EP1006213A2 - Process for regenerating a processing solution - Google Patents

Process for regenerating a processing solution Download PDF

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Publication number
EP1006213A2
EP1006213A2 EP99120998A EP99120998A EP1006213A2 EP 1006213 A2 EP1006213 A2 EP 1006213A2 EP 99120998 A EP99120998 A EP 99120998A EP 99120998 A EP99120998 A EP 99120998A EP 1006213 A2 EP1006213 A2 EP 1006213A2
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Prior art keywords
chamber
solution
anode
hypophosphite
exchange membrane
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EP99120998A
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German (de)
French (fr)
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EP1006213A3 (en
EP1006213B1 (en
Inventor
Reinhard Dr. Rer. Nat. Schwarz
Klaus Prof. Dr. Rer. Nat. Habil. Fischwasser
Annette Dipl.-Ing. Taubert (Fh)
Dieter Dipl.-Ing. Hahnewald
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Blasberg Werra Chemie GmbH
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Hahnewald GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths
    • 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
    • C25D21/22—Regeneration of process solutions by ion-exchange

Definitions

  • the invention relates to a method for regenerating a process solution, the is used in the chemical-reductive deposition of metal layers and Contains hypophosphite and orthophosphite, in which the process solution at least four chambers having an electrodialysis cell, one anode chamber containing dilute acid with an anode therein, a Cathode chamber with a cathode inside and two more, through one Anion exchange membrane separated and between these two Has chambers arranged chambers, of which a first chamber through a Anion exchange membrane is separated from the cathode chamber while a second chamber through a cation exchange membrane from the anode chamber is separated, in which the process solution when performing the method of the first Chamber is abandoned, causing the hypophosphite ions and contained therein Orthophosphite ions electrodialytically into the second chamber and simultaneously Hypophosphite ions are transported from the cathode chamber into the process solution are, and at which regenerated process solution is removed and another
  • Coating processes are increasingly being used in surface finishing those contained in an aqueous solution of non-ferrous metal ions by means of chemical Reduction on substrate surfaces made of metal or pretreated plastic as non-ferrous metals be deposited.
  • Coating metals are, for example, copper, Nickel, silver and gold. Hypophosphite, for example, is used as the reducing agent used. Since the chemical-reductive nickel deposition is a common in practice is used, the following statements refer - representative for all other usable metals - on nickel.
  • the reducing agent hypophosphite H 2 PO 2
  • the oxidized reducing agent orthophosphite HPO 3 2-
  • Side reactions such as the reduction of hypophosphite to elemental phosphorus, which is built into the deposited nickel layer, result in a consumption of about 3 mol hypophosphite per mol of deposited nickel.
  • the concentration of orthophosphite increases.
  • the process solution can be used from a certain orthophosphite concentration (Interference limit concentration) no longer for electroless nickel plating be used.
  • the process solution that is no longer usable is partly discarded and replaced by a fresh process solution.
  • Processed solutions are currently being processed disposed of through complex neutralization precipitation or externally at high costs. There are procedures in the literature to extend the useful life of the process solution known in which only the disruptive components at least partially from the Process solution removed and the used components - nickel ions and Reducing agent - to be added. Nevertheless, the process solutions are based on the Regeneration can only be used to a limited extent.
  • the invention has for its object the method described above to further develop that the disruptive orthophosphite in a simple manner from the Process solution can be removed, so that a longer service life of the same is achievable.
  • Electrodialysis will Orthophosphite in a mineral acid solution from which it is converted by means of weakly basic anion exchanger can be removed.
  • the hypophosphite containing solution emerging from the ion exchanger is the cathode compartment Electrolysis cell abandoned, from where it is electrodialytic without interfering foreign ions is returned to the process solution through the anion exchanger membrane.
  • the of Process solution depleted of orthophosphite can then be used directly for the process chemical-reductive deposition of nickel can be supplied.
  • the stability and the Functionality of the regenerated process solution are due to equimolar exchange guaranteed by orthophosphite against hypophosphite.
  • the electrodialysis cell EZ shown in Fig. 1 consists of four chambers. These are an anode chamber (1) with the anode (2) therein, the cathode chamber (3) with the cathode (4) therein and two further chambers, a first Chamber (5) and a second chamber (6), which is between the anode chamber (1) and the cathode chamber (3).
  • the anode (2) is insoluble
  • the Anode chamber (1) contains a dilute acid, preferably sulfuric acid.
  • the Cathode (4) consists, for example, of copper or steel.
  • the first chamber (5) is from the cathode compartment (3) through an anion exchange membrane (AM 1) and from the second chamber (6) through an anion exchange membrane (AM 2) separated. Between the second chamber (6) and the anode compartment (1) there is a cation exchange membrane (KM 1). To the second chamber (6) a weakly basic anion exchanger (T 1) is connected, which turns into The beginning of the procedure is wholly or partly in the hypophosphite loading. The The outlet of the anion exchanger (T 1) is connected to the cathode chamber (3).
  • the method according to the invention works with an arrangement according to FIG. 1 for example as follows:
  • the process solution (PL) to be regenerated is passed into the first chamber (5) of the electrodialysis cell (EZ).
  • the hypophosphite and orthophosphite ions contained in the process solution (PL) pass through the anion exchange membrane (AM 2) and reach the second chamber (6), which goes from the cation exchange membrane (KM 1) to the anode (2) is limited and contains a dilute acid.
  • hypophosphite and orthophosphite together with the electrodialytically transported anions hypophosphite and orthophosphite, they form the free acids hypophosphoric acid (phosphinic acid, H 3 PO 2 ) and phosphorous acid (phosphonic acid, H 3 PO 3 ). These anions are prevented from passing into the anode chamber (1) containing a dilute acid by the cation exchange membrane (KM 1). The acid mixture of phosphinic acid and phosphonic acid is passed through the weakly basic anion exchanger (T 1), which is located in the hypophosphite loading.
  • T 1 weakly basic anion exchanger
  • the anion exchanger (T 1) binds the orthophosphite ions and gives them Hypophosphite ions into the solution. Those still in solution Hypophosphite ions are not bound by the anion exchanger (T 1).
