EP0860517A1 - Method and composition for corrosion inhibiting water carrying metal systems - Google Patents

Method and composition for corrosion inhibiting water carrying metal systems Download PDF

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Publication number
EP0860517A1
EP0860517A1 EP98101043A EP98101043A EP0860517A1 EP 0860517 A1 EP0860517 A1 EP 0860517A1 EP 98101043 A EP98101043 A EP 98101043A EP 98101043 A EP98101043 A EP 98101043A EP 0860517 A1 EP0860517 A1 EP 0860517A1
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weight
silicates
water
phosphate
phosphates
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EP0860517B1 (en
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Peter Schmidt
Werner Wons
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BK Giulini GmbH
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Metakorin Wasser-Chemie GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors
    • C23F11/188—Mixtures of inorganic inhibitors containing phosphates

Definitions

  • the invention relates to a method for corrosion protection treatment of water-bearing systems, especially from low alloyed or unalloyed steel, made of copper or lead, as well as means and devices for carrying out the method.
  • EP 102587-B1 describes a method for Corrosion protection treatment of water-bearing systems with additives of phosphates and / or silicates, the water Sodium or potassium carbonates or bicarbonates in combination with these phosphates and / or silicates added will.
  • an agent is dosed into the water flow which trisodium phosphate, sodium silicate and sodium hydrogen carbonate contains.
  • EP 510989-A1 claims an agent for preventing the corrosion of cast iron in drinking water systems, which contains about three parts by weight of orthophosphate and one part by weight of sodium silicate, expressed as PO 4 or SiO 2 .
  • This agent By adding this agent to the drinking water, the precipitation of dissolved manganese and iron ions is to be prevented and the content of dissolved lead from the corrosion of lead pipes is to be reduced.
  • This publication confirms the synergistic effect of a preparation with phosphate and silicate compared to pure phosphate already reported by D. Liebich (Forumgate-Hygiene 40 (1989) pages 102 to 107).
  • the weight quantities of phosphate and silicate to be added in order to optimally utilize the synergistic effect are not constant, but rather depend, for example, on the type of water and on the operating conditions and the type of corrosion protection desired.
  • a high content of neutral salts such as chlorides and sulfates with low acid capacity promotes corrosion (DIN 50930 Part 2, Chapter 5.2).
  • a cover layer of iron hydroxides formed in the stationary flow mode which in itself slows down the corrosion process, can re-form in the case of non-steady-state operation, ie in the absence of oxygen (A. Kuch et al., Gwf-wasser / abement 127 (1986), pages 621-629 ).
  • every addition to drinking water must be limited to the necessary minimum. With regard to all flow systems, this applies in particular to phosphate, since it can lead to undesirable and harmful over-fertilization of surface waters via the waste water.
  • the object of the invention is a method for anti-corrosion treatment water-bearing metal systems by dosing a combination of phosphates and silicates in the water flow specify with which an optimal ratio at all times from silicate to phosphate while minimizing the Amount of phosphate can be observed.
  • phosphates and silicates can be added to any of these happen in a manner known to those skilled in the art. Both can be finely divided solid form through known mechanical metering devices be added. It is also possible to use the finely divided solid active ingredients before use by means of a to granulate a suitable, possibly water-soluble binder.
  • the silicates and the phosphates are preferred as concentrated aqueous solutions used. It goes without saying also possible a component in solid form as described and use the other as a solution.
  • Preferred silicate solutions contain alkali metal silicates, especially with a module from 1.8 to 3.5.
  • module denotes the molar ratio of silicon dioxide to alkali oxide.
  • Sodium silicate with a modulus of 2.6 to 3.5 is particularly preferred.
  • Aqueous silicate solutions with a content of at least 20% by weight of SiO 2 are advantageous.
  • the silicate solution contains a water-soluble carbonate or bicarbonate, for example sodium or potassium.
  • the amount of this carbonate or bicarbonate is limited by its solubility in the silicate solution. It is preferably - expressed as CO 3 - at least one tenth, particularly preferably at least one fifth of the weight fraction of SiO 2 in the solution.
  • the aqueous phosphate solution preferably has a concentration of at least 20% by weight of PO 4 .
  • Suitable phosphates are orthophosphates, in particular sodium orthophosphate, potassium orthophosphate, oligophosphates such as sodium and potassium diphosphate, sodium and potassium triphosphate, polyphosphates such as sodium and potassium polyphosphate or mixtures thereof. Solutions which contain both ortho- and oligo- and / or polyphosphates are preferred. The latter can convert to orthophosphates and serve as an orthophosphate reservoir for the protection of parts of the metal system that are remote from the plant, in particular unsteady-operated end strands, when the original orthophosphate for covering layer formation in the parts near the plant has been largely used up.
  • Preferred solutions contain 25 to 75% of the total phosphate as orthophosphate and 25 to 75% in the form of one or more oligo- or polyphosphates, each calculated as a proportion by weight of the total PO 4 .
  • the separate dosing of the phosphates and silicates can by means of multi-component metering devices known per se happen. These devices can be placed anywhere arranged upstream in front of the metal system to be protected be. Both components can be in the same place be added to the current, for example by means of opposite Nozzles. However, a component can also be added first and in the course of the current, for example by means of static internals or with the help of stirrers, mixed with the water flow and then the other component is added. in the the latter case is preferably first phosphate and then silicate added. In this way it can be used with some waters occurring when introducing the alkaline silicate component Precipitation of alkaline earth carbonates, which leads to annoying incrustation the dosing device can be avoided.
  • the metered amounts are preferably such that the concentration of the phosphate in the water stream is 0.1 to 6.7 mg PO 4 / l and that of the silicate is 1 to 40 mg SiO 2 / l.
  • the metered amounts of the silicate and phosphate solution are preferably adjusted or regulated independently of one another.
  • the basis for the setting variables can be, for example, preliminary tests with the given wall materials of the metallic water-carrying system. However, these quantities can also be determined according to the corrosive aggressiveness of the water that can be derived from the water analysis.
  • the doses of the silicates or phosphates over time changed can, for example, provide optimal protection against corrosion be maintained when water quality changes.
  • the dosage, in particular of the phosphate are withdrawn if there is in the Metal system an adequate corrosion-resistant top layer has trained. This is both in terms of environmental protection as well as economical in terms of economy.
  • a silicate solution suitable for carrying out the process according to the invention contains, in aqueous solution, alkali silicates in a concentration corresponding to at least 20% by weight SiO 2 and alkali metal carbonates and hydrogen carbonates in a concentration corresponding to at least 0.1% by weight CO 3 , preferably at least one tenth, particularly preferably at least one fifth of the weight fraction SiO 2 .
  • a phosphate solution suitable for carrying out the process according to the invention contains alkali orthophosphates and polyphosphates in aqueous solution, 25 to 75% by weight of the total phosphate, calculated as PO 4 , being present in the form of orthophosphate and polyphosphate.
  • the term polyphosphate is intended to include oligophosphates here.
  • the inventive method can not only the undesirable Rust coloration of the water in metal systems on the Base of iron, but also going into dissolution is harmful to health Amounts of copper and lead ions from copper or lead-containing systems with minimal use of materials avoided will.

