EP0025125A1 - Use of hydroxy carboxylic acids that contain sulphur as corrosion inhibitors for aqueous systems - Google Patents

Use of hydroxy carboxylic acids that contain sulphur as corrosion inhibitors for aqueous systems Download PDF

Info

Publication number
EP0025125A1
EP0025125A1 EP80104710A EP80104710A EP0025125A1 EP 0025125 A1 EP0025125 A1 EP 0025125A1 EP 80104710 A EP80104710 A EP 80104710A EP 80104710 A EP80104710 A EP 80104710A EP 0025125 A1 EP0025125 A1 EP 0025125A1
Authority
EP
European Patent Office
Prior art keywords
water
corrosion
systems
aqueous systems
corrosion inhibitors
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.)
Granted
Application number
EP80104710A
Other languages
German (de)
French (fr)
Other versions
EP0025125B1 (en
Inventor
Ulrich Dr. Zeidler
Volker Dr. Wehle
Ingo Wegener
Gabriele Rogall
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT80104710T priority Critical patent/ATE5488T1/en
Publication of EP0025125A1 publication Critical patent/EP0025125A1/en
Application granted granted Critical
Publication of EP0025125B1 publication Critical patent/EP0025125B1/en
Expired 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
    • 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

Definitions

  • the invention relates to the use of 2-hydroxyalkyl-carboxyalkyl sulfides or sulfoxides and their water-soluble salts - hereinafter abbreviated HCS - to prevent corrosion of metals, in particular in service water systems.
  • this phosphorus-containing combination can furthermore lead to the formation of apatite or apatite-like deposits when used in larger water hardness levels, which lead to malfunctions and are difficult to remove.
  • the use of these combinations with zinc salts at higher pH values (pH '> 8.0) generally leads to increased silting up of the system due to the precipitation of zinc hydroxide.
  • Potassium, sodium, ammonium or alkanolamine salts are particularly suitable as alkali salts.
  • the amounts which are expediently added to the process water system are in the range from 0.5 to 100 g / m 3 , preferably 5 to 50 g / m3.
  • the 2-hydroxyalkyl-carboxyalkyl sulfides used can be prepared by reacting the salt of a corresponding mercaptocarboxylic acid such as thioglycolic acid, 2-mercaptopropionic acid or 3-mercaptopropionic acid in a polar solvent with the stoichiometric amount of an epoxide with a chain length of C 8 to C 18 .
  • a corresponding mercaptocarboxylic acid such as thioglycolic acid, 2-mercaptopropionic acid or 3-mercaptopropionic acid
  • the corresponding sulfoxides are obtained from the sulfides by oxidation with hydrogen peroxide. If the alkali salts, such as in particular potassium, sodium and ammonium salts or also alkanolamine salts, are not obtained directly during the preparation, they can be prepared by neutralizing the corresponding acids. Conversely, the corresponding acids can also be obtained from the salts by appropriate acidification.
  • the alkali salts such as in particular potassium, sodium and ammonium salts or also alkanolamine salts
  • the stone protection and dispersing agents listed above are used in combination with HCS in amounts of 1 to 50 g / m 3 , preferably 3 to 10 g / m 3 .
  • non-ferrous metals such as in particular benzimidazole, benzotriazole or tolyltriazole
  • HCS benzimidazole
  • benzotriazole or tolyltriazole
  • the amounts used are in the range from 0.1 to 5 g / m 3 .
  • HCS can also be used in combination with zinc salts and / or compounds containing phosphorus.
  • Zinc chloride and zinc sulfate are particularly suitable as zinc salts. Quantities (calculated as zinc) of 0.5 to 10 g / m 3 , preferably 1 to 4 g / m corresponding to an amount of 0.5 to 10 or 1 to 4 ppm are used.
  • phosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid, as well as their water-soluble salts or mixtures of these compounds, are particularly suitable as the phosphorus-containing compound. Such a combination can significantly increase the protection against corrosion.
  • biocidal substances such as glutaraldehyde, glyoxal, pentachlorophenol sodium or alkyloligoamides, preferably in the form of a reaction product of dodecylpropylenediamine and e-caprolactam in a ratio of 1: 2.
  • sulfur-containing hydroxycarboxylic acids of the general formula 1 indicated or their water-soluble salts can also be used quite generally as corrosion inhibitors, in particular for iron and in particular also as corrosion inhibitors in cooling lubricants for metal cutting.
  • test sheets 75 x 12 x 1.5 mm are immersed in a 1 liter beaker filled with 1 liter of water and a certain amount of the substance to be examined for 3 hours at room temperature. During the test period, the aqueous solutions are stirred at a rate of 100 revolutions per minute in a series of 10 beakers. Then the sheets are cleaned of corrosion products and the weight losses are determined. The corrosion protection rates of the products, based on a blank value, are calculated from the mean values of three tests each; determined.
  • test water used as the corrosive medium had the following analytical data:
  • the table below shows the reduction in the corrosive attack of a water by adding the specified agents compared to the untreated water.
  • a technical cooling system with a content of 1.2 m and a circulation of 8 m 3 / h is operated with Düsseldorf city water.
  • the evaporation losses are compensated by adding fresh water to such an extent that the salinity does not exceed twice the original value.
  • an electro-chemically measured corrosion rate of 0.18 mm / a is set in the system.
  • HCS HCS was used together with other inhibitors and the corrosion rates, expressed in mm / year, were determined using the coupon method, in which the test water was passed through a coupon test section according to ASTM (D 2688/70) under the same conditions. was pumped.
  • X and Y are commercial products based on di-N-butylamines from pre-fatty acids or their alkali salts.
  • Emulsifiable cooling lubricant concentrates with a commercially available rust inhibitor (A) based on fatty acid polydiethanolamide (reaction products of 1 mol of fatty acid and 2 mol of diethanolamine) on the one hand and 2-hydroxy-C 10 -alkyl-ß-carboxyethyl sulfide (sodium salt) (B) on the other hand were produced .
  • A rust inhibitor
  • B 2-hydroxy-C 10 -alkyl-ß-carboxyethyl sulfide
  • Example 4 3% and 5% aqueous solutions were prepared from these concentrates and the rust protection was determined as indicated in Example 4 .

