EP0017302B1 - Method of rinsing during the phosphatizing of metals - Google Patents
Method of rinsing during the phosphatizing of metals Download PDFInfo
- Publication number
- EP0017302B1 EP0017302B1 EP80200302A EP80200302A EP0017302B1 EP 0017302 B1 EP0017302 B1 EP 0017302B1 EP 80200302 A EP80200302 A EP 80200302A EP 80200302 A EP80200302 A EP 80200302A EP 0017302 B1 EP0017302 B1 EP 0017302B1
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- EP
- European Patent Office
- Prior art keywords
- rinse
- stage
- rinsing
- post
- water
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- 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.)
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
Abstract
Description
Die Erfindung betrifft ein Spülverfahren bei der Aufbringung von Phosphatüberzügen auf Metallen, wobei die Metalloberfläche mindestens eine Vorspülstufe, eine Phosphatierstufe und mindestens zwei Nachspülstufen durchläuft und Spülwasser der ersten Nachspülstufe durch Zugabe von Fällungsmitteln von störenden Anionen und Kationen befreit und nach Schlammabtrennung wieder zu Spülzwecken eingesetzt wird.The invention relates to a rinsing process in the application of phosphate coatings to metals, the metal surface passing through at least one pre-rinsing stage, a phosphating stage and at least two rinsing stages and rinsing water of the first rinsing stage being freed from annoying anions and cations and being used again for rinsing purposes after sludge removal .
Der für Phosphatierverfahren typische Verfahrensgang besteht in der Reinigung der Metalloberflächen, der Vorspülung vor der Phosphatierung, der Phosphatierung selbst und der Nachspülung, die üblicherweise in mindestens zwei Stufen erfolgt.The typical process for phosphating processes consists in cleaning the metal surfaces, pre-rinsing before phosphating, phosphating itself and rinsing, which usually takes place in at least two stages.
Insbesondere in jüngerer Zeit hat es nicht an Bemühungen gefehlt, Spülverfahren zu entwikkein, die sich der Kreislaufführung der Spülbäder bedienen, um einerseits den Frischwasserbedarf zu reduzieren und anderseits die Abwasserbehandlung zu erleichtern bzw. die Abwassermengen zu senken.In recent times, in particular, there has been no lack of efforts to develop flushing processes which use the circulation of the flushing baths, on the one hand to reduce the need for fresh water and on the other hand to facilitate wastewater treatment or to reduce the wastewater quantities.
So ist es aus der DE-A1-2 527 853 und der GB-A-1 540 308 bekannt, bereits verwendetes und von störenden Verunreinigungen befreites Spülwasser im Gegenstrom zur Bewegung der Metalloberflächen erst durch die zweite Nachspülstufe, dann durch die erste Nachspülstufe, danach durch die letzte Vorspülstufe und schliesslich zurück in die Reinigungsvorrichtung zu führen.It is known from DE-A1-2 527 853 and GB-A-1 540 308 to use rinsing water that has already been used and freed from interfering contaminants in countercurrent to the movement of the metal surfaces only through the second rinsing stage, then through the first rinsing stage, and then through the last pre-rinse stage and finally back into the cleaning device.
Andere bekannte Verfahren beschränken sich auf eine Kreislaufführung über die zweite Nachspülstufe, die erste Nachspülstufe und die Reinigungsvorrichtung (H. Blum, «Die Entwicklung rohstoffsparender und umweltfreundlicher Phosphatierverfahren" in Jahrbuch Oberflächentechnik, Band 34 (1978), Metall-Verlag GmbH, Berlin, Seite 197, insbesondere Seite 202).Other known methods are limited to a circulation via the second rinse stage, the first rinse stage and the cleaning device (H. Blum, "The Development of Raw Material-Saving and Environmentally Friendly Phosphating Processes" in Yearbook Surface Technology, Volume 34 (1978), Metall-Verlag GmbH, Berlin, page 197, in particular page 202).