Abstract

Process for corrosion protective treatment of water-conveying metal systems involves separate dosing of phosphates and silicates into the water flow. Preferably, the silicates are dosed in amount 1.0-40 mg SiO2/l as an aqueous silicate solution with a modulus of 1.8-3.5 and a SiO2 concentration of ≥ 20 wt.%, while the phosphates are dosed in amount 0.1-6.7 mg PO4/l as an aqueous phosphate solution with a PO4 concentration of ≥ 20 wt.%. Also claimed is a medium which is used in the above corrosion protective treatment process and which contains, in aqueous solution, (a) alkali metal silicates, carbonates and hydrogen carbonates, with SiO2 and CO3 concentrations of 20 wt.% and 0.1 wt.%, respectively; or (b) alkali metal orthophosphates and polyphosphates in amount (based on total phosphate content, expressed as PO4) 25-75 wt.% each, the total PO4 concentration being ≥ 20 wt.%.

Description

Die Erfindung betrifft ein Verfahren zur Korrosionsschutzbehandlung von wasserführenden Systemen, insbesondere aus niedrig legiertem oder unlegiertem Stahl, aus Kupfer oder Blei, sowie Mittel und Vorrichtungen zur Durchführung des Verfahrens.The invention relates to a method for corrosion protection treatment of water-bearing systems, especially from low alloyed or unalloyed steel, made of copper or lead, as well as means and devices for carrying out the method.

