DE19529444A1 - Catalase inhibitors used to stabilise hydrogen peroxide - in industrial recycle waters, esp. in the paper industry - Google Patents

Catalase inhibitors used to stabilise hydrogen peroxide - in industrial recycle waters, esp. in the paper industry

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Publication number
DE19529444A1
DE19529444A1 DE1995129444 DE19529444A DE19529444A1 DE 19529444 A1 DE19529444 A1 DE 19529444A1 DE 1995129444 DE1995129444 DE 1995129444 DE 19529444 A DE19529444 A DE 19529444A DE 19529444 A1 DE19529444 A1 DE 19529444A1
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Germany
Prior art keywords
circulating water
alkali
catalase
ppm
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
DE1995129444
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German (de)
Inventor
Horst-Werner Dr Wollenweber
Karl-Heinz Dr Maurer
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Nopco Paper Technology Holding AS
Original Assignee
Henkel AG and Co KGaA
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Priority to DE1995129444 priority Critical patent/DE19529444A1/en
Publication of DE19529444A1 publication Critical patent/DE19529444A1/en
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • 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
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • 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
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Catalase inhibitors (I) are used to stabilise H2O2 in industrial recycle waters. The (I) may be present in combination with enzyme (II) and/or biocide (III).

Description

Die vorliegende Erfindung betrifft die Verwendung von Katalase-Inhibitoren zur Stabilisierung von Wasserstoffperoxid in Kreislaufwässern, insbeson­ dere in Kreislaufwässern der Papierindustrie, und ein Verfahren zur Sta­ bilisierung von Wasserstoffperoxid in derartigen Kreislaufwässern durch die Zugabe von Katalase-Inhibitoren.The present invention relates to the use of catalase inhibitors for the stabilization of hydrogen peroxide in circulating water, in particular in circulating water of the paper industry, and a process for sta bilization of hydrogen peroxide in such circulating water the addition of catalase inhibitors.

In Wasserkreisläufen der zellstoff- und papierverarbeitenden Industrie wird üblicherweise Wasserstoffperoxid zum Bleichen von Cellulose-Faser­ stoffen, die aus Holz oder Altpapier stammen, eingesetzt. Dabei muß man oft feststellen, daß Wasserstoffperoxid im Kreislaufwasser wesentlich rascher abgebaut wird, als dies aufgrund des beabsichtigten Bleichvorgangs zu erwarten wäre. Man nimmt als zumindest eine Ursache dieses Phänomens an, daß im System vorhandene Mikroorganismen, gegebenenfalls nach einer gewissen Adaption, mikrobielle Enzyme, sogenannte Katalasen, entwickeln, die Wasserstoffperoxid abbauen, und sich dadurch vor einer oxidativen Schädigung oder dem Abgetötetwerden bewahren. Aus diesem Grund muß man oft unverhältnismäßig viel Wasserstoffperoxid in solchen Kreislaufwässern einsetzen, um das gewünschte Bleichergebnis zu erzielen.In water cycles in the pulp and paper processing industry Usually hydrogen peroxide is used to bleach cellulose fiber substances that come from wood or waste paper. You have to often find that hydrogen peroxide is essential in circulating water is broken down more quickly than due to the intended bleaching process would be expected. One takes at least one cause of this phenomenon indicates that microorganisms present in the system, possibly after a certain adaptation, developing microbial enzymes, so-called catalases, break down the hydrogen peroxide, and thereby face an oxidative Preserve damage or death. Because of this, you often have to disproportionate amount of hydrogen peroxide in such circulating water to achieve the desired bleaching result.

Die vorliegende Erfindung will zur Lösung dieses Problems beitragen.The present invention seeks to solve this problem.