Abstract

1. The use of sulfur-containing hydroxycarboxylic acids corresponding to the following general formula see diagramm : EP0025125,P8,F1 in which R**1 is an alkyl radical containing from 6 to 16 carbon atoms and preferably from 6 to 12 carbon atoms, R**2 is an alkyl radical containing from 1 to 3 carbon atoms and n=1 or 0, or water-soluble salts thereof for preventing the corrosion of metals in aqueous systems in the pH range from 6 to 9, more particularly in industrial water systems.

Description

Gegenstand der Erfindung ist die Verwendung von 2-Hydroxyalkyl-carboxyalkyl-sulfiden oder =sulfoxiden sowie deren wasserlöslichen Salzen -im folgendensabgekürzt HCS- zur Verhinderung der Korrosion von Metallen, insbesondere in Brauchwassersystemen.The invention relates to the use of 2-hydroxyalkyl-carboxyalkyl sulfides or sulfoxides and their water-soluble salts - hereinafter abbreviated HCS - to prevent corrosion of metals, in particular in service water systems.

Die Behandlung von wasserführenden Anlagen wie Dampferzeugungsanlagen, Heizsystemen, Kühlwasserkreisläufen und Wasserleitungssystemen zum Schutz gegen den korrosiven Angriff des Wassers, der sich vorwiegend gegen unedle Werkstoffe, beispielsweise Stahl, Messing, Aluminium, Zink oder verzinkter Stahl richtet, wird seit langem in der Technik durchgeführt. Besonders bewährt hat sich hierbei die Verwendung von phosphorhaltigen Verbindungen, wie zum Beispiel Phosphonsäuren oder anorganischen Phosphaten, gegebenenfalls in Kombination mit Zinksalzen.The treatment of water-bearing systems such as steam generation systems, heating systems, cooling water circuits and water supply systems to protect against the corrosive attack of water, which is primarily directed against base materials such as steel, brass, aluminum, zinc or galvanized steel, has long been carried out in technology. The use of phosphorus-containing compounds, such as phosphonic acids or inorganic phosphates, if appropriate in combination with zinc salts, has proven particularly useful.

Diese Kombinationen haben eine gute technische Wirksamkeit.These combinations have good technical effectiveness.

Ihre Verwendung wird in jüngster Zeit jedoch mehr und mehr eingeschränkt durch die ökologischen und gesetzgeberischen Forderungen nach weitgehender oder absoluter Phosphor-Freiheit derartiger Produkte. Vom technischen Standpunkt haben derartige phosphathaltige Kombinationen weiter den Nachteil, daß sie häufig durch Eutrophierung des Kühlsystems zu verstärktem biologischem Wachstum führen und die zusätzliche Verwendung von Mikrobiziden erforderlich machen.However, their use has recently been increasingly restricted by the ecological and legislative demands for such products to be largely or completely free of phosphorus. From the technical point of view, such phosphate-containing combinations have the further disadvantage that they often lead to increased biological growth due to eutrophication of the cooling system and make the additional use of microbicides necessary.

Die Verwendung dieser phosphorhaltigen Kombination kann weiterhin beim Einsatz in größeren Wasserhärten zur Bildung von Apatit- oder apatitähnlichen Ablagerungen führen, die zu Betriebsstörungen führen und nur schwer zu entfernen sind. Der Einsatz dieser Kombinationen mit Zinksalzen bei höheren pH-Werten (pH '>8,0) führt im allgemeinen zu verstärkter Verschlammung des Systems durch die Ausfällung von Zinkhydroxid.The use of this phosphorus-containing combination can furthermore lead to the formation of apatite or apatite-like deposits when used in larger water hardness levels, which lead to malfunctions and are difficult to remove. The use of these combinations with zinc salts at higher pH values (pH '> 8.0) generally leads to increased silting up of the system due to the precipitation of zinc hydroxide.

