat the step of embodiment 1, difference is that the pH of mixed solution is 9.0, and measures residue concentration after mixing in 5,15,30,60,120 and 1080 minutes.The results are shown in the table 2, its co-stability that has proved hydrogen peroxide and sulphite has obtained further enhancing under pH9.0, wherein even observed the obvious residual concentration of peroxide and sulphite after 2 hours.
Table 2
Embodiment 3
Investigated the Synergistic biocidal performance of under the pH that raises, uniting when applying sulphite and hydrogen peroxide.Hereinafter the sulphite of concentration shown in the table 3 and peroxide are added into by in the following aqueous solution of forming: (a) deionized water, (b) NaHCO
3, gained carbonate buffer concentration is that 200ppm is (with CaCO
3The total alkalinity meter), (c) sulphite bleached pulp slurries, ultimate density is 0.05%, carries the related least concentration of residual sulphite of 6ppm, and (d) NaOH, to reach pH 9.0.
Micropopulation can provide in the following way: 24-48 hour preparation slurry slurries also at room temperature store before test, thereby allow the paramount testing level of growth of microorganism.For untreated control population, 1g cfu/mL=5.9 under the engaged test in 3 hours, 1g cfu/mL=6.5 under the engaged test in 24 hours.The colony that is reported counts for the oxygen bacterium of always having a liking for that is undertaken by the tryptone soya agar coated plate.This test result is shown in table 3.
Table 3
Seem that only the existence of sulphite does not obviously act on for the bacterial community under the 32-128ppm sulfite concentration.Different with it, hydrogen peroxide has shown the lower development level of sterilization effectiveness, and the 1g cfu/mL of gained reduced 1.2-3.5 in 3 hours, reduced 5.5 in 24 hours.Surprisingly, under contact in 3 hours, partially mixed sulphite/hydrogen peroxide system (Test No. 7 and 9) provides than the bigger effectiveness of independent hydrogen peroxide (Test No. 5).
Observed performance level has shown sulphite and the obvious synergy of peroxide under the peroxide concentrations that raises.The effectiveness because independent sulphite is not sterilized, viewed sulphite exist down, and the enhancing of hydrogen peroxide effectiveness is synergistic result.This result can be by people such as Kull (F.C.Kull, P.C.Elisman, H.D.Sylwestrowicz and P.K.Mayer, Appl.Microbiol, 1961,9,538) method is carried out quantitatively, has indicated in this method when observed index of cooperation according to equation 3 (SI) to have synergy less than 1.0 the time.
(3) SI=(level of A)/(level of significance of A)+(level of B)/(level of significance of B)
A is set to sulfite concentration, and B is set to peroxide concentrations, can obtain following result: because sulphite substantially can not sterilization, it is infinitely great that first denominator becomes, and making a value of winning is zero.If our level of significance is set to produce in 3 hours 1g cfu/mL is reduced to 3.5 level, second denominator becomes 160ppm (according to the Test No. 5 of table 3).Test No. 7 and 9 index of cooperation can generate bigger minimizing less than 1.0 because the target 1g cfu/mL minimizing 3.5 relevant with independent 160ppm hydrogen peroxide compared in these tests down can to obtain contact in 3 hours according to hereinafter equation 4 then.
(4)SI＝0+(＜160)/160＝(＜1.0)
Embodiment 4
Investigated under higher sulphite and concentration of hydrogen peroxide, to unite and applied the collaborative of sulphite and hydrogen peroxide.This condition is identical with embodiment 3.The micropopulation of untreated control is contact in 3 hours 1g cfu/mL=6.26 down, and contact in 24 hours is 1g cfu/mL=6.18 down.This results are shown in table 4.