Gegenstand der Erfindung ist die Verwendung von Katalase-Inhibitoren zur Stabilisierung von Wasserstoffperoxid in industriellen Kreislaufwässern, insbesondere in Kreislaufwässern der Papierindustrie.The invention relates to the use of catalase inhibitors for Stabilization of hydrogen peroxide in industrial circulating water, especially in circulation waters of the paper industry.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Stabilisierung von Wasserstoffperoxid in industriellen Kreislaufwässern, insbesondere in Kreislaufwässern der Papierindustrie, durch Zugabe von Katalase-Inhibito­ ren.Another object of the invention is a method for stabilization of hydrogen peroxide in industrial circulating water, especially in  Circulating water in the paper industry, by adding catalase inhibito ren.

Die Konzentration an Wasserstoffperoxid, die man in solchen Kreisläufwäs­ sern benötigt, hängt sehr stark vom Ausgangsmaterial, beispielsweise Alt­ papier, und von der gewünschten Erhöhung des Weißgrades ab. In der Regel liegt die Konzentration an Wasserstoffperoxid im Bereich von 5 mg/l bis 500 mg/l. Durch die erfindungsgemäße Verwendung beziehungsweise das er­ findungsgemäße Verfahren wird vorzugsweise erreicht, daß innerhalb eines Zeitraums von 0,5 Stunden bis I Stunde, insbesondere bis 2 Stunden, die Wasserstoffperoxidkonzentration im Kreislaufwasser nicht auf Werte unter­ halb von 50%, insbesondere nicht unterhalb von 70% der vom Betreiber gewünschten beziehungsweise benötigten Wasserstoffperoxidkonzentration zurückgeht, ohne daß im genannten Zeitraum Wasserstoffperoxid nachdosiert werden muß.The concentration of hydrogen peroxide found in such circuits sern depends very much on the starting material, such as old paper, and depending on the desired increase in whiteness. Usually the concentration of hydrogen peroxide is in the range of 5 mg / l to 500 mg / l. By using the invention or he The method according to the invention is preferably achieved within a Period from 0.5 hours to 1 hour, in particular up to 2 hours Hydrogen peroxide concentration in the circulating water is not below values half of 50%, especially not below 70% of that of the operator desired or required hydrogen peroxide concentration decreases without hydrogen peroxide being replenished in the period mentioned must become.

Zu den Katalase-Inhibitoren gehören insbesondere die aliphatischen, cycloaliphatischen, aromatischen und/oder heterocyclischen N-Hydroxy-, Oxim-, N-Oxid- und N-Dioxid-verbindungen, Azide, insbesondere Alkaliazide, Hydrazin, Hydraziniumsalze wie Hydraziniumhydrochlorid, Hydroxylamin, Hy­ droxylammoniumsalze, Hydroxamsäuren, Hydroxamsäureester und deren Gemische sowie deren Precursor, das heißt Verbindungen, die unter Anwendungsbedin­ gungen derartige Katalase-Inhibitoren freisetzen. Unter den Katalase-In­ hibitoren ist Hydroxylamin und/oder dessen Salze, insbesondere Hydroxyl­ ammoniumchlorid, Hydroxylammoniumbromid, Hydroxylammoniumsulfat und/oder -hydrogensulfat, besonders bevorzugt.The catalase inhibitors include in particular the aliphatic, cycloaliphatic, aromatic and / or heterocyclic N-hydroxy, Oxime, N-oxide and N-dioxide compounds, azides, especially alkali azides, Hydrazine, hydrazinium salts such as hydrazinium hydrochloride, hydroxylamine, Hy hydroxylammonium salts, hydroxamic acids, hydroxamic acid esters and mixtures thereof as well as their precursors, that is, compounds which are used under application conditions releases such catalase inhibitors. Among the catalase-in hibitoren is hydroxylamine and / or its salts, especially hydroxyl ammonium chloride, hydroxylammonium bromide, hydroxylammonium sulfate and / or -hydrogen sulfate, particularly preferred.

Der Katalase-Inhibitor ist vorzugsweise in Mengen von 5 ppm bis 10 000 ppm, insbesondere von 10 ppm bis 1000 ppm, im Kreislaufwasser enthalten.The catalase inhibitor is preferably in amounts from 5 ppm to 10,000 ppm, in particular from 10 ppm to 1000 ppm, contained in the circulating water.