Vom ökologischen Standpunkt aus ist in nicht geschlossenen Kühlsystemen die Verwendung von Zinksalzen in derartigen Kombinationsprodukten ebenfalls problematisch, da diese aufgrund der hohen Fischtoxizität zu einer starken Abwasserbelastung führen. Außerdem wird die Selbstreinigungskraft des Gewässers bereits ab 0,1 ppm Zink deutlich gehemmt.From an ecological point of view, the use of zinc salts in such combination products is also problematic in non-closed cooling systems, since these lead to a high level of wastewater pollution due to the high fish toxicity. In addition, the self-cleaning power of the water is significantly inhibited from 0.1 ppm zinc.

Es wurde nun gefunden, daß man diese Nachteile vermeiden kann, wenn man schwefelhaltige Hydroxycarbonsäuren der allgemeinen Formel

Figure imgb0001
oder deren wasserlösliche Salze, wobei R1 einen Alkylrest mit 6 bis 16, vorzugsweise 6 bis 12 C-Atomen und R2 einen Alkylrest mit 1 bis 3 C-Atomen und n = 1 oder 0 bedeutet, zur Verhinderung der Korrosion von Metallen in wäßrigen Systemen im pH-Bereich von 6 bis 9, insbesondere in Brauchwassersystemen, verwendet.It has now been found that these disadvantages can be avoided by using sulfur-containing hydroxycarboxylic acids of the general formula
Figure imgb0001
 or their water-soluble salts, where R 1 is an alkyl radical having 6 to 16, preferably 6 to 12 C atoms and R 2 is an alkyl radical with 1 to 3 carbon atoms and n = 1 or 0 means used to prevent corrosion of metals in aqueous systems in the pH range from 6 to 9, in particular in process water systems.

Als Alkalisalze kommen insbesondere Kalium-, Natrium-, Ammonium- oder auch Alkanolaminsalze in Betracht.Potassium, sodium, ammonium or alkanolamine salts are particularly suitable as alkali salts.

Die Mengen, die dem Brauchwassersystem zweckmäßigerweise zugegeben werden, liegen im Bereich von 0,5 bis 100 g/m3, vorzugsweise 5 bis 50 g/m3.The amounts which are expediently added to the process water system are in the range from 0.5 to 100 g / m 3 , preferably 5 to 50 g / m3.

Die zur Anwendung gelangenden 2-Hydroxyalkyl-carboxyalkylsulfide können hergestellt werden, indem man das Salz einer entsprechenden Mercaptocarbonsäure wie Thioglycolsäure, 2-Mercaptopropionsäure oder 3-Mercaptopropionsäure in einem polaren Lösungsmittel mit der stöchiometrischen Menge eines Epoxids mit einer Kettenlänge von C8 bis C18 umsetzt.The 2-hydroxyalkyl-carboxyalkyl sulfides used can be prepared by reacting the salt of a corresponding mercaptocarboxylic acid such as thioglycolic acid, 2-mercaptopropionic acid or 3-mercaptopropionic acid in a polar solvent with the stoichiometric amount of an epoxide with a chain length of C 8 to C 18 .

Die entsprechenden Sulfoxide werden erhalten aus den Sulfiden durch Oxidation mit Wasserstoffperoxid. Soweit die Alkalisalze, wie insbesondere Kalium-, Natrium- und Ammoniumsalze oder auch Alkanolaminsalze, nicht direkt bei der Herstellung anfallen, können sie durch Neutralisation der entsprechenden Säuren hergestellt werden. Umgekehrt lassen sich auch aus den Salzen durch entsprechendes Ansäuern die entsprechenden Säuren gewinnen.The corresponding sulfoxides are obtained from the sulfides by oxidation with hydrogen peroxide. If the alkali salts, such as in particular potassium, sodium and ammonium salts or also alkanolamine salts, are not obtained directly during the preparation, they can be prepared by neutralizing the corresponding acids. Conversely, the corresponding acids can also be obtained from the salts by appropriate acidification.

Die außerordentlich gute korrosionsinhibierende Wirkung der HCS ist insofern überraschend, als die Ausgangsstoffe wie zum Beispiel Thioglykolsäure und Mercaptopropionsäure keine für die Praxis ausreichende Korrosionsschutzwirkung aufweisen (Tabelle 2). Bemerkenswert ist die bereits hohe korrosionsinhibierende Wirkung des HCS ohne jeden Zusatz.The extraordinarily good corrosion-inhibiting effect of HCS is surprising insofar as the starting materials, such as thioglycolic acid and mercaptopropionic acid, do not have an adequate corrosion protection effect in practice (Table 2). The already high corrosion-inhibiting effect of the HCS without any additives is remarkable.

