EP2671972A1 - Use of a solution containing phosphonic acid and/or phosphonic acid derivatives during the degreasing of metal surfaces, degreasing solution and method for degreasing a metal surface - Google Patents

Use of a solution containing phosphonic acid and/or phosphonic acid derivatives during the degreasing of metal surfaces, degreasing solution and method for degreasing a metal surface Download PDF

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Publication number
EP2671972A1
EP2671972A1 EP13168021.7A EP13168021A EP2671972A1 EP 2671972 A1 EP2671972 A1 EP 2671972A1 EP 13168021 A EP13168021 A EP 13168021A EP 2671972 A1 EP2671972 A1 EP 2671972A1
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Prior art keywords
degreasing
solution
phosphonic acid
metal
metal surface
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EP13168021.7A
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German (de)
French (fr)
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EP2671972B1 (en
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Sascha ROTHFELD
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Stockmeier Chemie & Co KG GmbH
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Stockmeier Chemie & Co KG 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids

Definitions

  • the present invention relates to a use of a phosphonic or phosphonic acid derivative-containing solution, and a degreasing solution for use in degreasing metal surfaces, a use of the degreasing solution, and a degreasing method of a metal surface.
  • a use of a phosphonic acid and / or phosphonic acid derivative-containing solution in the degreasing of metal surfaces, in particular of iron or steel surfaces, in particular in hot-dip galvanizing means the removal of oils or fats from the metal surface.
  • the service life of baths can be additionally increased surprisingly.
  • the solution itself can be used as a bath or added during or after a degreasing process in a solution in the bath to adjust the changing by degreasing salt concentration of the bath.
  • a particularly favorable proportion of phosphonic acid or of the phosphonic acid derivative is from 0.0001 to 50% by weight, based on the total amount of free acid in a solution used for degreasing or pickling, in particular the bath solution.
  • the phosphonic acid-containing or phosphonklarederivat Vietnamese solution has a pH of less than 7, preferably less than 4.0.
  • a degreasing solution for use in the degreasing of metal surfaces contains a phosphonic acid and / or a phosphonic acid derivative and a surfactant.
  • the salt concentration of the solution can be adjusted so that the degreasing effect of the surfactant is maintained for a long time.
  • Such a degreasing solution can be used for a bath for degreasing a metal surface in hot-dip galvanizing, whereby a long service life of the bath is achieved.
  • the degreasing solution can be provided only after a few degreasing passes by adding phosphonic acid or phosphonic acid derivatives to a surfactant-containing solution.
  • the degreasing solution has a content of phosphorous acid of 0.001 to 100%, based on the amount of free acid in the degreasing solution.
  • a particularly good degreasing of a metal surface takes place at a surfactant content of 0.01 to 10% by weight.
  • the degreasing solution may additionally contain at least one solvent, an inhibitor, a solubilizer, an adjusting agent and / or a fragrance in a concentration of 0.001 to 10% by weight.
  • the degreasing solution can be used as a bath for degreasing metal surfaces, in particular of iron or steel surfaces, in particular in hot-dip galvanizing or in electroplating.
  • the surfactant-containing solution can be adjusted as a function of the salt content after each degreasing or after several degreasings, so that the service life of the surfactant-containing solution can be increased.
  • a proportion of the phosphonic acid or the phosphonic acid derivative in the solution in step c) of 0.0001 to 10% is sufficient.
  • an iron or steel surface is provided with a zinc layer which has partially diffused into the surface. At the same time, some of the iron molecules from the iron or steel surface diffuse into the zinc layer.
  • various known preparatory steps are applied prior to the application of the actual zinc layer, which u.a. depend on the quality of the surface to be coated.
  • an abrasive surface treatment in the form of sand blasting or the like. to remove rust or paint residue from the surface.
  • a pickling treatment is carried out to remove impurities which can be traced back to the metal itself. These are, for example, oxidation products, such as rust or scale.
  • the duration of the pickling process and the concentration of the pickling bath depend on the extent of the oxidation products occurring on the metal surface. In some cases, the degreasing is carried out in the stain, then it is called the pickling greasing.
  • the fluxing can also be carried out by means of a salt layer which floats on the zinc bath (so-called wet galvanizing).
  • wet galvanizing floats on the zinc bath
  • the surfaces to be treated should not be dried before galvanizing.
  • the metal surface can be dried, for example in drying ovens at 80-90 ° C.
  • the galvanizing is then carried out by immersing the metallic surface in a liquid zinc melt, preferably with at least 98% by weight of zinc.
  • a liquid zinc melt preferably with at least 98% by weight of zinc.
  • This preferably has a temperature of more than 420 ° C, more preferably between 440-465 ° C, or alternatively above 500 ° C. In this case, a mutual diffusion of both metal layers into each other.
  • post-processing operations e.g. Deburring, plastering, polishing, painting or powder coating take place.
  • hot-dip galvanizing plants usually have no wastewater treatment plant, but only so-called stationary rinsing.
  • the substances used in the hot-dip galvanizing are thus taken to subsequent baths. These baths are gradually consumed and must be disposed of externally. In order to minimize the environmental impact and to achieve a corresponding cost reduction, a longer service life of baths should be sought.
  • a bath is usually considered exhausted when the iron concentration and thus the salt concentration of the degreasing solution exceeds a certain level so that the degreasing surfactants present in the bath and the contaminants held in solution by the surfactants are no longer stable or soluble in the degreasing solution available.
  • An increase in salt concentration This is done automatically in acidic solutions as a rule, as with each degreasing inevitably iron ions are dissolved in the degreasing solution.
  • a known way to increase the service life is the use of phosphoric acid.
  • iron phosphates are precipitated, whereby the iron concentration and thus also the salt concentration of the solution - based on the ions in solution - is reduced overall.
  • the object of the present invention takes an alternative route by adding to the degreasing solution a cleaning agent or a solution containing a phosphonic acid or a phosphonic acid derivative.
  • a cleaning agent or a solution containing a phosphonic acid or a phosphonic acid derivative.
  • the addition of the phosphonic acid derivative-containing detergent surprisingly forms a precipitate, which on the one hand binds the excess iron. Additionally, organic contaminants are removed from the bath.
  • such a phosphonic acid derivative is HEDP (1-hydroxyethane- (1,1-diphosphonic acid), HEMPA (hexamethylenediamine-tetra (methylenephosphonic acid)), HDTMP (hexaethylenediamine-tetramethylenephosphonic acid), ATMP (aminotrimethylenephosphonic acid), EDTMP (ethylenediaminetetra (methylenephosphonic acid)), DTPMP (Diethylenetriaminepenta (methylenephosphonic acid)) and / or PBTC (2-phosphonobutane-1,2,4-tricarboxylic acid) .
  • HEMPA hexamethylenediamine-tetra (methylenephosphonic acid)
  • HDTMP hexaethylenediamine-tetramethylenephosphonic acid
  • ATMP aminotrimethylenephosphonic acid
  • EDTMP ethylenediaminetetra (methylenephosphonic acid)
  • DTPMP Diethylenetriaminepenta (methylenephosphonic acid)
  • the phosphonic acid derivative may be a derivative of a simple or complex phosphonic acid.
  • the added detergent preferably has a pH of less than 7.0, preferably a pH of less than 4.0.
  • the degreasing solution prepared from the cleaning agent can be used for metal degreasing, in particular in hot-dip galvanizing or in the galvanic treatment of metal surfaces.
  • the concentration of phosphonic acid or a phosphonic acid derivative in the degreasing solution is preferably 0.001 to 60%, in particular 0.1 to 10%, based on the amount of free acid present in the degreasing solution.
  • the degreasing solution contains at least one acid.
  • a phosphonic acid can also be added separately to an already existing cleaning solution for metal precipitation.
  • phosphonic acid or a phosphonic acid derivative of preferably 0.0001 to 10%, in particular 0.01 to 1%, based on the amount of free acid present, in be added to the degreasing solution.
  • a mineral acid and / or an organic acid may also be added to achieve enhanced precipitation formation.
  • Preferred mineral acids are hydrochloric acid, sulfuric acid, phosphoric acid and / or nitric acid.
  • Preferred organic acids are oxalic, tartaric, citric and / or acetic acid.
  • the concentration of the mineral acid and / or organic acid in the degreasing solution is preferably 0.1 to 90 wt .-%, based on the total weight of the solution.
  • the degreasing solution preferably contains surfactants, in particular nonionic, anionic and / or cationic surfactants, wherein a proportion of phosphonic acid or phosphonic acid derivative has a particularly positive effect on the solubility of nonionic surfactants, in particular in a particularly preferred concentration of 0.01 to 10 wt .-%, in particular 0.1-1 wt.% Based on the total weight of the degreasing solution.
  • surfactants in particular nonionic, anionic and / or cationic surfactants, wherein a proportion of phosphonic acid or phosphonic acid derivative has a particularly positive effect on the solubility of nonionic surfactants, in particular in a particularly preferred concentration of 0.01 to 10 wt .-%, in particular 0.1-1 wt.% Based on the total weight of the degreasing solution.
  • the degreasing solution may also contain inhibitors to minimize the uptake of iron ions from the treated metal surfaces.
  • inhibitors reduce the metal uptake and on the other hand reduce the formation of hydrogen and in some cases also reduce the diffusion of hydrogen into the metal structure.
  • the lifetime of pickling is increased, since the metal content then increases more slowly. Therefore, the inhibitor-containing pickling solutions are sometimes referred to as Sparbeizen.
  • the inhibitors are usually substances which coat the metal surface with a coating, partially monomolecular film.
  • Known inhibitors are unsaturated diols such as e.g. Butindiol or propynediol or their derivatives, organic sulfur compounds such as thiourea or its derivatives or nitrogen-containing compounds such.
  • Hexamethylenetetramine or quaternary nitrogen compounds or other inhibitors provide in a particularly preferred concentration of 0.001 to 10 wt.%, In particular 0.01 to 1 wt .-%, based on the total weight of the solution.
  • Further preferred additives of the degreasing solution are solvents, solubilizers, adjusters and / or fragrances, in each case in a preferred concentration of 0.001 to 10% by weight, in particular in a concentration of 0.01 to 5% by weight.