  • the regenerate (R) of Anion exchanger (T 1) contains all of the orthophosphite, which during the Procedure was bound. For reuse, the Anion exchanger (T 1) transferred back to the hypophosphite loading.
  • a regeneration circuit be set up.
  • the dosage of spent nickel for example, nickel hypophosphite can be used, which according to the arrow (P 2) in the first chamber (5), ie in the process solution (PL).
  • the electrodialysis cell (EZ) can be supplemented by additional chambers to increase the throughput.
  • this can be three additional chambers (7, 8 and 9) which are arranged between the first chamber (5) and the cathode chamber (3).
  • the chamber (7) has a combined function of anode chamber (1) on the one hand (release of protons) and cathode compartment (3) on the other hand (transport of hypophosphite into the process solution (PL)). It is separated from the first chamber (5) by an anion exchanger membrane (AM 3) and from the chamber (8) by a cation exchanger membrane (KM 2), which corresponds functionally to the second chamber (6).
  • the chamber (9) corresponds functionally to the first chamber (5). It is separated from the chamber (8) by an anion exchange membrane (AM 4) and from the cathode chamber (3) by the anion exchange membrane (AM 1).
  • the process solution (PL) becomes both the first chamber (5) and the chamber (9) given up.
  • the acid mixture of the second chamber (6) and the chamber (8) enters the anion exchanger (T 1).
  • the solution containing hypophosphite is added to the Cathode chamber (3) and passed into the chamber (7).
  • Regeneration circuit must be set up (arrow P 1) and nickel can be replenished (Arrows P 2).
  • a weakly acidic cation exchanger (T 2) which is connected at its inlet to the outlet of the anion exchanger (T 1) and opens at the outlet into the first chamber (5).
  • the process solution (PL) to be regenerated is depleted of nickel, since nickel ions are consumed by the chemical-reductive deposition process.
  • the cation exchanger (T 2) which is loaded with nickel, it is possible to introduce nickel into the process solution (PL) without disturbing foreign ions.
  • the procedure of the arrangement according to FIG. 3 is basically the same as that of FIG. 1.
  • the anode process can be used to remove electroless nickel replenish used nickel ions.
  • the electrodialysis cell (EZ) according to FIG. 4 is supplemented in comparison to that according to FIG. 1 by a further chamber (10) which is arranged between the anode chamber (1) and the second chamber (6). It is separated from the second chamber (6) by a cation exchange membrane (KM 3) which is only permeable to monovalent cations.
  • a nickel anode is used here as the anode (2).
  • nickel is dissolved anodically. It reaches the process solution (PL) electrodialytically.
  • the process solution (PL) is introduced into the chamber (1) delimited by the cation exchange membrane (KM 1) and the cation exchange membrane (KM 3).
  • the cation exchange membrane (KM 3) which is only permeable to monovalent cations, is necessary so that no nickel ions are transported into the regeneration circuit to remove the orthophophite.
  • Nickel ions migrate from the anode chamber (1) into the process solution (PL). she compensate for the deficit in nickel ions caused by electroless nickel deposition arose. At the same time, an equivalent amount of protons migrate through the Cation exchanger membrane (KM 3) from the chamber (10) into the second chamber 86). As a result, the one formed during the chemical-reductive nickel deposition Amount of acid removed from the process solution (PL). The one with nickel ions Enriched process solution (PL) is then in accordance with the arrow (P3) in the first chamber (5) passed by the anion exchange membrane (AM 2) and Anion exchange membrane (AM 1) is limited.
  • the anions migrate from the first chamber (5) into the second chamber (6) and form there together with the protons that were previously from the anode chamber (1) and the further chamber (10) electrodialytically into the second chamber (6) were transported, the corresponding free acids.
  • the other The procedure corresponds to the procedure described for FIG. 1.
  • the Nickel anode must be replaced here after the nickel has been used up.
  • the anodic nickel dissolution can also take place externally.
  • the nickel ions are then fed into the anode chamber (1). This is indicated by the arrow (P4).
  • An anode (2) made, for example, of steel or of platinized titanium expanded metal can then be used, so that no anode change is required.
  • the structure of the electrodialysis cell (EZ) according to FIG. 5 is otherwise identical to that of the electrodialysis cell (EZ) according to FIG. 4. This also applies to the procedure.
  • the same can be applied to the chamber (10) in accordance with FIG. 6 in only one partial stream (TL).
  • the nickel-enriched partial stream of the process solution (PL) emerging from the chamber (10) is combined with the process solution (PL) emerging from the first chamber (5) and to be used for further use.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Chemically Coating (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Chemical reduction metal plating solution regeneration uses a weakly basic anion exchanger (T1) for hypophosphite ion recycle to the cathodic chamber (3) of a multi-chamber electrodialysis cell. An acid mixture, formed in the second chamber (6) by entry of protons from the anodic chamber (1), is supplied to a hypophosphite-loaded weakly basic anion exchanger with its outlet connected to the cathodic chamber. A chemical reduction metal plating solution, containing hypophosphite and ortho phosphite, is regenerated in a multi-chamber electrodialysis cell having two chambers separated from one another by an anion exchange membrane and which are located between a dilute acid-containing anodic chamber and a cathodic chamber, the first chamber being separated from the cathode chamber by an anion exchange membrane and the second chamber being separated from the anodic chamber by a cation exchange membrane. The solution is delivered to the first chamber for hypophosphite and orthophosphite ion transport from the solution to the second chamber and simultaneous hypophosphite ion transport from the cathodic chamber into the solution, the resulting regenerated solution being discharged for reuse. Preferred Features: Part of the solution, leaving the weakly basic anion exchanger (T1), may be passed over a plating metal ion-loaded, weakly acidic anion exchanger within the first chamber (5) of the cell (EZ). A regeneration circuit is formed by a connection (P1) between the cathodic chamber (3) and the second chamber (6). A further chamber may be provided between the anodic chamber (1) and the second chamber and separated from the second chamber by a cation exchange membrane, this further chamber receiving plating metal ions from the anodic chamber and being supplied with part or all of the process solution (PL) which is then transferred to the first chamber. Plating metal additions are made to the first chamber or to the anodic chamber. The anode (2) may be an insoluble anode, preferably of steel or platinized expanded titanium, or a soluble anode of the plating metal.