Es ist bekannt, in wasserführenden Metallsystemen zur Verhinderung der Korrosion und der damit verbundenen Beeinträchtigung der Wasserqualität dem Wasser bestimmte chemische Stoffe zuzusetzen. Bei Durchflußsystemen, insbesondere für die Trinkwasserversorgung, kommen dabei nur wenige Stoffe in Frage, weil die Gesundheitsgefährdung der Verbraucher unbedingt und die Belastung des Abwassers soweit wie möglich vermieden werden müssen. Die EP 102587-B1 beschreibt ein Verfahren zur Korrosionsschutzbehandlung wasserführender Systeme durch Zusätze von Phosphaten und/oder Silikaten, wobei dem Wasser Natrium- oder Kaliumcarbonate oder -hydrogencarbonate in Kombination mit diesen Phosphaten und/oder Silikaten zugegeben werden. Hierzu wird in den Wasserstrom ein Mittel dosiert, welches Trinatriumphosphat, Natriumsilikat und Natriumhydrogencarbonat enthält.It is known to prevent in water-bearing metal systems the corrosion and the associated impairment the water quality certain chemical substances to add. In flow systems, especially for drinking water supply, there are only a few substances in question, because the health risk to consumers is imperative and the pollution of the wastewater should be avoided as far as possible have to. EP 102587-B1 describes a method for Corrosion protection treatment of water-bearing systems with additives of phosphates and / or silicates, the water Sodium or potassium carbonates or bicarbonates in combination with these phosphates and / or silicates added will. For this purpose, an agent is dosed into the water flow which trisodium phosphate, sodium silicate and sodium hydrogen carbonate contains.

Die EP 510989-A1 beansprucht ein Mittel zur Verhinderung der Korrosion von Gußeisen in Trinkwassersystemen, welches etwa drei Gewichtsteile Orthophosphat und ein Gewichtsteil Natriumsilikat, ausgedrückt als PO4 bzw. SiO2, enthält. Durch Zusatz dieses Mittels zum Trinkwasser soll die Ausfällung gelöster Mangan- und Eisenionen verhindert und der Gehalt an gelöstem Blei aus der Korrosion von Bleirohren vermindert werden. Durch diese Veröffentlichung wird der bereits von D. Liebich (Forum Städte-Hygiene 40 (1989) Seite 102 bis 107) berichtete synergistische Effekt einer Zubereitung mit Phosphat und Silikat gegenüber reinem Phosphat bestätigt.EP 510989-A1 claims an agent for preventing the corrosion of cast iron in drinking water systems, which contains about three parts by weight of orthophosphate and one part by weight of sodium silicate, expressed as PO 4 or SiO 2 . By adding this agent to the drinking water, the precipitation of dissolved manganese and iron ions is to be prevented and the content of dissolved lead from the corrosion of lead pipes is to be reduced. This publication confirms the synergistic effect of a preparation with phosphate and silicate compared to pure phosphate already reported by D. Liebich (Forum Städte-Hygiene 40 (1989) pages 102 to 107).

Die zur optimalen Ausnutzung des synergistischen Effekts zuzudosierenden Gewichtsmengen Phosphat und Silikat sind nicht konstant, sondern hängen beispielsweise von der Art des Wassers sowie von den Betriebsbedingungen und der Art des gewünschten Korrosionsschutzes ab. So fördert ein hoher Gehalt an Neutralsalzen wie Chloriden und Sulfaten bei geringer Säurekapazität die Korrosion (DIN 50930 Teil 2, Kapitel 5.2). Eine im stationären Durchflußbetrieb gebildete Deckschicht aus Eisenhydroxyden, die an sich den Korrosionsvorgang verlangsamt, kann sich bei instationärem Betrieb, d. h. bei Sauerstoffmangel, wieder zurückbilden (A. Kuch et al., gwf-wasser/abwasser 127 (1986), Seiten 621-629). Andererseits ist nach den gesetzlichen Vorschriften jeder Zusatz zum Trinkwasser auf das notwendige Minimum zu beschränken. Bezüglich aller Durchflußsysteme gilt dies insbesondere für Phosphat, da es über das Abwasser zu einer unerwünschten und schädlichen Überdüngung der Oberflächengewässer führen kann.The weight quantities of phosphate and silicate to be added in order to optimally utilize the synergistic effect are not constant, but rather depend, for example, on the type of water and on the operating conditions and the type of corrosion protection desired. A high content of neutral salts such as chlorides and sulfates with low acid capacity promotes corrosion (DIN 50930 Part 2, Chapter 5.2). A cover layer of iron hydroxides formed in the stationary flow mode, which in itself slows down the corrosion process, can re-form in the case of non-steady-state operation, ie in the absence of oxygen (A. Kuch et al., Gwf-wasser / abwasser 127 (1986), pages 621-629 ). On the other hand, according to the legal regulations, every addition to drinking water must be limited to the necessary minimum. With regard to all flow systems, this applies in particular to phosphate, since it can lead to undesirable and harmful over-fertilization of surface waters via the waste water.

