EP1831435B1 - Method for continuously operating acid or alkaline zinc or zinc alloy baths - Google Patents
Method for continuously operating acid or alkaline zinc or zinc alloy baths Download PDFInfo
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- EP1831435B1 EP1831435B1 EP05808579A EP05808579A EP1831435B1 EP 1831435 B1 EP1831435 B1 EP 1831435B1 EP 05808579 A EP05808579 A EP 05808579A EP 05808579 A EP05808579 A EP 05808579A EP 1831435 B1 EP1831435 B1 EP 1831435B1
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- Prior art keywords
- zinc
- phase
- bath
- separation
- zinc alloy
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
Definitions
- the invention relates to a method for the deposition of functional layers of acidic or alkaline zinc or zinc alloy baths, the organic additives selected from brighteners, wetting agents and complexing agents, a soluble zinc salt and optionally other metal salts selected from Fe, Ni, Co, Sn salts in which the bath can be continuously cleaned so that the process can be operated without interruption.
- a weakly acidic zinc bath therefore contains about 10-20 g / l of organic compounds, corresponding to a content of organically bound carbon (total organic carbon, TOC) of approx. 5-10 g / l.
- Losses of organic active substances occurring during production due to degradation processes and removal are to be compensated for by continuous replenishment.
- a charge throughput of 10 kAh 0.5 to 1.5 kg of organic compounds are metered in.
- the degree of determination of the organic impurities is the determination of the cloud point. Desired is a cloud point at the highest possible temperature, since above the temperature of the cloud point no satisfactory coating more.
- Bath dilution reduces the concentration of impurities in proportion to the degree of dilution.
- a dilution is easy to carry out, but has the disadvantage that the amount of electrolyte removed from the bath has to be supplied to cost-intensive disposal.
- a complete new approach of the bath can be considered in this context as a special case of Badver Mednung.
- Activated carbon treatment by stirring 0.5-2 g / l of activated carbon into the bath followed by filtration reduces the concentration of impurities by adsorption on the coal. Disadvantage of this method is that it is laborious is, causes only a relatively small reduction and removed a large part of the gloss-forming bath additives with.
- Alkaline Zn baths contain a factor of 5 to 10 lower proportion of organic additives as acidic baths. Accordingly, contamination by decomposition products is generally less critical. In the case of alkaline alloy baths, however, the addition of significant amounts of organic complexing agents is required to complex the alloying additive (Fe, Co, Ni, Sn). These are oxidatively degraded at the anode and the accumulated decomposition products have a negative effect on the production process.
- the EP 1 369 505 A2 discloses a method for purifying a zinc-nickel electrolyte in a galvanic process in which a portion of the process bath used in the process is evaporated until phase separation into a lower phase, at least one middle phase and an upper phase occurs, and the lower one and the upper phase are separated. This process requires several stages and is disadvantageous in terms of its energy requirements from a cost point of view.
- the DE 198 34 353 describes a galvanic bath for applying zinc-nickel coatings. To avoid the undesirable decomposition of additives at the anode, it is proposed to separate the anode from the alkaline electrolyte through an ion exchange membrane. However, the invention has the disadvantage that the use of such membranes is cost-intensive and maintenance-prone.
- the invention has for its object to provide a method and an apparatus for performing this method, with or with the time and effort of the bathroom cleaning with permanent guarantee of constant good bath quality and minimal use of chemicals can be reduced.
- the invention further relates to an apparatus for carrying out this method, comprising a container (1) for receiving a zinc or zinc alloy bath, an associated mixing device (2) with a further metering device (7) for receiving an acidic or alkaline Solution or an alkaline solid is connected, at least one separator (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally means (6) for receiving the aqueous phase from the at least one separating device (3) and (3'), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8 ') for receiving the solid phase from the separating device (3'), and for the recording required lines and optionally valves, the separation of the organic or enable solid phase.
- the at least one separating device (3) and (3 ') can have devices for stirring (4) and for temperature control (5).
- the order in which the organic and the solid phase are separated can be freely selected. Preferably, first the organic and then the solid phase is separated off.
- the mixing device (2) and the separating device (3) need not be spatially separated. It is possible first to mix the solution of the zinc and zinc alloy bath (1) and the solution from the metering device for receiving an acidic or alkaline solution or the basic solid (7) and then to separate the phases in the same container ,
- the separation of the organic phase in the device (3) and the inorganic phase in the device (3 ') can be carried out in one unit.
- the means for temperature control (5) must be heated to separate the organic phase and cooled to separate the solid phase.
- both the organic phase and the solid phase can be separated off first.
- a further separation unit 3 ' may expediently be used.
- the solid phase is separated. This is preferably done by cooling the solution, whereby the solubility of the ingredients is reduced so far that they crystallize and can be separated.
- Typical compounds which can be separated in this way from alkaline zinc and zinc alloy baths include carbonates, oxalates, sulfates and cyanides.
- the separation of toxic cyanides, which form by the anodic decomposition of nitrogen-containing compounds, for example from the complexing agents, is a desired positive effect of the method according to the invention.
- a preferred embodiment of the invention comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9) and having a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid via a pump or chute (9), at least one separating device (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally a device (6) for receiving the aqueous phase the separating device (3) or (3 '), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8') for receiving the solid phase from the separating device (3 ') and for the recording required lines and valves (11).
- the at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
- the separation of the organic and the solid phase can be carried out in the separation device (3) and (3 ') either simultaneously or in two steps one after the other.
- the solid phase can be separated by means of a crystallizer.
- a crystallizer Such systems for the separation of crystalline impurities from electroplating baths are known from the prior art and, for example, in US 5,376,256 described. Commercially, such a system is available from USFilter under the name CARBOLUX.
- the separation of organic and aqueous phase takes place by means of gravity.
- the device comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9), a separating device (3) connected to the mixing device (2) for receiving the removed one Part of the zinc or zinc alloy bath having a lower portion for separating the aqueous phase (3a) and a narrower upper portion for separating the organic phase (3b) and having an upper effluent for the organic phase (3c) and a lower effluent for the purified aqueous Phase (3d) is provided, optionally a further separation device (3 ') for separating the solid phase and a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid, via a pump or chute (9) the mixing device (2) is connected, optionally a device (6) for receiving the aqueous phase from the separating device (3) or (3 ') and at least one
- the at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
- the separator (3) has means for temperature control (5), which preferably consists of a jacket which surrounds the separator (3a) and (3b) and contains as heat carrier, for example water or oil and the uniform heat distribution in the system and the preheating of removed portion of the zinc or Zinkleg réellesbad allows.
- the temperature is adjusted so that the density of the organic phase is smaller than the density of the aqueous phase.
- the densities of the phases are plotted as a function of the temperature. Shown are two intersecting curves, where the temperature to the right of the intersection represents the preferred temperature range.
- the temperature is selected so that the density difference between the two phases is at least 1 - 1.5%.
- the course of the two phases takes place by means of gravity.
- the level difference of the process (3d-3c) is set to greater than 5 mm, preferably 0.8 to 1.5 cm at a total height of the device (3a) / (3b) of 1.50 - 2.50 m.
- the solid constituents crystallize at the bottom of the separation vessel to receive the withdrawn portion of the zinc or zinc alloy bath (3) and can be separated there by suitable means as already described above.
- the method according to the invention makes use of the fact that a phase separation occurs by lowering the pH or increasing the hydroxide ion concentration. If, for example, the pH of the bath is lowered to a pH ⁇ 1 by the addition of concentrated hydrochloric acid, the anionic surfactants contained in the bath are protonated so that they lose their emulsifying action. This leads to phase separation, i. in a separation of the zinc or zinc alloy bath in an aqueous phase and an organic phase, which is also referred to as oil phase hereinafter.
- the organic or oil phase contains a majority of Badverungraphyen.
- the oil phase may comprise up to 10% of the bath volume.
- phase separation is achieved by addition of preferably solid sodium hydroxide, with a concentration greater than 200 g / l of sodium hydroxide being advantageous.
- the oil phase floats either on the aqueous phase and can be transferred from there from the separator (3) in the container (8), or it forms on the bottom of the separator (3) and then from there into the Pumped container (8).
- the aqueous phase is added to the bath to adjust the pH of the bath to the set point, bath additives lost with the oil phase are replenished, and it can be produced again with good quality.
- the aqueous phase can be stored in a container (6) and added to the bath as needed.
- the acidified bath is preferably adjusted to a temperature of 20-70 ° C, more preferably 20-50 ° C for accelerating the phase separation, said temperature range being merely preferred and not critical, i. the process can also be carried out at a temperature in the range of 5 to 90 ° C.
- phase separation can also be effected by increasing the hydroxide ion concentration of the bath.
- phase separation occurs, for example, when the sodium hydroxide content is raised to a level> 200 g / l.
- sodium hydroxide in an amount of 1-10 kg / 10 kAh in the container (7) presented.
