EP1006213B1 - Procédé de régeneration d'une solution de traitement - Google Patents

Procédé de régeneration d'une solution de traitement Download PDF

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Publication number
EP1006213B1
EP1006213B1 EP99120998A EP99120998A EP1006213B1 EP 1006213 B1 EP1006213 B1 EP 1006213B1 EP 99120998 A EP99120998 A EP 99120998A EP 99120998 A EP99120998 A EP 99120998A EP 1006213 B1 EP1006213 B1 EP 1006213B1
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EP
European Patent Office
Prior art keywords
chamber
solution
anode
hypophosphite
separated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99120998A
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German (de)
English (en)
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EP1006213A2 (fr
EP1006213A3 (fr
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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Individual
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Publication of EP1006213A3 publication Critical patent/EP1006213A3/fr
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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.
  • As the chemical-reductive nickel deposition is a common in practice The procedure used is based on the following explanations - 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 orthophosphite destabilizes the process solution.
  • the process solution can therefore be used from a certain orthophosphite concentration (Interference limit concentration) no longer for electroless nickel plating be used.
  • the process solution that can no longer be used 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 - be replenished. Nevertheless, the process solutions are based on the Regeneration can only be used to a limited extent.
  • 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.
  • Used chemicals nickel ions and reducing agents
  • phosphinic acid addition to the Catholytes
  • the sulfate by adding barium hydroxide in the catholyte should be removed as barium sulfate.
  • the invention is based on the object, the method described above to further develop that the disruptive orthophosphite from the Process solution can be removed, so that a longer service life of the same is achievable.
  • Electrodialysis will Orthophosphite transferred into a mineral acid solution, from which it is 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 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.
  • 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 fed 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 exchanger 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.
  • 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 (delivery 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 compared 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) into the electrodialytic 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) according to FIG. 6 only in a partial stream (TL).
  • the nickel-enriched partial flow 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)

Claims (11)

  1. Procédé de régénération d'une solution de traitement qui est utilisée pour le dépôt de couches de métal par réduction chimique et contient de l'hypophosphite ainsi que de l'orthophosphite, dans lequel la solution de traitement est chargée dans une cellule d'électrodialyse présentant au moins quatre chambres, laquelle cellule présente une chambre anodique contenant un acide dilué et dans laquelle se trouve une anode, une chambre cathodique dans laquelle se trouve une cathode, ainsi que deux autres chambres, séparées l'une de l'autre par une membrane échangeuse d'anions et disposées entre ces deux chambres, dont une première chambre est séparée de la chambre cathodique par une membrane échangeuse d'anions tandis qu'une deuxième chambre est séparée de la chambre anodique par une membrane échangeuse de cations, procédé dans lequel la solution de traitement est chargée dans la première chambre lors de la réalisation du procédé, moyennant quoi les ions hypophosphites et orthophosphites qu'elle contient sont transportés par électrodialyse dans la deuxième chambre et en même temps les ions hypophosphites transportés de la chambre cathodique dans la solution de traitement, et dans lequel on prélève de la solution de traitement régénérée et on l'amène à une autre utilisation, caractérisé par le fait que le mélange acide formé dans la deuxième chambre (6) par arrivée de protons provenant de la chambre anodique (1) est amené à un échangeur d'anions faiblement basique (T 1) se trouvant dans la charge d'hypophosphite et dont la sortie est reliée à la chambre cathodique (3).
  2. Procédé selon la revendication 1, caractérisé par le fait qu'une partie de la solution sortant de l'échangeur d'anions faiblement basique (T 1) est conduite dans la première chambre (5) de la cellule d'électrodialyse (EZ) par un échangeur de cations faiblement acide (T 2) qui est préchargé avec des ions du métal de revêtement.
  3. Procédé selon la revendication 1 ou 2, caractérisé par le fait qu'un circuit de régénération est formé par une liaison (P 1) de la chambre cathodique (3) avec la deuxième chambre (6).
  4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que l'on charge du métal de revêtement dans la première chambre (5) pour son dosage ultérieur.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que l'on dispose entre la chambre anodique (1) et la deuxième chambre (6) une autre chambre (10) séparée de la deuxième chambre (6) par une membrane échangeuse de cations (KM 3), dans laquelle on introduit les ions du métal de revêtement sortant de la chambre anodique (1).
  6. Procédé selon la revendication 5, caractérisé par le fait que la solution de traitement (PL) est chargée dans la chambre supplémentaire (10) et amenée de là à la première chambre (5).
  7. Procédé selon la revendication 5, caractérisé par le fait qu'un courant partiel (TL) de la solution de traitement (PL) est conduit à travers la chambre supplémentaire (10).
  8. Procédé selon l'une des revendications 1 à 7, caractérisé par le fait que l'on utilise une anode insoluble (2) qui est de préférence en acier ou en titane déployé platiné.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé par le fait que l'on amène des ions du métal de revêtement à la chambre anodique (2).
  10. Procédé selon l'une des revendications 1 à 7, caractérisé par le fait que l'on utilise une anode soluble (2) constituée du métal de revêtement.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé par le fait que l'on utilise une cellule d'électrodialyse (EZ) avec une disposition multiple des chambres.
EP99120998A 1998-11-06 1999-11-04 Procédé de régeneration d'une solution de traitement Expired - Lifetime EP1006213B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19851180A DE19851180C1 (de) 1998-11-06 1998-11-06 Verfahren zum Regenerieren einer Prozeßlösung
DE19851180 1998-11-06