Im Handel sind Zubereitungen, bei denen das Gewichtsverhältnis Phosphat zu Silikat unterschiedlich eingestellt ist. Von diesen Zubereitungen kann im konkreten Fall diejenige ausgewählt werden, die dem Optimum am nächsten kommt. Es ist auch bekannt, zu Beginn des Phosphat/Silikat-Korrosionsschutzverfahrens eine höhere Phosphatkonzentration zu verwenden und später, wenn angenommen werden kann, daß sich hinreichend stabile Deckschichten ausgebildet haben, auf eine niedrigere Phosphatkonzentration umzustellen. Mit den genannten Produkten kann das optimale Phosphat/Silikat-Verhältnis jedoch nur zufällig und ausnahmsweise erreicht werden. Auch ist für die Anwendung des Zweistufenverfahrens oder bei wechselnder Wasserqualität die unwirtschaftliche Vorratshaltung mehrerer Produkte notwendig.There are preparations on the market in which the weight ratio Phosphate to silicate is set differently. Of these In the specific case, preparations can be selected be the closest to the optimum. It is also known at the beginning of the phosphate / silicate corrosion protection process to use a higher phosphate concentration and later, if it can be assumed that they are sufficiently stable Cover layers have formed on a lower phosphate concentration switch. With the mentioned products can the optimal phosphate / silicate ratio is only random and can be reached exceptionally. It is also for use of the two-stage process or with changing water quality the uneconomical stockpiling of several products is necessary.

Aufgabe der Erfindung ist es, ein Verfahren zur Korrosionsschutzbehandlung wasserführender Metallsysteme durch Dosierung einer Kombination von Phosphaten und Silikaten in den Wasserstrom anzugeben, mit dem zu jeder Zeit ein optimales Verhältnis von Silikat zu Phosphat bei gleichzeitiger Minimierung der Phosphatmenge eingehalten werden kann.The object of the invention is a method for anti-corrosion treatment water-bearing metal systems by dosing a combination of phosphates and silicates in the water flow specify with which an optimal ratio at all times from silicate to phosphate while minimizing the Amount of phosphate can be observed.

Diese Aufgabe wird durch ein Verfahren nach dem Anspruch 1 gelöst.This object is achieved by a method according to claim 1 solved.

Es wurde nämlich überraschenderweise festgestellt, daß die bekannte synergistische Korrosionsschutzwirkung von Phosphat/Silikat-Kombinationen auch dann eintritt, wenn Phosphat und Silikat dem Wasserstrom getrennt zugesetzt werden. Im allgemeinen hängt nämlich die Wirksamkeit solcher Komponenten durchaus davon ab, ob sie vorgemischt sind oder nicht. Beispielsweise wirkt das nach der Lehre der EP 102587 dem Phosphat-Silikat-Gemisch zugesetzte Hydrogencarbonat völlig anders als das bereits vorher im Wasser vorhandene.It was surprisingly found that the Known synergistic corrosion protection effect of phosphate / silicate combinations also occurs when phosphate and Silicate can be added to the water flow separately. In general namely depends on the effectiveness of such components depending on whether they are premixed or not. For example this works according to the teaching of EP 102587 the phosphate-silicate mixture added bicarbonate completely different than the one already in the water.

Der Zusatz der Phosphate und der Silikate kann auf jede dem Fachmann bekannte Weise geschehen. Beide können in fein verteilter fester Form durch bekannte mechanische Dosiereinrichtungen zugesetzt werden. Es ist auch möglich, die fein verteilten festen Wirkstoffe vor der Verwendung mittels eines geeigneten, ggf. wasserlöslichen Bindemittels zu granulieren. Bevorzugt werden die Silikate und die Phosphate als konzentrierte wässrige Lösungen eingesetzt. Es ist selbstverständlich auch möglich, eine Komponente in fester Form wie beschrieben und die andere als Lösung zu verwenden.The addition of phosphates and silicates can be added to any of these Happen in a manner known to those skilled in the art. Both can be finely divided solid form through known mechanical metering devices be added. It is also possible to use the finely divided solid active ingredients before use by means of a to granulate a suitable, possibly water-soluble binder. The silicates and the phosphates are preferred as concentrated aqueous solutions used. It goes without saying also possible a component in solid form as described and use the other as a solution.