Description

Die Erfindung bezieht sich auf ein Verfahren zum Regenerieren einer Prozeßlösung, die bei der chemisch-reduktiven Abscheidung von Metallschichten verwendet wird und Hypophosphit sowie Orthophosphit enthält, bei welchem die Prozeßlösung einer mindestens vier Kammern aufweisenden Elektrodialysezelle aufgegeben wird, die eine verdünnte Säure enthaltende Anodenkammer mit einer darin befindlichen Anode, eine Kathodenkammer mit einer darin befindlichen Kathode sowie zwei weitere, durch eine Anionenaustauscher-Membran voneinander getrennte und zwischen diesen beiden Kammern angeordnete Kammern aufweist, von denen eine erste Kammer durch eine Anionenaustauscher-Membran von der Kathodenkammer getrennt ist, während eine zweite Kammer durch eine Kationenaustauschermembran von der Anodenkammer getrennt ist, bei welchem die Prozeßlösung bei Durchführung des Verfahrens der ersten Kammer aufgegeben wird, wodurch die in ihr enthaltenen Hypophosphit-Ionen und Orthophosphit-Ionen elektrodialytisch in die zweite Kammer und gleichzeitig Hypophosphit-Ionen aus der Kathodenkammer in die Prozeßlösung transportiert werden, und bei welchem regenerierte Prozeßlösung entnommen und einer weiteren Verwendung zugeführt wird (DE-A-4 310 366 und US-A-5 419 821).The invention relates to a method for regenerating a process solution, the is used in the chemical-reductive deposition of metal layers and Contains hypophosphite and orthophosphite, in which the process solution at least four chambers having an electrodialysis cell, one anode chamber containing dilute acid with an anode therein, a Cathode chamber with a cathode inside and two more, through one Anion exchange membrane separated and between these two Has chambers arranged chambers, of which a first chamber through a Anion exchange membrane is separated from the cathode chamber while a second chamber through a cation exchange membrane from the anode chamber is separated, in which the process solution when performing the method of the first Chamber is abandoned, causing the hypophosphite ions and contained therein Orthophosphite ions electrodialytically into the second chamber and simultaneously Hypophosphite ions are transported from the cathode chamber into the process solution are, and at which regenerated process solution is removed and another Use is supplied (DE-A-4 310 366 and US-A-5 419 821).

Bei der Oberflächenveredlung werden verstärkt Beschichtungsverfahren eingesetzt, bei denen in einer wäßrigen Lösung enthaltene NE-Metallionen mittels chemischer Reduktion auf Substratoberflächen aus Metall oder vorbehandeltem Kunststoff als NE-Metalle abgeschieden werden. Beschichtungsmetalle sind beispielsweise Kupfer, Nickel, Silber und Gold. Als Reduktionsmittel wird beispielsweise Hypophosphit verwendet. Da die chemisch-reduktive Nickelabscheidung ein in der Praxis häufig verwendetes Verfahren ist, beziehen sich die folgenden Ausführungen - stellvertretend für alle anderen verwendbaren Metalle - auf Nickel.Coating processes are increasingly being used in surface finishing those contained in an aqueous solution of non-ferrous metal ions by means of chemical Reduction on substrate surfaces made of metal or pretreated plastic as non-ferrous metals be deposited. Coating metals are, for example, copper, Nickel, silver and gold. Hypophosphite, for example, is used as the reducing agent used. Since the chemical-reductive nickel deposition is a common in practice is used, the following statements refer - representative for all other usable metals - on nickel.

Bei der chemisch-reduktiven Abscheidung von Nickel wird das Reduktionsmittel Hypophosphit (H2PO2) verbraucht. Hingegen reichert sich das als Reaktionsprodukt gebildete oxidierte Reduktionsmittel Orthophosphit (HPO3 2-) in der Prozeßlösung an. Durch Nebenreaktionen, wie die Reduktion von Hypophosphit zu elementarem Phosphor, der in die abgeschiedene Nickelschicht eingebaut wird, ergibt sich ein Verbrauch von etwa 3 mol Hypophosphit pro mol abgeschiedenem Nickel. Das hat zur Folge, dass die Hypophosphit-Konzentration in der Prozeßlösung abnimmt und durch Zugabe von Ergänzungschemikalien wieder angehoben werden muß. Die Konzentration an Orthophosphit dagegen steigt an.In the chemical-reductive deposition of nickel, the reducing agent hypophosphite (H 2 PO 2 ) is consumed. In contrast, the oxidized reducing agent orthophosphite (HPO 3 2- ) formed as a reaction product accumulates in the process solution. Side reactions, such as the reduction of hypophosphite to elemental phosphorus, which is built into the deposited nickel layer, result in a consumption of about 3 mol hypophosphite per mol of deposited nickel. The consequence of this is that the hypophosphite concentration in the process solution decreases and has to be raised again by adding additional chemicals. The concentration of orthophosphite, however, increases.

Mit steigender Konzentration destabilisiert das Orthophosphit die Prozeßlösung. Das führt zu einer rauhen, ungleichmäßigen Nickelabscheidung und zu Ausfällungen in der Prozeßlösung. Daher kann die Prozeßlösung ab einer bestimmten Orthophosphit-Konzentration (Störgrenzkonzentration) nicht mehr zur stromlosen Vernickelung eingesetzt werden. Die nicht mehr nutzbare Prozeßlösung wird zum Teil verworfen und durch eine frische Prozeßlösung ersetzt. Abgearbeitete Prozeßlösungen werden derzeit durch eine aufwendige Neutralisationsfällung oder extern mit hohen Kosten entsorgt. Zur Verlängerung der Nutzungsdauer der Prozeßlösung sind aus der Literatur Verfahren bekannt, bei denen nur die störenden Komponenten zumindest teilweise aus der Prozeßlösung entfernt und die verbrauchten Komponenten - Nickelionen und Reduktionsmittel - nachdosiert werden. Trotzdem sind die Prozeßlösungen nach der Regeneration nur noch beschränkt einsatzfähig.With increasing concentration, the orthophosphite destabilizes the process solution. The leads to rough, uneven nickel deposition and precipitation in the Process solution. Therefore, the process solution can be used from a certain orthophosphite concentration (Interference limit concentration) no longer for electroless nickel plating be used. The process solution that is no longer usable is partly discarded and replaced by a fresh process solution. Processed solutions are currently being processed disposed of through complex neutralization precipitation or externally at high costs. There are procedures in the literature to extend the useful life of the process solution known in which only the disruptive components at least partially from the Process solution removed and the used components - nickel ions and Reducing agent - to be added. Nevertheless, the process solutions are based on the Regeneration can only be used to a limited extent.

Bei dem bekannten Verfahren nach der eingangs erwähnten DE-A-4 310 366 wird zum Regenerieren der Prozeßlösung eine Elektrodialysezelle eingesetzt. Die Reduktion des bei der stromlosen Metallabscheidung gebildeten Orthophosphits soll im Kathodenraum der Elektrodialysezelle erfolgen. Wie die Praxis gezeigt hat, kann das Orthophosphit mit diesem Verfahren jedoch nicht kathodisch zu Hypophosphit reduziert werden, da sich im Regenerierkreislauf kontinuierlich Orthophosphit anreichert, bis die Störgrenzkonzentration der Prozeßlösung erreicht wird. Damit kann kein Orthophosphit mehr aus der abgearbeiteten Prozeßlösung entfernt werden. Erst nach einem Verwurf der Regenerierlösung und dem Einsatz einer frischen, orthophosphitfreien Regenerierlösung, wäre dieses Verfahren kurzzeitig - bis zur erneuten Einstellung des Gleichgewichts - wieder einsatzfähig. In the known method according to DE-A-4 310 366 mentioned at the outset, Regenerate the process solution used an electrodialysis cell. The reduction of Orthophosphite formed in the electroless metal deposition is said to be in the cathode compartment the electrodialysis cell. As practice has shown, the orthophosphite can with However, this method cannot be reduced cathodically to hypophosphite, since Orthophosphite continuously accumulates in the regeneration circuit until the Interference limit concentration of the process solution is reached. So no orthophosphite more can be removed from the processed process solution. Only after a discard the regeneration solution and the use of a fresh, orthophosphite-free Regeneration solution, this process would be brief - until the setting of the Balance - ready for use again.