- Solid sodium hydroxide can then be dissolved from the container (7) in the mixing device (2) in parts of the bath and pumped into the separation means (3) or (3 ') - there occurs a phase separation, wherein in the Usually a lower solid, mostly crystalline phase and a partially crystalline upper phase occur. The upper phase is then separated and transferred to the container (8).
- the bath may be cooled to a temperature in the range of -5 to 30 ° C, and preferably 0-8 ° C to remove unwanted inorganic components by crystallization. This is preferably done in the second separation device (3 '), but both devices can also be realized in a single unit.
- This crystalline precipitate can in turn be separated off in a container (8 ') and the remaining aqueous electrolyte phase can be supplied to the bath, optionally with heating.
- the aqueous phase is transferred into the container (6).
- the aqueous phase can be stored in a container (6) and added to the bath as needed.
- the oil phase formed in the separator (3) is discharged via appropriate lines and collected in a separate container (8) and disposed of.
- the crystalline phase formed in the separation device (3 ') is discharged via corresponding lines and collected and disposed of in a separate container (8').
- the lines are provided at the separation devices (3) and (3 ') so that both a settling at the bottom of the separation vessel as well as a floating phase on the aqueous phase can be separated. Expediently, devices for physical phase differentiation are provided.
- the method according to the invention can be automated by means of a controller with the aid of pH sensors, temperature sensors, fill level meters and the said devices for physical phase differentiation.
- the controller registers the level in the separating devices (3) and (3 ') and automatically actuates a pump as soon as it falls below a predetermined minimum value.
- the pump then transfers as long as a proportionate solution from the zinc or zinc alloy bath (1) until a predetermined maximum level is reached in the separation devices.
- the controller controls the optionally provided in the separators means for stirring (4) and the temperature control (5) of the removed part of the bath.
- the controller also ensures the metered addition of an acidic or alkaline solution or an alkaline solid from the metering device (7).
- the control unit switches off the stirring and temperature control devices, so that a phase separation is made possible.
- the regenerated phase is transferred to a device (6) which, for example (ie with a total bath volume of 20,000 l), can take up a solution amount of 200 l.
- the device may also be provided with level gauges and level control devices and is connected to the bath (1).
- bath solution (1) which has been regenerated from the device (6) is introduced into the bath (1) to correct the pH or the hydroxide ion concentration is transferred. While the process of the present invention has been described above essentially with reference to the use of an acid for phase separation, it may also be carried out using bases such as, preferably, alkali or alkaline earth hydroxides, and especially sodium hydroxide, as mentioned.
- a significant advantage of the method according to the invention is that the production process does not have to be interrupted for cleaning or replacement of the bath. Impurities can be removed continuously or discontinuously and any required bath components can be added.
- phase separation is achieved by the addition of an acid or base, which would have to be added to the zinc or zinc alloy bath anyway due to process control.
- a bath sample of a weakly acid zinc bath with a TOC content of 30.2 g / l and 2.6 ml / l brightener and 35.8 ml / l additional solution was lowered to pH ⁇ 1 with 20 ml / l hydrochloric acid (37%).
- a device according to FIG. 2 with a separation unit (3) and a container (6) for receiving the aqueous phase from the separation tank (3) used. A slow separation of two phases was observed. Within 24 h, 25 ml / l of a dark brown, viscous phase settled on the bottom of the vessel.
- the clear supernatant solution contained, after analysis, 21.5 g / l TOC, 1.5 ml / l brightener, and 26.4 ml / l adjuvant.
- Testing by Hull cell after adjusting the pH to the working range (pH 5) showed a predominantly shiny sheet, but with burns in the high current density range.
- the cloud point of the bath before treatment was 50 ° C, after treatment and adjustment at 75 ° C.
- a bath sample with a TOC content of 30.2 g / l and 2.6 ml / l brightener and 35.8 ml / l additional solution was lowered to pH ⁇ 1 with 20 ml / l hydrochloric acid (37%).
- a device according to FIG. 3 with a separation unit (3) and a container (6) for receiving the aqueous phase from the separation tank (3) used.
- the level difference (3c) - (3d) was 15 mm, the total height of the device (3a) + (3b) 2 m.
- the sample was heated to 50 ° C. Within 2 h separated 55 ml / l of a dark brown oil phase above the aqueous phase.
- the clear aqueous phase contained by analysis 13.1 g / l TOC, 0.6 ml / l brightener and 21.8 ml / l additional solution.
- Testing by Hull cell after adjustment of the pH to the working range (pH 5) showed a uniformly shiny sheet with low fogging in the low current density range.
- the cloud point of the bath before treatment was 50 ° C, after treatment and adjustment at 85 ° C.
- the separated oil phase consists of 10-15% of functional bath additives and 85-90% of impurities.
- the separation unit (3 ') comprised a crystallizer from Carbolux.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Abscheidung funktionaler Schichten aus sauren oder alkalischen Zink- oder Zinklegierungsbädern, die organische Zusätze ausgewählt aus Glanzmitteln, Netzmitteln und Komplexbildnern, ein lösliches Zinksalz und gegebenenfalls weitere Metallsalze ausgewählt aus Fe-, Ni-, Co-, Sn-Salzen enthalten, bei dem das Bad kontinuierlich gereinigt werden kann, so dass das Verfahren ohne Unterbrechung betrieben werden kann.The invention relates to a method for the deposition of functional layers of acidic or alkaline zinc or zinc alloy baths, the organic additives selected from brighteners, wetting agents and complexing agents, a soluble zinc salt and optionally other metal salts selected from Fe, Ni, Co, Sn salts in which the bath can be continuously cleaned so that the process can be operated without interruption.
Um die Abscheidung funktionaler Schichten aus Zinkbädern zu ermöglichen werden dem Bad organische Glanzbildner und Netzmittel zugesetzt. Bei Neuansatz enthält beispielsweise ein schwachsaures Zinkbad deshalb ca. 10-20 g/l organischer Verbindungen, entsprechend einem Gehalt an organisch gebundenem Kohlenstoff (Total Organic Carbon, TOC) von ca. 5-10 g/l.In order to enable the deposition of functional layers of zinc baths, organic brighteners and wetting agents are added to the bath. In the case of a new formulation, for example, a weakly acidic zinc bath therefore contains about 10-20 g / l of organic compounds, corresponding to a content of organically bound carbon (total organic carbon, TOC) of approx. 5-10 g / l.
Während der Produktion auftretende Verluste an organischen Wirkstoffen durch Abbauprozesse und Ausschleppung müssen durch kontinuierliche Nachdosierung kompensiert werden. Typischerweise werden bei Ladungsdurchsatz von 10 kAh 0,5 bis 1,5 kg organischer Verbindungen zudosiert. Durch Ausschleppung werden über 10 kAh ca. 0,2 bis 0,8 kg organischer Verbindungen ausgetragen.Losses of organic active substances occurring during production due to degradation processes and removal are to be compensated for by continuous replenishment. Typically, at a charge throughput of 10 kAh, 0.5 to 1.5 kg of organic compounds are metered in. By extraction, about 0.2 to 0.8 kg of organic compounds are discharged over 10 kAh.
Durch die Differenz von zudosierten und ausgeschleppten organischen Verbindungen kommt es im Verlauf der Produktion zu einem Anstieg des Gehalts im Bad. Bei einem Gesamtgehalt vom ungefähr 2- bis 3-fachen im Vergleich zum Neuansatz sollte theoretisch ein stationärer Organikgehalt erreicht werden. Dies entspräche TOC Werten von ca. 15-25 g/l.The difference between dosed and removed organic compounds leads to an increase in the bath content during production. At a total content of about 2 to 3 times compared to New approach should theoretically be achieved a stationary organic content. This would correspond to TOC values of about 15-25 g / l.
In der Praxis kommt es, abweichend vom zu erwartenden Verlauf, häufig zu sehr viel stärkeren Anreicherungen organischer Verbindungen. Dies liegt zum Einen an der Einschleppung von Verunreinigungen durch ungenügende Vorbehandlung der zu beschichtenden Ware, zum Anderen an stark überhöhter Dosierung der Zusätze, die häufig angewendet wird, um extreme dekorative Anforderungen auch an schwierig zu beschichtender Ware zu realisieren.In practice, deviating from the expected course, often to much stronger accumulations of organic compounds. This is partly due to the introduction of impurities due to insufficient pretreatment of the product to be coated, on the other hand to greatly excessive dosage of additives, which is often used to realize extreme decorative requirements even on difficult to be coated goods.
Mit zunehmendem Gehalt organischer Verunreinigungen treten zunehmende dekorative Probleme bei der Beschichtung auf und führen zu verminderter Produktivität. Zur Verminderung der dekorativen Probleme werden in der Regel erhöhte Dosierungen der organischen Badzusätze vorgenommen, wodurch der Gehalt an Abbauprodukten weiter ansteigt.As the content of organic contaminants increases, increasing decorative problems of coating occur and result in decreased productivity. To reduce the decorative problems usually increased dosages of organic bath additives are made, whereby the content of degradation products continues to increase.