Bevorzugte Silikatlösungen enthalten Alkalimetallsilikate, insbesondere mit einem Modul von 1,8 bis 3,5. Mit Modul wird das Molverhältnis von Siliciumdioxid zu Alkalioxid bezeichnet. Preferred silicate solutions contain alkali metal silicates, especially with a module from 1.8 to 3.5. With module denotes the molar ratio of silicon dioxide to alkali oxide.

Besonders bevorzugt ist Natriumsilikat mit einem Modul von 2,6 bis 3,5. Vorteilhaft sind wässrige Silikatlösungen mit einem Gehalt von mindestens 20 Gew.-% SiO2.Sodium silicate with a modulus of 2.6 to 3.5 is particularly preferred. Aqueous silicate solutions with a content of at least 20% by weight of SiO 2 are advantageous.

Bei einer weiteren bevorzugten Ausführungsform der Erfindung enthält die Silikatlösung ein wasserlösliches Carbonat oder Hydrogencarbonat, beispielsweise des Natriums oder des Kaliums. Die Menge dieses Carbonats oder Hydrogencarbonats ist nach oben hin durch seine Löslichkeit in der Silikatlösung begrenzt. Vorzugsweise beträgt sie - ausgedrückt als CO3 - mindestens ein Zehntel, besonders bevorzugt mindestens ein Fünftel des Gewichtanteiles SiO2 in der Lösung.In a further preferred embodiment of the invention, the silicate solution contains a water-soluble carbonate or bicarbonate, for example sodium or potassium. The amount of this carbonate or bicarbonate is limited by its solubility in the silicate solution. It is preferably - expressed as CO 3 - at least one tenth, particularly preferably at least one fifth of the weight fraction of SiO 2 in the solution.

Die wässrige Phosphatlösung hat bevorzugt eine Konzentration von mindestens 20 Gew.-% PO4. Als Phosphate kommen Orthophosphate, insbesondere Natriumorthophosphat, Kaliumorthophosphat, Oligophosphate wie Natrium- und Kaliumdiphosphat, Natrium- und Kaliumtriphosphat, Polyphosphate wie Natrium- und Kaliumpolyphosphat oder Gemische hiervon, in Betracht. Bevorzugt sind Lösungen, die sowohl Ortho- als auch Oligo- und/oder Polyphosphate enthalten. Letztere können sich zu Orthophosphaten umsetzen und dienen als Orthophosphat-Reservoir für den Schutz werksferner Teile des Metallsystems, insbesondere instationär betriebener Endstränge, wenn das ursprünglich vorhandene Orthophosphat zur Deckschichtbildung in den werksnahen Teilen zum großen Teil aufgebraucht wurde. Bevorzugte Lösungen enthalten 25 bis 75 % des Gesamtphosphates als Orthophosphat und 25 bis 75 % in Form eines oder mehrerer Oligo- oder Polyphosphate, jeweils als Gewichtsanteil am Gesamt-PO4 gerechnet.The aqueous phosphate solution preferably has a concentration of at least 20% by weight of PO 4 . Suitable phosphates are orthophosphates, in particular sodium orthophosphate, potassium orthophosphate, oligophosphates such as sodium and potassium diphosphate, sodium and potassium triphosphate, polyphosphates such as sodium and potassium polyphosphate or mixtures thereof. Solutions which contain both ortho- and oligo- and / or polyphosphates are preferred. The latter can convert to orthophosphates and serve as an orthophosphate reservoir for the protection of parts of the metal system that are remote from the plant, in particular unsteady-operated end strands, when the original orthophosphate for covering layer formation in the parts near the plant has been largely used up. Preferred solutions contain 25 to 75% of the total phosphate as orthophosphate and 25 to 75% in the form of one or more oligo- or polyphosphates, each calculated as a proportion by weight of the total PO 4 .

Die Formulierung "PO4" ohne Ladungsangabe dient, wie auch "SiO2" und "CO3", lediglich der Definition der stöchiometrischen Rechengröße und nicht der Beschreibung des tatsächlichen ionischen Zustands.Like "SiO 2 " and "CO 3 ", the formulation "PO 4 " without charge information only serves to define the stoichiometric calculation quantity and not to describe the actual ionic state.