In der Praxis spielt für das korrosive Verhalten eines Brauchwassers in hohem Maße die Anwesenheit oder Entstehung von ablagerungsbildenden Trübstoffen wie zum Beispiel Härteausfällungen, Tonsubstanzen und Eisenhydroxide eine wesentliche Rolle. Durch Verhinderung dieser Ablagerungen wird das korrosive Verhalten eines Wassers weiterhin verbessert. Daher ist es im allgemeinen vorteilhaft, dem zu behandelnden Wasser außer HCS weitere an sich bekannte Steinschutz- und Dispergiermittel zuzusetzen. Als geeignete Zusätze haben sich insbesondere Polyacrylate oder Acrylsäure-Methacrylsäurecopolymerisate mit einem Molgewicht von 500 bis 4000 oder Ethylenoxid-Propylenoxid-Blockpolymere mit einem Molgewicht von 500 bis 3000 und einem Ethylenoxid-Propylenoxidverhältnis von . 10 : 90 bis 30 : 70 erwiesen.In practice, the presence or formation of sediment-forming cloudy substances such as hardness precipitates, clay substances and iron hydroxides play a major role in the corrosive behavior of industrial water. Preventing these deposits further improves the corrosive behavior of water. It is therefore generally advantageous to add to the water to be treated, in addition to HCS, other stone protection and dispersing agents known per se. Particularly suitable additives have been polyacrylates or acrylic acid-methacrylic acid copolymers with a molecular weight of 500 to 4000 or ethylene oxide-propylene oxide block polymers with a molecular weight of 500 to 3000 and an ethylene oxide-propylene oxide ratio of. 10: 90 to 30: 70.

Die oben angeführten Steinschutz- und Dispergiermittel werden bei Kombination mit HCS in Mengen von 1 bis 50 g/m3, vorzugsweise 3 bis 10 g/m3 verwendet.The stone protection and dispersing agents listed above are used in combination with HCS in amounts of 1 to 50 g / m 3 , preferably 3 to 10 g / m 3 .

Je nach den Verhältnissen in der Praxis kann es vorteilhaft sein, zusammen mit HCS spezielle Inhibitoren für Buntmetalle, wie insbesondere Benzimidazol, Benzotriazol oder Tolyltriazol, in Kombination zu verwenden. Die verwendeten Mengen liegen im Bereich von 0,1 bis 5 g/m 3 . Depending on the conditions in practice, it may be advantageous to use special inhibitors for non-ferrous metals, such as in particular benzimidazole, benzotriazole or tolyltriazole, in combination with HCS. The amounts used are in the range from 0.1 to 5 g / m 3 .

Spielen die ökologischen Aspekte keine gravierende Rolle, wie insbesondere bei geschlossenen Kühlsystemen, so kann HCS auch mit Zinksalzen und/oder phosphorhaltigen Verbindungen kombiniert eingesetzt werden.If the ecological aspects do not play a major role, as in particular with closed cooling systems, HCS can also be used in combination with zinc salts and / or compounds containing phosphorus.

Als Zinksalze kommen insbesondere Zinkchlorid und Zinksulfat in Betracht. Dabei werden Mengen (berechnet als Zink) von 0,5 bis 10 g/m3, vorzugsweise 1 bis 4 g/m entsprechend einer Menge von 0,5 bis 10 beziehungsweise 1 bis 4 ppm verwendet.Zinc chloride and zinc sulfate are particularly suitable as zinc salts. Quantities (calculated as zinc) of 0.5 to 10 g / m 3 , preferably 1 to 4 g / m corresponding to an amount of 0.5 to 10 or 1 to 4 ppm are used.

Als phosphorhaltige Verbindung kommen insbesondere komplexierende Phosphonsäuren, wie beispielsweise 1-Hydroxyethan-1,1-diphosphonsäure, Aminotrimethylenphosphonsäure und 2-Phosphono-butan-1,2,4-tricarbonsäure sowie deren wasserlösliche Salze oder Gemische dieser Verbindungen in Betracht. Durch derartige Kombination kann der Korrosionsschutz noch erheblich verstärkt werden.Complexing phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid, as well as their water-soluble salts or mixtures of these compounds, are particularly suitable as the phosphorus-containing compound. Such a combination can significantly increase the protection against corrosion.

In bestimmten Fällen kann es auch vorteilhaft sein, weiterhin biozide Substanzen wie Glutaraldehyd, Glyoxal, Pentachlorphenolnatrium oder Alkyloligoamiden, vorzugsweise in Form eines Umsetzungsproduktes von Dodecylpropylendiamin und E-Caprolactam im Verhältnis 1 : 2 zuzusetzen.In certain cases it can also be advantageous to continue adding biocidal substances such as glutaraldehyde, glyoxal, pentachlorophenol sodium or alkyloligoamides, preferably in the form of a reaction product of dodecylpropylenediamine and e-caprolactam in a ratio of 1: 2.