Als Messgröße für den Grad der Ermittlung der organischen Verunreinigungen dient die Ermittlung des Trübungspunktes. Gewünscht ist ein Trübungspunkt bei möglichst hoher Temperatur, da oberhalb der Temperatur des Trübungspunktes keine zufriedenstellende Beschichtung mehr erfolgt.As a measure of the degree of determination of the organic impurities is the determination of the cloud point. Desired is a cloud point at the highest possible temperature, since above the temperature of the cloud point no satisfactory coating more.
Als Abhilfemaßnahmen sind mehrere Methoden bekannt, die nachstehend beschrieben sind:Remedies are several methods that are described below:
Eine Badverdünnung vermindert die Konzentration der Verunreinigungen proportional dem Verdünnungsgrad. Eine Verdünnung ist einfach durchführbar, hat jedoch den Nachteil, dass die dem Bad entnommene Elektrolytmenge der kostenintensiven Entsorgung zugeführt werden muss. Ein kompletter Neuansatz des Bades kann in diesem Zusammenhang als Spezialfall der Badverdünnung betrachtet werden.Bath dilution reduces the concentration of impurities in proportion to the degree of dilution. A dilution is easy to carry out, but has the disadvantage that the amount of electrolyte removed from the bath has to be supplied to cost-intensive disposal. A complete new approach of the bath can be considered in this context as a special case of Badverdünnung.
Eine Aktivkohlebehandlung durch Einrühren von 0,5-2 g/l Aktivkohle ins Bad und anschließende Filtration vermindert die Konzentration an Verunreinigungen durch Adsorption an der Kohle. Nachteil dieser Methode ist, dass sie arbeitsaufwendig ist, nur eine relativ geringe Absenkung bewirkt und einen großen Teil der glanzbildenden Badzusätze mit entfernt.Activated carbon treatment by stirring 0.5-2 g / l of activated carbon into the bath followed by filtration reduces the concentration of impurities by adsorption on the coal. Disadvantage of this method is that it is laborious is, causes only a relatively small reduction and removed a large part of the gloss-forming bath additives with.
Alkalische Zn-Bäder enthalten einen um den Faktor 5 bis 10 geringeren Anteil organischer Zusätze als saure Bäder. Entsprechend ist die Verunreinigung durch Abbauprodukte in der Regel weniger kritisch. Im Falle alkalischer Legierungsbäder ist allerdings zur Komplexierung des Legierungszusatzes (Fe, Co, Ni, Sn) die Zugabe erheblicher Mengen organischer Komplexbildner erforderlich. Diese werden an der Anode oxidativ abgebaut und die akkumulierten Zersetzungsprodukte wirken sich negativ auf den Produktionsprozess aus.Alkaline Zn baths contain a factor of 5 to 10 lower proportion of organic additives as acidic baths. Accordingly, contamination by decomposition products is generally less critical. In the case of alkaline alloy baths, however, the addition of significant amounts of organic complexing agents is required to complex the alloying additive (Fe, Co, Ni, Sn). These are oxidatively degraded at the anode and the accumulated decomposition products have a negative effect on the production process.
Die
Die
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren sowie eine Vorrichtung zur Durchführung dieses Verfahrens bereitzustellen, mit dem bzw. mit der der Zeit- und Arbeitsaufwand der Badreinigung bei dauerhafter Gewährleistung konstant guter Badqualität und minimalem Chemikalieneinsatz herabgesetzt werden kann.The invention has for its object to provide a method and an apparatus for performing this method, with or with the time and effort of the bathroom cleaning with permanent guarantee of constant good bath quality and minimal use of chemicals can be reduced.
Gegenstand der Erfindung ist ein Verfahren zur Abscheidung funktionaler Schichten aus sauren oder alkalischen Zink- oder Zinklegierungsbädern, die organische Zusätze ausgewählt aus Glanzmitteln, Netzmitteln und Komplexbildnern, ein lösliches Zinksalz und gegebenenfalls weitere Metallsalze ausgewählt aus Fe-, Ni-, Co-, Sn-Salzen enthalten, das die folgenden Stufen umfasst:
- (i) Bereitstellen des Zink- oder Zinklegierungsbades enthaltend die vorgenannten Komponenten,
- (ii) Abscheiden einer Zink- oder Zinklegierungsschicht auf dem zu beschichtenden Werkstück nach an sich bekannten Verfahren,
- (iii) Entnahme eines Teils des Zink- oder Zinklegierungsbades und Überführen des entnommenen Teils in eine Einrichtung zur Phasentrennung,
- (iv) Zugabe einer Säure bzw. Base zu dem entnommenen sauren bzw. alkalischen Teil,
- (v) Einstellen der Temperatur zur Beschleunigung der Phasentrennung,
- (vi) Abtrennen der organischen Phase und gegebenenfalls festen Phase,
- (vii) Rückführen der wässrigen Phase in das Zink- oder Zinklegierungsbad in der Weise, dass der pH-Wert bzw. Hydroxid-Gehalt des Zink- oder Zinklegierungsbads in dessen Arbeitsbereich bleibt, so dass das Bad ohne Unterbrechung betrieben werden kann, und
- (vii) Ergänzen verbrauchter Komponenten des Zink- oder Zinklegierungsbades.
- (i) providing the zinc or zinc alloy bath containing the aforementioned components,
- (ii) depositing a zinc or zinc alloy layer on the workpiece to be coated by methods known per se,
- (iii) removing a portion of the zinc or zinc alloy bath and transferring the removed portion to a phase separation device;
- (iv) adding an acid or base to the withdrawn acidic or alkaline part respectively,
- (v) adjusting the temperature to accelerate the phase separation,
- (vi) separating the organic phase and optionally solid phase,
- (vii) returning the aqueous phase to the zinc or zinc alloy bath such that the pH or hydroxide content of the zinc or zinc alloy bath remains within its working range so that the bath can be operated without interruption, and
- (vii) replenish used components of the zinc or zinc alloy bath.
Die Erfindung betrifft weiterhin eine Vorrichtung zur Durchführung dieses Verfahrens, die einen Behälter (1) für die Aufnahme eines Zink- oder Zinklegierungsbades, eine damit verbundene Mischeinrichtung (2), die mit einer weiteren Dosiereinrichtung (7) für die Aufnahme einer sauren bzw. alkalischen Lösung oder eines alkalischen Feststoffes verbunden ist, mindestens eine Trenneinrichtung (3) und (3') zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades, optional eine Einrichtung (6) für die Aufnahme der wässrigen Phase aus der mindestens einen Trennvorrichtung (3) und (3'), einen Behälter (8) für die Aufnahme der organischen Phase aus der Trenneinrichtung (3), gegebenenfalls einen Behälter (8') für die Aufnahme der festen Phase aus der Trenneinrichtung (3'), und für die Aufnahme benötigte Leitungen und gegebenenfalls Ventile, die die Abtrennung der organischen bzw. festen Phase ermöglichen.The invention further relates to an apparatus for carrying out this method, comprising a container (1) for receiving a zinc or zinc alloy bath, an associated mixing device (2) with a further metering device (7) for receiving an acidic or alkaline Solution or an alkaline solid is connected, at least one separator (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally means (6) for receiving the aqueous phase from the at least one separating device (3) and (3'), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8 ') for receiving the solid phase from the separating device (3'), and for the recording required lines and optionally valves, the separation of the organic or enable solid phase.
Die mindestens eine Trenneinrichtung (3) und (3') kann Einrichtungen zum Rühren (4) und zur Temperaturkontrolle (5) aufweisen.The at least one separating device (3) and (3 ') can have devices for stirring (4) and for temperature control (5).
Die
- (1) einen Behälter für die Aufnahme des Zink- oder Zinklegierungsbades,
- (2) eine Mischeinrichtung,
- (3) und (3') eine Trenneinrichtung zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades,
- (4) Einrichtungen zum Rühren,
- (5) Einrichtungen zur Temperaturkontrolle,
- (6) eine Vorrichtung für die Aufnahme der wässrigen Phase aus der Trenneinrichtung (3) und (3'),
- (7) eine Dosiereinrichtung für die Aufnahme einer sauren bzw. alkalischen Lösung oder eines alkalischen Feststoffes,
- (8) und (8') Behälter für die Aufnahme der organischen Phase aus der Trenneinrichtung (3) und die Aufnahme der festen Phase aus dem Trenneinrichtung (3').
- (1) a container for holding the zinc or zinc alloy bath,
- (2) a mixing device,
- (3) and (3 ') a separating device for receiving the removed part of the zinc or zinc alloy bath,
- (4) facilities for stirring,
- (5) temperature control equipment,
- (6) a device for receiving the aqueous phase from the separating device (3) and (3 '),
- (7) a metering device for receiving an acidic or alkaline solution or an alkaline solid,
- (8) and (8 ') container for receiving the organic phase from the separator (3) and the inclusion of the solid phase from the separator (3').
Die Reihenfolge, in der die organische und die feste Phase abgetrennt werden, kann frei gewählt werden. Bevorzugt wird zunächst die organische und dann die feste Phase abgetrennt.The order in which the organic and the solid phase are separated can be freely selected. Preferably, first the organic and then the solid phase is separated off.