Nachteilig bei den bekannten Verfahren ist, dass entweder die Frischwasserersparnis nicht befriedigt oder durch den Eintrag von Spülwasser aus der ersten Nachspülstufe in die Vorspülstufe beträchtliche Mengen Phosphatierungsmittel eingeschleppt werden. Diese können eine, die einwandfreie Schichtausbildung in der Phosphatierungsstufe beeinträchtigende Vorpassivierung bewirken.A disadvantage of the known methods is that either the fresh water savings are not satisfied or that considerable amounts of phosphating agent are introduced by the introduction of rinse water from the first rinse stage into the pre-rinse stage. These can cause a pre-passivation, which impairs the perfect layer formation in the phosphating stage.
Aufgabe der Erfindung ist es, ein Spülverfahren zur Verfügung zu stellen, das die Nachteile der bekannten Verfahren vermeidet, einen geringen Frischwasserbedarf hat und Vorpassivierungserscheinungen ausschliesst.The object of the invention is to provide a rinsing process which avoids the disadvantages of the known processes, has a low fresh water requirement and rules out pre-passivation phenomena.
Die Aufgabe wird gelöst, indem das eingangs genannte Spülverfahren entsprechend der Erfindung derart ausgestaltet wird, dass man praktisch das gesamte gereinigte Spülwasser nach Durchgang allein durch die zweite Nachspülstufe NS2 der Vorspülstufe VS zuführt und anschliessend in die erste Nachspülstufe NS1 zurückführt.The object is achieved in that the rinsing method mentioned at the outset is designed in accordance with the invention in such a way that practically all of the cleaned rinsing water after passing through the second rinsing stage NS2 is fed to the pre-rinsing stage VS and then returned to the first rinsing stage NS1.
Hierbei wird das in der Reinigungsvorrichtung gereinigte Wasser in die zweite Nachspülstufe und von dort in die Vorspülstufe geleitet. Anschliessend wird das Spülwasser der Vorspülstufe in die erste Nachspülstufe geführt. Dieses Verfahren, das ein in sich geschlossenes System darstellt, gestattet eine Frischwassereinsparung von etwa 90%. Es ist vorzugsweise für Phosphatierungsverfahren geeignet, die mit Wasserstoffperoxid-Beschleunigern arbeiten.Here, the water cleaned in the cleaning device is passed into the second rinse stage and from there into the pre-rinse stage. The rinse water from the pre-rinse stage is then led into the first rinse stage. This process, which is a self-contained system, allows fresh water savings of around 90%. It is preferably suitable for phosphating processes that work with hydrogen peroxide accelerators.
Bei der Durchführung des Verfahrens besteht die Möglichkeit, die Vorspülstufe in zwei Behandlungszonen aufzuteilen. In diesem Fall wird das Wasser, das der Vorspülstufe zugeführt wird, entweder auf beide Behandlungszonen aufgeteilt oder aber zunächst der zweiten und danach der ersten Spülzone der Vorspülstufe - in Richtung des Flusses der Metalloberflächen gesehen - zugeführt. Das Spülwasser wird danach in die erste Nachspülstufe zurückgeführt.When carrying out the method, it is possible to divide the pre-rinse stage into two treatment zones. In this case, the water that is fed to the pre-rinse stage is either divided between the two treatment zones or first to the second and then to the first rinse zone of the pre-rinse stage, as viewed in the direction of the flow of the metal surfaces. The rinse water is then returned to the first rinse stage.
In ähnlicher Weise lässt sich auch die zweite Nachspülstufe in zwei Spülzonen aufteilen. In diesem Fall wird das Spülwasser der letzten Nachspülzone der zweiten Nachspülstufe der ersten Nachspülzone zugeleitet und von dort der Vorspülstufe zugeführt.Similarly, the second rinse stage can also be divided into two rinse zones. In this case, the rinse water from the last rinse zone is fed to the second rinse stage of the first rinse zone and from there to the pre-rinse stage.
Im Bedarfsfall können die aus der zweiten Nachspülstufe austretenden Metalloberflächen noch einer weiteren Spülbehandlung mit Frischwasser unterworfen werden, das dann der zweiten Nachspülstufe zuläuft.If necessary, the metal surfaces emerging from the second rinse stage can be subjected to a further rinse treatment with fresh water, which then flows to the second rinse stage.
In den einzelnen Spülstufen kann im Tauchen und/oder im Spritzen gearbeitet werden.The individual rinsing stages can be used for diving and / or spraying.