Table 4
As shown in table 4, concentration is that the application of the sulphite of 128-512ppm does not obviously act on for micropopulation.Different with it, concentration is that the hydrogen peroxide of 120-160ppm has shown the lower development level of sterilization effectiveness, and the 1g cfu/mL of gained reduced 3.3-4.0 in 3 hours, reduced 3.7-5.5 in 24 hours.Equally surprisingly, the sulphite of some mixing/hydrogen peroxide system provides higher effectiveness than independent hydrogen peroxide.Observed performance level has shown sulphite and the obvious synergy of peroxide under the peroxide concentrations that raises.Render a service because sulphite itself does not show sterilization, the enhancing that hydrogen peroxide was renderd a service under viewed sulphite existed is synergistic result.Test No. 9 may fully strictly prove collaborative.Reduce 4.2 if required effect is set to 1g cfu/mL, we can see this effect that realizes of needs＞512ppm sulphite.The amount that realizes the independent hydrogen peroxide of this effect is 150ppm or higher.This has formed equation 5:
(5)SI＝32/(＞512)+(＜120)/150＝(＜0.063)+(＜0.8)＝(＜0.86)
Embodiment 5
Further having investigated the sterilization of the solution that comprises sulphite and hydrogen peroxide under the situation of no slurry renders a service.Measured to 83 and the nutriment of 830ppm sulphite under existing in the effectiveness of inhibition of the pseudomonas aeruginosa that grows.Use the Butterfield buffer solution of pH 7.0 to dilute the pseudomonas aeruginosa culture fluid that contains sulphite at 1: 99 then.Hereinafter the sulfite concentration in the table 5 is the concentration of final dilution.Then dilution is contacted 3 hours at 37 ℃ with the 50ppm hydrogen peroxide.Untreated control population (test 1) is 1g cfu/mL=6.0.This test result is shown in table 5.
Table 5
As shown in table 5, hydrogen peroxide is renderd a service (1g cfu/mL reduces 1.5) astoundingly greater than rendeing a service (1g cfu/mL reduces 0.9) to not containing the observed sterilization of the pseudomonas aeruginosa that grows under the sulphite situation for the sterilization that is diluted to the pseudomonas aeruginosa of 8.3ppm when 830ppm sulphite is grown and applied.Like this, the interpolation wonderful enhancing that sterilization is renderd a service for hydrogen peroxide by sulphite has obtained further checking when not containing slurry.
Embodiment 6
Investigated residual H
2O
2There is the stability of the active halogen species of nitrogen combination down.Measure free and total cl concn by standard DPD method, and by the total H of acid accumulator sulfite titrimetry
2O
2Concentration.MCDMH concentration is the concentration that the gross activity halogen deducts free reactive halogen.H
2O
2Concentration is that total oxide concentration deducts MCDMH concentration.With 2.1ppm (0.062mM) H
2O
2With 1ppm (0.014mM) NaOCl (with Cl
2Meter) merging makes the stoichiometry of two kinds of materials reduce immediately, the H that obtains
2O
2Residue is～1.6ppm (0.048mM), does not have the free chlorine that can survey.Above reaction and display is in equation 6.
(6)NaOCl+H
2O
2→H
2O+NaCl+O
2
H
2O
2Existing down, the inherent instability of reactive halogen is shown in table 6.
Table 6
1)-(Hach Co., Loveland CO) measure to adopt HACH HYP-1 hydrogen peroxide test kit
Embodiment 7
Investigated with hydrogen peroxide merge forward direction NaOCl solution add equimolar 5, the effect of 5-dimethyl hydantoin (DMH).It the results are shown in table 7.MCDMH concentration is free reactive halogen concentration for the gross activity halogen concentration deducts.H
2O
2Concentration is that total oxide concentration deducts MCDMH concentration.
Table 7
1)-(Hach Co., Loveland CO) measure to adopt HACH HYP-1 hydrogen peroxide test kit
The interpolation that can see DMH can be stablized active chlorine and the hydrogen peroxide when merging simultaneously.Even after 1 hour time of contact, do not observe tangible decomposition yet.
Claims (22)
1. the method for controlling microbial growth in the aqueous system that contains sulphite and/or bisulfite residue, described method comprise to pH adds the composition that comprises at least a per-compound greater than 5 described aqueous system.
