DE4409990A1 - Process for preventing corrosion of metals in aqueous systems - Google Patents

Process for preventing corrosion of metals in aqueous systems

Info

Publication number
DE4409990A1
DE4409990A1 DE4409990A DE4409990A DE4409990A1 DE 4409990 A1 DE4409990 A1 DE 4409990A1 DE 4409990 A DE4409990 A DE 4409990A DE 4409990 A DE4409990 A DE 4409990A DE 4409990 A1 DE4409990 A1 DE 4409990A1
Authority
DE
Germany
Prior art keywords
methylene blue
sodium
water circuit
metals
acids
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.)
Withdrawn
Application number
DE4409990A
Other languages
German (de)
Inventor
Rolf Dipl Ing Scharmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schilling Chemie U Produk GmbH
Original Assignee
Schilling Chemie U Produk GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schilling Chemie U Produk GmbH filed Critical Schilling Chemie U Produk GmbH
Priority to DE4409990A priority Critical patent/DE4409990A1/en
Priority to DE59508882T priority patent/DE59508882D1/en
Priority to EP95103622A priority patent/EP0674021B1/en
Priority to AT95103622T priority patent/ATE197970T1/en
Publication of DE4409990A1 publication Critical patent/DE4409990A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C23F11/10—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 organic inhibitors
    • 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
    • C23F11/10—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 organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/165—Heterocyclic compounds containing sulfur as hetero atom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

Methylene blue (I) is used to inhibit corrosion of metals in aq. systems.

Description

Die Erfindung betrifft eine Verwendung von 3,7- Bis(dimethylamino)-phenothiaziniumchlorid, im folgenden Methylenblau genannt.The invention relates to the use of 3.7- Bis (dimethylamino) phenothiazinium chloride, hereinafter Called methylene blue.

Aus dem Lexikon Römpp, 9. Auflage, Bd. 4, S. 2749 ist es bekannt, daß Methylenblau in der Teichwirtschaft gegen Algen und Pilze wirkt.From the Lexicon Römpp, 9th edition, Vol. 4, p. 2749, it is known that methylene blue in the Pond management works against algae and fungi.

In der DE 28 12 261 A1 ist erwähnt, daß Methylenblau eine antimikrobielle Wirkung hat. Die DE 31 35 194 C2 beschreibt die Verhinderung von Algen- und Schleimbakterienwachstum in wäßrigen Systemen durch Zugabe von Methylenblau.DE 28 12 261 A1 mentions that methylene blue is a has antimicrobial effects. DE 31 35 194 C2 describes the prevention of algae and mucus bacteria growth in aqueous systems by adding methylene blue.

Die Behandlung von wasserführenden Systemen zum Schutz gegen den korrosiven Angriff des Wassers gehört seit langem zum Stand der Technik.The treatment of water-bearing systems for protection against the corrosive attack of water has long belonged the state of the art.

Besonders bewährt hat sich hierbei die Verwendung von phosphorhaltigen Verbindungen, wie z. B. Phosphonsäuren oder anorganischen Phosphaten, häufig in Kombination mit Schwer­ metallsalzen (Zinksalze, Natriummolybdate, Natriumchromate) sowie Natriumnitrit, Natriumnitrat, Natriumborat, Natrium­ benzoat und Triazolderivate. The use of phosphorus-containing compounds, such as. B. phosphonic acids or inorganic phosphates, often in combination with heavy metal salts (zinc salts, sodium molybdates, sodium chromates) as well as sodium nitrite, sodium nitrate, sodium borate, sodium benzoate and triazole derivatives.  

Diese Kombinationen haben eine gute technische Wirksamkeit. Ihre Verwendung wird in jüngster Zeit jedoch mehr und mehr eingeschränkt durch ökologische und gesetzgeberische For­ derungen.These combinations have good technical effectiveness. However, their use has been increasing more and more recently restricted by ecological and legislative For changes.

Speziell bei offenen Kühlwassersystemen regelt der Anhang 31 zu Paragraph 7a des Wasserhaushaltsgesetzes "Abwasser aus Kühlkreisläufen" Art und Menge der zur Wasserbehandlung in solchen Systemen einzusetzenden Stoffe, wobei besonders die Anwendung von Mikrobiciden stark eingeschränkt wird.The appendix regulates especially for open cooling water systems 31 to paragraph 7a of the Water Resources Act "Wastewater from cooling circuits "type and amount of water treatment Substances to be used in such systems, especially the use of microbicides is severely restricted.