Das getrennte Dosieren der Phosphate und der Silikate kann mittels an sich bekannter Mehrkomponenten-Dosiereinrichtungen geschehen. Diese Vorrichtungen können an beliebiger Stelle stromaufwärts vor dem zu schützenden Metallsystem angeordnet sein. Dabei können beide Komponenten an der gleichen Stelle dem Strom zugefügt werden, etwa mittels gegenüberliegender Düsen. Es kann aber auch zunächst eine Komponente zugesetzt und im Stromverlauf, beispielsweise mittels statischer Einbauten oder mit Hilfe von Rührern, mit dem Wasserstrom gemischt und dann die andere Komponente zugesetzt werden. Im letzteren Fall wird bevorzugt zunächst Phosphat und dann Silikat zudosiert. Auf diese Weise kann die bei manchen Wässern beim Einbringen der alkalischen Silikatkomponente auftretende Ausfällung von Erdalkalicarbonaten, die zur störenden Verkrustung der Dosiervorrichtung führen kann, vermieden werden.The separate dosing of the phosphates and silicates can by means of multi-component metering devices known per se happen. These devices can be placed anywhere arranged upstream in front of the metal system to be protected be. Both components can be in the same place be added to the current, for example by means of opposite Nozzles. However, a component can also be added first and in the course of the current, for example by means of static internals or with the help of stirrers, mixed with the water flow and then the other component is added. in the the latter case is preferably first phosphate and then silicate added. In this way it can be used with some waters occurring when introducing the alkaline silicate component Precipitation of alkaline earth carbonates, which leads to annoying incrustation the dosing device can be avoided.

Die Dosiermengen werden vorzugsweise so bemessen, daß im Wasserstrom die Konzentration des Phosphats 0,1 bis 6,7 mg PO4/l, die des Silikats 1 bis 40 mg SiO2/l beträgt. Vorzugsweise werden die dosierten Mengen der Silikat- und Phosphatlösung unabhängig voneinander eingestellt oder geregelt. Grundlage für die Einstellgrößen können beispielsweise Vorversuche mit den jeweils gegebenen Wandmaterialien des metallischen wasserführenden Systems sein. Man kann aber diese Größen auch nach der aus der Wasseranalyse ableitbaren korrosiven Aggressivität des Wassers festlegen.The metered amounts are preferably such that the concentration of the phosphate in the water stream is 0.1 to 6.7 mg PO 4 / l and that of the silicate is 1 to 40 mg SiO 2 / l. The metered amounts of the silicate and phosphate solution are preferably adjusted or regulated independently of one another. The basis for the setting variables can be, for example, preliminary tests with the given wall materials of the metallic water-carrying system. However, these quantities can also be determined according to the corrosive aggressiveness of the water that can be derived from the water analysis.

Bei einer vorteilhaften Ausführungsform des Verfahrens werden die Dosiermengen der Silikate bzw. Phosphate im Laufe der Zeit verändert. Dadurch kann beispielsweise ein optimaler Korrosionsschutz aufrechterhalten werden, wenn sich die Wasserqualität ändert. Andererseits kann auch die Dosierung, insbesondere des Phosphats, zurückgenommen werden, wenn sich in dem Metallsystem eine ausreichende korrosionshemmende Deckschicht ausgebildet hat. Dies ist sowohl hinsichtlich des Umweltschutzes als auch mit Bezug auf die Wirtschaftlichkeit günstig.In an advantageous embodiment of the method the doses of the silicates or phosphates over time changed. This can, for example, provide optimal protection against corrosion be maintained when water quality changes. On the other hand, the dosage, in particular of the phosphate, are withdrawn if there is in the Metal system an adequate corrosion-resistant top layer has trained. This is both in terms of environmental protection as well as economical in terms of economy.

Eine zur Ausführung des erfindungsgemäßen Verfahrens geeignete Silikatlösung enthält in wässriger Lösung Alkalisilikate in einer Konzentration entsprechend mindestens 20 Gew.-% SiO2 sowie Alkalicarbonate und Hydrogencarbonate in einer Konzentration entsprechend mindestens 0,1 Gew.-% CO3, vorzugsweise mindestens ein Zehntel, besonders bevorzugt mindestens ein Fünftel des Gewichtsanteils SiO2.A silicate solution suitable for carrying out the process according to the invention contains, in aqueous solution, alkali silicates in a concentration corresponding to at least 20% by weight SiO 2 and alkali metal carbonates and hydrogen carbonates in a concentration corresponding to at least 0.1% by weight CO 3 , preferably at least one tenth, particularly preferably at least one fifth of the weight fraction SiO 2 .