Publications (3)

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EP1006213A2 EP1006213A2 (fr) 2000-06-07
EP1006213A3 EP1006213A3 (fr) 2000-08-09
EP1006213B1 true EP1006213B1 (fr) 2004-12-15

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EP (1) EP1006213B1 (fr)
AT (1) ATE284980T1 (fr)
DE (2) DE19851180C1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10240350B4 (de) * 2002-08-28 2005-05-12 Atotech Deutschland Gmbh Vorrichtung und Verfahren zum Regenerieren eines stromlosen Metallabscheidebades
DE10322120A1 (de) * 2003-05-12 2004-12-09 Blasberg Werra Chemie Gmbh Verfahren und Vorrichtungen zur Verlängerung der Nutzungsdauer einer Prozesslösung für die chemisch-reduktive Metallbeschichtung
DE102004038693B4 (de) * 2004-08-10 2010-02-25 Blasberg Werra Chemie Gmbh Vorrichtung und Verfahren zur Entfernung von Fremdstoffen aus Prozesslösungen und Verfahren zur Regenerierung eines Kationenaustauschers
DE502005003655D1 (de) 2005-05-25 2008-05-21 Enthone Verfahren und Vorrichtung zur Einstellung der Ionenkonzentration in Elektrolyten
DE102010015361A1 (de) 2010-04-16 2011-10-20 Atotech Deutschland Gmbh Membranelektrolysestapel, diesen enthaltende Elektrodialyseeinrichtung sowie Verfahren zum Regenerieren eines außenstromlos arbeitenden Bades zur Metallabscheidung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2726969A (en) * 1953-12-03 1955-12-13 Gen Motors Corp Chemical reduction plating process
DE4310366C1 (de) * 1993-03-30 1994-10-13 Fraunhofer Ges Forschung Verfahren zum Regenerieren von wässrigen, außenstromlos arbeitenden Beschichtungsbädern
US5419821A (en) * 1993-06-04 1995-05-30 Vaughan; Daniel J. Process and equipment for reforming and maintaining electroless metal baths

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Publication number Publication date
EP1006213A2 (fr) 2000-06-07
ATE284980T1 (de) 2005-01-15
DE59911270D1 (de) 2005-01-20
EP1006213A3 (fr) 2000-08-09
DE19851180C1 (de) 2000-04-20

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