Überraschenderweise wurde gefunden, daß die Wasserstoffperoxid-stabili­ sierende Wirkung des Katalase-Inhibitors verstärkt werden kann, wenn im Kreislaufwasser eine Kombination aus Katalase-Inhibitor und Enzym und/oder insbesondere schleimbilungsverhinderndem Biozid vorliegt. Dies kann im Rahmen des erfindungsgemäßen Verfahrens durch die Zugabe der separaten Wirkstoffe in das Kreislaufwasser oder durch die Zugabe von Zubereitungen, welche die genannten Kombinationen enthalten, erreicht werden. Ein weite­ rer Gegenstand der Erfindung ist daher ein Mittel zur Stabilisierung von Wasserstoffperoxid in industriellen Kreislaufwässern, insbesondere in Kreislaufwässern der Papierindustrie, welches Katalase-Inhibitor und Enzym und/oder Biozid enthält.Surprisingly, it was found that the hydrogen peroxide stabili effect of the catalase inhibitor can be enhanced if in Circulation water a combination of catalase inhibitor and enzyme and / or in particular there is a biocide which prevents mucilage. This can be done in The process of the invention by adding the separate Active substances in the circulating water or by adding preparations,  which contain the combinations mentioned can be achieved. A wide one The subject of the invention is therefore a means for stabilizing Hydrogen peroxide in industrial circulating water, especially in Circulating water in the paper industry, which catalase inhibitor and enzyme and / or contains biocide.

Das Enzym wird vorzugsweise aus Protease, Xylanase, Glucanase, Levanase, Hemicellulase, Cellulase und deren Mischungen ausgewählt. Dabei ist darauf zu achten, daß man möglichst Katalase-freie Enzymqualitäten einsetzt. Man kann die Enzyme im Kreislaufwasser auch in situ durch Mikroorganismen er­ zeugen, welche in der Lage sind, solche Enzyme herzustellen und zu expri­ mieren. Im Rahmen der letztgenannten Variante der Erfindung ist es mög­ lich, solche Mikroorganismen dem Kreislaufwasser zuzusetzen oder durch die Zugabe von Nährlösungen, beispielsweise der aus der deutschen Patentan­ meldung DE 43 31 022 bekannten Stickstoff- und Phosphorquellen, das Wachstum solcher Mikroorganismen zu fördern.The enzyme is preferably made from protease, xylanase, glucanase, levanase, Hemicellulase, cellulase and mixtures thereof selected. It is on it to ensure that you use catalase-free enzyme qualities if possible. Man the enzymes in the circulating water can also be generated in situ by microorganisms testify who are able to produce such enzymes and to expri lubricate. In the latter variant of the invention, it is possible Lich to add such microorganisms to the circulating water or through the Adding nutrient solutions, for example that from the German patent DE 43 31 022 known nitrogen and phosphorus sources, the To promote the growth of such microorganisms.