Eine zur Ausführung des erfindungsgemäßen Verfahrens geeignete Phosphatlösung enthält in wässriger Lösung Alkaliortho- und Polyphosphate, wobei jeweils 25 bis 75 Gew.-% des Gesamtphosphats, als PO4 gerechnet, in Form von Ortho- und von Polyphosphat vorliegt. Der Begriff Polyphosphat soll hier Oligophosphate einschließen.A phosphate solution suitable for carrying out the process according to the invention contains alkali orthophosphates and polyphosphates in aqueous solution, 25 to 75% by weight of the total phosphate, calculated as PO 4 , being present in the form of orthophosphate and polyphosphate. The term polyphosphate is intended to include oligophosphates here.

Gegenüber den Verfahren nach dem Stand der Technik, bei denen Silikat-Phosphat-Gemische dem Wasserstrom zudosiert werden, zeichnet sich das erfindungsgemäße Verfahren dadurch aus, daß die getrennt zudosierten Silikat- und Phosphatlösungen wesentlich höher konzentriert sein können, als die Phosphat-Silikat-Zubereitung nach dem Stand der Technik. Hieraus ergeben sich beispielsweise weitere wirtschaftliche Vorteile bei Transport- und Lagerhaltung. Dies wird auch durch die DE 4321883-A1 belegt, die einen anderen Weg zur Realisierung solcher Vorteile vorschlägt.Compared to the methods according to the prior art, in which Silicate-phosphate mixtures are metered into the water stream, The process according to the invention is characterized in that the separately added silicate and phosphate solutions are essential can be more concentrated than the phosphate-silicate preparation According to the state of the art. This results in For example, other economic advantages in transportation and Warehousing. This is also documented by DE 4321883-A1, which is another way of realizing such benefits proposes.

Mittels des erfindungsgemäßen Verfahrens kann auch bei Änderungen der Wasserqualität und der Betriebsbedingungen lediglich durch Einstellung der Dosiermengen das optimale Silikat-Phosphat-Verhältnis aufrechterhalten werden. Diese Einstellung ist wesentlich einfacher und schneller durchführbar als die Beschaffung und Verwendung einer neuen Kombinationszubereitung.With the method according to the invention, changes can also be made water quality and operating conditions only the optimal silicate-phosphate ratio by adjusting the dosing quantities be maintained. This setting is much easier and faster to implement than that Procurement and use of a new combination preparation.

Durch das erfindungsgemäße Verfahren kann nicht nur die unerwünschte Rostfärbung des Wassers in Metallsystemen auf der Basis von Eisen, sondern auch das Inlösunggehen gesundheitsschädlicher Mengen von Kupfer- und Bleiionen aus kupfer- bzw. bleihaltigen Systemen mit minimalem Materialeinsatz vermieden werden.The inventive method can not only the undesirable Rust coloration of the water in metal systems on the Base of iron, but also going into dissolution is harmful to health Amounts of copper and lead ions from copper or lead-containing systems with minimal use of materials avoided will.

Claims (11)