Gemäß der ebenfalls eingangs erwähnten US-A-5 419 821 werden daher dem Regenerierkreislauf zur Entfernung des Orthophosphits Magnesium- oder Calciumhydroxid zugesetzt, um das Orthophosphit in Form von schwerlöslichen Salzen aus dem Regenerierkreislauf zu entfernen. Die durch den Abscheidevorgang verbrauchten Chemikalien (Nickelionen und Reduktionsmittel) sollen in Form von Nickelsulfat (Zugabe in die Prozeßlösung) und Phosphinsäure (Zugabe in den Katholyten) zugeführt werden, wobei das Sulfat durch Zusatz von Bariumhydroxid in den Katholyten als Bariumsulfat wieder ausgekreist werden soll. Durch den erforderlichen Verwurf der Regenerierlösung oder die Ausfällung des Orthophosphits in Form von schwerlöslichen Erdalkalisalzen werden durch die beiden beschriebenen Verfahren ein hoher Chemikalienbedarf und ein hohes Abfallaufkommen verursacht.According to US-A-5 419 821, which was also mentioned at the beginning, the Regeneration circuit to remove the orthophosphite magnesium or Calcium hydroxide added to the orthophosphite in the form of sparingly soluble salts to be removed from the regeneration circuit. The through the separation process Used chemicals (nickel ions and reducing agents) are said to be in the form of Nickel sulfate (addition to the process solution) and phosphinic acid (addition to the Catholytes) are supplied, the sulfate by adding barium hydroxide in the catholyte should be removed as barium sulfate. By the necessary discard of the regeneration solution or the precipitation of the orthophosphite in Forms of poorly soluble alkaline earth salts are described by the two Process causes a high need for chemicals and a high amount of waste.

Der Erfindung liegt die Aufgabe zugrunde, das eingangs beschriebene Verfahren so weiterzubilden, daß das störende Orthophosphit auf einfache Weise aus der Prozeßlösung enfernt werden kann, so daß eine längere Nutzungsdauer derselben erreichbar ist.The invention has for its object the method described above to further develop that the disruptive orthophosphite in a simple manner from the Process solution can be removed, so that a longer service life of the same is achievable.

Diese Aufgabe wird gemäß der Erfindung dadurch gelöst, daß das in der zweiten Kammer durch Zutritt von Protonen aus der Anodenkammer gebildete Säuregemisch einem in der Hypophosphit-Beladung befindlichen, schwachbasischen Anionenaustauscher zugeführt wird, der mit seinem Auslaß an die Kathodenkammer angeschlossen ist.This object is achieved according to the invention in that the second Chamber formed by the entry of protons from the anode chamber mixture of acids a weakly basic in the hypophosphite load Anion exchanger is supplied with its outlet to the cathode chamber connected.

Bei diesem Verfahren werden Elektrodialyse und Ionenaustausch in einfacher Arbeitsweise kombiniert, und zwar derart vorteilhaft, daß das Hypophosphit stöchiometrisch wieder in die Prozeßlösung eingeschleust werden kann, wodurch dieselbe voll funktionsfähig erhalten bleibt. Durch die Elektrodialyse wird das Orthophosphit in eine mineralsaure Lösung überführt, aus der es mittels des schwachbasischen Anionenaustauschers entfernt werden kann. Die Hypophosphit enthaltende, aus dem Ionenaustauscher austretende Lösung wird dem Kathodenraum der Elektrolysezelle aufgegeben, von wo es ohne störende Fremdionen elektrodialytisch durch die Anionentauscher-Membran in die Prozeßlösung zurückgeführt wird. Die von Orthophosphit abgereicherte Prozeßlösung kann dann direkt dem Verfahren zur chemisch-reduktiven Abscheidung von Nickel zugeführt werden. Die Stabilität und die Funktionsfähigkeit der regenerierten Prozeßlösung sind durch äquimolaren Austausch von Orthophosphit gegen Hypophosphit gewährleistet.This process makes electrodialysis and ion exchange easier Combined operation, and so advantageous that the hypophosphite stoichiometrically can be reintroduced into the process solution, whereby it remains fully functional. Electrodialysis will Orthophosphite in a mineral acid solution from which it is converted by means of weakly basic anion exchanger can be removed. The hypophosphite containing solution emerging from the ion exchanger is the cathode compartment Electrolysis cell abandoned, from where it is electrodialytic without interfering foreign ions is returned to the process solution through the anion exchanger membrane. The of Process solution depleted of orthophosphite can then be used directly for the process chemical-reductive deposition of nickel can be supplied. The stability and the Functionality of the regenerated process solution are due to equimolar exchange guaranteed by orthophosphite against hypophosphite.

Vorteilhafte Ausgestaltungen der Erfindung gehen aus den Unteransprüchen hervor.Advantageous embodiments of the invention emerge from the subclaims.

Das Verfahren nach der Erfindung wird im folgenden anhand der Zeichnungen in Ausführungsbeispielen erläutert.The method according to the invention is described below with reference to the drawings in Exemplary embodiments explained.

Es zeigen:

  • Fig. 1 eine für das Verfahren nach der Erfindung verwendbare Anordnung in schematischer Darstellung.
  • Fig. 2 und 3 zwei unterschiedliche, gegenüber Fig. 1 ergänzte Ausführungsformen der Anordnung.
  • Fig. 4 bis 6 gegenüber Fig. 1 abgewandelte Ausführungsformen der Anordnung.
    • Show it:
  • Fig. 1 shows a usable for the method according to the invention arrangement in a schematic representation.
  • 2 and 3 two different, compared to FIG. 1, supplemented embodiments of the arrangement.
  • 4 to 6 compared to Fig. 1 modified embodiments of the arrangement.