Abstract

Use of phosphonic acid solution (S1) containing phosphonic acid and/or its derivative for degreasing metal surface e.g. iron or steel surface during hot-dip galvanizing process is claimed. Independent claims are included for the following: (1) degreasing solution used for degreasing metal surface, which contains phosphonic acid and/or its derivative, and a surfactant; (2) use of degreasing solution for degreasing metal surface; and (3) degreasing of metal surface.

Description

Die vorliegende Erfindung betrifft eine Verwendung einer phosphonsäure- oder phosphonsäurederivathaltigen Lösung, sowie eine entfettende Lösung zur Verwendung bei der Entfettung von Metalloberflächen, eine Verwendung der entfettenden Lösung, sowie Verfahren zur Entfettung einer Metalloberfläche.The present invention relates to a use of a phosphonic or phosphonic acid derivative-containing solution, and a degreasing solution for use in degreasing metal surfaces, a use of the degreasing solution, and a degreasing method of a metal surface.

Es sind Verfahren bei der Feuerverzinkung bekannt, bei welchen saure Lösungen zur Entfettung von Metalloberflächen verwendet werden, insbesondere Salzsäurelösungen oder Phosphorsäurelösungen, um die Standzeit von Bädern zu erhöhen.There are known processes in hot-dip galvanizing in which acidic solutions are used for degreasing metal surfaces, in particular hydrochloric acid solutions or phosphoric acid solutions, in order to increase the service life of baths.

Es ist Aufgabe der vorliegenden Erfindung, die Standzeit von Bädern bei der Entfettung von Metalloberflächen zusätzlich zu erhöhen.It is an object of the present invention to additionally increase the service life of baths during the degreasing of metal surfaces.

Die Erfindung löst diese Aufgabe durch die Merkmale der Ansprüche 1, 4, 8 oder 9.The invention solves this problem by the features of claims 1, 4, 8 or 9.

Erfindungsgemäß erfolgt eine Verwendung einer phosphonsäure- und/oder phosphonsäurederivathaltigen Lösung bei der Entfettung von Metalloberflächen, insbesondere von Eisen- oder Stahloberflächen, insbesondere bei der Feuerverzinkung. Entfettung bedeutet in diesem Fall die Entfernung von Ölen oder Fetten von der Metalloberfläche.According to the invention, a use of a phosphonic acid and / or phosphonic acid derivative-containing solution in the degreasing of metal surfaces, in particular of iron or steel surfaces, in particular in hot-dip galvanizing. Degreasing in this case means the removal of oils or fats from the metal surface.

Durch die erfindungsgemäße Verwendung kann die Standzeit von Bädern zusätzlich überraschend erhöht werden. Dabei kann die Lösung selbst als Bad genutzt werden oder während oder nach eines Entfettungsvorganges in eine Lösung im Bad zugegeben werden, um die sich durch die Entfettung ändernde Salzkonzentration des Bades einzustellen.By the use according to the invention, the service life of baths can be additionally increased surprisingly. In this case, the solution itself can be used as a bath or added during or after a degreasing process in a solution in the bath to adjust the changing by degreasing salt concentration of the bath.

Vorteilhafte Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche.Advantageous embodiments of the invention are the subject of the dependent claims.

Ein besonders günstiger Anteil an Phosphonsäure oder des Phosphonsäurederivates beträgt 0,0001 bis 50 Gew.%, bezogen auf die Gesamtmenge an freier Säure in einer zur Entfettung bzw. Beizung verwendeten Lösung, insbesondere der Badlösung, beträgt.A particularly favorable proportion of phosphonic acid or of the phosphonic acid derivative is from 0.0001 to 50% by weight, based on the total amount of free acid in a solution used for degreasing or pickling, in particular the bath solution.

Um einen möglichst optimalen Fällungsniederschlag zur Senkung der Salzkonzentration in der entfettenden Lösung des Bades zu erreichen, ist es von Vorteil, wenn die phosphonsäurehaltige oder phosphonsäurederivathaltige Lösung einen pH-Wert von weniger als 7, vorzugsweise weniger als 4,0, aufweist.In order to achieve the best possible precipitation precipitation to reduce the salt concentration in the degreasing solution of the bath, it is advantageous if the phosphonic acid-containing or phosphonsäurederivathaltige solution has a pH of less than 7, preferably less than 4.0.

Erfindungsgemäß enthält eine entfettende Lösung zur Verwendung bei der Entfettung von Metalloberflächen, insbesondere von Eisen- oder Stahloberflächen, eine Phosphonsäure und/oder ein Phosphonsäurederivat und ein Tensid. Durch die Phosphonsäure und/oder das Phosphonsäurederivat kann die Salzkonzentration der Lösung derart eingestellt werden, dass die entfettende Wirkung des Tensids über lange Zeit aufrechterhalten wird. Eine solche entfettende Lösung kann für ein Bad zur Entfettung einer Metalloberfläche bei Feuerverzinkung eingesetzt werden, wodurch eine hohe Standzeit des Bades erzielt wird. Dabei kann die entfettende Lösung auch erst nach einigen Entfettungsdurchgängen durch Zugabe von Phosphonsäure oder Phosphonsäurederivaten zu einer tensidhaltigen Lösung bereitgestellt werden.According to the invention, a degreasing solution for use in the degreasing of metal surfaces, in particular of iron or steel surfaces, contains a phosphonic acid and / or a phosphonic acid derivative and a surfactant. By the phosphonic acid and / or the phosphonic acid derivative, the salt concentration of the solution can be adjusted so that the degreasing effect of the surfactant is maintained for a long time. Such a degreasing solution can be used for a bath for degreasing a metal surface in hot-dip galvanizing, whereby a long service life of the bath is achieved. The degreasing solution can be provided only after a few degreasing passes by adding phosphonic acid or phosphonic acid derivatives to a surfactant-containing solution.

Unterstützend kann die entfettende Lösung, zusätzlich zur Phosphonsäure oder dem Phosphonsäurederivat, eine oder mehrere weitere Säuren aufweisen, wobei die Lösung einen pH-Wert von weniger als 7, vorzugsweise weniger als 4,0, aufweist. Dadurch wird die Verringerung der Salzkonzentration der entfettenden Lösung durch Fällung zusätzlich unterstützt.In support of the degreasing solution, in addition to the phosphonic acid or the phosphonic acid derivative, one or more other acids, wherein the solution has a pH of less than 7, preferably less as 4.0, has. Thereby, the reduction of the salt concentration of the degreasing solution by precipitation is additionally supported.

Optimalerweise weist die entfettende Lösung einen Gehalt an Phosphonsäure von 0,001 bis 100%, bezogen auf die Menge an freier Säure in der entfettenden Lösung, auf.Optimally, the degreasing solution has a content of phosphorous acid of 0.001 to 100%, based on the amount of free acid in the degreasing solution.

Eine besonders gute Entfettung einer Metalloberfläche findet bei einem Tensidgehalt von 0,01 bis 10 Gew.% statt.A particularly good degreasing of a metal surface takes place at a surfactant content of 0.01 to 10% by weight.

Weiterhin kann die entfettende Lösung zusätzlich zumindest ein Lösungsmittel, einen Inhibitor, einen Lösevermittler, ein Stellmittel und/oder einen Duftstoff in einer Konzentration von 0,001 bis 10 Gew.% enthalten.In addition, the degreasing solution may additionally contain at least one solvent, an inhibitor, a solubilizer, an adjusting agent and / or a fragrance in a concentration of 0.001 to 10% by weight.

Die entfettende Lösung kann als Bad zur Entfettung von Metalloberflächen, insbesondere von Eisen oder Stahloberflächen, insbesondere bei der Feuerverzinkung oder in der Galvanotechnik verwendet werden.The degreasing solution can be used as a bath for degreasing metal surfaces, in particular of iron or steel surfaces, in particular in hot-dip galvanizing or in electroplating.

Erfindungsgemäß weist ein Verfahren zur Entfettung einer Metalloberfläche, insbesondere einer Eisen- oder Stahloberfläche, insbesondere bei der Feuerverzinkung, die folgenden Schritte auf:

  1. a) Vorlage einer tensidhaltigen Lösung mit einem pH-Wert von weniger als 7,0 zur Entfettung der Metalloberfläche,
  2. b) Entfetten der Metalloberfläche durch Einbringen in die tensidhaltige Lösung; und
  3. c) Zugabe einer phosphonsäure- und/oder phosphonsäurederivathaltigen Lösung vor, während oder nach dem Entfetten der Metalloberfläche in die tensidhaltige Lösung zur Verminderung des Salzgehaltes in der Lösung.
According to the invention, a method for degreasing a metal surface, in particular an iron or steel surface, in particular in hot-dip galvanizing, comprises the following steps:
  1. a) presentation of a surfactant-containing solution having a pH of less than 7.0 for degreasing the metal surface,
  2. b) degreasing the metal surface by incorporation into the surfactant-containing solution; and
  3. c) adding a phosphonic acid and / or phosphonic acid derivative before, during or after degreasing the metal surface in the surfactant-containing solution to reduce the salt content in the solution.

Durch die Zugabe der phosphonsäure- und/oder phosphonsäurederivathaltigen Lösung in Schritt c) kann eine Einstellung der tensidhaltigen Lösung in Abhängigkeit vom Salzgehalt nach jeder Entfettung oder nach mehreren Entfettungen erfolgen, so dass die Standzeit der tensidhaltigen Lösung erhöht werden kann.By adding the solution containing phosphonic acid and / or phosphonic acid derivative in step c), the surfactant-containing solution can be adjusted as a function of the salt content after each degreasing or after several degreasings, so that the service life of the surfactant-containing solution can be increased.

Um eine materialsparende Dosierung zu ermöglichen, ist ein Anteil der Phosphonsäure oder des Phosphonsäurederivates in der Lösung in Schritt c) von 0,0001 bis 10% ausreichend.In order to enable a material-saving dosage, a proportion of the phosphonic acid or the phosphonic acid derivative in the solution in step c) of 0.0001 to 10% is sufficient.

Die erfindungsgemäße Verwendung wird nachfolgend anhand eines bevorzugten Ausführungsbeispiels näher erläutert.The use according to the invention is explained in more detail below with reference to a preferred embodiment.

Bei der Feuerverzinkung wird eine Eisen- oder Stahloberfläche mit einer Zinkschicht versehen, welche teilweise in die Oberfläche eindiffundiert ist. Zugleich diffundiert ein Teil der Eisenmoleküle aus der Eisen oder Stahloberfläche in die Zinkschicht. Dabei werden vor dem Aufbringen der eigentlichen Zinkschicht verschiedene bekannte vorbereitende Schritte angewandt, welche u.a. von der Güte der zu beschichtenden Oberfläche abhängen.In hot-dip galvanizing, an iron or steel surface is provided with a zinc layer which has partially diffused into the surface. At the same time, some of the iron molecules from the iron or steel surface diffuse into the zinc layer. In this case, various known preparatory steps are applied prior to the application of the actual zinc layer, which u.a. depend on the quality of the surface to be coated.

In einem optionalen ersten Schritt kann beispielsweise eine abrasive Oberflächenbehandlung in Form von Sandbestrahlen o.ä. erfolgen, um Rost oder Lackrückstände von der Oberfläche zu entfernen.In an optional first step, for example, an abrasive surface treatment in the form of sand blasting or the like. to remove rust or paint residue from the surface.

Im Anschluss daran erfolgt ein Entfetten der zu beschichtenden metallischen Oberflächen oder der Metallteile insgesamt. Üblicherweise werden hierfür saure oder alkalische Lösungen verwandt. Oft weisen beispielsweise Eisen- oder Stahloberflächen bei der Lieferung einen Mineralölfilm auf, um einer Korrosion vorzubeugen. Dieser Ölfilm kann zusätzlich einen Korrosionsschutz und weitere Additive enthalten. Bei der Verzinkung ist dieser Ölfilm allerdings hinderlich, da er eine Kontaktierung der Zinkionen mit der Stahl- oder Eisenoberfläche behindert. Somit ist ein Entfetten der Metalloberfläche notwendig.This is followed by degreasing of the metallic surfaces to be coated or the metal parts as a whole. Usually acidic or alkaline solutions are used for this purpose. For example, iron or steel surfaces often have a mineral oil film on delivery to prevent corrosion. This oil film may additionally contain corrosion protection and other additives. In the case of galvanizing, however, this oil film is a hindrance because it impedes contacting of the zinc ions with the steel or iron surface. Thus, a degreasing of the metal surface is necessary.

Nach dem Entfetten kann eine Spülung in Wasser erfolgen, um die Verschleppung in die nachfolgenden Bäder (meist saure Beizlösungen) zu vermeiden bzw. zu minimieren.After degreasing, it is possible to rinse in water in order to avoid or minimize the carryover to the subsequent baths (usually acid pickling solutions).

Nach dem Entfetten bzw. Spülen erfolgt eine Beizbehandlung zum Entfernen von Verunreinigungen, welche sich auf das Metall selbst zurückführen lassen. Dies sind beispielsweise Oxidationsprodukte, wie Rost oder Zunder. Die Dauer des Beizvorgangs und die Konzentration des Beizbades hängen vom Umfang der auf der Metalloberfläche vorkommenden Oxidationsprodukte ab. In einigen Fällen wird die Entfettung auch in der Beize durchgeführt, dann spricht man vom Beizentfetten.After degreasing or rinsing, a pickling treatment is carried out to remove impurities which can be traced back to the metal itself. These are, for example, oxidation products, such as rust or scale. The duration of the pickling process and the concentration of the pickling bath depend on the extent of the oxidation products occurring on the metal surface. In some cases, the degreasing is carried out in the stain, then it is called the pickling greasing.

Um Säure- und Salzreste nicht in nachfolgende Verfahrensstufen zu verschleppen, kann im Anschluss an das Beizen ein weiteres Spülen mit Lösungsmittel - beispielsweise Wasser - durchgeführt werden.In order not to delay acid and salt residues in subsequent process stages, a further rinsing with solvent - for example water - can be carried out after pickling.

Nach dem Beizen oder Spülen ist es außerdem üblich, die metallische Oberfläche einer Feinstreinigung in einem chloridhaltigen Flussmittelbad (dieser Prozeß wird Fluxen genannt, bei einer wässrigen Anwendung üblicherweise Trockenflux) zu unterziehen, um die Stahloberfläche zu aktivieren und damit die Benetzungsfähigkeit zu erhöhen.After pickling or rinsing, it is also common to subject the metallic surface of a microfine in a chloride-containing flux bath (this process is called fluxing, usually dry-flux in an aqueous application) to activate the steel surface and thereby increase wetting ability.

Ersatzweise kann das Fluxen auch mittels einer Salzschicht, welche auf dem Zinkbad schwimmt, durchgeführt werden (sogenanntes Nassverzinken). In diesem Fall sollte die zu behandelnden Oberflächen vor dem Verzinken nicht getrocknet werden.Alternatively, the fluxing can also be carried out by means of a salt layer which floats on the zinc bath (so-called wet galvanizing). In this case, the surfaces to be treated should not be dried before galvanizing.

Nach dem Fluxen kann ein Trocknen der Metalloberfläche, beispielsweise in Trockenöfen bei 80-90°C, erfolgen.After fluxing, the metal surface can be dried, for example in drying ovens at 80-90 ° C.

Im Anschluss erfolgt das Verzinken durch Eintauchen der metallischen Oberfläche in eine flüssige Zinkschmelze, mit vorzugsweise mindestens 98 Gew.-% Zink. Diese weist vorzugsweise eine Temperatur von mehr als 420°C auf, besonders bevorzugt zwischen 440-465°C, oder alternativ oberhalb von 500°C. Dabei erfolgt eine wechselseitige Diffusion beider Metallschichten ineinander.The galvanizing is then carried out by immersing the metallic surface in a liquid zinc melt, preferably with at least 98% by weight of zinc. This preferably has a temperature of more than 420 ° C, more preferably between 440-465 ° C, or alternatively above 500 ° C. In this case, a mutual diffusion of both metal layers into each other.

Im Anschluss an das Verzinken können nachbearbeitende Arbeitsschritte, z.B. Entgraten, Verputzen, Polieren, Lackieren oder Pulverbeschichten erfolgen.Following galvanizing, post-processing operations, e.g. Deburring, plastering, polishing, painting or powder coating take place.

Zusätzlich kann ein sogenanntes Entzinken in verdünnter Salzsäure erfolgen, bei dem bereits verzinkte Metallschichten wieder entfernt werden können. Dadurch kann eine Fehlverzinkung wieder abgelöst werdenIn addition, a so-called dezincing can take place in dilute hydrochloric acid, in which already galvanized metal layers can be removed again. As a result, a Fehlverzinkung be replaced again

Feuerverzinkereien haben allerdings üblicherweise keine Abwasseranlage, sondern nur sogenannte Standspülen. Die in der Feuerverzinkung eingesetzten Stoffe werden somit in nachfolgende Bäder verschleppt. Diese Bäder sind nach und nach verbraucht und müssen extern entsorgt werden. Um die Umweltbelastungen zu minimieren und eine entsprechende Kostensenkung zu erreichen, sollte eine längere Standzeit von Bädern angestrebt werden.However, hot-dip galvanizing plants usually have no wastewater treatment plant, but only so-called stationary rinsing. The substances used in the hot-dip galvanizing are thus taken to subsequent baths. These baths are gradually consumed and must be disposed of externally. In order to minimize the environmental impact and to achieve a corresponding cost reduction, a longer service life of baths should be sought.

Ein Bad gilt in der Regel dann als erschöpft, wenn die Eisenkonzentration und somit die Salzkonzentration der entfettenden Lösung einen bestimmten Gehalt überschreitet, so dass die im Bad enthaltenen entfettungswirksamen Tenside und die von den Tensiden in Lösung gehaltenen Verunreinigungen nicht mehr stabil oder löslich in der Entfettungslösung vorliegen. Eine Erhöhung der Salzkonzentration erfolgt dabei in sauren Lösungen in der Regel ganz automatisch, da bei jedem Entfettungsvorgang zwangsläufig auch Eisenionen in der entfettenden Lösung gelöst werden.A bath is usually considered exhausted when the iron concentration and thus the salt concentration of the degreasing solution exceeds a certain level so that the degreasing surfactants present in the bath and the contaminants held in solution by the surfactants are no longer stable or soluble in the degreasing solution available. An increase in salt concentration This is done automatically in acidic solutions as a rule, as with each degreasing inevitably iron ions are dissolved in the degreasing solution.

Eine bekannte Möglichkeit zur Erhöhung der Standzeit ist der Einsatz von Phosphorsäure. Dadurch werden Eisenphosphate ausgefällt, wodurch die Eisenkonzentration und somit auch die Salzkonzentration der Lösung - bezogen auf die in Lösung befindlichen Ionen - insgesamt gesenkt wird.A known way to increase the service life is the use of phosphoric acid. As a result, iron phosphates are precipitated, whereby the iron concentration and thus also the salt concentration of the solution - based on the ions in solution - is reduced overall.

Der Gegenstand der vorliegenden Erfindung beschreitet demgegenüber einen alternativen Weg, indem der entfettenden Lösung ein Reinigungsmittel bzw. eine Lösung enthaltend eine Phosphonsäure oder ein Phosphonsäurederivat zugesetzt wird. Durch den Zusatz des phosphonsäurederivathaltigen Reinigungsmittels bildet sich überraschend ein Niederschlag aus, welcher einerseits das überschüssige Eisen bindet. Zusätzlich werden organische Verunreinigungen aus dem Bad entfernt.The object of the present invention, in contrast, takes an alternative route by adding to the degreasing solution a cleaning agent or a solution containing a phosphonic acid or a phosphonic acid derivative. The addition of the phosphonic acid derivative-containing detergent surprisingly forms a precipitate, which on the one hand binds the excess iron. Additionally, organic contaminants are removed from the bath.

Dies ist insoweit überraschend, da Phosphonsäurederivate eigentlich als komplexierend gelten und durch deren Zusatz die Salzkonzentration weiter erhöht wird. Trotz alledem wird die Standzeit eines Bades durch den Zusatz dieser Derivate drastisch erhöht, so dass eine Entfettungswirkung des Bades über einen längeren Zeitpunkt aufrecht erhalten bleibt.This is surprising inasmuch as phosphonic acid derivatives are actually considered to be complexing and, by virtue of their addition, the salt concentration is further increased. Despite all this, the life of a bath is drastically increased by the addition of these derivatives, so that a degreasing effect of the bath is maintained over a longer time.

Vorzugsweise ist ein solches Phosphonsäurederivat HEDP (1-Hydroxyethan-(1,1-diphosphonsäure), HEMPA (Hexamethylendiamin-tetra(methylenphosphonsäure)), HDTMP (Hexaethylenediamine-tetramethylenphosphonsäure), ATMP (Aminotrimethylenphosphonsäure), EDTMP (Ethylendiamintetra(methylenphosphonsäure)), DTPMP (Diethylentriaminpenta(methylenphosphonsäure)) und/oder PBTC (2-Phosphonobutan-1,2,4-tricarbonsäure). Diese Verbindungen werden üblicherweise als Korrosionsinhibitoren eingesetzt und/oder dienen dazu, Metallionen in Lösung zu halten. Interessanterweise konnte trotzdem die Bildung eines Niederschlages bei der Zugabe einer der vorgenannten Verbindungen zu einer entfettenden Lösung beobachtet werden.Preferably, such a phosphonic acid derivative is HEDP (1-hydroxyethane- (1,1-diphosphonic acid), HEMPA (hexamethylenediamine-tetra (methylenephosphonic acid)), HDTMP (hexaethylenediamine-tetramethylenephosphonic acid), ATMP (aminotrimethylenephosphonic acid), EDTMP (ethylenediaminetetra (methylenephosphonic acid)), DTPMP (Diethylenetriaminepenta (methylenephosphonic acid)) and / or PBTC (2-phosphonobutane-1,2,4-tricarboxylic acid) .These compounds are commonly used as corrosion inhibitors and / or serve to keep metal ions in solution, although interestingly, the formation of a precipitate be observed in the addition of one of the aforementioned compounds to a degreasing solution.

Durch eine bevorzugte Dosierung eines Phosphonsäurederivate kann eine Einstellung des Eisengehaltes in der Lösung des Bades erfolgen, was praktisch zu einer nahezu unbegrenzten Standzeit des Bades führt.By a preferred dosage of a phosphonic acid derivatives, an adjustment of the iron content in the solution of the bath can take place, which practically leads to a virtually unlimited service life of the bath.

Bei dem Phosphonsäurederivat kann es sich um ein Derivat einer einfachen oder komplexen Phosphonsäure handeln.The phosphonic acid derivative may be a derivative of a simple or complex phosphonic acid.

Das zugesetzte Reinigungsmittel weist vorzugsweise einen pH-Wert von weniger als 7,0 auf, vorzugsweise einen pH-Wert von weniger als 4,0.The added detergent preferably has a pH of less than 7.0, preferably a pH of less than 4.0.

Die aus dem Reinigungsmittel hergestellte entfettende Lösung kann zur Metallentfettung, insbesondere bei der Feuerverzinkung oder bei der galvanischen Behandlung von Metalloberflächen, verwendet werden.The degreasing solution prepared from the cleaning agent can be used for metal degreasing, in particular in hot-dip galvanizing or in the galvanic treatment of metal surfaces.

Die Konzentration an Phosphonsäure oder einem Phosphonsäurederivat in der entfettenden Lösung beträgt bevorzugt 0,001 bis 60%, insbesondere 0,1 bis 10%, bezogen auf die vorhandene Menge an freier Säure in der entfettenden Lösung. Dabei enthält die entfettende Lösung in jedem Fall zumindest eine Säure.The concentration of phosphonic acid or a phosphonic acid derivative in the degreasing solution is preferably 0.001 to 60%, in particular 0.1 to 10%, based on the amount of free acid present in the degreasing solution. In each case, the degreasing solution contains at least one acid.

Dabei kann eine Phosphonsäure auch separat einer bereits bestehenden Reinigungslösung zur Metallfällung zugesetzt werden.In this case, a phosphonic acid can also be added separately to an already existing cleaning solution for metal precipitation.

Vor, während oder nach der Entfettung, also dem Eintauchen der Metalloberfläche in ein saures Bad, kann Phosphonsäure oder ein Phosphonsäurederivat von bevorzugt 0,0001 bis 10%, insbesondere 0,01 bis 1 %, bezogen auf die vorhandene Menge an freier Säure, in der entfettenden Lösung zudosiert werden.Before, during or after degreasing, ie immersing the metal surface in an acidic bath, phosphonic acid or a phosphonic acid derivative of preferably 0.0001 to 10%, in particular 0.01 to 1%, based on the amount of free acid present, in be added to the degreasing solution.