Die Mischeinrichtung (2) und die Trenneinrichtung (3) brauchen räumlich nicht getrennt zu sein. Es ist möglich, zunächst die Lösung aus dem Zink- und Zinklegierungsbad (1) und die Lösung aus dem Dosiereinrichtung für die Aufnahme einer sauren bzw. alkalischen Lösung oder des basischen Feststoffes (7) zu mischen und danach die Trennung der Phasen im selben Behältnis vorzunehmen.The mixing device (2) and the separating device (3) need not be spatially separated. It is possible first to mix the solution of the zinc and zinc alloy bath (1) and the solution from the metering device for receiving an acidic or alkaline solution or the basic solid (7) and then to separate the phases in the same container ,
Weiterhin können auch die Trennung der organischen Phase in der Einrichtung (3) und der anorganischen Phase in der Einrichtung (3') in einer Einheit erfolgen. In diesem Fall muss mittels den Einrichtungen zur Temperaturkontrolle (5) zur Abtrennung der organischen Phase geheizt und zur Abtrennung der festen Phase gekühlt werden. Dabei kann sowohl die organische Phase als auch die feste Phase als erstes abgetrennt werden.Furthermore, the separation of the organic phase in the device (3) and the inorganic phase in the device (3 ') can be carried out in one unit. In this case, the means for temperature control (5) must be heated to separate the organic phase and cooled to separate the solid phase. In this case, both the organic phase and the solid phase can be separated off first.
Die Kombination beider Trennungsschritte für die organische und die feste Phase ist auch in den nachfolgend erläuterten bevorzugten Ausführungsformen der erfindungsgemäßen Vorrichtung möglich, ohne dass dies gesondert erwähnt wird.The combination of both separation steps for the organic and the solid phase is also possible in the preferred embodiments of the device according to the invention explained below, without this being mentioned separately.
Bei der Verwendung saurer Zink- und Zinklegierungsbäder ist im Allgemeinen die Verwendung einer Trenneinheit (3) ausreichend, da nur eine Abtrennung einer organischen Phase erforderlich ist.When using acidic zinc and zinc alloy baths, the use of a separation unit (3) is generally sufficient because only separation of an organic phase is required.
Bei der Verwendung alkalischer Zink- und Zinklegierungsbäder kann zweckmäßigerweise eine weitere Trenneinheit 3' verwendet werden. In dieser wird die feste Phase abgetrennt. Dies erfolgt bevorzugt durch Kühlen der Lösung, wodurch die Löslichkeit der Bestandteile soweit herabgesetzt wird, dass diese auskristallisieren und abgetrennt werden können.When using alkaline zinc and zinc alloy baths, a further separation unit 3 'may expediently be used. In this, the solid phase is separated. This is preferably done by cooling the solution, whereby the solubility of the ingredients is reduced so far that they crystallize and can be separated.
Typische Verbindungen, die auf diesem Wege aus alkalischen Zink- und Zinklegierungsbädern abgetrennt werden können, umfassen Carbonate, Oxalate, Sulfate und Cyanide. Insbesondere die Abtrennung von giftigen Cyaniden, die sich durch die anodische Zersetzung stickstoffhaltiger Verbindungen beispielsweise aus den Komplexbildnern bilden, ist ein gewünschter positiver Effekt des erfindungsgemäßen Verfahrens.Typical compounds which can be separated in this way from alkaline zinc and zinc alloy baths include carbonates, oxalates, sulfates and cyanides. In particular, the separation of toxic cyanides, which form by the anodic decomposition of nitrogen-containing compounds, for example from the complexing agents, is a desired positive effect of the method according to the invention.
Eine bevorzugte Ausführungsform der Erfindung umfasst einen Behälter (1) für die Aufnahme eines Zink- oder Zinklegierungsbades, eine damit über eine Pumpe (9) verbundene Mischeinrichtung (2), der mit einer Dosiereinrichtung (7) für die Aufnahme einer sauren bzw. alkalischen Lösung oder eines alkalischen Feststoffes über eine Pumpe oder Schütte (9) verbunden ist, mindestens eine Trenneinrichtung (3) und (3') zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades, optional eine Einrichtung (6) für die Aufnahme der wässrigen Phase aus der Trenneinrichtung (3) oder (3'), einen Behälter (8) für die Aufnahme der organischen Phase aus der Trenneinrichtung (3), optional einen Behälter (8') für die Aufnahme der festen Phase aus der Trenneinrichtung (3') und für die Aufnahme benötigte Leitungen und Ventile (11).A preferred embodiment of the invention comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9) and having a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid via a pump or chute (9), at least one separating device (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally a device (6) for receiving the aqueous phase the separating device (3) or (3 '), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8') for receiving the solid phase from the separating device (3 ') and for the recording required lines and valves (11).
Die mindestens eine Trenneinrichtung (3) und (3') sowie die Mischeinrichtung (2) kann Einrichtungen zum Rühren (4) und zur Temperaturkontrolle (5) aufweisen.The at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
Die
- (1) einen Behälter für die Aufnahme des Zink- oder Zinklegierungsbades,
- (2) eine Mischeinrichtung,
- (3) und (3') eine Trenneinrichtung zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades,
- (4) Einrichtungen zum Rühren,
- (5) Einrichtungen zur Temperaturkontrolle,
- (6) eine Einrichtung für die Aufnahme der wässrigen Phase aus dem mindestens einen Trennbehälter (3) oder (3'),
- (7) eine Dosiereinrichtung für die Aufnahme einer sauren bzw. alkalischen Lösung oder eines alkalischen Feststoffes,
- (8) und (8') Behälter für die Aufnahme der organischen Phase aus dem Trennbehälter (3) und die Aufnahme der festen Phase aus dem Trennbehälter (3'),
- (9) eine Pumpe oder Schütte.
- (1) a container for holding the zinc or zinc alloy bath,
- (2) a mixing device,
- (3) and (3 ') a separating device for receiving the removed part of the zinc or zinc alloy bath,
- (4) facilities for stirring,
- (5) temperature control equipment,
- (6) means for receiving the aqueous phase from the at least one separation vessel (3) or (3 '),
- (7) a metering device for receiving an acidic or alkaline solution or an alkaline solid,
- (8) and (8 ') containers for receiving the organic phase from the separation tank (3) and the inclusion of the solid phase from the separation tank (3'),
- (9) a pump or chute.
Die Abtrennung der organischen und der festen Phase kann in der Trenneinrichtung (3) und (3') entweder gleichzeitig oder in zwei Schritten nacheinander erfolgen.The separation of the organic and the solid phase can be carried out in the separation device (3) and (3 ') either simultaneously or in two steps one after the other.
Bevorzugt kann die feste Phase mittels eines Kristallisators abgetrennt werden. Solche Systeme zur Abtrennung kristalliner Verunreinigungen aus galvanischen Bädern sind aus dem Stand der Technik bekannt und beispielsweise in
Gemäß einer besonders bevorzugten Ausführungsform zur Reinigung von Zink- oder Zinklegierungsbäder erfolgt die Abtrennung von organischer und wässriger Phase mittels Schwerkraft. In diesem Fall umfasst die Vorrichtung einen Behälter (1) für die Aufnahme eines Zink- oder Zinklegierungsbades, einen damit über eine Pumpe (9) verbundene Mischeinrichtung (2), eine mit der Mischeinrichtung (2) verbundene Trenneinrichtung (3) zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades, der einen unteren Teil zur Abtrennung der wässrigen Phase (3a) und einen schmaleren oberen Teil zur Abtrennung der organischen Phase (3b) aufweist und mit einem oberen Abfluss für die organische Phase (3c) und einem unteren Abfluss für die gereinigte wässrige Phase (3d) versehen ist, optional eine weitere Trenneinrichtung (3') zur Abtrennung der festen Phase sowie eine Dosiereinrichtung (7) für die Aufnahme einer sauren bzw. alkalischen Lösung oder eines alkalischen Feststoffes, der über eine Pumpe oder Schütte (9) mit der Mischeinrichtung (2) verbunden ist, optional eine Einrichtung (6) für die Aufnahme der wässrigen Phase aus der Trenneinrichtung (3) bzw. (3') und mindestens einen Behälter (8) und (8') für die Aufnahme der organischen oder festen Phase aus der Trenneinrichtung (3) und (3').According to a particularly preferred embodiment for the purification of zinc or zinc alloy baths, the separation of organic and aqueous phase takes place by means of gravity. In this case, the device comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9), a separating device (3) connected to the mixing device (2) for receiving the removed one Part of the zinc or zinc alloy bath having a lower portion for separating the aqueous phase (3a) and a narrower upper portion for separating the organic phase (3b) and having an upper effluent for the organic phase (3c) and a lower effluent for the purified aqueous Phase (3d) is provided, optionally a further separation device (3 ') for separating the solid phase and a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid, via a pump or chute (9) the mixing device (2) is connected, optionally a device (6) for receiving the aqueous phase from the separating device (3) or (3 ') and at least one container (8) and (8') for receiving the organic or solid phase from the separator (3) and (3 ').