    • Die in Fig. 1 dargestellte Elektrodialysezelle EZ besteht aus vier Kammern. Das sind eine Anodenkammer (1) mit der darin befindlichen Anode (2), die Kathodenkammer (3) mit der darin befindlichen Kathode (4) sowie zwei weitere Kammern, eine erste Kammer (5) und eine zweite Kammer (6), die sich zwischen der Anodenkammer (1) und der Kathodenkammer (3) befinden. Die Anode (2) besteht in unlöslicher Ausführung beispielsweise aus Stahl oder aus platiniertem Titan-Streckmetall. Die Anodenkammer (1) enthält eine verdünnte Säure, vorzugsweise Schwefelsäure. Die Kathode (4) besteht beispielsweise aus Kupfer oder Stahl.The electrodialysis cell EZ shown in Fig. 1 consists of four chambers. These are an anode chamber (1) with the anode (2) therein, the cathode chamber (3) with the cathode (4) therein and two further chambers, a first Chamber (5) and a second chamber (6), which is between the anode chamber (1) and the cathode chamber (3). The anode (2) is insoluble For example, made of steel or platinum-coated expanded titanium. The Anode chamber (1) contains a dilute acid, preferably sulfuric acid. The Cathode (4) consists, for example, of copper or steel.

    Die erste Kammer (5) ist vom Kathodenraum (3) durch eine Anionenaustauscher-Membran (AM 1) und von der zweiten Kammer (6) durch eine Anionenaustauscher-Membran (AM 2) getrennt. Zwischen der zweiten Kammer (6) und dem Anodenraum (1) befindet sich eine Kationenaustauscher-Membran (KM 1). An die zweite Kammer (6) ist ein schwachbasischer Anionenaustauscher (T 1) angeschlossen, der sich zu Beginn des Verfahrens ganz oder teilweise in der Hypophosphit-Beladung befindet. Der Auslaß des Anionenaustauschers (T 1) ist mit der Kathodenkammer (3) verbunden.The first chamber (5) is from the cathode compartment (3) through an anion exchange membrane (AM 1) and from the second chamber (6) through an anion exchange membrane (AM 2) separated. Between the second chamber (6) and the anode compartment (1) there is a cation exchange membrane (KM 1). To the second chamber (6) a weakly basic anion exchanger (T 1) is connected, which turns into The beginning of the procedure is wholly or partly in the hypophosphite loading. The The outlet of the anion exchanger (T 1) is connected to the cathode chamber (3).

    Das Verfahren nach der Erfindung arbeitet mit einer Anordnung nach Fig. 1 beispielsweise wie folgt:The method according to the invention works with an arrangement according to FIG. 1 for example as follows:

    Die zu regenerierende Prozeßlösung (PL) wird in die erste Kammer (5) der Elektrodialysezelle (EZ) geleitet. Die in der Prozeßlösung (PL) enthaltenen Hypophosphit- und Orthophosphit-Ionen treten durch die Anionenaustauscher-Membran (AM 2) hindurch und gelangen in die zweite Kammer (6), die von der Kationenaustauscher-Membran (KM 1) zur Anode (2) begrenzt ist und in der sich eine verdünnte Säure befindet. Aus der Anodenkammer (1) gelangen Protonen, die durch Wasserzersetzung an der Anode (2) gebildet werden, in die zweite Kammer (6). Sie bilden zusammen mit dem elektrodialytisch transportierten Anionen Hypophosphit und Orthophosphit die freien Säuren Hypophosphorsäure (Phosphinsäure, H3PO2) und Phosphorige Säure (Phosphonsäure, H3PO3). Durch die Kationenaustauscher-Membran (KM 1) werden diese Anionen am Übertritt in die eine verdünnte Säure enthaltende Anodenkammer (1) gehindert. Die Säuremischung von Phosphinsäure und Phosphonsäure wird über den schwachbasischen Anionenaustauscher (T 1) geleitet, der sich in der Hypophosphit-Beladung befindet.The process solution (PL) to be regenerated is passed into the first chamber (5) of the electrodialysis cell (EZ). The hypophosphite and orthophosphite ions contained in the process solution (PL) pass through the anion exchange membrane (AM 2) and reach the second chamber (6), which goes from the cation exchange membrane (KM 1) to the anode (2) is limited and contains a dilute acid. Protons, which are formed by water decomposition at the anode (2), reach the second chamber (6) from the anode chamber (1). Together with the electrodialytically transported anions hypophosphite and orthophosphite, they form the free acids hypophosphoric acid (phosphinic acid, H 3 PO 2 ) and phosphorous acid (phosphonic acid, H 3 PO 3 ). These anions are prevented from passing into the anode chamber (1) containing a dilute acid by the cation exchange membrane (KM 1). The acid mixture of phosphinic acid and phosphonic acid is passed through the weakly basic anion exchanger (T 1), which is located in the hypophosphite loading.

    Der Anionenaustauscher (T 1) bindet die Orthophosphit-Ionen und gibt die Hypophosphit-Ionen in die Lösung ab. Die noch in der Lösung befindlichen Hypophosphit-Ionen werden vom Anionenaustauscher (T 1) nicht gebunden. Der Ablauf des Anionenaustauschers (T 1) wird in die Kathodenkammer (3) der Elektrodialysezelle (EZ) geleitet. Von dort werden die Hypophosphit-Ionen elektrodialytisch durch die Anionenaustauscher-Membran (AM 1) in die Prozeßlösung (PL) transportiert. Sobald die Kapazität des Anionenaustauschers (T 1) erschöpft ist, wird er beispielsweise mit Natronlauge regeneriert. Das Regenerat (R) des Anionenaustauschers (T 1) enthält das gesamte Orthophosphit, das während des Verfahrensablaufs gebunden wurde. Für den erneuten Einsatz wird der Anionenaustauscher (T 1) wieder in die Hypophosphit-Beladung überführt.The anion exchanger (T 1) binds the orthophosphite ions and gives them Hypophosphite ions into the solution. Those still in solution Hypophosphite ions are not bound by the anion exchanger (T 1). The Drain of the anion exchanger (T 1) in the cathode chamber (3) Electrodialysis cell (EZ) directed. From there the hypophosphite ions electrodialytically through the anion exchange membrane (AM 1) into the process solution (PL) transported. As soon as the capacity of the anion exchanger (T 1) is exhausted, For example, it is regenerated with sodium hydroxide solution. The regenerate (R) of Anion exchanger (T 1) contains all of the orthophosphite, which during the Procedure was bound. For reuse, the Anion exchanger (T 1) transferred back to the hypophosphite loading.