Phosphorhaltige Kombinationen haben den Nachteil, daß sie häufig durch Eutrophierung des Wassersystems verstärkt zu biologischem Wachstum führen und die zusätzliche Verwendung von Mikrobiciden erforderlich machen. Die Verwendung dieser phosphorhaltigen Kombinationen kann weiterhin bei Einsatz von Wässern mit größerer Wasserhärte zur Bildung von Apatit oder apatitähnlichen Ablagerungen führen, die zu Betriebs­ störungen führen und nur sehr schwer zu entfernen sind.Combinations containing phosphorus have the disadvantage that they often exacerbated by eutrophication of the water system lead to biological growth and additional use of microbicides. The use of this Combinations containing phosphorus can continue to be used of water with greater water hardness to form apatite or apatite-like deposits that lead to operational cause malfunctions and are very difficult to remove.

Der Einsatz dieser Kombination mit Zinksalzen bei höheren pH-Werten (pH < 8,0) führt im allgemeinen zu verstärkter Verschlammung des Systems durch die Ausfällung von Zink­ hydroxid.The use of this combination with zinc salts at higher pH values (pH <8.0) generally lead to increased Silting up of the system due to the precipitation of zinc hydroxide.

Bei der Anwendung von Methylenblau als Korrosionsinhibitor in solchen Systemen werden die Anforderungen nach Anhang 31 zu Paragraph 7a WHG erfüllt.When using methylene blue as a corrosion inhibitor in such systems the requirements of Annex 31 to paragraph 7a WHG fulfilled.

Überraschenderweise wurde gefunden, daß Methylenblau eine gute Korrosionsschutzwirkung hat, ohne die genannten tech­ nischen Nachteile aufzuweisen. Dabei wird Methylenblau auf den Metalloberflächen adsorbiert. Diese Adsorption wird offensichtlich begünstigt durch die aromatische Struktur der Verbindung; der Effekt wird durch das Ringstick­ stoffatom zusätzlich unterstützt.Surprisingly, it was found that methylene blue is a has good corrosion protection without the tech to show any disadvantages. This turns methylene blue on adsorbed on the metal surfaces. This adsorption will obviously favored by the aromatic structure  the connection; the effect is through the ringstick additional support for the atom.

Ursache der stark kathodisch wirksamen Inhibition des Methylenblau ist eine Transporthemmung im Diffusionsfilm. Offenbar besteht die transporthemmende Substanz aus schwer löslichen Verbindungen, die sich im kathodischen Bereich an der Metalloberfläche bilden. Zusätzlich begünstigt Methylenblau bei Eisenwerkstoffen die Ausbildung einer Magnetitschutzschicht durch teilweise Stabilisierung der bei der Korrosion im ersten Stadium gebildeten Eisen-II- ionen.Cause of the strongly cathodically effective inhibition of the Methylene blue is an inhibitor of transport in the diffusion film. Apparently the transport-inhibiting substance consists of heavy soluble compounds that are in the cathodic range form the metal surface. Favored additionally Methylene blue in the formation of iron materials Protective magnetite layer by partially stabilizing the iron II formed during corrosion in the first stage ions.

Die Mengen, die dem wäßrigen System hier zweckmäßigerweise zugegeben werden, liegen im Bereich von 0,1-1000 g/m³, vorzugsweise 1-10 g/m.The amounts that are expedient to the aqueous system here added are in the range of 0.1-1000 g / m³, preferably 1-10 g / m.

Die Herstellung von Methylenblau erfolgt nach an sich bekannten Methoden und ist nicht Gegenstand der Erfindung.Methylene blue is produced per se known methods and is not the subject of the invention.

Claims (5)