Die mindestens eine Trenneinrichtung (3) und (3') sowie die Mischeinrichtung (2) können Einrichtungen zum Rühren (4) und zur Temperaturkontrolle (5) aufweisen.The at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
Die
- (1) einen Behälter für die Aufnahme des Zink- oder Zinklegierungsbades,
- (2) eine Mischeinrichtung,
- (3) und (3') eine Trenneinrichtung zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades,
- (4) Einrichtungen zum Rühren,
- (5) Einrichtungen zur Temperaturkontrolle,
- (6) eine Einrichtung für die Aufnahme der wässrigen Phase aus der mindestens einen Trenneinrichtung (3) und (3'),
- (7) eine Dosiereinrichtung für die Aufnahme einer sauren bzw. alkalischen Lösung oder eines alkalischen Feststoffes,
- (8) und (8') Behälter für die Aufnahme der organischen Phase aus der Trenneinrichtung (3) und die Aufnahme der festen Phase aus der Trenneinrichtung (3'),
- (9) eine Pumpe oder Schütte.
- (1) a container for holding the zinc or zinc alloy bath,
- (2) a mixing device,
- (3) and (3 ') a separating device for receiving the removed part of the zinc or zinc alloy bath,
- (4) facilities for stirring,
- (5) temperature control equipment,
- (6) a device for receiving the aqueous phase from the at least one separating device (3) and (3 '),
- (7) a metering device for receiving an acidic or alkaline solution or an alkaline solid,
- (8) and (8 ') containers for receiving the organic phase from the separating device (3) and for receiving the solid phase from the separating device (3'),
- (9) a pump or chute.
Die Trenneinrichtung (3) weist Einrichtungen zur Temperaturkontrolle (5) auf, die vorzugsweise aus einem Mantel besteht, der die Trenneinrichtung (3a) und (3b) umgibt und als Wärmeträger beispielsweise Wasser oder Öl enthält und die gleichmäßige Wärmeverteilung im System sowie die Vorwärmung des entnommenen Teils des Zink- oder Zinklegierungsbades ermöglicht. Dabei wird die Temperatur so eingestellt, dass die Dichte der organischen Phase kleiner als die Dichte der wässrigen Phase ist. In
Die
- (1) einen Behälter für die Aufnahme des Zink- oder Zinklegierungsbades,
- (2) eine Mischeinrichtung,
- (3) und (3') eine Trenneinrichtung zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades,
- (3a) einen unteren Teil der Trenneinrichtung,
- (3b) einen oberen Teil der Trenneinrichtung,
- (3c) einen oberen Ablauf für die organische Phase,
- (3d) einen unteren Ablauf für die gereinigte wässrige Phase,
- (4) Einrichtungen zum Rühren,
- (5) Einrichtungen zur Temperaturkontrolle,
- (6) eine Einrichtung für die Aufnahme der wässrigen Phase aus der mindestens einen Trenneinrichtung (3) und (3'),
- (7) eine Dosiereinrichtung für die Aufnahme einer sauren bzw. alkalischen Lösung oder eines alkalischen Feststoffes,
- (8) und (8') Behälter für die Aufnahme der organischen Phase aus der Trenneinrichtung (3) und die Aufnahme der festen Phase aus der Trenneinrichtung (3'),
- (9) eine Pumpe / Schütte.
- (1) a container for holding the zinc or zinc alloy bath,
- (2) a mixing device,
- (3) and (3 ') a separating device for receiving the removed part of the zinc or zinc alloy bath,
- (3a) a lower part of the separating device,
- (3b) an upper part of the separating device,
- (3c) an upper sequence for the organic phase,
- (3d) a lower effluent for the purified aqueous phase,
- (4) facilities for stirring,
- (5) temperature control equipment,
- (6) a device for receiving the aqueous phase from the at least one separating device (3) and (3 '),
- (7) a metering device for receiving an acidic or alkaline solution or an alkaline solid,
- (8) and (8 ') containers for receiving the organic phase from the separating device (3) and for receiving the solid phase from the separating device (3'),
- (9) a pump / chute.
Für die Abtrennung der Ölphase zur Reinigung alkalischer Zink- und Zinklegierungsbäder kann im Prinzip die gleiche Vorrichtung verwendet werden.For the separation of the oil phase for the purification of alkaline zinc and zinc alloy baths can be used in principle the same device.
In diesem Fall kristallisieren die festen Bestandteil am Boden des Trennbehälters zur Aufnahme des entnommenen Teils des Zink- oder Zinklegierungsbades (3) aus und können dort über geeignete Mittel, wie sie im Vorigen bereits beschrieben sind, abgetrennt werden.In this case, the solid constituents crystallize at the bottom of the separation vessel to receive the withdrawn portion of the zinc or zinc alloy bath (3) and can be separated there by suitable means as already described above.
Im Weiteren wird das erfindungsgemäße Verfahren näher erläutert:In addition, the method according to the invention is explained in more detail:
Üblicherweise werden saure Zinkbäder oder Zinklegierungsbäder mit einem pH-Wert im Bereich von 4 bis 6, basische Zinkbäder oder Zinklegierungsbäder mit einem Hydroxidgehalt von 80 - 250 g/l bezogen auf Natriumhydroxid betrieben. Die Angabe des Hydroxidgehalts erfolgt in g/l und nicht in pH-Einheiten, da im hohen pH-Bereich, wie er bei den gegebenen Mengen vorherrscht, die Menge an Hydroxid zuverlässiger anzugeben ist.Usually, acidic zinc baths or zinc alloy baths having a pH in the range of 4 to 6, basic zinc baths or zinc alloy baths having a hydroxide content of 80 to 250 g / l based on sodium hydroxide are operated. The indication of the hydroxide content is in g / l and not in pH units, as in high pH range, as prevails at the given amounts, the amount of hydroxide is more reliable.
Das erfindungsgemäße Verfahren macht sich die Tatsache zunutze, dass es durch eine Absenkung des pH-Werts bzw. Erhöhung der Hydroxidionenkonzentration zu einer Phasentrennung kommt. Wird beispielsweise der pH des Bades durch Zugabe von konzentrierter Salzsäure auf einen pH < 1 abgesenkt, werden die im Bad enthaltenen anionischen Tenside protoniert, so dass sie ihre emulgierende Wirkung verlieren. Dies führt zu einer Phasentrennung, d.h. in eine Trennung des Zink- oder Zinklegierungsbades in eine wässrige Phase und eine organische Phase, die im Weiteren auch als Ölphase bezeichnet wird. Die organische bzw. Ölphase enthält einen Großteil der Badverunreinigungen. Die Ölphase kann bis zu 10% des Badvolumens umfassen.The method according to the invention makes use of the fact that a phase separation occurs by lowering the pH or increasing the hydroxide ion concentration. If, for example, the pH of the bath is lowered to a pH <1 by the addition of concentrated hydrochloric acid, the anionic surfactants contained in the bath are protonated so that they lose their emulsifying action. This leads to phase separation, i. in a separation of the zinc or zinc alloy bath in an aqueous phase and an organic phase, which is also referred to as oil phase hereinafter. The organic or oil phase contains a majority of Badverunreinigungen. The oil phase may comprise up to 10% of the bath volume.
In alkalischen Zink- und Zinklegierungsbädern wird die Phasentrennung durch Zugabe bevorzugt von festem Natriumhydroxid erreicht, wobei eine Konzentration größer als 200 g/l Natriumhydroxid vorteilhaft ist.In alkaline zinc and zinc alloy baths, the phase separation is achieved by addition of preferably solid sodium hydroxide, with a concentration greater than 200 g / l of sodium hydroxide being advantageous.
Die im Folgenden verwendeten Bezugszeichen beziehen sich auf die
Aufgrund des typischerweise 1-2% betragenden Unterschiedes zwischen kathodischer und anodischer Stromausbeute müssen einem schwachsauren Zinkbad 0,5 bis 1 l konzentrierte Salzsäure pro 10 kAh zudosiert werden, um den pH-Wert im Arbeitsbereich zu halten. Diese Säuremenge ist ausreichend, um 30-60 l des Bades auf pH < 1 abzusenken. Die Säure wird einem Teilvolumen des Bades zugesetzt, die sich bildende Ölphase wird abgetrennt, und zur pH-Korrektur wird das angesäuerte Bad dem Hauptbad wieder zugeführt.Due to the typically 1-2% difference between cathodic and anodic current efficiency must be a weak acid Zinc bath 0.5 to 1 l of concentrated hydrochloric acid per 10 kAh be added to keep the pH in the work area. This amount of acid is sufficient to lower 30-60 l of the bath to pH <1. The acid is added to a partial volume of the bath, the oil phase that forms is separated, and for pH correction, the acidified bath is returned to the main bath.