Die vorgehend beschriebenen schwefelhaltigen Hydroxycarbonsäuren der angegebenen allgemeinen Formel 1 oder deren wasserlöslichen Salze können jedoch darüber hinaus ganz allgemein als Korrosionsinhibitoren, insbesondere für Eisen sowie insbesondere auch als Korrosionsinhibitor in Kühlschmiermitteln für die spanabhebende Metallbearbeitung eingesetzt werden.However, the above-described sulfur-containing hydroxycarboxylic acids of the general formula 1 indicated or their water-soluble salts can also be used quite generally as corrosion inhibitors, in particular for iron and in particular also as corrosion inhibitors in cooling lubricants for metal cutting.

B e i s p i e l eExample Beispiel 1example 1

Die Bestimmung des korrosiven Verhaltens erfolgte nach der nachstehend beschriebenen Methode:Corrosive behavior was determined using the method described below:

Je drei sorgfältig gereinigte Testbleche (75 x 12 x 1,5 mm) werden in ein 1-1-Becherglas, das mit 1 1 Wasser und einer bestimmten Menge der zu untersuchenden Substanz gefüllt ist, bei Raumtemperatur 3 Stunden eingetaucht. Während der Versuchsdauer werden in einer Reihenordnung von insgesamt 10 Bechergläsern die wäßrigen Lösungen mit 100 Umdrehungen pro Minute gerührt. Anschließend werden die Bleche von Korrosionsprodukten gereinigt und die Gewichtsverluste bestimmt. Aus den Mittelwerten von je drei Versuchen werden die Korrosionsschutzraten der Produkte, bezogen auf einen Blindwert; ermittelt.Three carefully cleaned test sheets (75 x 12 x 1.5 mm) are immersed in a 1 liter beaker filled with 1 liter of water and a certain amount of the substance to be examined for 3 hours at room temperature. During the test period, the aqueous solutions are stirred at a rate of 100 revolutions per minute in a series of 10 beakers. Then the sheets are cleaned of corrosion products and the weight losses are determined. The corrosion protection rates of the products, based on a blank value, are calculated from the mean values of three tests each; determined.

Das als korrosives Medium benutzte Versuchswasser hatte folgende analytischen Daten:

Figure imgb0002
The test water used as the corrosive medium had the following analytical data:
Figure imgb0002

Die nachstehende Tabelle gibt die Verringerung des korrosiven Angriffs eines Wassers bei Zusatz der im einzelnen aufgeführten Mittel gegenüber dem unbehandelten Wasser wieder.

Figure imgb0003
Figure imgb0004
 The table below shows the reduction in the corrosive attack of a water by adding the specified agents compared to the untreated water.
Figure imgb0003
Figure imgb0004

Beispiel 2Example 2

Ein technisches Kühlsystem mit einem Inhalt von 1,2 m und einer Umwälzung.von 8 m3/h wird mit Düsseldorfer Stadtwasser betrieben. Die Verdampfungsverluste werden durch Frischwasserzugabe soweit ausgeglichen, daß der Salzgehalt nicht den 2-fachen Wert des ursprünglichen Wertes übersteigt. Ohne jede Korrosionsschutzbehandlung des Kreislaufwassers stellt sich im System eine elektro-chemisch gemessene Korrosionsrate von 0,18 mm/a ein.A technical cooling system with a content of 1.2 m and a circulation of 8 m 3 / h is operated with Düsseldorf city water. The evaporation losses are compensated by adding fresh water to such an extent that the salinity does not exceed twice the original value. Without any anti-corrosion treatment of the circuit water, an electro-chemically measured corrosion rate of 0.18 mm / a is set in the system.

Bei Zugabe des erfindungsgemäßen Korrosionsinhibitors in Mengen von 50 g/m3 , bezogen auf das Kreislaufwasser, stellt sich eine Korrosionsrate von 0,064 mm/a ein. Dieser Wert ist als hervorragend anzusehen.When the corrosion inhibitor according to the invention is added in amounts of 50 g / m 3 , based on the circulating water, a corrosion rate of 0.064 mm / a is established. This value can be regarded as excellent.

Das erfindungsgemäße Mittel hat folgende Zusammensetzung:

  • 15 % 2-Hydroxy-C14-alkyl-α- carboxyethyl-sulfid, Na- triumsalz
  • 10 % eines Dispergiermittels (niedermolekulares Copolymerisat aus Acrylsäure-Methacrylsäure) (Molgewicht 1000)
  • 10 % eines Dispergiermittels auf Basis eines Blockpolymeren mit einem Molgewicht von 2000 und ei- nem Ethylenoxid/Propylenoxid-Verhältnis von 20 : 80
  • 0,5 % Benztriazol-1,2,3
  • 64,5 % Wasser
The composition according to the invention has the following composition:
  • 15% 2-hydroxy-C 14 alkyl-α- carboxyethyl sulfide, Na - triumsalz
  • 10% of a dispersant (low molecular weight copolymer of acrylic acid-methacrylic acid) (molecular weight 1000)
  • 10% of a dispersant based on a block polymer with a molecular weight of 2000 and an ethylene oxide / propylene oxide ratio of from 20: 80
  • 0.5% benzotriazole-1,2,3
  • 64.5% water