2. the method for claim 1, wherein this per-compound is selected from hydrogen peroxide, alkali metal percarbonate, alkaline earth metal percarbonate, alkali metal perborate, alkaline earth metal perborate, alkali metal persulphate, alkaline earth metal persulfate, organic peroxide acid and composition thereof.
3. method as claimed in claim 2, wherein this per-compound is a hydrogen peroxide.
4. as any described method of claim 1-3, wherein said composition further comprises bleach-activating.
5. method as claimed in claim 4, wherein said bleach-activating are tetra acetyl ethylene diamine.
6. as any described method of claim 1-5, wherein this pH is between 6 and 11.
7. method as claimed in claim 6, wherein this pH is between 7.5 and 10.
8. as any described method of claim 1-7, wherein the pH of aqueous system regulates by the compound that employing is selected from alkali metal hydroxide, alkaline earth metal hydroxide, alkaline metal bicarbonate, alkaline earth metal heavy carbonate, alkali carbonate, alkaline earth metal carbonate, alkali metal silicate or its mixture.
9. as any described method of claim 1-8, the concentration of this sulphite and/or bisulfite and the per-compound that just the added 1-300ppm that respectively does for oneself wherein.
10. the method for stabilizing active halogen biocide in containing the aqueous system of peroxide, described method are included in before this reactive halogen biocide and the described aqueous system that contains peroxide merge, and add the N-hydrogen compound to this reactive halogen biocide.
11. method as claimed in claim 10, wherein by the stable reactive halogen of N-hydrogen compound (with Cl
2Meter) concentration is 0.1-20ppm.
12. as claim 10 or 11 described methods, wherein this N-hydrogen compound is selected from ammonia, ammonium salt, for example ammonium sulfate and ammonium bromide; the nitrogenous compound of carbon containing hydrogen bond not, urea for example, biuret, sulfamic acid and isocyanuric acid; the N-hydrogen compound that replaces, sulfonyloxy methyl amine for example, para toluene sulfonamide; 5,5-dialkylhydantoin, barbiturates; methyl uracil, imidazoline, pyrrolidones; morpholine, antifebrin, acetamide; N-ethyl-acetamide, phthalimide, benzamide; succimide, N-monomethylolurea, N-methyl urea; acetyl group-urea, uramido methyl formate, methyl carbamate; the phthaloyl hydrazine, pyrroles, indoles; formamide, N-methylformamide, dicyandiamide; urethanes, 1,3-dimethyl biuret; the aminomethyl phenyl biuret, 4,4-dimethyl-2-oxazolidone; the 6-methyluracil, 2-imidazolone, ethylidene-urea; the 2-pyrimidone, azetidine-2-ketone, 2-Pyrrolidone; caprolactam, phenylsulfinyl imines, phenylsulfinyl imido grpup acid amides; the diaryl sulfenimide, dialkyl group sulfenimide, isothiazoline-1; the 1-dioxide, hydantoins, glycine; piperidines, piperazine, monoethanolamine; glycine amide, creatine, glycoluril and composition thereof.
13. method as claimed in claim 12, wherein this N-hydrogen compound is 5, the 5-dimethyl hydantoin.
14. method as claimed in claim 12, wherein this N-hydrogen compound is urea, ammonia or ammonium salt.
15. as any described method of claim 10-14, wherein this peroxide is selected from hydrogen peroxide, alkali metal percarbonate, alkaline earth metal percarbonate, alkali metal perborate, alkaline earth metal perborate, alkali metal persulphate, alkaline earth metal persulfate, organic peroxide acid and composition thereof.
16. method as claimed in claim 15, wherein this peroxide is a hydrogen peroxide.
17. as any described method of claim 10-16, wherein this aqueous system is selected from the slurries of pulping and papermaking, the slurries that reclaim slurry, slurry thick stock, deinking slush pulp, slurry or biomass bleaching slurries and liquid, fabric liquid lime chloride and clay slurry.
18. as any described method of claim 10-16, wherein this aqueous system is selected from waste water, papermaking liquid and water, pond and thermal water, industrial colling, the water that is exposed to reverse osmosis filter or ion exchange resin and the aqueous system in the field use that comprises fractionating tank and down-hole application.
19. as any described method of claim 10-16, wherein this aqueous system is selected from and is used for food and crop protection and uses, and comprises fruits and vegetables cleaning, meat and poultry processing, beverage processing, fish culture and aquatic products industry, the aqueous solution.
20. as any described method of claim 10-19, wherein this aqueous system that comprises peroxide obtains by any described method of claim 1-9.
21. determine the method for peroxide concentrations in the aqueous system in the presence of sulphite and/or bisulfite, described method comprises the steps:
(i) the excessive N-stabilized hydrogen active chlorine compound that adds the amount of determining stays a certain amount of unreacted N-stabilized hydrogen active chlorine compound simultaneously to destroy this sulphite and/or bisulfite immediately,
(ii) measure the amount of unreacted N-stabilized hydrogen active chlorine compound, thereby determine sulphite and/or bisulfite concentration, and
(iii) determine peroxide concentrations.
22. method as claimed in claim 21, wherein this N-stabilized hydrogen active chlorine compound is a 1-chloro-5, the 5-dimethyl hydantoin.
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| PCT/EP2009/006975 WO2010034519A2 (en) | 2008-09-26 | 2009-09-28 | Synergistic peroxide based biocidal compositions |
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| CN103053613A (en) * | 2011-10-21 | 2013-04-24 | 纳尔科公司 | Improved biological control by using chlorine-stabilizing agent mixture |
| CN103061206A (en) * | 2011-10-21 | 2013-04-24 | 纳尔科公司 | Application of composition of sulfamic acid or salts thereof and ammonium salt and/or amine or other biocides containing halogens in papermaking field |
| CN106170458A (en) * | 2014-04-14 | 2016-11-30 | 艺康美国股份有限公司 | Slurry biocide |
| CN114680348A (en) * | 2020-12-31 | 2022-07-01 | 广东美的白色家电技术创新中心有限公司 | Cleaning device |
| CN115474609A (en) * | 2021-06-16 | 2022-12-16 | 苏州北辰新材料科技有限公司 | Disinfectant, preparation method thereof and film |
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| KR101784513B1 (en) | 2017-03-30 | 2017-10-11 | 허운덕 | Herbicide compositions for controlling pests of horticultural products comprising rare-earth elements as active ingredients and method for manufacturing the same |
| KR101915411B1 (en) | 2017-09-26 | 2018-11-05 | 허운덕 | Herbicide compositions for controlling pests of horticultural products comprising rare-earth elements as active ingredients |
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| CN103061206A (en) * | 2011-10-21 | 2013-04-24 | 纳尔科公司 | Application of composition of sulfamic acid or salts thereof and ammonium salt and/or amine or other biocides containing halogens in papermaking field |
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| CN106170458A (en) * | 2014-04-14 | 2016-11-30 | 艺康美国股份有限公司 | Slurry biocide |
| CN106170458B (en) * | 2014-04-14 | 2020-02-07 | 艺康美国股份有限公司 | Slurry biocide |
| CN114680348A (en) * | 2020-12-31 | 2022-07-01 | 广东美的白色家电技术创新中心有限公司 | Cleaning device |
| CN114680348B (en) * | 2020-12-31 | 2023-11-03 | 广东美的白色家电技术创新中心有限公司 | Cleaning device |
| CN115474609A (en) * | 2021-06-16 | 2022-12-16 | 苏州北辰新材料科技有限公司 | Disinfectant, preparation method thereof and film |
| CN115474609B (en) * | 2021-06-16 | 2024-01-26 | 苏州北辰新材料科技有限公司 | Disinfectant, preparation method thereof and film layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5670334B2 (en) | 2015-02-18 |
| CN106417360A (en) | 2017-02-22 |
| EP2346337A2 (en) | 2011-07-27 |
| JP2015028015A (en) | 2015-02-12 |
| WO2010034519A8 (en) | 2011-06-23 |
| WO2010034519A2 (en) | 2010-04-01 |
| WO2010034519A3 (en) | 2011-04-28 |
| JP2012503614A (en) | 2012-02-09 |
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