Bei typischen Durchsatzwerten von 100 kAh pro Tag können damit täglich 300-600 l Bad ausgeölt werden. Ein typisches Badvolumen von 20.000 l kann dadurch in 30-60 Arbeitstagen gereinigt und im weiteren Verlauf auf stabil niedrigem TOC-Niveau gehalten werden.At typical throughput values of 100 kAh per day, it is possible to oil 300-600 l baths per day. A typical bath volume of 20,000 l can thus be cleaned in 30-60 working days and maintained at a stable low TOC level.
Bei dem erfindungsgemäßen Verfahren werden bei einem Gesamtbadvolumen von beispielsweise 20.000 l 100 bis 200 l des Badvolumens in die Trenneinrichtung (3) umgepumpt und mit 15-20 ml/l Salzsäure (35-37%) angesäuert. Bei dem erfindungsgemäßen Verfahren können auch andere Säuren verwendet werden, wobei jedoch Mineralsäuren und insbesondere Salzsäure bevorzugt sind. In der Trenneinrichtung (3) wird das angesäuerte Bad zur Beschleunigung der Phasentrennung vorzugsweise auf eine Temperatur von 20-70°C, besonders bevorzugt auf 20-50°C eingestellt, wobei der genannte Temperaturbereich lediglich bevorzugt und nicht kritisch ist, d.h. das Verfahren kann auch bei einer Temperatur im Bereich von 5 bis 90°C durchgeführt werden.In the method according to the invention 100 to 200 l of the bath volume are pumped into the separator (3) and acidified with 15-20 ml / l hydrochloric acid (35-37%) at a total bath volume of, for example, 20,000 l. Other acids can also be used in the process according to the invention, although mineral acids and in particular hydrochloric acid are preferred. In the separator (3), the acidified bath is preferably adjusted to a temperature of 20-70 ° C, more preferably 20-50 ° C for accelerating the phase separation, said temperature range being merely preferred and not critical, i. the process can also be carried out at a temperature in the range of 5 to 90 ° C.
Wie bereits erwähnt kann eine Phasentrennung auch durch Erhöhung der Hydroxidionenkonzentration des Bades bewirkt werden. Eine solche Phasentrennung tritt beispielsweise auf, wenn der Natriumhydroxidgehalt auf einen Wert > 200 g/l angehoben wird.As already mentioned, a phase separation can also be effected by increasing the hydroxide ion concentration of the bath. Such phase separation occurs, for example, when the sodium hydroxide content is raised to a level> 200 g / l.
Dabei wird zur Ergänzung von Verschleppungsverlusten nötige Base, beispielsweise (unter Berücksichtigung der vorgenannten Badgröße) Natriumhydroxid in einer Menge von 1-10 kg/10 kAh in dem Behälter (7) vorgelegt. Festes Natriumhydroxid kann dann aus dem Behälter (7) in der Mischeinrichtung (2) in Teilen des Bades gelöst werden und in die Trenneinrichtungen (3) bzw. (3') gepumpt werden - dort kommt es zu einer Phasentrennung, wobei in der Regel eine untere feste, zumeist kristalline Phase und eine teilkristalline obere Phase auftreten. Die obere Phase wird anschließend abgetrennt und in den Behälter (8) überführt.In this case, to supplement carry-over losses necessary base, for example (taking into account the aforementioned bath size) sodium hydroxide in an amount of 1-10 kg / 10 kAh in the container (7) presented. Solid sodium hydroxide can then be dissolved from the container (7) in the mixing device (2) in parts of the bath and pumped into the separation means (3) or (3 ') - there occurs a phase separation, wherein in the Usually a lower solid, mostly crystalline phase and a partially crystalline upper phase occur. The upper phase is then separated and transferred to the container (8).
Danach kann das Bad auf eine Temperatur im Bereich von -5 bis 30°C und vorzugsweise 0-8°C abgekühlt werden, um nicht gewünschte anorganische Komponenten durch Kristallisation zu entfernen. Dies erfolgt vorzugsweise in der zweiten Trenneinrichtung (3'), beide Einrichtungen können jedoch auch in einer einzigen Einheit realisiert sein. Dieser kristalline Niederschlag kann wiederum in einem Behälter (8') abgetrennt und die verbleibende wässrige Elektrolytphase dem Bad gegebenenfalls unter Erwärmung zugeführt werden.Thereafter, the bath may be cooled to a temperature in the range of -5 to 30 ° C, and preferably 0-8 ° C to remove unwanted inorganic components by crystallization. This is preferably done in the second separation device (3 '), but both devices can also be realized in a single unit. This crystalline precipitate can in turn be separated off in a container (8 ') and the remaining aqueous electrolyte phase can be supplied to the bath, optionally with heating.
So wird nach erfolgter Phasentrennung die wässrige Phase in den Behälter (6) überführt. Um im Bad eine konstante Hydroxidionenkonzentration zu erreichen, kann die wässrige Phase in einem Behälter (6) gespeichert werden und nach Bedarf dem Bad zudosiert werden.Thus, after the phase separation, the aqueous phase is transferred into the container (6). In order to achieve a constant hydroxide ion concentration in the bath, the aqueous phase can be stored in a container (6) and added to the bath as needed.
Die in der Trenneinrichtung (3) gebildete Ölphase wird über entsprechende Leitungen ausgebracht und in einem separatem Behälter (8) gesammelt und entsorgt. Die in der Trenneinrichtung (3') gebildete kristalline Phase wird über entsprechende Leitungen ausgebracht und in einem separatem Behälter (8') gesammelt und entsorgt. Die Leitungen sind dabei an den Trenneinrichtungen (3) und (3') so vorgesehen, dass sowohl eine sich am Boden des Trennbehälters absetzende als auch eine auf der wässrigen Phase aufschwimmende Phase abgetrennt werden können. Zweckmäßigerweise werden dabei Einrichtungen zur physikalischen Phasenunterscheidung vorgesehen.The oil phase formed in the separator (3) is discharged via appropriate lines and collected in a separate container (8) and disposed of. The crystalline phase formed in the separation device (3 ') is discharged via corresponding lines and collected and disposed of in a separate container (8'). The lines are provided at the separation devices (3) and (3 ') so that both a settling at the bottom of the separation vessel as well as a floating phase on the aqueous phase can be separated. Expediently, devices for physical phase differentiation are provided.
Bei Bedarf einer pH-Korrektur bzw. Korrektur der Hydroxidionenkonzentration in dem Zink- oder Zinklegierungsbad (1) wird der behandelte Teil aus dem Behälter (6) in das Bad gepumpt.If necessary, a pH correction or correction of hydroxide ion concentration in the zinc or zinc alloy bath (1), the treated part from the container (6) is pumped into the bath.
Das erfindungsgemäße Verfahren kann über eine Steuerung mit Hilfe von pH-Sensoren, Temperaturfühlern, Füllstandsmessern und den genannten Einrichtungen zur physikalischen Phasenunterscheidung automatisiert werden.The method according to the invention can be automated by means of a controller with the aid of pH sensors, temperature sensors, fill level meters and the said devices for physical phase differentiation.
Die Steuerung registriert unter Anderem den Füllstand in den Trenneinrichtungen (3) und (3') und betätigt automatisch eine Pumpe sobald dieser unter einen vorgegebenen Mindestwert abfällt. Die Pumpe überführt dann solange anteilig Lösung aus dem Zink- oder Zinklegierungsbad (1) bis ein vorgegebener Höchststand in den Trenneinrichtungen erreicht ist. Weiterhin kontrolliert die Steuerung die in den Trenneinrichtungen gegebenenfalls vorgesehenen Einrichtungen zum Rühren (4) und der Temperaturkontrolle (5) des entnommenen Teils des Bades.Among other things, the controller registers the level in the separating devices (3) and (3 ') and automatically actuates a pump as soon as it falls below a predetermined minimum value. The pump then transfers as long as a proportionate solution from the zinc or zinc alloy bath (1) until a predetermined maximum level is reached in the separation devices. Furthermore, the controller controls the optionally provided in the separators means for stirring (4) and the temperature control (5) of the removed part of the bath.
Die Steuerung sorgt weiterhin für die Zudosierung einer sauren bzw. alkalischen Lösung bzw. eines alkalischen Feststoffes aus der Dosiereinrichtung (7).The controller also ensures the metered addition of an acidic or alkaline solution or an alkaline solid from the metering device (7).
Sobald eine vorgegebene Temperatur in der Einrichtung (3) bzw. (3') erreicht wird, schaltet die Steuerungseinheit die Rühr- und Temperaturkontrolleinrichtungen ab, sodass eine Phasentrennung ermöglicht wird.As soon as a predetermined temperature is reached in the device (3) or (3 '), the control unit switches off the stirring and temperature control devices, so that a phase separation is made possible.