Beispiel 3Example 3

In einem Langzeitversuch über 4 Wochen wurde HCS mit anderen Inhibitoren zusammen eingesetzt und die Korrosionsraten, in mm/Jahr ausgedrückt, mittels der Coupon-Methode bestimmt, indem unter jeweils gleichen Bedingungen das Testwasser durch eine Coupon-Versuchsstrecke gemäß ASTM (D 2688/70) gepumpt wurde.In a long-term test over 4 weeks, HCS was used together with other inhibitors and the corrosion rates, expressed in mm / year, were determined using the coupon method, in which the test water was passed through a coupon test section according to ASTM (D 2688/70) under the same conditions. was pumped.

Die Versuchsbedingungen waren weiterhin folgende:

Figure imgb0005
The test conditions were still as follows:
Figure imgb0005

Durchflußgeschwindigkeit: 1250 1/h entsprechend 1 m/s

  • Versuchstemperatur: Anfang : 15°C Ende : 30°C
Flow rate: 1250 1 / h corresponding to 1 m / s
  • Test temperature: start: 15 ° C end: 30 ° C

Skizze der apparativen AnordnungSketch of the apparatus arrangement

Figure imgb0006
Figure imgb0007

  • HCS-1 : 2-Hydroxy-C14-alkyl-ß-carboxyethyl-sulfoxid, Na-Salz
  • HCS-2 : 2-Hydroxy-C12-alkyl-α-carboxyethyl-sulfid, Na-Salz
  • HCS-3 : 2-Hydroxy-C14alkyl-α-carboxyethyl-sulfid, Na-Salz
  • HEDP : 1-Hydroxyethan-1,1-diphosphonsäure
  • ATMP : Amino-trimethylen-phosphonsäure
Figure imgb0006
Figure imgb0007
  • HCS-1: 2-hydroxy-C 14 alkyl-β-carboxyethyl sulfoxide, Na salt
  • HCS-2: 2-hydroxy-C 12 alkyl-α-carboxyethyl sulfide, Na salt
  • HCS-3: 2-hydroxy-C 14 alkyl-α-carboxyethyl sulfide, Na salt
  • HEDP: 1-hydroxyethane-1,1-diphosphonic acid
  • ATMP: amino-trimethylene-phosphonic acid

Beispiel 4Example 4

Gegenüber Eisen wurden Korrosionstests durchgeführt. Dabei wurde der Filterpapierkorrosionstest nach IP 287 T in Anlehnung an DIN 51 360 verwendet. Bei diesem Test werden auf einem Filterpapierkissen Zonen mit einer wäßrigen Lösung, die einen Korrosionsinhibitor (Aktivlösung) enthält, behandelt und der Verrostungsgrad bestimmt.Corrosion tests were carried out on iron. The filter paper corrosion test according to IP 287 T based on DIN 51 360 was used. In this test, zones are treated on a filter paper cushion with an aqueous solution which contains a corrosion inhibitor (active solution) and the degree of rusting is determined.

Entsprechend den angegebenen Produkten bedeutet

Figure imgb0008
Figure imgb0009
Figure imgb0010
 Corresponds to the specified products
Figure imgb0008
Figure imgb0009
Figure imgb0010

Bei X und Y handelt.es sich um handelsübliche Produkte auf Basis von Di-N-butylaminen von Vorlauffettsäuren beziehungsweise deren Alkalisalze.

Figure imgb0011
X and Y are commercial products based on di-N-butylamines from pre-fatty acids or their alkali salts.
Figure imgb0011

Beispiel 5Example 5

Es wurden emulgierbare Kühlschmiermittelkonzentrate mit einem handelsüblichen Rostschutzmittel (A) auf Basis von Fettsäurepolydiethanolamid (Umsetzungsprodukte von 1 Mol Fettsäure und 2 Mol Diethanolamin) einerseits und 2-Hydroxy-C10-alkyl-ß-carboxyethyl-sulfid (Natriumsalz) (B) andererseits hergestellt.

Figure imgb0012
Emulsifiable cooling lubricant concentrates with a commercially available rust inhibitor (A) based on fatty acid polydiethanolamide (reaction products of 1 mol of fatty acid and 2 mol of diethanolamine) on the one hand and 2-hydroxy-C 10 -alkyl-ß-carboxyethyl sulfide (sodium salt) (B) on the other hand were produced .
Figure imgb0012

Von diesen Konzentraten wurden 3%ige und 5%ige wäßrige Lösungen hergestellt und der Rostschutz wie in Beispiel 4 angegeben bestimmt.

