Classifications

• • 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
  • 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
• • 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

Definitions

• the invention relates to a method for controlling microbial growth in aqueous systems containing sulfite and/or bisulfite residues, such as solutions or suspensions obtained after appli- cation of sulfite-based reducing bleaches. It further relates to a method for stabilizing active halogen biocides in peroxide-containing aqueous systems.
• bleaches are frequently used in paper making applications. Such bleaching processes typically employ bisulfite or bisulfite generating solutions. While enhancing paper brightness, the use of such solutions can also result in sulfite residues in the produced pulp. Sulfite residues make pulp preservation and subsequent paper machine deposit control more difficult as many major paper slimicides and preservatives such as dibromonitrilopropionamide, isothiazolinones, and, in particular, oxidizing biocides are unstable in the presence of sulfite.
• microbial growth in an aqueous system containing sulfite and/or bisulfite residues is controlled by adjusting and maintaining a pH >5, preferably pH 6-11, and more preferably 7.5-10, in the aqueous system and adding a peroxy compound.
• Preferred peroxy compounds include hydrogen peroxide, inorganic peroxy compounds such as alkali metal or alkaline earth metal perborates, percarbonates or persulfates, organic peroxy acids such as peracetic or perbenzoic acid, other organic peroxy compounds such as urea peroxide, and mixtures of the beforementioned.
• the term "persulfates” includes both mono- persulfates (i.e., the salts of peroxymonosulfuric acid, H 2 SO 5 ) and peroxydisulfates (i.e., the salts of peroxydisulfuric acid, H 2 S 2 O 8 ).
• the efficacy of the peroxy compounds may be increased by the addition of bleach activators such as tetraacetylethylenediamine (TAED).
• TAED tetraacetylethylenediamine
• a particularly preferred peroxy compound is hydrogen peroxide.
• the pH of the aqueous system can be controlled and/or buffered, if necessary, by addition of bases or basic salts such as alkali or alkaline earth metal hydroxides, carbonates, bicarbonates, borates, metasilicate, or mixtures thereof.
• bases or basic salts such as alkali or alkaline earth metal hydroxides, carbonates, bicarbonates, borates, metasilicate, or mixtures thereof.
• the concentrations of sulfite and/or bisulfite and peroxy compound immediately after addition of the peroxy compound are 1 to 300 ppm each, more preferably 5 to 200 ppm and most preferred 10 to 100 ppm each.
• an active halogen bio- cide in an aqueous system containing peroxides or peroxide residues is stabilized by adding an N-hydrogen compound to the active halogen biocide before combining the biocide with the peroxide containing aqueous system.
• an N-hydrogen compound is an organic or inorganic compound having at least one hydrogen atom directly bound to a nitrogen atom.
• Active halogen biocides are biocides containing halogen, in particular chlorine or bromine, in the oxidation state 0 or +1, such as elemental chlorine or bromine and hypochlorite or hypo- bromite.
• the concentration of active halogen (as Cl 2 ) stabilized by an N-hy- drogen compound is 0.1 to 20 ppm.
• the expression “as Cl 2” denotes the concentration of elemental chlorine that is stoichiometrically equivalent to the concentration of active halogen in a given system.
• N-hydrogen compounds are selected from the group consisting of ammonia, ammonium salts, such as ammonium sulfate and ammonium bromide, other nitrogen compounds containing no carbon-hydrogen bonds, such as urea, biuret, isocyanuric acid, and sulfamic acid, organic N-hydrogen compounds such as p-toluenesulfonamide, 5,5-dialkyl- hydantoins, methanesulfonamide, barbituric acid, 5-methyluracil, imidazoline, pyrrolidone, morpholine, acetanilide, acetamide, N-ethylacetamide, phthalimide, benzamide, succinimide, N-methylolurea, iV-methylurea, acetylurea, methyl allophanate, methyl carbamate, phthalo- hydrazide, pyrrole, indole, formamide, N-methylform
• the ⁇ -hydrogen compound is 5,5-dimethylhydantoin, urea, ammonia, or an ammonium salt.
• the peroxide or peroxide residue in the aqueous system is preferably hydrogen peroxide, an alkali metal or alkaline earth metal percarbonate, perborate, or persulfate, an organic peroxy acid, or a mixture of two or more of the beforementioned, hydrogen peroxide being most preferred.
• Preferred applications of either finding, namely the synergistic performance of peroxide treated sulfite pulps and the stabilization of active halogen against degradation by peroxides or peroxide residues are in pulp and paper processing, recycle pulping and papermaking, deinking, pulp bleaching, biomass bleaching, textile bleaching or clay slurry bleaching.
• Preferred aqueous systems are pulp and papermaking slurries and liquors, recycle pulp slurries, pulp thick stock, deinking pulp slurries, pulp or biomass bleaching slurries and liquids, textile bleaching liquids and clay slurries.
• Still other preferred applications are in aqueous systems found in food and crop protection applications, including fruit and vegetable washes, meat and poultry processing, beverage processing, fish farming, and aquaculture.
• the aqueous system containing peroxides is obtained by the addition of a composition comprising at least one peroxy compound to said aqueous system at a pH greater than 5
• aqueous system is selected from the group consisting of pulp and papermaking slurries, recycle pulp slurries, pulp thick stock, deinking pulp slurries, pulp or biomass bleaching slurries and liquids, textile bleaching solutions, and clay slurries.
• optimized cost performance can be achieved through the co-application of sulfite and peroxy compounds, optionally in combination with activators such as tetraacetylethylenediamine, co-application of peroxy compounds with active halogens, or co- application of sulfite and peroxy compounds followed by co-application or generation of peroxy compounds with active halogens.
• activators such as tetraacetylethylenediamine
• co-application of peroxy compounds with active halogens co-application of peroxy compounds with active halogens