Wie beschrieben, wird die regenerierte Phase in eine Einrichtung (6) überführt, die beispielsweise (d.h. bei einem Gesamtbadvolumen von 20.000 l) eine Lösungsmenge von 200 l aufnehmen kann. Die Einrichtung kann ebenfalls mit Füllstandsmessern und Einrichtungen zur Niveaukontrolle versehen werden und ist mit dem Bad (1) verbunden. Sobald der pH-Wert bzw. die Hydroxidionenkonzentration des Bades (1) außerhalb des vorgegebenen Arbeitsbereichs liegt, was über pH-Sensoren festgestellt werden kann, wird aus der Einrichtung (6) regenerierte Badlösung in das Bad (1) zur Korrektur des pH-Wert bzw. der Hydroxidionenkonzentration überführt. Während das erfindungsgemäße Verfahren voranstehend im Wesentlichen unter Bezugnahme auf die Verwendung einer Säure zur Phasetrennung erläutert wurde, kann es wie erwähnt auch unter Verwendung von Basen wie vorzugsweise Alkali- oder Erdalkalihydroxiden und insbesondere Natriumhydroxid durchgeführt werden.As described, the regenerated phase is transferred to a device (6) which, for example (ie with a total bath volume of 20,000 l), can take up a solution amount of 200 l. The device may also be provided with level gauges and level control devices and is connected to the bath (1). As soon as the pH or the hydroxide ion concentration of the bath (1) lies outside the prescribed operating range, which can be determined by means of pH sensors, bath solution (1) which has been regenerated from the device (6) is introduced into the bath (1) to correct the pH or the hydroxide ion concentration is transferred. While the process of the present invention has been described above essentially with reference to the use of an acid for phase separation, it may also be carried out using bases such as, preferably, alkali or alkaline earth hydroxides, and especially sodium hydroxide, as mentioned.
Ein wesentlicher Vorteil des erfindungsgemäßen Verfahrens ist es, dass der Produktionsprozess nicht zur Reinigung bzw. zum Austausch des Bades unterbrochen werden muss. Verunreinigungen können kontinuierlich oder diskontinuierlich entfernt und erforderliche Badkomponenten nachdosiert werden.A significant advantage of the method according to the invention is that the production process does not have to be interrupted for cleaning or replacement of the bath. Impurities can be removed continuously or discontinuously and any required bath components can be added.
Gegenüber den im Stand der Technik bekannten Verfahren ist das erfindungsgemäße Verfahren somit wesentlich einfacher und kostengünstiger in seiner Durchführung. Ein Vorteil gegenüber Verfahren im Stand der Technik ist insbesondere, dass eine Phasentrennung durch die Zugabe einer Säure bzw. Base erreicht wird, die dem Zink- oder Zinklegierungsbad aufgrund der Prozessführung sowieso zugeführt werden müsste.Compared with the methods known in the art, the method according to the invention is thus much simpler and cheaper to carry out. An advantage over prior art methods is, in particular, that phase separation is achieved by the addition of an acid or base, which would have to be added to the zinc or zinc alloy bath anyway due to process control.
Die nachfolgenden Beispiele dienen der Erläuterung des erfindungsgemäßen Reinigungs- bzw. Regenerationsverfahrens:The following examples serve to explain the cleaning or regeneration process according to the invention:
Eine Badprobe eines schwachsauren Zinkbades mit einem TOC-Gehalt von 30,2 g/l und 2,6 ml/l Glanzzusatz sowie 35,8 ml/l Zusatzlösung wurde mit 20 ml/l Salzsäure (37%) auf pH < 1 abgesenkt. Dabei wurde eine Vorrichtung gemäß
Eine Badprobe mit einem TOC-Gehalt von 30,2 g/l und 2,6 ml/l Glanzzusatz sowie 35,8 ml/l Zusatzlösung wurde mit 20 ml/l Salzsäure (37%) auf pH < 1 abgesenkt. Dabei wurde eine Vorrichtung gemäß
Aus den Analysenwerten lässt sich abschätzen, dass die abgetrennte Ölphase zu 10-15% aus funktionalen Badzusätzen und zu 85-90% aus Verunreinigungen besteht.From the analytical data it can be estimated that the separated oil phase consists of 10-15% of functional bath additives and 85-90% of impurities.
Für das Beispiel wurde eine Vorrichtung gemäß
In einer Probe eines alkalischen Zink-Nickel-Produktionsbades (ca. 2.000 Ah/l Durchsatz) wurden 90 g/l NaOH aufgelöst. Auf der Badoberfläche schied sich ca. 50 ml/l einer zähen, teilkristallinen Masse ab. Auf dem Gefäßboden bildete sich ca. 10 g/l einer kristallinen Ausfällung. Die Elektrolytphase wurde von den festen Phasen getrennt und vergleichend zum Ausgangsbad analysiert.
Claims (17)
- A process for the deposition of functional layers from acidic or alkaline zinc or zinc alloy baths containing organic additives selected from brighteners, surfactants and complexing agents; a soluble zinc salt and optionally further metal salts selected from Fe, Ni, Co, Sn salts, which process comprises the following steps:(i) providing a zinc or zinc alloy bath containing the aforementioned components,(ii) depositing a zinc or zinc alloy layer on the workpiece to be coated according to processes which are known as such,(iii) withdrawing a part of the zinc or zinc alloy bath and transferring the withdrawn part to a device for phase separation,(iv) adding an acid or base to the withdrawn acidic or alkaline part,(v) adjusting the temperature for acceleration of the phase separation,(vi) separating the organic phase and, if present, the solid phases,(vii) recycling the aqueous phase to the zinc or zinc alloy bath in such a way that the pH or hydroxide content of the zinc or zinc alloy bath remains within its operating range so that the bath can be operated without interruption, and(viii) replenishing spent components of the zinc or zinc alloy bath.
- Process according to claim 1 wherein the withdrawal of the part of the zinc bath and the recycling are carried out continuously or discontinuously.
- Process according to claim 1 wherein the addition of the acid and the phase separation are carried out at a temperature within the range of 5-90°C, preferably 20-50°C.
- Process according to claim 1 wherein the addition of the base and the phase separation are carried out at a temperature within the range of -5-30°C, preferably 0-8°C and, after separation of the organic phase, the bath is cooled to a temperature within the range of -5-20°C, preferably 0-8°C in order to obtain a solid inorganic phase which is separated before recycling the aqueous phase to the zinc or zinc alloy bath.
- Process according to claim 1 wherein the acid used is a mineral acid, in particular, hydrochloric acid, and the base used is an alkali or alkaline earth hydroxide, in particular, sodium hydroxide.
- Process according to claim 1 wherein the regeneration rate is 0.1-20% of the bath volume per day.
- Process according to claim 1 wherein the recycling of the aqueous phase is carried out in such a way that the pH or the hydroxide ion concentration of the zinc or zinc alloy bath remains constant.
- Process according to claim 1 wherein the formation of the organic phase in the container is detected by a sensor, the sensor initiating the removal of the organic phase from the container.
- Apparatus for carrying out the process according to claim 1 comprising a container (1) for containing the zinc or zinc alloy bath, a mixing device (2) connected thereto, which is connected to a further dosing device (7) containing an acidic or alkaline solution or an alkaline solid, at least separation device (3) and (3') for receiving the withdrawn part of the zinc or zinc alloy bath, a container (8) for receiving the organic phase from the separation device (3), optionally a container (8') for receiving the solid phase from the separation device (3'), and conduits required for transfer, which allow the separation of the organic and/or solid phase.
- Apparatus according to claim 1 comprising a container (1) for containing the zinc or zinc alloy bath, a mixing device (2) which is connected thereto via a pump and which is connected to a dosing device (7) containing an acidic or alkaline solution or an alkaline solid via a pump or chute (9), at least one separation device (3) and (3') for receiving the withdrawn part of the zinc or zinc alloy bath, a container (8) for receiving the organic phase from the separation device (3), optionally a container (8') for receiving the solid phase from the separation device (3') and conduits and valves required for transfer.
- Apparatus according to claim 9 comprising a container (1) for containing a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9), a separation device (3) connected to the mixing device (2) for receiving the withdrawn part of the zinc or zinc alloy bath having a lower part for separating the aqueous phase (3a) and a narrower upper part for separating the organic phase (3b) and provided with an upper outlet for the organic phase (3c) and a lower outlet for the purified aqueous phase (3d), a dosing device (7) containing an acidic or alkaline solution or an alkaline solid which is connected to the mixing device (2) via a pump or chute (9) and at least one container (8) and (8') for receiving the organic or solid phase from the separation device (3) and (3').
- Apparatus according to claim 11 wherein the apparatus comprises a further separation device (3') for separating the solid phase.
- Apparatus according to claims 9 to 12 wherein the separation device (3) or (3') comprises means for stirring (4) and for temperature control (5) which are connected to a control unit.
- Apparatus according to claims 9 to 13 wherein the apparatus further comprises a device (6) for receiving the aqueous phase from the separation device (3) or (3').
- Apparatus according to claims 9 to 13 wherein the mixing device (2) and the separation device (3) are not spacially separated.
- Apparatus according to claims 9, 10 or 12 wherein the separation devices (3) and (3') are realised within a single unit.