Figure imgb0013
3% and 5% aqueous solutions were prepared from these concentrates and the rust protection was determined as indicated in Example 4 .
Figure imgb0013

Claims (4)

1. Verwendung von schwefelhaltigen Hydroxicarbonsäuren der allgemeinen Formel
Figure imgb0014
oder deren wasserlösliche Salze, wobei R1 einen Alkylrest mit 6 bis 16, vorzugsweise 6 bis 12 C-Atomen und R2 einen Alkylrest mit 1 bis 3 C-Atomen und n = 1 oder 0 bedeutet, zur Verhinderung der Korrosion von Metallen in wäßrigen Systemen im pH-Bereich von 6 bis 9, insbesondere in Brauchwassersystemen.1. Use of sulfur-containing hydroxycarboxylic acids of the general formula
Figure imgb0014
 or their water-soluble salts, where R 1 is an alkyl radical with 6 to 16, preferably 6 to 12 C atoms and R 2 is an alkyl radical with 1 to 3 C atoms and n = 1 or 0, to prevent corrosion of metals in aqueous Systems in the pH range from 6 to 9, especially in service water systems. 2. Verwendung nach Anspruch 1 in Brauchwassersystemen in einer Menge von 0,5 bis 100 g/m3, vorzugsweise 5 bis 50 g/m3.2. Use according to claim 1 in industrial water systems in an amount of 0.5 to 100 g / m 3 , preferably 5 to 50 g / m 3 . 3. Verwendung nach Anspruch 1 bis 2 in Kombination mit zusätzlichen Steinschutz- und Dispergiermitteln, vorzugsweise auf Basis von Polyacrylaten beziehungsweise Acrylsäure-Methacrylsäurecopolymerisaten oder Ethylenoxid-Propylenoxid-Blockpolymeren.3. Use according to claim 1 to 2 in combination with additional Steinschutz- and dispersants, preferably based on polyacrylates or acrylic acid-Methacrylsäurecopolymerisaten or ethylene oxide-propylene oxide block olymeren p. 4. Verwendung nach Anspruch 1 bis 3 in Kombination mit zusätzlichen,an sich bekannten Korrosionsinhibitoren für Buntmetalle, vorzugsweise Benzimidazol.4. Use according to claim 1 to 3 in combination with additional, known corrosion inhibitors for non-ferrous metals, preferably benzimidazole.
EP80104710A 1979-08-17 1980-08-09 Use of hydroxy carboxylic acids that contain sulphur as corrosion inhibitors for aqueous systems Expired EP0025125B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80104710T ATE5488T1 (en) 1979-08-17 1980-08-09 USE OF SULFUR CONTAINING HYDROXYCARBONIC ACIDS AS CORROSION INHIBITORS FOR AQUEOUS SYSTEMS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792933388 DE2933388A1 (en) 1979-08-17 1979-08-17 CORROSION INHIBITORS
DE2933388 1979-08-17

Publications (2)

Publication Number Publication Date
EP0025125A1 true EP0025125A1 (en) 1981-03-18
EP0025125B1 EP0025125B1 (en) 1983-11-30

Family

ID=6078710

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80104710A Expired EP0025125B1 (en) 1979-08-17 1980-08-09 Use of hydroxy carboxylic acids that contain sulphur as corrosion inhibitors for aqueous systems

Country Status (3)

Country Link
EP (1) EP0025125B1 (en)
AT (1) ATE5488T1 (en)
DE (1) DE2933388A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0354871A2 (en) * 1988-07-21 1990-02-14 Ciba-Geigy Ag Corrosion inhibition
DE102006054761A1 (en) * 2006-11-14 2008-05-15 Hansgrohe Ag Provision of water-bearing components from brass alloys with reduced metal ion release
WO2014124826A1 (en) 2013-02-13 2014-08-21 Basf Se Anti-freeze concentrate having corrosion protection and aqueous coolant composition produced therefrom
US9080093B2 (en) 2013-02-13 2015-07-14 Basf Se Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200109112A1 (en) * 2018-10-08 2020-04-09 Ecolab Usa Inc. Sulfide-based compounds and uses thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE916878C (en) * 1941-05-16 1954-08-19 Dehydag Gmbh Process for reducing the corrosive influence of water and aqueous solutions on iron
FR1195917A (en) * 1957-06-29 1959-11-20 Naarden Chem Fab Odoriferous thiolactones
US2981686A (en) * 1958-10-30 1961-04-25 Shell Oil Co Metal working lubricants
FR2336389A1 (en) * 1975-12-24 1977-07-22 Hoechst Ag THIOL-CARBOXYLIC ACID ESTERS AND THEIR PREPARATION
EP0000337A1 (en) * 1977-07-07 1979-01-24 Henkel Kommanditgesellschaft auf Aktien Use of telomers formed from mercaptans and acrylic compounds as scale and/or corrosion inhibitors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE916878C (en) * 1941-05-16 1954-08-19 Dehydag Gmbh Process for reducing the corrosive influence of water and aqueous solutions on iron
FR1195917A (en) * 1957-06-29 1959-11-20 Naarden Chem Fab Odoriferous thiolactones
US2981686A (en) * 1958-10-30 1961-04-25 Shell Oil Co Metal working lubricants
FR2336389A1 (en) * 1975-12-24 1977-07-22 Hoechst Ag THIOL-CARBOXYLIC ACID ESTERS AND THEIR PREPARATION
EP0000337A1 (en) * 1977-07-07 1979-01-24 Henkel Kommanditgesellschaft auf Aktien Use of telomers formed from mercaptans and acrylic compounds as scale and/or corrosion inhibitors