Zu den geeigneten Bioziden gehören insbesondere Alkalichlorit, Alkaliper­ oxid, Peroxycarbonsäuren, 1,4-Bis(bromacetoxy)buten, Tetramethyl-thiuram­ disulfid. 3,5-Dimethyl-tetrahydro-1,3,5-thiadiazin-2-thion, Bromhydroxy­ acetophenon, Dialkali-cyano-dithioimidocarbonat, N-(2-Chlorbenzoylethyl)­ hexaminiumhalogenid, Methylen-bis-thiocyanat, Alkali-N-hydroxymethyl-N′- methyl-dithiocarbamat, Alkali-2-Mercaptobenzothiazol, 2-Oxo-2-(4-hydroxy­ phenyl)-acethydroximsäurechlorid, 2-Brom-2-Nitro-1,3-propandiol, 5-Chlor- 2-methyl-4-isothiazolin-3-on, 2-Methyl-4-isothiazolin-3-on, N,N′-Dihy­ droxymethylenharnstoff, 1,6-Dihydroxy-2,5-dioxahexan, 2,2-Dibrom-3-ni­ tril-propionamid, Phenyl-(2-chlor-2-cyan-vinyl)-sulfon, Phenyl-(1,2-di­ chlor-2-cyan-vinyl)-sulfon, 2-Phenyl-sulfonylpropionitril, 1,2-Benziso­ thiazolin-3-on, 1,2-Dibrom-2,4-dicyanobutan, 4,5-Dichlor-(3H)-1,2-di­ thiol-3-on, β-Brom-β-nitrostyrol, Formaldehyd, Glutardialdehyd und deren
Mischungen, wobei Alkali bevorzugt für Natrium und/oder Kalium und Halo­ gen bevorzugt für Chlor steht. Unter den Peroxycarbonsäuren ist Peressig­ säure bevorzugt.Suitable biocides include, in particular, alkali chlorite, alkali peroxide, peroxycarboxylic acids, 1,4-bis (bromoacetoxy) butene, tetramethyl-thiuram disulfide. 3,5-dimethyl-tetrahydro-1,3,5-thiadiazine-2-thione, bromohydroxy acetophenone, dialkali-cyano-dithioimidocarbonate, N- (2-chlorobenzoylethyl) hexaminium halide, methylene-bis-thiocyanate, alkali-N-hydroxymethyl N'-methyl-dithiocarbamate, alkali-2-mercaptobenzothiazole, 2-oxo-2- (4-hydroxyphenyl) -acethydroximoyl chloride, 2-bromo-2-nitro-1,3-propanediol, 5-chloro-2-methyl- 4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N, N'-dihydroxyethylene urea, 1,6-dihydroxy-2,5-dioxahexane, 2,2-dibromo-3-nitrile -propionamide, phenyl- (2-chloro-2-cyano-vinyl) sulfone, phenyl- (1,2-di chloro-2-cyano-vinyl) sulfone, 2-phenylsulfonylpropionitrile, 1,2-benzisothiazoline -3-one, 1,2-dibromo-2,4-dicyanobutane, 4,5-dichloro- (3H) -1,2-di thiol-3-one, β-bromo-β-nitrostyrene, formaldehyde, glutardialdehyde and their
Mixtures, where alkali is preferably sodium and / or potassium and halo is preferably chlorine. Peracetic acid is preferred among the peroxycarboxylic acids.

Durch die erfindungsgemäße Verwendung beziehungsweise das erfindungsgemäße Verfahren sind signifikante Einsparungen an Wasserstoffperoxid möglich.Through the use according to the invention or the inventive Processes, significant savings in hydrogen peroxide are possible.

Claims (19)