Zusätzlich zur Zugabe der Phosphonsäure oder des Phosphonsäurederivates kann auch eine Mineralsäure und/oder eine organische Säure zugegeben werden, um eine verstärkte Reinigungs- bzw. Niederschlagsbildung zu erreichen. Bevorzugte Mineralsäuren sind dabei Salzsäure, Schwefelsäure, Phosphorsäure und/oder Salpetersäure. Bevorzugte organische Säuren sind Oxalsäure, Weinsäure, Zitronensäure und/oder Essigsäure.In addition to the addition of the phosphonic acid or the phosphonic acid derivative, a mineral acid and / or an organic acid may also be added to achieve enhanced precipitation formation. Preferred mineral acids are hydrochloric acid, sulfuric acid, phosphoric acid and / or nitric acid. Preferred organic acids are oxalic, tartaric, citric and / or acetic acid.

Die Konzentration der Mineralsäure und/oder organischen Säure in der entfettenden Lösung beträgt vorzugsweise 0,1 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Lösung.The concentration of the mineral acid and / or organic acid in the degreasing solution is preferably 0.1 to 90 wt .-%, based on the total weight of the solution.

Zusätzlich enthält die entfettende Lösung vorzugsweise Tenside, insbesondere nichtionische, anionische und/oder kationische Tenside, wobei sich ein Anteil an Phosphonsäure oder Phosphonsäurederivat besonders positiv auf die Löslichkeit von nichtionischen Tensiden auswirkt, insbesondere in einer besonders bevorzugten Konzentration von 0,01 bis 10 Gew.-%, insbesondere 0,1-1 Gew.% bezogen auf das Gesamtgewicht der entfettenden Lösung.In addition, the degreasing solution preferably contains surfactants, in particular nonionic, anionic and / or cationic surfactants, wherein a proportion of phosphonic acid or phosphonic acid derivative has a particularly positive effect on the solubility of nonionic surfactants, in particular in a particularly preferred concentration of 0.01 to 10 wt .-%, in particular 0.1-1 wt.% Based on the total weight of the degreasing solution.

Unabhängig von der besonders bevorzugten Erhöhung der Wirksamkeit der Tenside in Lösung für die Zugabe an Phosphonsäure oder Phosphonsäurederivat hat der Einsatz von phosphonsäure- oder phosphonsäurederivathaltiger Lösung auch zu einer Erhöhung der Löslichkeit von Fetten und Ölen in einer tensidfreien Lösung, so dass der Einsatz auch bei einer Entfettung von Metallen mit tensidfreien entfettenden Lösungen Vorteile hat. Allerdings ist die entfettende Wirkung einer tensidhaltigen Lösung in Kombination mit einer Phosphonsäure oder einem Phosphonsäurederivat wesentlich höher.Regardless of the particularly preferred increase in the effectiveness of surfactants in solution for the addition of phosphonic acid or phosphonic acid derivative, the use of phosphonic or phosphonsäurederivathaltiger solution also to an increase in the solubility of fats and oils in a surfactant-free solution, so that the use of a Degreasing metals with surfactant-free degreasing solutions has advantages. However, the degreasing effect of a surfactant-containing solution in combination with a phosphonic acid or a phosphonic acid derivative is much higher.

Darüber hinaus kann die entfettende Lösung auch Inhibitoren enthalten, um die Aufnahme von Eisenionen aus den behandelten Metalloberflächen zu minimieren. Inhibitoren vermindern einerseits die Metallaufnahme und reduzieren andererseits die Bildung von Wasserstoff und sollen teilweise auch das Eindiffundieren von Wasserstoff in das Metallgefüge vermindern. Außerdem wird die Standzeit von Beizen erhöht, da der Metallgehalt dann langsamer steigt. Deshalb werden die Inhibitor-haltigen Beizlösungen teilweise auch als Sparbeizen bezeichnet. Die Inhibitoren sind üblicherweise Stoffe, welche die Metalloberfläche mit einem Überzug, teilweise monomolekularen Film überziehen. Bekannte Inhibitoren sind ungesättigte Diole wie z.B. Butindiol oder Propindiol bzw. deren Derivate, organische Schwefelverbindungen wie Thioharnstoff bzw. dessen Derivate oder Stickstoff-haltige Verbindungen wie z.B. Hexamethylentetramin oder quarternäre Stickstoffverbindungen oder andere Inhibitoren. Diese legen in einer besonders bevorzugten Konzentration von 0,001 bis 10 Gew.%, insbesondere 0,01 - 1 Gew.-%, bezogen auf das Gesamtgewicht der Lösung vor.In addition, the degreasing solution may also contain inhibitors to minimize the uptake of iron ions from the treated metal surfaces. On the one hand, inhibitors reduce the metal uptake and on the other hand reduce the formation of hydrogen and in some cases also reduce the diffusion of hydrogen into the metal structure. In addition, the lifetime of pickling is increased, since the metal content then increases more slowly. Therefore, the inhibitor-containing pickling solutions are sometimes referred to as Sparbeizen. The inhibitors are usually substances which coat the metal surface with a coating, partially monomolecular film. Known inhibitors are unsaturated diols such as e.g. Butindiol or propynediol or their derivatives, organic sulfur compounds such as thiourea or its derivatives or nitrogen-containing compounds such. Hexamethylenetetramine or quaternary nitrogen compounds or other inhibitors. These provide in a particularly preferred concentration of 0.001 to 10 wt.%, In particular 0.01 to 1 wt .-%, based on the total weight of the solution.