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0354871A2 (en) * 1988-07-21 1990-02-14 Ciba-Geigy Ag Corrosion inhibition
EP0354871A3 (en) * 1988-07-21 1990-10-17 Ciba-Geigy Ag Corrosion inhibition
US5013482A (en) * 1988-07-21 1991-05-07 Ciba-Geigy Corporation Corrosion inhibition
AU614636B2 (en) * 1988-07-21 1991-09-05 Ciba Specialty Chemicals Holding Inc. Corrosion inhibition
DE102006054761A1 (en) * 2006-11-14 2008-05-15 Hansgrohe Ag Provision of water-bearing components from brass alloys with reduced metal ion release
WO2014124826A1 (en) 2013-02-13 2014-08-21 Basf Se Anti-freeze concentrate having corrosion protection and aqueous coolant composition produced therefrom
US9080093B2 (en) 2013-02-13 2015-07-14 Basf Se Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom
US9458369B2 (en) 2013-02-13 2016-10-04 Basf Se Antifreeze concentrate with corrosion protection and aqueous coolant composition produced therefrom

Also Published As

Publication number Publication date
DE2933388C2 (en) 1987-03-12
ATE5488T1 (en) 1983-12-15
DE2933388A1 (en) 1981-03-26
EP0025125B1 (en) 1983-11-30

Similar Documents

Publication Publication Date Title
EP0150706B1 (en) Cotelomer compounds
DE2333353C2 (en) Process for preventing corrosion in water-bearing systems and anti-corrosion agents for carrying out the process
DE1937617C3 (en) Corrosion inhibiting agent
EP0127572B1 (en) Process for inhibiting corrosion and/or scale deposits
DE2505435C3 (en) Use of carboxy-alkane compounds of phosphorus as corrosion inhibitors
DE2447895A1 (en) CORROSION PROTECTION AGENT
DE2225645A1 (en) PROCESS FOR PREVENTING CORROSION AND STONE SETTING IN WATER SYSTEMS
DE10003515A1 (en) Composition protecting against scale and / or corrosion
CH631212A5 (en) USE OF CYCLOHEXANEHEXACARBONIC ACIDS AS A CORROSION INHIBITOR FOR FUEL WATER SYSTEMS.
DE2601402A1 (en) PROCESS FOR INHIBITING CORROSION AND COATING ON IRON SURFACES
EP0025863B1 (en) Use of 1,2,4-triazole derivatives as corrosion inhibitors for non ferrous metals
DE2611813A1 (en) IMINOALKYLIMINOPHOSPHONATE, METHOD FOR THEIR PRODUCTION AND USE
DE2338352A1 (en) CORROSION PROTECTION AGENT FOR INHIBITING WATER CORROSION
EP0025125B1 (en) Use of hydroxy carboxylic acids that contain sulphur as corrosion inhibitors for aqueous systems
DE2016686A1 (en) Anti-corrosive agents
DE3223940A1 (en) TREATMENT LIQUID FOR CORROSION PROTECTION OF METAL SURFACES AND CONCENTRATE FOR THEIR PRODUCTION
DE19648843C2 (en) Melamine polycarboxamides and their use as anti-corrosion agents
US2221339A (en) Utilization of metallo-organic compounds for treatment of circulating waters and surfaces coming into contact with water
DE2036628C2 (en) Antifreeze
DE2240736C3 (en) Agent for inhibiting metal corrosion and process for its manufacture
EP0004665B1 (en) Corrosion inhibitor for water conduits
EP0218798A2 (en) Process and composition for inhibiting corrosion and incrustation in water systems
DE3909075A1 (en) Novel polymers
EP0249148A2 (en) 2-Hydroxydodecylmonoesters of dicarboxylic acids, their salts and their use as corrosion inhibitors in aqueous systems
WO1985005380A1 (en) Corrosion inhibiting water additives and preparation process thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH FR GB IT LI NL

17P Request for examination filed

Effective date: 19810717

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH FR GB IT LI NL

AK Designated contracting states

Designated state(s): AT BE CH FR GB IT LI NL

REF Corresponds to:

Ref document number: 5488

Country of ref document: AT

Date of ref document: 19831215

Kind code of ref document: T

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19860731

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19870831

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19880809

Ref country code: AT

Effective date: 19880809

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19890301

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19890714

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890808

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890824

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19900831

Ref country code: CH

Effective date: 19900831

Ref country code: BE

Effective date: 19900831

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19900831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST