CN106417360A - Synergistic peroxide based biocidal compositions - Google Patents

Synergistic peroxide based biocidal compositions Download PDF

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Publication number
CN106417360A
CN106417360A CN201610631117.9A CN201610631117A CN106417360A CN 106417360 A CN106417360 A CN 106417360A CN 201610631117 A CN201610631117 A CN 201610631117A CN 106417360 A CN106417360 A CN 106417360A
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peroxide
compound
hydrogen
methods
sulphite
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菲利普·戈尔登·斯维尼
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Lonza AG
Lonza LLC
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Lonza LLC
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    • 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
    • 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
    • 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

The collaborative microbicide composition based on peroxide
The application is Application No. 200980138285.2, and the applying date is September in 2009 28, and artificially grand Sa is public for application Department, invention and created name is the division Shen of the application for a patent for invention of " the collaborative Biocidal composition based on peroxide " Please.
Technical field
The present invention relates in the aqueous systems comprising sulphite and/or bisulfite residue, (for example application is based on The solution obtaining after the reducing bleach of sulphite or suspension) the middle method controlling growth of microorganism.The present invention is further The method being related to stabilizing active halogen bactericidal agent in aqueous systems containing peroxide.
Background technology
Reducing bleach is applied too heavily in papermaking.This kind of bleaching process generally adopts bisulfite or generates weight sulfurous The solution of hydrochlorate.While strengthening paper brightness, the use of this kind of solution also can lead to sulfurous acid in the slurry being generated Salt residue.Sulphite makes slurry preservation and subsequent paper machine depositional control become increasingly difficult, because many paper kill Acarasiales agent and preservative such as dibromo nitro propionamide, OIT, particularly oxidation bactericidal agent is in the presence of sulphite Become unstable.
It is surprising that having been found that under the pH optimizing, in the system comprise to remain sulphite, apply oxidation Bactericidal agent can not only succeed, or even is provided that collaborative control of microorganisms.In particular, it was found that after optimizing pH, sulfurous Hydrochlorate bleached pulp by effectively, or even synergistically can be processed with hydrogen peroxide, to be bleached and control of microorganisms.
Sulphite is to acid medium (pH<5) in, the quick neutralization of hydrogen peroxide is it is known that and be standard peroxidating The basis of hydrogen titration assay method.It has been found that under the pH raising, when these generally incompatible materials can coexist one section Between, this time be enough to allow bleaching and control of microorganisms application.
Content of the invention
According to the present invention, the growth of microorganism in aqueous systems containing sulphite and/or bisulfite residue can Control in the following way：Aqueous systems are adjusted and maintains pH>5, preferably pH6-11, more preferably 7.5-10, and added Oxygen compound.The pH scope being defined by upper and lower bound in the present invention and any number scope should be understood also to include The subrange that all combinations by any upper limit and any lower limit are formed.
Preferably per-compound includes hydrogen peroxide, inorganic peroxy compounds such as alkali metal or alkaline-earth metal perboric acid Salt, percarbonate or persulfate, organic peroxide acid such as peracetic acid or benzylhydroperoxide, other organic per-compounds are for example Urea peroxide, and the mixture of aforesaid compound.Term " persulfate " includes single persulfate simultaneously and (for example, crosses a sulphur Sour H2SO5Salt) and peroxydisulfate (that is, peroxy-disulfuric acid H2S2O8Salt).
The effect of per-compound can be improved by adding bleach-activating such as tetra acetyl ethylene diamine (TAED).
Particularly preferred per-compound is hydrogen peroxide.
If necessary, the pH of aqueous systems can by add alkali or basic salt such as alkali metal or alkaline earth metal hydroxide, Carbonate, heavy carbonate, borate, metasilicate or its mixture are controlled and/or buffer.
In a preferred embodiment, this sulphite and/or bisulfite and the firm per-compound adding Concentration is respectively 1-300ppm, more preferably respectively 5-200ppm, most preferably respectively 10-100ppm.
The application that can be benefited from the sulphite/peroxide compatibleization according to the present invention includes pulping and papermaking, recovery Paper pulping is bleached with papermaking, slurry or biomass, fabric is bleached and similar application.
Will be described aqueous due to aqueous systems (such as slurry slurries) are processed with per-compound (such as hydrogen peroxide) Form peroxide or the residue of finite concentration scope, the therefore arbitrarily follow-up bactericidal agent applying is for peroxide in system Process or peroxide residue keep stablize extremely important.It has been found that comprising the solution of hydrogen peroxide, the making of such as dilution Pulp material, the reactive halogen of available stabilisation is successfully processed.This additional result is unexpected, as it is well known that active halogen Plain material can be neutralized (hydrogen peroxide can be simultaneously as Oxidizing and Reducing Agents) in the presence of a peroxide.
Also especially find there is the nitrogen halogen-containing active halogen species of knot beat all steady in the presence of a peroxide Fixed.According to the present invention, the reactive halogen bactericidal agent in the aqueous systems containing peroxide or peroxide residue can pass through Reactive halogen bactericidal agent is added N- hydrogen compound to this bactericidal agent before being merged with aqueous systems containing peroxide and is stabilized.This Place and N- hydrogen compound hereafter are the organic or inorganic compounds with the hydrogen atom that at least one is bonded directly to nitrogen-atoms.
This novel method is best suitable for for simultaneously using the application of peroxide and reactive halogen.
Reactive halogen bactericidal agent is halogen (the particularly chlorine or bromine, such as element chlorine or bromine comprising to be in oxidation state 0 or+1 And secondary aluminate or hypobromite) bactericidal agent.
In a preferred embodiment, the reactive halogen being stabilized by N- hydrogen compound is (with Cl2Meter) concentration be 0.1-20ppm.Herein and below statement " with Cl2Be equivalent to active halogen concentration in given system in meter " expression stoichiometry Elemental chlorine concentration.
Preferably N- hydrogen compound is selected from ammonia, ammonium salt, such as ammonium sulfate and ammonium bromide, other nitrifications without C-H bond Thing, such as urea, biuret, isocyanuric acid and sulfamic acid, organic N- hydrogen compound, such as para toluene sulfonamide, 5,5- bis- Alkyl-hydantoins, methylsulfonamides, barbiturates, methyl uracil, imidazoline, pyrrolidones, morpholine, antifebrin, Acetamide, N- ethyl acetamide, phthalimide, benzamide, succimide, N- monomethylolurea, N- MU, acetyl group Urea, uramido methyl formate, methyl carbamate, phthaloyl hydrazine, pyrroles, indoles, formamide, N-METHYLFORMAMIDE, dicyandiamide, amino Ethyl formate, 1,3- dimethyl biuret, tolyl biuret, 4,4- dimethyl -2- oxazolidones, 6- methyluracil, 2- Imidazolone, ethylidene-urea, 2- pyrimidone, azetidine -2- ketone, 2-Pyrrolidone, caprolactam, phenylsulfinyl imines, benzene is sub- Sulfimide base acid amides, diaryl-or dialkyl group sulfenimide, isothiazoline -1,1- dioxide, hydantoins, sweet ammonia Acid, 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 systems or peroxide residue are preferably hydrogen peroxide, alkali metal or alkaline earth gold Belong to percarbonate, perborate or persulfate, organic peroxide acid or the aforementioned mixture of two or more, most preferably peroxide Change hydrogen.
(that is, the synergisticing performance of sulphite slurry of peroxide treatment and reactive halogen are directed to peroxide for arbitrary discovery Stability of solution drops in compound or peroxide residue) advantageous applications be slurry and sheet processing, reclaim slurrying and papermaking, Deinking, slurry bleaching, biomass bleaching, fabric bleaching or clay slurry bleaching.Preferably aqueous systems are slurry and papermaking pulp-liquor With liquid, recovery slurry slurries, slurry thick stock, deinking slush pulp, slurry or biomass bleaching slurries and liquid, fabric bleaching liquid Body and clay slurry.
Other preferably applications are water process, such as waste water, papermaking liquid and water, pond and thermal water, industry cooling Water, expose water to reverse osmosis filter or ion exchange resin, and include fractionating tank and down-hole application or crust disappears Field use aqueous systems in poison.
Other preferably applications are that food and crop protection application (include fruits and vegetables cleaning, meat and poultry to add Work, beverage processing, fish culture and aquatic products industry) the middle aqueous systems finding.