Die Beseitigung der störenden Anionen und Kationen erfolgt in an sich bekannter Weise. Phosphate und Schwermetalle können beispielsweise durch Neutralisation mit Erdalkalihydroxyd, insbesondere Kalkmilch, ausgefällt werden. Die Reaktionsmischung wird dabei auf einen pH-Wert von etwa 8,5 gebracht. Gelöste Alkaliionen werden nicht ausgefällt, stören im allgemeinen aber weniger, zumindest solange nicht eine übermässige Anreicherung in den Spülbädern eintritt. Eine derartige übermässige Anreicherung kann vermieden werden, indem man z. B. bei der Formulierung der Entfettungs- und der Phospatierbäder im Rahmen des Möglichen die Verwendung von Ionen vermeidet, die bei der Behandlung mit Erdalkalihydroxyd lösliche Salze ergeben.The disruptive anions and cations are removed in a manner known per se. Phosphates and heavy metals can be precipitated, for example, by neutralization with alkaline earth metal hydroxide, especially milk of lime. The reaction mixture is brought to a pH of about 8.5. Dissolved alkali ions are not precipitated, but generally cause less interference, at least as long as there is no excessive accumulation in the rinsing baths. Such excessive enrichment can be avoided by e.g. B. in the formulation of degreasing and phosphating baths to the extent possible avoids the use of ions which result in soluble salts in the treatment with alkaline earth metal hydroxide.
Der bei der Neutralisation des abgezogenen Spülbades entstehende Niederschlag kann durch die bekannten Methoden der Schlammabtrennung, z.B. durch Sedimentation und/oder Filtration, von der Lösung entfernt werden.The precipitate resulting from the neutralization of the removed rinsing bath can be removed by the known methods of sludge separation, e.g. be removed from the solution by sedimentation and / or filtration.
Besonders vorteilhafte Ergebnisse lassen sich durch Einsatz eines Schrägklärers erzielen. Der abgetrennte Schlamm kann zur weiteren Einengung einem Schlammeindickbehälter und einer Filterpresse zugeführt werden.Particularly advantageous results can be achieved by using an inclined clarifier. The separated sludge can be fed to a sludge thickener and a filter press for further concentration.
Sofern erforderlich, kann das Spülwasser über einen Tensidadsorber geleitet werden. Dies empfiehlt sich, wenn in der Entfettungsstufe eine tensidhaltige Lösung eingesetzt wird.If necessary, the rinse water can be passed through a surfactant adsorber. This is recommended if a surfactant-containing solution is used in the degreasing stage.
Weiterhin ist die Möglichkeit gegeben, den in der Phosphatierungsstufe anfallenden Schlamm in die Arbeitsweise zur Reinigung des Spülwassers einzubeziehen. Die Schlammabtrennung erfolgt dabei in der üblichen Weise, jedoch wird der Dünnschlamm mit in die Aufbereitungsanlage zur Reaktion mit geeigneten Fällungsmitteln eingeführt.There is also the possibility of the sludge obtained in the phosphating stage to be included in the method of cleaning the rinsing water. The sludge is separated off in the usual manner, but the thin sludge is also introduced into the treatment plant for reaction with suitable precipitants.
Das erfindungsgemässe Spülverfahren wird anhand der Figur näher und beispielsweise erläutert. Sie stellt ein Fliessschema für das Spülwasser dar.The flushing method according to the invention is explained in more detail and, for example, using the figure. It represents a flow diagram for the rinse water.
Gemäss Figur werden die zunächst entfetteten Metalloberflächen durch die Vorspülstufe VS, die Phosphatierstufe P, die erste Nachspülstufe NS1 und die zweite Nachspülstufe NS2 geführt. Das Spülwasser gelangt dabei aus der Reinigungsvorrichtung R zunächst in die zweite Nachspülstufe NS2 und von dort in die Vorspülstufe VS. Nach Austritt aus der Vorspülstufe VS wird es in die erste Nachspülstufe NS1 zurückgeführt und anschliessend der Reinigungsvorrichtung R aufgegeben.According to the figure, the initially degreased metal surfaces are passed through the pre-rinsing stage VS, the phosphating stage P, the first rinsing stage NS1 and the second rinsing stage NS2. The rinse water first passes from the cleaning device R into the second rinse stage NS2 and from there into the pre-rinse stage VS. After exiting the pre-rinse stage VS, it is returned to the first rinse stage NS1 and then fed to the cleaning device R.