Weitere bevorzugte Zusätze der Entfettungslösung sind Lösemittel, Lösevermittler, Stellmittel und/oder Duftstoffe jeweils in einer bevorzugten Konzentration von 0,001 bis 10 Gew.-%, insbesondere in einer Konzentration von 0,01 bis 5 Gew.-%.Further preferred additives of the degreasing solution are solvents, solubilizers, adjusters and / or fragrances, in each case in a preferred concentration of 0.001 to 10% by weight, in particular in a concentration of 0.01 to 5% by weight.

Claims (11)

Verwendung einer phosphonsäure- und/oder phosphonsäurederivathaltigen Lösung bei der Entfettung von Metalloberflächen, insbesondere von Eisen- oder Stahloberflächen, insbesondere bei der Feuerverzinkung.Use of a phosphonic acid and / or phosphonic acid derivative-containing solution in the degreasing of metal surfaces, in particular of iron or steel surfaces, in particular in hot-dip galvanizing. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass der Anteil der Phosphonsäure oder des Phosphonsäurederivates in der Lösung 0,0001 bis 50 Gew.%, bezogen auf die Gesamtmenge an freier Säure in der zur Entfettung bzw. Beizung verwendeten Lösung beträgt.Use according to Claim 1, characterized in that the proportion of phosphonic acid or phosphonic acid derivative in the solution is 0.0001 to 50% by weight, based on the total amount of free acid in the solution used for degreasing or pickling. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Lösung einen pH-Wert von weniger als 7, vorzugsweise weniger als 4,0 aufweist.Use according to claim 1 or 2, characterized in that the solution has a pH of less than 7, preferably less than 4.0. Entfettende Lösung zur Verwendung bei der Entfettung von Metalloberflächen, insbesondere von Eisen- oder Stahloberflächen, dadurch gekennzeichnet, dass die entfettende Lösung eine Phosphonsäure und/oder ein Phosphonsäurederivat und ein Tensid enthält.A degreasing solution for use in the degreasing of metal surfaces, in particular of iron or steel surfaces, characterized in that the degreasing solution contains a phosphonic acid and / or a phosphonic acid derivative and a surfactant. Entfettende Lösung nach Anspruch 4, dadurch gekennzeichnet, dass die entfettende Lösung eine Säure aufweist und einen pH-Wert von weniger als 7, vorzugsweise weniger als 4,0.A degreasing solution according to claim 4, characterized in that the degreasing solution has an acid and a pH of less than 7, preferably less than 4.0. Entfettende Lösung nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, dass die entfettende Lösung einen Gehalt an Phosphonsäure von 0,001 bis 50%, bezogen auf die Menge an freier Säure in der entfettenden Lösung aufweist.Degreasing solution according to one of claims 4 or 5, characterized in that the degreasing solution has a content of phosphonic acid of 0.001 to 50%, based on the amount of free acid in the degreasing solution. Entfettende Lösung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die entfettende Lösung einen Tensidgehalt von 0,01 bis 10 Gew.% aufweist.Degreasing solution according to one of the preceding claims, characterized in that the degreasing solution has a surfactant content of 0.01 to 10 wt.%. Entfettende Lösung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die entfettende Lösung zusätzlich zumindest ein Lösungsmittel, ein Inhibitor, ein Lösevermittler, ein Stellmittel und/oder einen Duftstoff in einer Konzentration von 0,001 bis 10 Gew.% enthält.Degreasing solution according to one of the preceding claims, characterized in that the degreasing solution additionally contains at least one solvent, an inhibitor, a solubilizer, an adjusting agent and / or a fragrance in a concentration of 0.001 to 10 wt.%. Verwendung der entfettenden Lösung bei der Entfettung von Metalloberflächen, insbesondere von Eisen oder Stahloberflächen, insbesondere bei der Feuerverzinkung.Use of the degreasing solution in the degreasing of metal surfaces, in particular of iron or steel surfaces, in particular in hot-dip galvanizing. Verfahren zur Entfettung einer Metalloberfläche, insbesondere einer Eisen-oder Stahloberfläche, insbesondere bei der Feuerverzinkung, gekennzeichnet durch die folgenden Schritte: a) Vorlage einer tensidhaltigen Lösung mit einem pH-Wert von weniger als 7,0 zur Entfettung der Metalloberfläche b) Entfetten der Metalloberfläche durch Einbringen in die tensidhaltige Lösung; und c) Zugabe einer phosphonsäure- und/oder phosphonsäurederivathaltigen Lösung vor, während oder nach dem Entfetten der Metalloberfläche in die tensidhaltige Lösung zur Verminderung des Metallionengehaltes in der Lösung. Process for degreasing a metal surface, in particular an iron or steel surface, in particular in hot-dip galvanizing, characterized by the following steps: a) Presentation of a surfactant-containing solution having a pH of less than 7.0 for degreasing the metal surface b) degreasing the metal surface by incorporation into the surfactant-containing solution; and c) adding a phosphonic acid and / or phosphonic acid derivative before, during or after degreasing the metal surface in the surfactant-containing solution to reduce the metal ion content in the solution. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass der Anteil der Phosphonsäure oder des Phosphonsäurederivates in der Lösung 0,0001 bis 10Gew.%, bezogen auf die Gesamtmenge an freier Säure in der zur Entfettung bzw. Beizung verwendeten Lösung beträgt.A method according to claim 10, characterized in that the proportion of the phosphonic acid or the Phosphonsäurederivates in the solution 0.0001 to 10Gew.%, Based on the total amount of free acid in the solution used for degreasing or pickling.
EP13168021.7A 2012-06-08 2013-05-16 Use of a solution containing phosphonic acid and/or phosphonic acid derivatives during the degreasing of metal surfaces, degreasing solution and method for degreasing a metal surface Active EP2671972B1 (en)

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EP1310306A1 (en) * 2001-11-08 2003-05-14 Benteler Automobiltechnik GmbH & Co. KG Process for cleaning metallic components
WO2008122478A1 (en) * 2007-04-04 2008-10-16 Henkel Ag & Co. Kgaa Bleach-containing detergent or cleaning agent
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