Find (that is, the synergisticing performance of the sulphite slurry of peroxide treatment and reactive halogen pin in conjunction with both Stability of solution is dropped to hydrogen peroxide or peroxide residue) define the cost effective control of microorganisms that can be used for papermaking The definition of scheme.The program includes carrying out slurry bleaching with sulphite, then uses peroxide treatment, then combines having nitrogen In the presence of the reactive halogen bactericidal agent of halogen by this slurry conversion be paper.
In a preferred embodiment, the aqueous systems that this comprises peroxide can be by described aqueous more than 5 to pH System is added the composition comprising at least one per-compound and is obtained.
In the application of preferred merging method, this aqueous systems is selected from the slurries of pulping and papermaking, reclaims the slurry of slurry Liquid, 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 be by combining applying sulphite and per-compound (optionally in combination with activator such as tetrem Acyl ethylenediamine), combine applying per-compound and reactive halogen or combine applying sulphite and per-compound subsequently Combine applying or generation per-compound and active halogen usually optimizes cost performance.This combine applying be now subjected to these materials Quickly neutralize mutually and be prohibited.Present invention demonstrates the method for the even collaborative compound using these types of joint.
It is a further object of this invention to determining peroxide in the aqueous systems containing sulphite and/or bisulfite The analysis method of concentration.The method comprises the steps：
I () adds the excessive N- stabilized hydrogen active chlorine compound of determination amount to destroy this sulphite and/or weight immediately Sulphite, leaves a certain amount of unreacted N- stabilized hydrogen active chlorine compound simultaneously,
(ii) measure the amount of unreacted N- stabilized hydrogen active chlorine compound, so that it is determined that sulphite and/or weight sulfurous Hydrochlorate concentration, and
(iii) peroxide concentrations are determined.
In step (ii), the amount of unreacted N- stabilized hydrogen active chlorine compound can be by any methods known in the art Measurement, especially by the known DPD method measurement according to ISO 7393-2.Sulphite and/or bisulfite concentration pair The unreacted N- hydrogen recording in the amount of the N- stabilized hydrogen active chlorine compound that Ying Yu adds in the step (i) and step (ii) is steady Surely change the difference of the amount of active chlorine compound.
In step (iii), peroxide concentrations can pass through the determination of one of methods known in the art, for example can be by with iodine Change potassium to be determined using thiosulfatimetry as indicator.
The preferred N- stabilized hydrogen active chlorine compound adopting in above-mentioned analysis method is in 1- chloro- 5,5- dimethyl second Uride (MCDMH).
Following non-limiting example purpose is more specifically to illustrate the present invention.
Embodiment
State common (decimal system) logarithm of the colony forming single-digit amount during " 1g cfu/mL " represents every milliliter, be Term " minimizing " with reference to when represent in every milliliter of before processing colony forming single-digit amount and process after in every milliliter bacterium colony form list The common logarithm of the ratio of bit quantity.Unless otherwise specified, all percentages or ppm concentration are the concentration based on weight.
Embodiment 1
The aqueous solution comprising sulphite and hydrogen peroxide is mixed to get sulfite content (with SO at 21 DEG C3 2- Meter) it is the solution that 20.0ppm and pH are 6.7 for 40ppm, content of hydrogen peroxide.Solution temperature is maintained 21 DEG C, upon mixing 15th, residual sulphite and peroxide content are measured within 30 and 60 minutes.This step includes residual with respect to estimating to sample interpolation Stay the 1- chloro- 5,5- dimethyl hydantoin (MCDMH) of the excessive known quantity of cigarette sulphates content.Then pass through standard DPD total The remaining MCDMH concentration of halogen method measurement.Neutralize MCDMH, the concentration of sulphite because sulphite is rapid under all pH What the interpolation concentration for MCDMH deducted MCDMH records concentration, see below equation 1.The step in H2O2It is effective for leaving, Because H2O2Do not react with MCMDH, and do not disturb gross activity halogen method, because the method is carried out at approximately neutral pH.
(1) [sulphite]=[MCDMHAdd]-[MCDMHRecord]
H2O2The H that concentration can be recorded using acid thiosulfatimetry by record KI indicator2O2Concentration is carried out really Fixed (HACH HYP-1 hydrogen peroxide test kit-Hach Co., Loveland, CO).Because this titration is entered at acidic OK, the method can obtain the H excessive with respect to sample sulfite salinity2O2Concentration.Because sulfite concentration can be by MCMDH analysis and equation 1 obtain, H2O2Concentration can be calculated by below equation 2：
(2)[H2O2]=[H2O2 record]+[sulphiteCalculate]
The evaluated error of the method is ± 1ppm.
This result is shown in table 1, and the obvious residual of the two kinds of materials which show or even observe after 30 minutes is dense Degree.
Table 1
Embodiment 2
The step repeating embodiment 1, difference is that the pH of mixed solution is 9.0, and upon mixing 5,15,30,60,120 Measure debris concentration with 1080 minutes.Result is shown in table 2, which demonstrates the co-stability of hydrogen peroxide and sulphite Further enhanced under pH9.0, be observed wherein or even after 2 hours the bright of peroxide and sulphite Aobvious residual concentration.
Table 2
Embodiment 3
Investigate the collaborative sterilization ability combined under the pH raising when applying sulphite and hydrogen peroxide.Table 3 below Shown in the sulphite of concentration and peroxide be added in the aqueous solution consisting of：(a) deionized water, (b) NaHCO3, gained carbonate buffer concentration is 200ppm (with CaCO3Total alkaline meter), (c) sulphite bleached pulp slurries, Final concentration of 0.05%, carry the residual sulphite association least concentration of 6ppm, and (d) NaOH, to reach pH 9.0.
Micropopulation can provide in the following way：24-48 hour prepares slurry slurries at room temperature before testing Storage, thus allow growth of microorganism to highest testing level.For untreated control population, 1g under engaged test in 3 hours Cfu/mL=5.9,1g cfu/mL=6.5 under engaged test in 24 hours.The colony being reported is by tryptone soya agar The always thermophilic oxygen bacterium that coated plate is carried out counts.This test result is shown in table 3.
Table 3
Seem the presence of only sulphite for the bacterial community under 32-128ppm sulfite concentration not substantially Effect.Different, hydrogen peroxide shows the relatively low development level of sterility, and the 1g cfu/mL of gained subtracted in 3 hours Few 1.2-3.5, reduced 5.5 in 24 hours.It is surprising that under contact in 3 hours, the sulphite/mistake of part mixing Oxidation hydrogen system (Test No. 7 and 9) provides the effect bigger than independent hydrogen peroxide (Test No. 5).
The performance level observed shows that sulphite and peroxide are obvious under the peroxide concentrations raising Synergy.Because single sulphite does not have sterility, hydrogen peroxide effect in the presence of observed sulphite Enhancing be synergistic result.This result can pass through Kull et al. (F.C.Kull, P.C.Elisman, H.D.Sylwestrowicz and P.K.Mayer, Appl.Microbiol, 1961,9,538) method carries out quantitation, the method In specify when observe the index of cooperation according to equation 3 (SI) be less than 1.0 when there is synergy.
(3) SI=(level of A)/(level of significance of A)+(level of B)/(level of significance of B)
A is set to sulfite concentration, B is set to peroxide concentrations, can get following result：Due to sulfurous acid Salt substantially can not be sterilized, and the denominator of Section 1 becomes infinity so that the value of Section 1 is zero.If level of significance is set by we It is set to the level that the 1g cfu/mL producing in 3 hours is reduced to 3.5, the denominator of Section 2 becomes 160ppm (according to table 3 Test No. 5).Then it is less than 1.0 according to the index of cooperation that equation 4 hereafter can get the lower Test No. 7 and 9 of contact in 3 hours, because The target 1g cfu/mL minimizing 3.5 that single 160ppm hydrogen peroxide is compared in these tests can generate bigger minimizing.
(4) SI=0+ (<160)/160=(<1.0)
Embodiment 4
Investigate and combined the association applying sulphite and hydrogen peroxide under higher sulphite and concentration of hydrogen peroxide With.This condition is same as Example 3.The micropopulation of untreated control is the lower 1g cfu/mL=6.26 of contact in 3 hours, 24 The lower 1g cfu/mL=6.18 of hour contact.This result is shown in table 4.