• co-applications have been prohibited to date by the rapid mutual neutralization of these species.
• the current invention demonstrates methodologies for utilizing these classes of compounds cooperatively and even synergistically.
• Another object of the invention is an analytical method for determining peroxide concentrations in aqueous systems containing sulfite and/or bisulfite.
• the method comprises the steps of:
• the amount of unreacted N-hydrogen-stabilized active chlorine compound in step (ii) may be measured by any method known in the art, in particular by the well-known DPD method according to ISO 7393-2.
• the sulfite and/or bisulfite concentration corresponds to the difference of the amount of N-hydrogen-stabilized active chlorine compound added in step (i) and the amount of unreacted N-hydrogen-stabilized active chlorine compound measured in step (ii).
• step (iii) can be achieved by one of the methods known in the art, for example by titration with thiosulfate using potassium iodide as indicator.
• a preferred N-hydrogen-stabilized active chlorine compound to be used in the above analytical method is l-chloro-5,5-dimethylhydantoin (MCDMH).
• Ig cfu/mL denotes the common (decadic) logarithm of the number of colony- forming units per milliliter or, in connection with the term “reduction”, the common logarithm of the quotient of the number of colony-forming units per milliliter before treatment and the number of colony-forming units after treatment. Unless otherwise indicated all concentrations in percent or ppm are expressed on a weight basis.
• Aqueous solutions containing sodium sulfite and hydrogen peroxide were mixed at 21 °C to obtain a solution having a sulfite content (as SO 3 ) of 40 ppm, a hydrogen peroxide content of 20.0 ppm and a pH of 6.7.
• the temperature of the solution was maintained at 21 °C and the residual sulfite and peroxide content was determined at 15, 30 and 60 minutes after mixing.
• the procedure consisted of adding a known amount of l-chloro-5,5-dimethylhydantoin (MCDMH) to the samples in excess of the estimated residual sulfite content. The remaining MCDMH concentration was then measured by standard DPD total halogen methodologies.
• the H 2 O 2 concentration was determined by recording the concentration of H 2 O 2 measured using acidic thiosulfate titration with KI indicator (HACH HYP-I hydrogen peroxide test kit — Hach Co., Loveland, CO). Since this titration is run at acidic pH, this method yields the concentration of H 2 O 2 in excess of the sulfite concentration contained in the sample. As the sulfite concentration is known from the MCMDH analysis and Equation 1, the H 2 O 2 concentration can be calculated using the following Equation 2:
• the estimated error in the methodology is ⁇ 1 ppm
• Example 2 The procedure of Example 1 was repeated with the difference that the pH of the mixed solution was 9.0 and the residual concentrations were determined 5, 15, 30, 60, 120 and 1080 minutes after mixing. The results are shown in Table 2 which demonstrates that the co-stability of hydrogen peroxide and sulfite is even further enhanced at pH 9.0 where a significant residual concentration of both peroxide and sulfite was observed even after a period of 2 h. Table 2
• Synergistic biocidal performance upon co-application of sulfite with hydrogen peroxide at elevated pH was investigated.
• the sulfite and peroxide concentrations indicated in Table 3 below were added to an aqueous solution made from: (a) deionized water, (b) NaHCO 3 to achieve a carbonate buffer concentration of 200 ppm (as CaCO 3 total alkalinity), (c) sulfite bleached pulp slurry to achieve a final consistency of 0.05%, carrying an associated minimal concentration of residual sulfite of 6 ppm, and (d) NaOH to achieve a pH of 9.0.
• the microbial population was that provided by preparing the pulp slurry 24—48 h prior to testing and storing at room temperature, thus allowing microbial growth to a high test level.
• Populations reported are total aerobic counts using tryptone soy agar plating. The test results are shown in Table 3.
• the stability of nitrogen-bound active halogen species in the presence of residual H 2 O 2 was investigated. Free and total chlorine concentrations were measured by standard DPD methodology and the total H 2 O 2 concentration by acidic sulfite titration.
• the concentration of MCDMH is the concentration of the total active halogen less the concentration of free active halogen.
• the concentration of H 2 O 2 is the total oxidant concentration less the MCDMH concentration.
• the effect of the addition of a molar equivalent of 5,5-dimethylhydantoin (DMH) to NaOCl solutions prior to combination with hydrogen peroxide was investigated.
• the results are shown in Table 7.
• the concentration of MCDMH is the concentration of the total active halogen less the concentration of free active halogen.
• the concentration Of H 2 O 2 is the total oxidant concentration less the MCDMH concentration.

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• Life Sciences & Earth Sciences (AREA)
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• Engineering & Computer Science (AREA)
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• Pest Control & Pesticides (AREA)
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• Agronomy & Crop Science (AREA)
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• Food Science & Technology (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Toxicology (AREA)
• Treatment Of Water By Oxidation Or Reduction (AREA)
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• Apparatus For Disinfection Or Sterilisation (AREA)
• Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

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• 2009
  • 2009-09-28 WO PCT/EP2009/006975 patent/WO2010034519A2/en active Application Filing
  • 2009-09-28 JP JP2011528251A patent/JP5670334B2/ja active Active
  • 2009-09-28 CN CN2009801382852A patent/CN102176830A/zh active Pending
  • 2009-09-28 CN CN201610631117.9A patent/CN106417360A/zh active Pending
  • 2009-09-28 EP EP09778746A patent/EP2346337A2/en not_active Withdrawn
• 2014
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