- Apparatus according to claims 9 to 16 wherein the apparatus further comprises a container for receiving the regenerated aqueous phase from which the recycling of the aqueous phase can be carried out according to the process of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004061255A DE102004061255B4 (en) | 2004-12-20 | 2004-12-20 | Process for the continuous operation of acidic or alkaline zinc or zinc alloy baths and apparatus for carrying it out |
| PCT/EP2005/012689 WO2006066689A2 (en) | 2004-12-20 | 2005-11-28 | Method for continuously operating acid or alkaline zinc or zinc alloy baths |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1831435A2 EP1831435A2 (en) | 2007-09-12 |
| EP1831435B1 true EP1831435B1 (en) | 2008-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP05808579A Revoked EP1831435B1 (en) | 2004-12-20 | 2005-11-28 | Method for continuously operating acid or alkaline zinc or zinc alloy baths |
Country Status (11)
| Country | Link |
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| US (1) | US8475874B2 (en) |
| EP (1) | EP1831435B1 (en) |
| JP (1) | JP4764886B2 (en) |
| KR (1) | KR101237037B1 (en) |
| CN (1) | CN101278077B (en) |
| AT (1) | ATE413479T1 (en) |
| BR (1) | BRPI0519144A2 (en) |
| CA (1) | CA2591932A1 (en) |
| DE (2) | DE102004061255B4 (en) |
| ES (1) | ES2313434T3 (en) |
| WO (1) | WO2006066689A2 (en) |
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| DE102007040005A1 (en) | 2007-08-23 | 2009-02-26 | Ewh Industrieanlagen Gmbh & Co. Kg | Depositing functional layers from electroplating bath, circulates zinc-nickel electrolyte between bath and regeneration unit providing ozone- and ultraviolet light treatment |
| DE102008058086B4 (en) * | 2008-11-18 | 2013-05-23 | Atotech Deutschland Gmbh | Method and device for cleaning electroplating baths for the deposition of metals |
| CN102234795B (en) * | 2011-06-02 | 2016-09-07 | 杭州震达五金机械有限公司 | Zinc-based multi-element alloy deposition liquid for bimetallic composite wire rod processing |
| CN102324276B (en) * | 2011-06-02 | 2017-02-22 | 杭州震达五金机械有限公司 | Production process of copper coated aluminum-magnesium bimetallic conductor |
| US9120111B2 (en) | 2012-02-24 | 2015-09-01 | Rain Bird Corporation | Arc adjustable rotary sprinkler having full-circle operation and automatic matched precipitation |
| US9156043B2 (en) | 2012-07-13 | 2015-10-13 | Rain Bird Corporation | Arc adjustable rotary sprinkler with automatic matched precipitation |
| CN103668192A (en) * | 2012-09-01 | 2014-03-26 | 无锡新大中薄板有限公司 | Four-element zinc-tin-nickel-iron soaking technique of aluminum alloy plate |
| CN104911683A (en) * | 2015-05-05 | 2015-09-16 | 武汉科技大学 | Method for side-stream removal of iron ions in zinc sulfate electroplating solution |
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| US2434191A (en) * | 1942-02-02 | 1948-01-06 | Du Pont | Removing organic impurities from copper-cyanide electroplating baths |
| US2861927A (en) * | 1956-04-25 | 1958-11-25 | Westinghouse Electric Corp | Process for adjusting the components in aqueous alkali cyanide electrolytes |
| US3821095A (en) * | 1972-09-26 | 1974-06-28 | M & T Chemicals Inc | Zinc electroplating process and electrolyte therefor |
| US3887445A (en) * | 1974-04-26 | 1975-06-03 | R O Hull & Company Inc | Method for the reduction of zinc ion concentration and removal of organic impurities in a neutral or acidic, aqueous zinc plating bath |
| JPS5262136A (en) * | 1975-11-18 | 1977-05-23 | Kosaku Kk | Regeneration method of inferion plating bath |
| DE3138792C2 (en) | 1981-09-30 | 1986-08-21 | Basf Ag, 6700 Ludwigshafen | Use of benzalacetone in its raw form as a top shine builder in acidic galvanic zinc baths |
| JPS6096781A (en) | 1983-11-01 | 1985-05-30 | Ube Ind Ltd | Regeneration of potassium hydroxide electrolyte |
| JPH0726239B2 (en) * | 1989-07-04 | 1995-03-22 | 三菱電機株式会社 | How to collect the plating solution |
| US5246591A (en) * | 1990-07-13 | 1993-09-21 | Pact, Incorporated | Separation of metal ions on an anion exchange resin by chromatographic elution |
| DE4200774C2 (en) | 1992-01-15 | 1993-11-25 | Rene Leutwyler | Process for removing carbonates from galvanic baths |
| DE4410347A1 (en) * | 1994-03-25 | 1995-09-28 | Rene Leutwyler | Process for removing inorganic metal compounds from solutions |
| DE19525509C2 (en) | 1994-07-22 | 1997-10-02 | Lpw Anlagen Gmbh | Use of the UV / H¶2¶O¶2¶ oxidation treatment for operational reuse or reprocessing of a bath for the electroplating of objects with metallic coatings |
| DE19506297A1 (en) * | 1995-02-23 | 1996-08-29 | Schloemann Siemag Ag | Process and plant for the regeneration of sulfate electrolyte in steel strip galvanizing |
| DE19810859A1 (en) | 1998-03-13 | 1999-09-16 | A C K Aqua Concept Gmbh Wasser | Treating galvanic bath |
| DE19834353C2 (en) * | 1998-07-30 | 2000-08-17 | Hillebrand Walter Gmbh & Co Kg | Alkaline zinc-nickel bath |
| US6391209B1 (en) * | 1999-08-04 | 2002-05-21 | Mykrolis Corporation | Regeneration of plating baths |
| DE19956666B4 (en) | 1999-11-25 | 2009-10-29 | Enthone Gmbh | Process for the continuous deposition of glare-free metal coatings on a metallic surface |
| US6602395B1 (en) * | 2000-04-11 | 2003-08-05 | Innovative Technology Licensing, Llc | Patterning of polymer light emitting devices using electrochemical polymerization |
| JP2001316894A (en) * | 2000-05-08 | 2001-11-16 | Tokyo Electron Ltd | Liquid treatment device, liquid treatment system, and liquid treatment method |
| JP3568460B2 (en) | 2000-07-03 | 2004-09-22 | 大日本スクリーン製造株式会社 | Plating solution regeneration device, substrate plating device and plating system |
| JP2002253899A (en) | 2001-02-27 | 2002-09-10 | Emiko Watanabe | Clothes drying auxiliary tool |
| JP2002322599A (en) * | 2001-04-23 | 2002-11-08 | Shigeo Hoshino | Method for plating with trivalent chromium |
| DE10225203A1 (en) * | 2002-06-06 | 2003-12-18 | Goema Ag | Method and device for returning rinsing water and cleaning a process bath |
-
2004
- 2004-12-20 DE DE102004061255A patent/DE102004061255B4/en not_active Revoked
-
2005
- 2005-11-28 KR KR1020077014826A patent/KR101237037B1/en active IP Right Grant
- 2005-11-28 JP JP2007545870A patent/JP4764886B2/en not_active Expired - Fee Related
- 2005-11-28 CN CN2005800425142A patent/CN101278077B/en not_active Expired - Fee Related
- 2005-11-28 BR BRPI0519144-0A patent/BRPI0519144A2/en not_active Application Discontinuation
- 2005-11-28 WO PCT/EP2005/012689 patent/WO2006066689A2/en active Application Filing
- 2005-11-28 US US11/722,137 patent/US8475874B2/en not_active Expired - Fee Related
- 2005-11-28 DE DE502005005921T patent/DE502005005921D1/en active Active
- 2005-11-28 ES ES05808579T patent/ES2313434T3/en active Active
- 2005-11-28 AT AT05808579T patent/ATE413479T1/en not_active IP Right Cessation
- 2005-11-28 CA CA002591932A patent/CA2591932A1/en not_active Abandoned
- 2005-11-28 EP EP05808579A patent/EP1831435B1/en not_active Revoked
Also Published As
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| US8475874B2 (en) | 2013-07-02 |
| US20090130315A1 (en) | 2009-05-21 |
| JP4764886B2 (en) | 2011-09-07 |
| CA2591932A1 (en) | 2006-06-29 |
| DE102004061255B4 (en) | 2007-10-31 |
| WO2006066689A3 (en) | 2007-11-08 |
| ES2313434T3 (en) | 2009-03-01 |
| CN101278077B (en) | 2013-01-09 |
| CN101278077A (en) | 2008-10-01 |
| JP2008524436A (en) | 2008-07-10 |
| KR101237037B1 (en) | 2013-02-25 |
| WO2006066689A2 (en) | 2006-06-29 |
| BRPI0519144A2 (en) | 2008-12-30 |
| DE102004061255A1 (en) | 2006-06-29 |
| EP1831435A2 (en) | 2007-09-12 |
| DE502005005921D1 (en) | 2008-12-18 |
| KR20070086772A (en) | 2007-08-27 |
| ATE413479T1 (en) | 2008-11-15 |
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