    Durch eine durch den Pfeil (P 1) angedeutete Verbindung der Kathodenkammer (3) mit der zweiten Kammer (6), die durch die Anionenaustauscher-Membran (AM 2) und die Kationenaustauscher-Membran (KM 1) begrenzt ist, kann ein Regenerierkreislauf eingerichtet werden. Während des Verfahrensablaufs kann zur Nachdosierung von verbrauchtem Nickel beispielsweise Nickelhypophosphit verwendet werden, das gemäß dem Pfeil (P 2) in die erste Kammer (5), also in die Prozeßlösung (PL) gegeben wird.Through a connection of the cathode chamber (3) indicated by the arrow (P 1) the second chamber (6) through the anion exchange membrane (AM 2) and Cation exchanger membrane (KM 1) is limited, a regeneration circuit be set up. During the course of the process, the dosage of spent nickel, for example, nickel hypophosphite can be used, which according to the arrow (P 2) in the first chamber (5), ie in the process solution (PL).

    Zur Erhöhung des Durchsatzes kann die Elektrodialysezelle (EZ) durch weitere Kammern ergänzt werden. Das können gemäß Fig. 2 drei zusätzliche Kammern (7, 8 und 9) sein, die zwischen der ersten Kammer (5) und der Kathodenkammer (3) angeordnet werden. Die Kammer (7) hat darin eine kombinierte Funktion von Anodenkammer (1) einerseits (Abgabe von Protonen) und Kathodenraum (3) andererseits (Transport von Hypophosphit in die Prozeßlösung (PL)). Sie ist von der ersten Kammer (5) durch eine Anionenaustauscher-Membran (AM 3) und von der Kammer (8) durch eine Kationenaustauscher-Membran (KM 2) getrennt, die funktionsmäßig der zweiten Kammer (6) entspricht. Analog dazu entspricht die Kammer (9) funktionsmäßig der ersten Kammer (5). Sie ist von der Kammer (8) durch eine Anionenaustauscher-Membran (AM 4) und von der Kathodenkammer (3) durch die Anionenaustauscher-Membran (AM 1) getrennt.The electrodialysis cell (EZ) can be supplemented by additional chambers to increase the throughput. According to FIG. 2, this can be three additional chambers (7, 8 and 9) which are arranged between the first chamber (5) and the cathode chamber (3). The chamber (7) has a combined function of anode chamber (1) on the one hand (release of protons) and cathode compartment (3) on the other hand (transport of hypophosphite into the process solution (PL)). It is separated from the first chamber (5) by an anion exchanger membrane (AM 3) and from the chamber (8) by a cation exchanger membrane (KM 2), which corresponds functionally to the second chamber (6). Similarly, the chamber (9) corresponds functionally to the first chamber (5). It is separated from the chamber (8) by an anion exchange membrane (AM 4) and from the cathode chamber (3) by the anion exchange membrane (AM 1).

    Die Prozeßlösung (PL) wird sowohl der ersten Kammer (5) als auch der Kammer (9) aufgegeben. Das Säuregemisch der zweiten Kammer (6) und der Kammer (8) gelangt in den Anionenaustauscher (T 1). Die Hypophosphit enthaltende Lösung wird in die Kathodenkammer (3) und in die Kammer (7) geleitet. Auch hier kann ein Regenerierkreislauf eingerichtet sein (Pfeil P 1) und es kann Nickel nachdosiert werden (Pfeile P 2).The process solution (PL) becomes both the first chamber (5) and the chamber (9) given up. The acid mixture of the second chamber (6) and the chamber (8) enters the anion exchanger (T 1). The solution containing hypophosphite is added to the Cathode chamber (3) and passed into the chamber (7). Here too one can Regeneration circuit must be set up (arrow P 1) and nickel can be replenished (Arrows P 2).

    Bei der Ausführungsform der Anordnung nach Fig. 3 ist zusätzlich ein schwachsaurer Kationenaustauscher (T 2) vorhanden, der mit seinem Einlaß mit dem Auslaß des Anionenaustauschers (T 1) verbunden ist und mit seinem Auslaß in die erste Kammer (5) mündet. Bei dieser Ausführungsform ist berücksichtigt, daß die zu regenerierende Prozeßlösung (PL) an Nickel verarmt ist, da durch den chemisch-reduktiven Abscheideprozeß Nickelionen verbraucht werden. Durch den Einsatz des Kationenaustauschers (T 2), der mit Nickel beladen ist, ist es möglich, Nickel ohne störende Fremdionen in die Prozeßlösung (PL) einzuführen. Das Verfahren läuft bei der Anordnung nach Fig. 3 grundsätzlich genauso ab, wie bei der nach Fig. 1. Es wird hier nur ein Teilstrom der aus dem Anionenaustauscher (T 1) austretenden Lösung abgezweigt und über den Kationenaustauscher (T 2) geführt. Dieser Teilstrom der Lösung entlädt den in der Nickelform befindlichen Kationenaustauscher (T 2). Er wird direkt in die Prozeßlösung (PL) geleitet. Auf diese Weise werden der Prozeßlösung (PL) Nickelionen ohne störendes Anion wieder zugeführt. Nachdem das Nickel vollständig vom Kationenaustauscher (T 2) entfernt wurde, wird derselbe mit Natronlauge in die Natrium-Form überführt und wieder mit Nickelionen beladen.In the embodiment of the arrangement according to FIG. 3 there is additionally a weakly acidic cation exchanger (T 2) which is connected at its inlet to the outlet of the anion exchanger (T 1) and opens at the outlet into the first chamber (5). In this embodiment, it is taken into account that the process solution (PL) to be regenerated is depleted of nickel, since nickel ions are consumed by the chemical-reductive deposition process. By using the cation exchanger (T 2), which is loaded with nickel, it is possible to introduce nickel into the process solution (PL) without disturbing foreign ions. The procedure of the arrangement according to FIG. 3 is basically the same as that of FIG. 1. Here, only a partial stream of the solution emerging from the anion exchanger (T 1) is branched off and passed over the cation exchanger (T 2). This partial flow of the solution discharges the cation exchanger (T 2) in the nickel form. It is fed directly into the process solution (PL). In this way, nickel ions are fed back into the process solution (PL) without an interfering anion. After the nickel has been completely removed from the cation exchanger (T 2), the latter is converted into the sodium form with sodium hydroxide solution and again loaded with nickel ions.

    Bei den Ausführungsformen der Anordnung nach den Fig. 4 bis 6 ist berücksichtigt, daß der Anodenprozeß genutzt werden kann, um die bei der stromlosen Nickelabscheidung verbrauchten Nickelionen nachzudosieren.In the embodiments of the arrangement according to FIGS. 4 to 6 it is taken into account that The anode process can be used to remove electroless nickel replenish used nickel ions.

    Die Elektrodialysezelle (EZ) nach Fig. 4 ist gegenüber der nach Fig. 1 um eine weitere Kammer (10) ergänzt, die zwischen der Anodenkammer (1) und der zweiten Kammer (6) angeordnet ist. Sie ist von der zweiten Kammer (6) durch eine Kationenaustauscher-Membran (KM 3) getrennt, die nur für einwertige Kationen durchlässig ist. Als Anode (2) wird hier eine Nickelanode verwendet. Während des Verfahrens wird Nickel anodisch aufgelöst. Es gelangt elektrodialytisch in die Prozeßlösung (PL). Die Prozeßlösung (PL) wird in die von der Kationenaustauscher-Membran (KM 1) und der Kationenaustauscher-Membran (KM 3) begrenzten Kammer (1) eingeleitet. Die nur für einwertige Kationen durchlässige Kationenaustauscher-Membran (KM 3) ist erforderlich, damit keine Nickelionen in den Regenerierkreislauf zur Entfernung des Orthophophits transportiert werden. The electrodialysis cell (EZ) according to FIG. 4 is supplemented in comparison to that according to FIG. 1 by a further chamber (10) which is arranged between the anode chamber (1) and the second chamber (6). It is separated from the second chamber (6) by a cation exchange membrane (KM 3) which is only permeable to monovalent cations. A nickel anode is used here as the anode (2). During the process, nickel is dissolved anodically. It reaches the process solution (PL) electrodialytically. The process solution (PL) is introduced into the chamber (1) delimited by the cation exchange membrane (KM 1) and the cation exchange membrane (KM 3). The cation exchange membrane (KM 3), which is only permeable to monovalent cations, is necessary so that no nickel ions are transported into the regeneration circuit to remove the orthophophite.

    Aus der Anodenkammer (1) wandern Nickelionen in die Prozeßlösung (PL). Sie gleichen das Defizit an Nickelionen aus, das durch die stromlose Nickelabscheidung entstanden ist. Gleichzeitig wandert eine äquivalente Menge an Protonen durch die Kationenaustauscher-Membran (KM 3) aus der Kammer (10) in die zweite Kammer 86). Dadurch wird die bei der chemisch-reduktiven Nickelabscheidung gebildete Säuremenge wieder aus der Prozeßlösung (PL) entfernt. Die mit Nickelionen angereicherte Prozeßlösung (PL) wird anschließend entsprechend dem Pfeil (P3) in die erste Kammer (5) geleitet, die von der Anionenaustauscher-Membran (AM 2) und der Anionenaustauscher-Membran (AM 1) begrenzt ist. Angetrieben durch das elektrische Feld, wandern die Anionen (Hypophosphit und Orthophosphit) aus der ersten Kammer (5) in die zweite Kammer (6) und bilden dort zusammen mit den Protonen, die zuvor aus der Anodenkammer (1) und der weiteren Kammer (10) elektrodialytisch in die zweite Kammer (6) transportiert wurden, die entsprechenden freien Säuren. Der weitere Verfahrensablauf entspricht dem für Fig. 1 beschriebenen Vefahrensablauf. Die Nickelanode muß hier nach Verbrauch des Nickels ausgewechselt werden.Nickel ions migrate from the anode chamber (1) into the process solution (PL). she compensate for the deficit in nickel ions caused by electroless nickel deposition arose. At the same time, an equivalent amount of protons migrate through the Cation exchanger membrane (KM 3) from the chamber (10) into the second chamber 86). As a result, the one formed during the chemical-reductive nickel deposition Amount of acid removed from the process solution (PL). The one with nickel ions Enriched process solution (PL) is then in accordance with the arrow (P3) in the first chamber (5) passed by the anion exchange membrane (AM 2) and Anion exchange membrane (AM 1) is limited. Powered by the electric Field, the anions (hypophosphite and orthophosphite) migrate from the first chamber (5) into the second chamber (6) and form there together with the protons that were previously from the anode chamber (1) and the further chamber (10) electrodialytically into the second chamber (6) were transported, the corresponding free acids. The other The procedure corresponds to the procedure described for FIG. 1. The Nickel anode must be replaced here after the nickel has been used up.

    Gemäß Fig. 5 kann die anodische Nickelauflösung auch extern erfolgen. Die Nickelionen werden dann der Anodenkammer (1) aufgegeben. Das ist durch den Pfeil (P4) angedeutet. Es kann dann weiter eine beispielsweise aus Stahl oder aus platiniertem Titan-Streckmetall bestehende Anode (2) verwendet werden, so daß kein Anodenwechsel erforderlich ist. Der Aufbau der Elektrodialysezelle (EZ) nach Fig. 5 ist sonst identisch mit dem der Elektrodialysezelle (EZ) nach Fig. 4. Das gilt auch für den Verfahrensablauf. 5 , the anodic nickel dissolution can also take place externally. The nickel ions are then fed into the anode chamber (1). This is indicated by the arrow (P4). An anode (2) made, for example, of steel or of platinized titanium expanded metal can then be used, so that no anode change is required. The structure of the electrodialysis cell (EZ) according to FIG. 5 is otherwise identical to that of the electrodialysis cell (EZ) according to FIG. 4. This also applies to the procedure.

    Zur verbesserten Regelung der Nickelionenkonzentration und des pH-Wertes der Prozeßlösung (PL) kann dieselbe gemäß Fig. 6 der Kammer (10) auch nur in einem Teilstrom (TL) aufgegeben werden. Der aus der Kammer (10) austretende, mit Nickel angereicherte Teilstrom der Prozeßlösung (PL) wird mit der aus der ersten Kammer (5) austretenden, der weiteren Verwendung zuzuführenden Prozeßlösung (PL) vereinigt.To improve the control of the nickel ion concentration and the pH of the process solution (PL), the same can be applied to the chamber (10) in accordance with FIG. 6 in only one partial stream (TL). The nickel-enriched partial stream of the process solution (PL) emerging from the chamber (10) is combined with the process solution (PL) emerging from the first chamber (5) and to be used for further use.

    Claims (11)

    Verfahren zum Regenerieren einer Prozeßlösung, die bei der chemischreduktiven Abscheidung von Metallschichten verwendet wird und Hypophosphit sowie Orthophosphit enthält, bei welchem die Prozeßlösung einer mindestens vier Kammern aufweisenden Elektrodialysezelle aufgegeben wird, die eine verdünnte Säure enthaltende Anodenkammer mit einer darin befindlichen Anode, eine Kathodenkammer mit einer darin befindlichen Kathode sowie zwei weitere, durch eine Anionenaustauscher-Membran voneinander getrennte und zwischen diesen beiden Kammern angeordnete Kammern aufweist, von denen eine erste Kammer durch eine Anionenaustauscher-Membran von der Kathodenkammer getrennt ist, während eine zweite Kammer durch eine Kationenaustauschermembran von der Anodenkammer getrennt ist, bei welchem die Prozeßlösung bei Durchführung des Verfahrens der ersten Kammer aufgegeben wird, wodurch die in ihr enthaltenen Hypophosphit-Ionen und Orthophosphit-Ionen elektrodialytisch in die zweite Kammer und gleichzeitig Hypophosphit-Ionen aus der Kathodenkammer in die Prozeßlösung transportiert werden, und bei welchem regenerierte Prozeßlösung entnommen und einer weiteren Verwendung zugeführt wird, dadurch gekennzeichnet, dass das in der zweiten Kammer (6) durch Zutritt von Protonen aus der Anodenkammer (1) gebildete Säuregemisch einem in der Hypophosphit-Beladung befindlichen, schwachbasischen Anionenaustauscher (T 1) zugeführt wird, der mit seinem Auslaß an die Kathodenkammer (3) angeschlossen ist.Process for regenerating a process solution which is used in the chemically reductive deposition of metal layers and contains hypophosphite and orthophosphite, in which the process solution is applied to an electrodialysis cell having at least four chambers, which contains a dilute acid-containing anode chamber with an anode therein, a cathode chamber with a has cathode therein and two further chambers separated from one another by an anion exchange membrane and arranged between these two chambers, of which a first chamber is separated from the cathode chamber by an anion exchange membrane, while a second chamber is separated from the anode chamber by a cation exchange membrane is, in which the process solution is given to the first chamber when the method is carried out, as a result of which the hypophosphite ions and orthophosphite ions contained therein are electrodialytically introduced into the second chamber and the like Hypophosphite ions are transported from the cathode chamber into the process solution at an early stage, and in which regenerated process solution is removed and used for further use, characterized in that the acid mixture formed in the second chamber (6) by the entry of protons from the anode chamber (1) a weakly basic anion exchanger (T 1) which is located in the hypophosphite load and which is connected with its outlet to the cathode chamber (3). Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß ein Teil der aus dem schwachbasischen Anionenaustauscher (T 1) austretenden Lösung über einen schwachsauren Kationenaustauscher (T 2) in die erste Kammer (5) der Elektrodialysezelle (EZ) geleitet wird, der mit Ionen des Beschichtungsmetalls vorbeladen ist. A method according to claim 1, characterized in that a part of the from the weakly basic anion exchanger (T 1) emerging solution over a weakly acidic cation exchanger (T 2) in the first chamber (5) Electrodialysis cell (EZ) is conducted with ions of the coating metal is preloaded. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß durch eine Verbindung (P 1) der Kathodenkammer (3) mit der zweiten Kammer (6) ein Regenerierkreislauf gebildet wird.A method according to claim 1 or 2, characterized in that by a Connection (P 1) of the cathode chamber (3) with the second chamber (6) Regeneration cycle is formed. Verfahren nach einem der Anspprüche 1 bis 3, dadurch gekennzeichnet, daß Beschichtungsmetall zu dessen Nachdosierung der ersten Kammer (5) aufgegeben wird.Method according to one of claims 1 to 3, characterized in that Coating metal for replenishing the first chamber (5) is abandoned. Verfahren nach einem der Ansprüch 1 bis 4, dadurch gekennzeichnet, daß zwischen Anodenkammer (1) und zweiter Kammer (6) eine weitere, von der zweiten Kammer (6) durch eine Kationenaustauscher-Membran (KM 3) getrennte Kammer (10) angeordnet wird, in welche aus der Anodenkammer (1) austretende Ionen des Beschichtungsmetalls eingeleitet werden.Method according to one of claims 1 to 4, characterized in that between the anode chamber (1) and the second chamber (6) another, of the second chamber (6) through a cation exchange membrane (KM 3) separate chamber (10) is arranged, into which from the anode chamber (1) escaping ions of the coating metal are introduced. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Prozeßlösung (PL) der weiteren Kammer (10) aufgegeben und von dort der ersten Kammer (5) zugeleitet wird.A method according to claim 5, characterized in that the process solution (PL) the further chamber (10) and from there the first chamber (5) is forwarded. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß ein Teilstrom (TL) der Prozeßlösung (PL) durch die weitere Kammer (10) geleitet wird.A method according to claim 5, characterized in that a partial stream (TL) of Process solution (PL) is passed through the further chamber (10). Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß eine unlösliche Anode (2) eingesetzt wird, die vorzugsweise aus Stahl oder platiniertem Titan-Streckmetall besteht.Method according to one of claims 1 to 7, characterized in that a insoluble anode (2) is used, which is preferably made of steel or platinized titanium expanded metal. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Anodenkammer (2) Ionen des Beschichtungsmetalls zugeführt werden.Method according to one of claims 1 to 8, characterized in that the Anode chamber (2) ions of the coating metal are supplied. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß eine lösliche, aus dem Beschichtungsmetall bestehende Anode (2) verwendet wird. Method according to one of claims 1 to 7, characterized in that a soluble anode (2) consisting of the coating metal is used. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß eine Elektrodialysezelle (EZ) mit einer Mehrfachanordnung der Kammern eingesetzt wird.Method according to one of claims 1 to 10, characterized in that a Electrodialysis cell (EZ) used with a multiple arrangement of the chambers becomes.
    EP99120998A 1998-11-06 1999-11-04 Process for regenerating a processing solution Expired - Lifetime EP1006213B1 (en)

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    US5419821A (en) * 1993-06-04 1995-05-30 Vaughan; Daniel J. Process and equipment for reforming and maintaining electroless metal baths

    Cited By (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2011128376A1 (en) 2010-04-16 2011-10-20 Atotech Deutschland Gmbh Membrane electrolysis stack, electrodialysis device including the stack and method for the regeneration of an electroless plating bath
    DE102010015361A1 (en) 2010-04-16 2011-10-20 Atotech Deutschland Gmbh Membrane electrolysis stack, this containing electrodialysis device and method for regenerating a stromloslos working bath for metal deposition
    US9669361B2 (en) 2010-04-16 2017-06-06 Atotech Deutschland Gmbh Membrane electrolysis stack, electrodialysis device including the stack and method for the regeneration of an electroless plating bath

    Also Published As

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    ATE284980T1 (en) 2005-01-15
    EP1006213A3 (en) 2000-08-09
    EP1006213B1 (en) 2004-12-15
    DE19851180C1 (en) 2000-04-20
    DE59911270D1 (en) 2005-01-20

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