Verfahren zur Korrosionsschutzbehandlung wasserführender Metallsysteme durch Dosierung einer Kombination von Phosphaten und Silikaten in den Wasserstrom, dadurch gekennzeichnet, daß Phosphate und Silikate getrennt voneinander zudosiert werden.Process for the corrosion protection treatment of water-bearing metal systems by metering a combination of phosphates and silicates into the water stream, characterized in that phosphates and silicates are metered in separately from one another. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Silikate als wäßrige Silikatlösung mit einem Modul von 1,8 bis 3,5 und einer Konzentration von mindestens 20 Gew.-% SiO2 zudosiert werden.Process according to Claim 1, characterized in that the silicates are metered in as an aqueous silicate solution with a modulus of 1.8 to 3.5 and a concentration of at least 20% by weight of SiO 2 . Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Silikatlösung ein lösliches Carbonat oder Hydrogencarbonat enthält.A method according to claim 2, characterized in that the silicate solution contains a soluble carbonate or hydrogen carbonate. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß die Phosphate als wäßrige Phosphatlösung mit einer Konzentration von mindestens 20 Gew.-% PO4 zudosiert werden.Process according to Claims 1 to 3, characterized in that the phosphates are metered in as an aqueous phosphate solution with a concentration of at least 20% by weight of PO 4 . Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Phosphat in der Phosphatlösung zu jeweils 25 bis 75 Gew.-% als Ortho- und Polyphosphat vorliegt. A method according to claim 4, characterized in that the phosphate is present in the phosphate solution in each case 25 to 75% by weight as orthophosphate and polyphosphate. Verfahren nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß mit Bezug auf die Stromrichtung des Wassers die Dosierung des Phosphats vor der Dosierung des Silikats erfolgt.Process according to Claims 1 to 5, characterized in that, with reference to the direction of flow of the water, the phosphate is metered in before the silicate is metered in. Verfahren nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß die Gewichtsmengen der zudosierten Silikate und Phosphate so bemessen werden, daß dem Wasserstrom 1,0 bis 40 mg/l SiO2 und 0,1 bis 6,7 mg/l PO4 zugesetzt werden.Process according to Claims 1 to 6, characterized in that the amounts by weight of the silicates and phosphates added are dimensioned such that 1.0 to 40 mg / l SiO 2 and 0.1 to 6.7 mg / l PO 4 are added to the water stream . Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Gewichtsmengen der zudosierten Silikate und Phosphate aufgrund von Wasseranalysen und/oder Vorversuchen festgelegt werden.A method according to claim 7, characterized in that the weight amounts of the added silicates and phosphates are determined on the basis of water analyzes and / or preliminary tests. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Gewichtsmengen der zudosierten Silikate und Phosphate im Laufe der Zeit verändert werden.A method according to claim 7 or 8, characterized in that the amounts by weight of the added silicates and phosphates are changed over time. Mittel zur Korrosionsschutzbehandlung wasserführender Metallsysteme in einem Verfahren nach einem der vorhergehenden Ansprüche, enthaltend in wäßriger Lösung Alkalisilikate, -carbonate und -hydrogencarbonate in Konzentrationen von mindestens 20 Gew.-% SiO2 bzw. 0,1 Gew.-% CO3.Agent for the anti-corrosion treatment of water-bearing metal systems in a process according to one of the preceding claims, containing, in aqueous solution, alkali silicates, carbonates and bicarbonates in concentrations of at least 20% by weight SiO 2 or 0.1% by weight CO 3 . Mittel zur Korrosionsschutzbehandlung wasserführender Metallsysteme in einem Verfahren nach einem der Ansprüche 1 bis 9, enthaltend Alkaliortho- und -polyphosphate, wobei der Gewichtsanteil der Ortho- und Polyphosphaten am Gesamtphosphatgehalt, ausgedrückt als PO4, jeweils 25 bis 75 Gew.-% und die Gesamtkonzentration an PO4 mindestens 20 Gew.-% beträgt.Agent for the anti-corrosion treatment of water-bearing metal systems in a process according to one of claims 1 to 9, containing alkali ortho- and polyphosphates, the weight fraction of the orthophosphates and polyphosphates in the total phosphate content, expressed as PO 4 , in each case 25 to 75% by weight and the total concentration of PO 4 is at least 20% by weight.
EP98101043A 1997-02-19 1998-01-22 Method for corrosion inhibiting water carrying metal systems Expired - Lifetime EP0860517B1 (en)

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DE19706410A DE19706410C2 (en) 1997-02-19 1997-02-19 Process and agent for the anti-corrosion treatment of water-bearing metal systems
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EP1780310A2 (en) 2005-10-18 2007-05-02 Henkel Kommanditgesellschaft Auf Aktien Method for corrosion protection of metallic water suppling lines by using corrosion inhibitors
EP2147989A1 (en) * 2008-07-18 2010-01-27 Airedale Chemical Company Limited Treatment solution
DE102014003770A1 (en) 2014-03-17 2015-09-17 Kurita Water Industries, Ltd. Process for corrosion inhibition of aquiferous systems
EP3808875A1 (en) * 2019-10-01 2021-04-21 Bwt Ag Anti-corrosion inhibitor solution for water-bearing conduits and installation systems

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EP3808875A1 (en) * 2019-10-01 2021-04-21 Bwt Ag Anti-corrosion inhibitor solution for water-bearing conduits and installation systems

Also Published As

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ATE207553T1 (en) 2001-11-15
EP0860517B1 (en) 2001-10-24
DE19706410C2 (en) 2001-04-05
DE59801830D1 (en) 2001-11-29
DE19706410A1 (en) 1998-08-27

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