1. Verwendung von Katalase-Inhibitoren zur Stabilisierung von Wasser­ stoffperoxid in industriellen Kreislaufwässern.1. Use of catalase inhibitors to stabilize water peroxide in industrial circulating water. 2. Verwendung von Katalase-Inhibitoren zur Stabilisierung von Wasser­ stoffperoxid in Kreislaufwässern der Papierindustrie.2. Use of catalase inhibitors to stabilize water peroxide in circulating water in the paper industry. 3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß im Kreislaufwasser eine Kombination aus Katalase-Inhibitor und Enzym vorliegt.3. Use according to claim 1 or 2, characterized in that in Circulation water is a combination of catalase inhibitor and enzyme is present. 4. Verwendung nach Anspruch 3, dadurch gekennzeichnet, daß das Enzym aus Protease, Xylanase, Glucanase, Levanase, Hemicellulase, Cellulase und deren Mischungen ausgewählt wird.4. Use according to claim 3, characterized in that the enzyme Protease, xylanase, glucanase, levanase, hemicellulase, cellulase and whose mixtures are selected. 5. Verwendung nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß die Enzyme im Kreislaufwasser in situ durch Mikroorganismen erzeugt wer­ den.5. Use according to claim 3 or 4, characterized in that the Enzymes in circulating water are generated in situ by microorganisms the. 6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß im Kreislaufwasser eine Kombination aus Katalase-Inhibitor und Biozid vorliegt.6. Use according to one of claims 1 to 5, characterized in that that in the circulating water a combination of catalase inhibitor and Biocide is present. 7. Verwendung nach Anspruch 6, dadurch gekennzeichnet, daß das Biozid ausgewählt wird aus Alkalichlorit, Alkaliperoxid, Peroxycarbonsäuren, 1,4-Bis(bromacetoxy)buten, Tetramethyl-thiuram-disulfid. 3,5-Dimethyl­ tetrahydro-1,3,5-thiadiazin-2-thion, Bromhydroxyacetophenon, Dialka­ li-cyano-dithioimidocarbonat, N-(2-Chlorbenzoylethyl)-hexaminiumha­ logenid, Methylen-bis-thiocyanat, Alkali-Nhydroxy-methyl-N′-methyl­ dithiocarbamat, Alkal 1-2-Mercaptobenzothiazol, 2-Oxo-2-(4-hydroxy­ phenyl)-acethydroximsäurechlorid, 2-Brom-2-Ni-tro-1,3-propandiol, 5- Chlor-2-methyl-4-isothiazolin-3-on, 2-Methyl-4-isothiazolin-3-on, N,N′-Dihydroxymethylenharnstoff, 1,6-Dihydroxy-2,5-dioxahexan, 2,2- Dibrom-3-nitril-propionamid, Phenyl-(2-chlor-2-cyan-vinyl)-sulfon, Phenyl-(1,2-dichlor-2-cyanvinyl)-sulfon, 2-Phenyl-sulfonylpropio­ nitril, 1,2-Benzisothiazolin-3-on, 1,2-Dibrom-2,4-dicyanobutan, 4,5- Dichlor-(3H)-1,2-dithiol-3-on, β-Brom-β-nitrostyrol, Formaldehyd, Glutardialdehyd und deren Mischungen.7. Use according to claim 6, characterized in that the biocide is selected from alkali chlorite, alkali peroxide, peroxycarboxylic acids, 1,4-bis (bromoacetoxy) butene, tetramethylthiuram disulfide. 3,5-dimethyl tetrahydro-1,3,5-thiadiazine-2-thione, bromohydroxyacetophenone, Dialka li-cyano-dithioimidocarbonate, N- (2-chlorobenzoylethyl) hexaminiumha logenide, methylene bis-thiocyanate, alkali Nhydroxy-methyl-N'-methyl dithiocarbamate, alkali 1-2-mercaptobenzothiazole, 2-oxo-2- (4-hydroxy phenyl) -acethydroximoyl chloride, 2-bromo-2-nitro-1,3-propanediol, 5- Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N, N'-dihydroxymethylene urea, 1,6-dihydroxy-2,5-dioxahexane, 2,2- Dibromo-3-nitrile-propionamide, phenyl (2-chloro-2-cyano-vinyl) sulfone, Phenyl- (1,2-dichloro-2-cyanovinyl) sulfone, 2-phenylsulfonylpropio  nitrile, 1,2-benzisothiazolin-3-one, 1,2-dibromo-2,4-dicyanobutane, 4,5- Dichloro- (3H) -1,2-dithiol-3-one, β-bromo-β-nitrostyrene, formaldehyde, Glutardialdehyde and mixtures thereof. 8. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Katalase-Inhibitor ausgewählt wird aus aliphatischen, cyclo­ aliphatischen, aromatischen und/oder heterocyclischen N-Hydroxy-, Oxim-, N-Oxid- und N-Dioxid-verbindungen, Aziden, Hydrazin, Hydrazi­ niumsalzen, Hydroxylamin, Hydroxylammoniumsalzen, Hydroxamsäuren, Hydroxamsäureestern und deren Gemischen.8. Use according to one of claims 1 to 7, characterized in that the catalase inhibitor is selected from aliphatic, cyclo aliphatic, aromatic and / or heterocyclic N-hydroxy, Oxime, N-oxide and N-dioxide compounds, azides, hydrazine, hydrazi nium salts, hydroxylamine, hydroxylammonium salts, hydroxamic acids, Hydroxamic acid esters and mixtures thereof. 9. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Katalase-Inhibitor in Mengen von 5 ppm bis 10 000 ppm, insbe­ sondere von 10 ppm bis 1000 ppm, im Kreislaufwasser enthalten ist.9. Use according to one of claims 1 to 8, characterized in that that the catalase inhibitor in amounts of 5 ppm to 10,000 ppm, esp special from 10 ppm to 1000 ppm, is contained in the circulating water. 10. Verfahren zur Stabilisierung von Wasserstoffperoxid in industriellen Kreislaufwässern, insbesondere in Kreislaufwässern der Papierindu­ strie, durch Zugabe von Katalase-Inhibitoren.10. Process for the stabilization of hydrogen peroxide in industrial Circulating water, especially in circulating water of the paper industry strie, by adding catalase inhibitors. 11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß man den Kata­ lase-Inhibitor in solchen Mengen zum Kreislaufwasser gibt, daß in diesem eine Konzentration im Bereich von 5 ppm bis 10 000 ppm, insbe­ sondere von 10 ppm bis 1000 ppm erreicht wird.11. The method according to claim 10, characterized in that the kata Lase inhibitor in such amounts to the circulating water that in this a concentration in the range of 5 ppm to 10,000 ppm, esp special from 10 ppm to 1000 ppm is achieved. 12. Verfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, daß man Katalase-Inhibitor und Enzym, allein oder zusammen, dem Kreislaufwas­ ser zusetzt.12. The method according to claim 10 or 11, characterized in that Catalase inhibitor and enzyme, alone or together, the circulatory system he adds. 13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, daß das Enzym aus Protease, Xylanase, Glucanase, Levanase, Hemicellulase, Cellulase und deren Mischungen ausgewählt wird.13. The method according to claim 12, characterized in that the enzyme Protease, xylanase, glucanase, levanase, hemicellulase, cellulase and whose mixtures are selected. 14. Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, daß man dem Kreislaufwasser Mikroorganismen zusetzt, welche in der Lage sind, Enzyme in situ herzustellen und zu exprimieren. 14. The method according to claim 12 or 13, characterized in that one adds microorganisms to the circulating water, which are able to To produce and express enzymes in situ.   15. Verfahren nach einem der Ansprüche 12 bis 14, dadurch gekennzeichnet, daß man dem Kreislaufwasser eine Nährlösung für Mikroorganismen zu­ setzt, welche in der Lage sind, Enzyme in situ herzustellen und zu exprimieren.15. The method according to any one of claims 12 to 14, characterized in that the nutrient solution for microorganisms is added to the circulating water who are able to produce and add enzymes in situ express. 16. Verfahren nach einem der Ansprüche 10 bis 15, dadurch gekennzeichnet, daß man Katalase-Inhibitor und Biozid, allein oder zusammen, dem Kreislaufwasser zusetzt.16. The method according to any one of claims 10 to 15, characterized in that catalase inhibitor and biocide, alone or together, the Circulating water clogged. 17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß das Biozid ausgewählt wird aus Alkalichlorit, Alkaliperoxid, Peroxycarbonsäuren, 1,4-Bis(bromacetoxy)buten, Tetramethyl-thiuram-disulfid. 3,5-Dime­ thyl-tetrahydro-1,3,5-thiadiazin-2-thion, Bromhydroxyacetophenon, Di­ alkali-cyano-dithioimidocarbonat, N-(2-Chlorbenzoylethyl)-hexamini­ umhalogenid, Methylen-bis-thiocyanat, Alkali-N-hydroxymethyl-N′-me­ thyl-dithiocarbamat, Alkali-2-Mercaptobenzothiazol, 2-Oxo-2-(4-hy­ droxyphenyl)-acethydroximsäurechlorid, 2-Brom-2-Nitro-1,3-propandi­ ol, 5-Chlor-2-methyl-4-isothiazolin-3-on, 2-Methyl-4-isothiazolin- 3-on, N,N′-Dihydroxymethylenharnstoff, 1,6-Dihydroxy-2,5-dioxahexan, 2,2-Dibrom-3-nitril-propionamid, Phenyl-(2-chlor-2-cyan-vinyl)-sul­ fon, Phenyl-(1,2-dichlor-2-cyan-vinyl)-sulfon, 2-Phenyl-sulfonylpro­ pionitril, 1,2-Benzisothiazolin-3-on, 1,2-Dibrom-2,4-dicyanobutan, 4,5-Dichlor-(3H)-1,2-dithiol-3-on, β-Brom-β-nitrostyrol, Formalde­ hyd, Glutardialdehyd und deren Mischungen.17. The method according to claim 16, characterized in that the biocide is selected from alkali chlorite, alkali peroxide, peroxycarboxylic acids, 1,4-bis (bromoacetoxy) butene, tetramethylthiuram disulfide. 3.5 dime ethyl tetrahydro-1,3,5-thiadiazine-2-thione, bromohydroxyacetophenone, Di alkali-cyano-dithioimidocarbonate, N- (2-chlorobenzoylethyl) hexamini halide, methylene bis-thiocyanate, alkali N-hydroxymethyl-N'-me ethyl dithiocarbamate, alkali 2-mercaptobenzothiazole, 2-oxo-2- (4-hy droxyphenyl) acethydroximoyl chloride, 2-bromo-2-nitro-1,3-propanedi ol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin- 3-one, N, N'-dihydroxymethylene urea, 1,6-dihydroxy-2,5-dioxahexane, 2,2-dibromo-3-nitrile-propionamide, phenyl- (2-chloro-2-cyano-vinyl) -sul phon, phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone, 2-phenylsulfonylpro pionitrile, 1,2-benzisothiazolin-3-one, 1,2-dibromo-2,4-dicyanobutane, 4,5-dichloro- (3H) -1,2-dithiol-3-one, β-bromo-β-nitrostyrene, formaldehyde hyd, glutardialdehyde and mixtures thereof. 18. Verfahren nach einem der Ansprüche 10 bis 17, dadurch gekennzeichnet, daß der Katalase-Inhibitor ausgewählt wird aus aliphatischen, cyclo­ aliphatischen, aromatischen und/oder heterocyclischen N-Hydroxy-, Oxim-, N-Oxid- und N-Dioxid-verbindungen, Aziden, Hydrazin, Hydrazi­ niumsalzen, Hydroxylamin, Hydroxylammoniumsalzen, Hydroxamsäuren, Hydroxamsäureestern und deren Gemischen.18. The method according to any one of claims 10 to 17, characterized in that the catalase inhibitor is selected from aliphatic, cyclo aliphatic, aromatic and / or heterocyclic N-hydroxy, Oxime, N-oxide and N-dioxide compounds, azides, hydrazine, hydrazi nium salts, hydroxylamine, hydroxylammonium salts, hydroxamic acids, Hydroxamic acid esters and mixtures thereof. 19. Mittel zur Stabilisierung von Wasserstoffperoxid in industriellen Kreislaufwässern, insbesondere in Kreislaufwässern der Papierin­ dustrie, dadurch gekennzeichnet, daß es Katalase-Inhibitor und Enzym und/oder Biozid enthält.19. Means for stabilizing hydrogen peroxide in industrial Circulation waters, especially in paper circulation waters  dustrie, characterized in that it is catalase inhibitor and enzyme and / or contains biocide.
DE1995129444 1995-08-10 1995-08-10 Catalase inhibitors used to stabilise hydrogen peroxide - in industrial recycle waters, esp. in the paper industry Ceased DE19529444A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6432262B1 (en) 2000-06-08 2002-08-13 Lonza, Inc. Method of bleaching recycled papers with hydrogen peroxide stabilized with a methylolhydantoin

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6432262B1 (en) 2000-06-08 2002-08-13 Lonza, Inc. Method of bleaching recycled papers with hydrogen peroxide stabilized with a methylolhydantoin
US6696093B2 (en) 2000-06-08 2004-02-24 Lonza Inc. Aldehyde donors for stabilizing peroxides
EP1294980B2 (en) † 2000-06-08 2015-10-07 Lonza Inc. Aldehyde donors for stabilizing peroxides in papermaking applications

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