Table 4
As shown in table 4, the application of the sulphite for 128-512ppm for the concentration does not have obvious effect for micropopulation. Different, concentration is that the hydrogen peroxide of 120-160ppm shows the relatively low development level of sterility, the 1g cfu/ of gained ML reduced 3.3-4.0 in 3 hours, reduced 3.7-5.5 in 24 hours.Same it is surprising that the sulfurous of some mixing Hydrochlorate/hydrogen peroxide system provides higher effect than single hydrogen peroxide.The performance level observed shows sulfurous The hydrochlorate and peroxide obvious synergy under the peroxide concentrations raising.Because sulphite itself does not show sterilizing Effect, the enhancing of hydrogen peroxide effect in the presence of observed sulphite is synergistic result.Test No. 9 may be complete Entirely strictly demonstrate collaborative.If required effect is arranged to 1g cfu/mL and reduces 4.2, it may be seen that needing> 512ppm sulphite realizing this effect.The amount realizing the independent hydrogen peroxide of this effect is 150ppm or higher.This Define equation 5：
(5) SI=32/ (>512)+(<120)/150=(<0.063)+(<0.8)=(<0.86)
Embodiment 5
The sterility of the solution comprising sulphite and hydrogen peroxide has been investigated further in the case of no slurry.Survey Measure the effect to the pseudomonas aeruginosa of growth in the nutriment in the presence of 83 and 830ppm sulphite.Then use pH 7.0 Butterfield buffer solution 1:The pseudomonas aeruginosa containing sulphite for 99 dilutions.Sulphite in table 5 below is dense Degree is the concentration of final dilution.Then dilution is contacted 3 hours with 50ppm hydrogen peroxide at 37 DEG C.Untreated control Colony's (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 for being diluted to the copper of 8.3ppm in the growth of 830ppm sulphite and when applying The sterility (1g cfu/mL reduces 1.5) of green pseudomonad is astoundingly more than to without growth in the case of sulphite The effect (1g cfu/mL reduce 0.9) observed of pseudomonas aeruginosa.So, by the interpolation of sulphite for peroxide The wonderful enhancing changing hydrogen sterility has obtained further checking when without slurry.
Embodiment 6
Investigate residual H2O2In the presence of nitrogen binding activity halogen species stability.Free by the measurement of standard DPD method With total cl concn, and pass through the total H of acid accumulator sulfite titrimetry2O2Concentration.It is free that MCDMH concentration is that gross activity halogen deducts The concentration of reactive halogen.H2O2Concentration is that total oxide concentration deducts MCDMH concentration.By 2.1ppm (0.062mM) H2O2With 1ppm (0.014mM) NaOCl is (with Cl2Meter) merge the stoichiometry of two kinds of materials is reduced immediately, the H obtaining2O2Residue be～ 1.6ppm (0.048mM), does not have measurable free chlorine.Above reaction is shown in equation 6.
(6)NaOCl+H2O2→H2O+NaCl+O2
H2O2In the presence of the inherent instability of reactive halogen be shown in table 6.
Table 6
1)- measured using HACH HYP-1 hydrogen peroxide test kit (Hach Co., Loveland, CO)
Embodiment 7
Investigate and added equimolar 5,5- dimethyl hydantoin to NaOCl solution before merging with hydrogen peroxide (DMH) effect.Its result is shown in table 7.MCDMH concentration deducts free active halogen concentration for gross activity halogen concentration.H2O2 Concentration is that total oxide concentration deducts MCDMH concentration.
Table 7
1)- measured using HACH HYP-1 hydrogen peroxide test kit (Hach Co., Loveland, CO)
Can see DMH interpolation can Simultaneous Stabilization merge when Active Chlorine and hydrogen peroxide.Even in the contact of 1 hour Also obvious decomposition is not observed after time.

Claims (22)

1. the method controlling growth of microorganism in the aqueous systems containing sulphite and/or bisulfite residue, institute The described aqueous systems that the method for stating includes being more than 5 to pH add the composition comprising at least one per-compound.
2. the method for claim 1, wherein this per-compound are selected from hydrogen peroxide, alkali metal percarbonate, alkaline earth Metal percarbonate salts, alkali metal perborate, alkaline earth perborate salts, alkali metal persulphate, alkali earth persulfates, Organic peroxide acid and its mixture.
3. method as claimed in claim 2, wherein this per-compound are hydrogen peroxide.
4. the method as described in claim 1-3 any one, wherein said composition comprises bleach-activating further.
5. method as claimed in claim 4, wherein said bleach-activating is tetra acetyl ethylene diamine.
6. the method as described in claim 1-5 any one, wherein this pH are between 6 and 11.
7. method as claimed in claim 6, wherein this pH are between 7.5 and 10.
8. the method as described in claim 1-7 any one, the pH of the wherein aqueous decorum passes through using selected from alkali metal hydrogen-oxygen Compound, alkaline earth metal hydroxide, alkaline metal bicarbonate, alkaline-earth metal heavy carbonate, alkali carbonate, alkaline-earth metal carbon The compound of hydrochlorate, alkali metal silicate or its mixture is adjusted.
9. the method as described in claim 1-8 any one, wherein this sulphite and/or bisulfite and firm interpolation The concentration of per-compound be respectively 1-300ppm.
10. in aqueous systems containing peroxide stabilizing active halogen bactericidal agent method, methods described includes in this active halogen Before plain bactericidal agent is merged with described aqueous systems containing peroxide, add N- hydrogen compound to this reactive halogen bactericidal agent.
11. methods as claimed in claim 10, wherein by the stable reactive halogen of N- hydrogen compound (with Cl2Meter) concentration be 0.1-20ppm.
12. methods as described in claim 10 or 11, wherein this N- hydrogen compound are selected from ammonia, ammonium salt, such as ammonium sulfate and bromine Change ammonium, without the nitrogen compound of C-H bond, such as urea, biuret, sulfamic acid and isocyanuric acid, substituted N- hydrogen compound, Such as methylsulfonamides, para toluene sulfonamide, 5,5- dialkylhydantoin, barbiturates, methyl uracil, imidazoline, Pyrrolidones, morpholine, antifebrin, acetamide, N- ethyl-acetamide, phthalimide, benzamide, succimide, N- mono- Methylolurea, N- MU, acetyl group-urea, uramido methyl formate, methyl carbamate, phthaloyl hydrazine, pyrroles, indoles, formyl Amine, N-METHYLFORMAMIDE, dicyandiamide, urethanes, 1,3- dimethyl biuret, tolyl 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 sulfenimide, dialkyl group sulfenimide, different Thiazoline -1,1- dioxide, hydantoins, glycine, piperidines, piperazine, monoethanolamine, glycine amide, creatine, glycoluril and its mixed Compound.
13. methods as claimed in claim 12, wherein this N- hydrogen compound are 5,5- dimethyl hydantoins.
14. methods as claimed in claim 12, wherein this N- hydrogen compound are urea, ammonia or ammonium salt.
15. methods as described in claim 10-14 any one, wherein this peroxide are selected from hydrogen peroxide, alkali metal mistake Carbonate, alkaline earth perborate salts, alkali metal perborate, alkaline earth perborate salts, alkali metal persulphate, alkaline earth gold Belong to persulfate, organic peroxide acid and its mixture.
16. methods as claimed in claim 15, wherein this peroxide are hydrogen peroxide.
17. methods as described in claim 10-16 any one, wherein this aqueous systems be selected from pulping and papermaking slurries, Reclaim the slurries of slurry, slurry thick stock, deinking slush pulp, slurry or biomass bleaching slurries and liquid, fabric liquid lime chloride and Clay slurry.
18. methods as described in claim 10-16 any one, wherein this aqueous systems be selected from waste water, papermaking liquid and water, Pond and thermal water, the water of industrial colling, exposure to reverse osmosis filter or ion exchange resin and including fractionating tank With the aqueous systems in the field use of down-hole application.
19. methods as described in claim 10-16 any one, wherein this aqueous systems are selected from protects for food and crops Shield application, include fruits and vegetables clean, meat and processing of poultry, beverage processing, fish culture and aquatic products industry, aqueous solution.
20. methods as described in claim 10-19 any one, the aqueous systems that wherein this comprises peroxide have passed through power Profit requires the method described in 1-9 any one to obtain.
21. methods determining peroxide concentrations in the aqueous systems in the presence of sulphite and/or bisulfite, described Method comprises the steps：
I () adds the excessive N- stabilized hydrogen active chlorine compound of determination amount to destroy this sulphite and/or weight sulfurous immediately Hydrochlorate, leaves a certain amount of unreacted N- stabilized hydrogen active chlorine compound simultaneously,
(ii) measure the amount of unreacted N- stabilized hydrogen active chlorine compound, so that it is determined that sulphite and/or bisulfite Concentration, and
(iii) peroxide concentrations are determined.
22. methods as claimed in claim 21, wherein this N- stabilized hydrogen active chlorine compound are 1- chloro- 5,5- dimethyl second Interior uride.
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