1. Verwendung von 3,7-Bis(dimethylamino)- phenothiaziniumchlorid (Methylenblau) zur Verhinderung der Korrosion von Metallen in wäßrigen Systemen.1. Use of 3,7-bis (dimethylamino) - phenothiazinium chloride (methylene blue) for prevention corrosion of metals in aqueous systems. 2. Verwendung nach Anspruch 1, wobei das Methylenblau in einer Menge von 0,1-1000 g/m³, vorzugsweise 1-10 g/m³, zugesetzt wird.2. Use according to claim 1, wherein the methylene blue in an amount of 0.1-1000 g / m³, preferably 1-10 g / m³, is added. 3. Verwendung von Methylenblau nach Anspruch 1 oder 2, in einer Kombination mit zusätzlichen Härtestabilisa­ toren und Dispergiermitteln, vorzugsweise auf Basis von Polyacrylsäuren, Polycarbonsäuren und Phosphonsäuren sowie deren Natriumsalzen.3. Use of methylene blue according to claim 1 or 2, in combination with additional hardness stabilizers gates and dispersants, preferably based on Polyacrylic acids, polycarboxylic acids and phosphonic acids as well as their sodium salts. 4. Verwendung von Methylenblau nach einem der Ansprüche 1 bis 3, in Kombination mit zusätzlichen bekannten Korrosions­ inhibitoren, vorzugsweise Natriummolybdat, Natrium­ silikate, Natriumphosphate, Natriumnitrat, spezielle Phoshonsäuren und Phosphonate sowie Zinksalzen. 4. Use of methylene blue according to one of claims 1 to 3, in combination with additional known corrosion inhibitors, preferably sodium molybdate, sodium silicates, sodium phosphates, sodium nitrate, special Phoshonic acids and phosphonates as well as zinc salts.   5. Verwendung von Methylenblau nach einem der Ansprüche 1 bis 4 in einem Kühlkreislauf, einer Luftbefeuchtungs­ anlage, einem Prozeßwasserkreislauf, einem Heizungs­ wasserkreislauf, einem Heißwasserkreislauf oder einem Kaltwasserkreislauf.5. Use of methylene blue according to one of claims 1 to 4 in a cooling circuit, a humidifier plant, a process water circuit, a heating water circuit, a hot water circuit or one Cold water circuit.
DE4409990A 1994-03-23 1994-03-23 Process for preventing corrosion of metals in aqueous systems Withdrawn DE4409990A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE4409990A DE4409990A1 (en) 1994-03-23 1994-03-23 Process for preventing corrosion of metals in aqueous systems
DE59508882T DE59508882D1 (en) 1994-03-23 1995-03-14 Process for preventing corrosion of metals in aqueous systems
EP95103622A EP0674021B1 (en) 1994-03-23 1995-03-14 Process for inhibiting metal corrosion in aquous systems
AT95103622T ATE197970T1 (en) 1994-03-23 1995-03-14 METHOD FOR PREVENTING CORROSION OF METALS IN AQUEOUS SYSTEMS

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE4409990A DE4409990A1 (en) 1994-03-23 1994-03-23 Process for preventing corrosion of metals in aqueous systems

Publications (1)

Publication Number Publication Date
DE4409990A1 true DE4409990A1 (en) 1995-09-28

Family

ID=6513602

Family Applications (2)

Application Number Title Priority Date Filing Date
DE4409990A Withdrawn DE4409990A1 (en) 1994-03-23 1994-03-23 Process for preventing corrosion of metals in aqueous systems
DE59508882T Expired - Fee Related DE59508882D1 (en) 1994-03-23 1995-03-14 Process for preventing corrosion of metals in aqueous systems

Family Applications After (1)

Application Number Title Priority Date Filing Date
DE59508882T Expired - Fee Related DE59508882D1 (en) 1994-03-23 1995-03-14 Process for preventing corrosion of metals in aqueous systems

Country Status (3)

Country Link
EP (1) EP0674021B1 (en)
AT (1) ATE197970T1 (en)
DE (2) DE4409990A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4427038C2 (en) * 1994-07-29 1998-05-20 Schilling Chemie Gmbh U Produk Process for the removal of oxygen dissolved in water, especially in water-bearing, closed systems

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1361613A (en) * 1962-05-08 1964-05-22 Shell Res Ltd Improvements to cooling or lubricating compositions for metalworking
DE1696316C2 (en) * 1962-08-14 1974-10-03 Fritz Dr. 8500 Nuernberg Boehmlaender Use of hydrazine hydrate or hydrazine salt for corrosion protection in salt solutions, especially in cooling circuit salt solutions and cooling brines
CH458013A (en) * 1964-03-21 1968-06-15 Bayer Ag Process for the corrosion protection of metallic objects
DE2919197A1 (en) * 1979-05-12 1980-11-27 Hoechst Ag METHOD FOR PRODUCING VINYL CHLORIDE POLYMERISATS
US4311599A (en) * 1980-11-12 1982-01-19 Nalco Chemical Company Reduced methylene blue for oxygen removal

Also Published As

Publication number Publication date
EP0674021B1 (en) 2000-12-06
ATE197970T1 (en) 2000-12-15
EP0674021A1 (en) 1995-09-27
DE59508882D1 (en) 2001-01-11

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