Spülwasserverluste infolge von Verdampfung oder mechanischem Austrag werden durch Zugabe von Frischwasser, das zweckmässigerweise der Nachspülstufe NS2 zugeführt wird, ausgeglichen. Der Pfeil an der Reinigungsvorrichtung R deutet den Austrag von Schlamm an.Losing water losses due to evaporation or mechanical discharge are compensated for by adding fresh water, which is expediently fed to the post-rinsing stage NS2. The arrow on the cleaning device R indicates the discharge of sludge.
Claims (1)
- Rinsing process in connection with the application of phosphate coatings on metals, in which process the metal surfaces are passed to at least one pre-rinse stage, a phosphatizing stage and at least two post-rinse stages and rinse water of the first post-rinse stage is purified from contaminating anions and cations by an addition of precipitants and after removal of sludge is re-used for rinsing purposes, characterized in that practically the total quantity of the purified rinse water after passing solely the second post-rinse stage (NS2) is introduced into the pre-rinse stage (VS) and thereafter recycled into the first post-rinse stage (NS1).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80200302T ATE5003T1 (en) | 1979-04-07 | 1980-04-01 | FLUSHING PROCEDURE FOR THE APPLICATION OF PHOSPHATE COATINGS ON METALS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7912299 | 1979-04-07 | ||
GB7912299 | 1979-04-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0017302A1 EP0017302A1 (en) | 1980-10-15 |
EP0017302B1 true EP0017302B1 (en) | 1983-10-12 |
Family
ID=10504422
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80200302A Expired EP0017302B1 (en) | 1979-04-07 | 1980-04-01 | Method of rinsing during the phosphatizing of metals |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0017302B1 (en) |
AT (1) | ATE5003T1 (en) |
DE (1) | DE3065238D1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4307591A1 (en) * | 1992-06-22 | 1994-09-15 | Eisenmann Kg Maschbau | Process for the reduction of nitrite concentration in phosphate bath systems |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU591231B2 (en) * | 1986-02-18 | 1989-11-30 | Parker Chemical Company | Aluminum cleaning process |
DE102008038653A1 (en) * | 2008-08-12 | 2010-03-25 | Henkel Ag & Co. Kgaa | Successive anti-corrosive pretreatment of metal surfaces in a multi-stage process |
CN109989091A (en) * | 2019-04-17 | 2019-07-09 | 镇江耐丝新型材料有限公司 | A kind of steel wire electrolytic phosphating system |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB150475A (en) * | 1919-06-28 | 1920-09-09 | Frank Silson | Improved device for transmitting and magnifying sound |
DE1805655C2 (en) * | 1968-10-28 | 1974-10-17 | Steuler Industriewerke Gmbh | Process for flushing objects with liquids |
GB1345716A (en) * | 1971-03-22 | 1974-02-06 | Oxy Effluent Control Ltd | Method and apparatus for rinsing contaminated articles |
DE2729006A1 (en) * | 1977-06-28 | 1979-01-04 | Didier Werke Ag | Rinsing metal workpieces after surface treatment - using water in closed circuit with distn. plant to avoid pollution (NL 2.1.79) |
GB1540308A (en) * | 1977-12-08 | 1979-02-07 | Pyrene Chemical Services Ltd | Process for the treatment of metal surfaces |
-
1980
- 1980-04-01 AT AT80200302T patent/ATE5003T1/en not_active IP Right Cessation
- 1980-04-01 EP EP80200302A patent/EP0017302B1/en not_active Expired
- 1980-04-01 DE DE8080200302T patent/DE3065238D1/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4307591A1 (en) * | 1992-06-22 | 1994-09-15 | Eisenmann Kg Maschbau | Process for the reduction of nitrite concentration in phosphate bath systems |
Also Published As
Publication number | Publication date |
---|---|
EP0017302A1 (en) | 1980-10-15 |
DE3065238D1 (en) | 1983-11-17 |
ATE5003T1 (en) | 1983-10-15 |
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