EP3274489B1 - Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc electrolytes and zinc alloy electrolytes for the purpose of deposition of metal in electroplating systems - Google Patents

Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc electrolytes and zinc alloy electrolytes for the purpose of deposition of metal in electroplating systems Download PDF

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EP3274489B1
EP3274489B1 EP16711218.4A EP16711218A EP3274489B1 EP 3274489 B1 EP3274489 B1 EP 3274489B1 EP 16711218 A EP16711218 A EP 16711218A EP 3274489 B1 EP3274489 B1 EP 3274489B1
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Prior art keywords
anolyte
anode
exchange membrane
chamber
zinc
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German (de)
French (fr)
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EP3274489A2 (en
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Hartmut Trenkner
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Coventya International GmbH
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Coventya International GmbH
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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
    • C25D21/22—Regeneration of process solutions by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • 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
    • 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
    • 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 an anode in the electroplating application for use in strongly alkaline, galvanic electrolytes based on sodium hydroxide for the deposition of zinc and zinc alloys on substrates of steel and zinc die-casting.
  • the state of the art is to use most often insoluble anodes of steel, stainless steel or nickel-plated steel in alkaline galvanizing electrolytes.
  • Different geometric shapes are selected, eg plates in rectangular shape, expanded metal in rectangular or cylindrical shape, Round rods, pipes and others.
  • the zinc-nickel electrolyte is separated from the anode by a perfluorinated cation exchange membrane. Diluted sulfuric acid is used as the anolyte, and platinum-plated titanium as the anode material.
  • a sodium hydroxide solution is used, which offers the advantage that no hydrogen ions (protons) from the anolyte on the cation exchange membrane in the zinc-nickel electrolyte described and can dilute this by reaction with hydroxide ions to water or in the presence of Cyanide ions in the zinc-nickel electrolyte can react when passing through the membrane to dangerous hydrogen cyanide.
  • the US 2005/189231 A1 relates to baths, processes and systems for galvanizing zinc-nickel ternary and higher alloys, the system having a partition wall for forming a cathode chamber and an anode chamber, the plating bath being located only in the cathode chamber.
  • the DE 690 13 825 T2 discloses a process for the continuous removal and recovery of ethylenediaminetetraacetic acid (EDTA) from the process water of electroless copper plating and apparatuses for carrying out this process.
  • EDTA ethylenediaminetetraacetic acid
  • the DE 40 16 000 A1 discloses an apparatus for the treatment of particular metal-containing liquids by ion exchange and simultaneous or periodic regeneration of the ion exchange resin by electrodialysis.
  • the US 5,162,079 A discloses a method and apparatus for plating metals in which the metal salt concentration within the plating bath is reduced by providing an insoluble anode assembly in the bath.
  • the invention is based on extensive laboratory investigations, the results of which form the basis for the description of the structural design and the function of the two-chamber electrodialysis cell.
  • a galvanic plant with a two-chamber electrodialysis cell as anode in an alkaline zinc and zinc alloy electrolyte characterized in that the two-chamber electrodialysis cell contains an anode which is separated from an alkaline zinc or zinc alloy electrolyte by a cation and an anion exchange membrane in which the cation exchange membrane and the anion exchange membrane form two separate anolyte chambers, wherein an inner anolyte chamber in which the anode is located is permeable by a first anolyte and an outer anolyte chamber has openings with inflow and outflow means for filling with a second anolyte or overflowing one having second anolyte .
  • the invention further relates to the use of a two-chamber electrodialysis cell with anion and cation exchange membrane as an anode in an alkaline zinc and zinc alloy electrolyte of a galvanic plant for the purpose of metal deposition, characterized in that the two-chamber electrodialysis cell contains an anode, which by the cation and an anion exchange membrane is separated from the alkaline zinc or zinc alloy electrolyte, wherein the cation exchange membrane and anion exchange membrane form two separate anolyte chambers, wherein an inner anolyte chamber, in which the anode is located, is permeable by a first anolyte and an outer anolyte chamber openings with inflow and outflow means for filling with a second anolyte or overflow of a second anolyte .
  • the function of the two-compartment electrodialysis cell prevents an increase in the sodium hydroxide concentration and the volume of the zinc-nickel electrolyte.
  • the inner chamber with the anode (7) is separated from the outer chamber by a cation exchange membrane (4). This in turn is separated from the zinc-nickel electrolyte by an anion exchange membrane (3).
  • the inner anolyte chamber is connected via fittings (1), (2) with an anolyte circuit.
  • the anodic reaction reduces the sodium hydroxide concentration in the anolyte circulatory system.
  • the sodium hydroxide concentration in the outer chamber increases due to the "ion inflow" of Na + anolyte and OH - zinc-nickel to values greater than 300 g / l. Osmosis deprives the zinc-nickel electrolyte of water via the anion exchange membrane.
  • the sodium hydroxide volume in the outer chamber increases and can be returned via the fitting (10) with hose (11) in the anolyte circuit or zinc-nickel electrolyte.
  • concentrations and volumes of anolyte and zinc-nickel electrolyte can thus be kept stable.
  • the two-chamber electrodialysis cell is preferably suitable for use in strongly alkaline, galvanic zinc-nickel electrolytes, which are based on sodium hydroxide and amine-containing additives, since the efficiency of the deposition process is particularly strongly influenced positively.
  • the cathodic current efficiency remains at a high level. Process reliability is increased. Additional disposal costs are eliminated. Process chemicals are saved.
  • two ion exchange membranes become a solid electrodialysis module, as in US Pat FIGS. 1 and 2 shown, joined together so that two anolyte chambers (5) and (6) arise.
  • the anode can be made of a stainless steel tube (7) whose diameter and length can be different depending on the application and which is tapered on one side and a circular stainless steel board (14) which is firmly connected to the anode tube (eg welded) constructed his.
  • a common pipe diameter for the application would be eg 2 inches.
  • Two holes of different diameter in the board are used for screwing or welding the inlet and outlet fittings (1), (2) for the Anolyte sodium hydroxide solution (concentration about 160 g / l), hereinafter referred to as "Anolyte 1".
  • the inlet and outlet fittings may be hose nozzles of different diameter, wherein the smaller diameter is to be used for the inlet, in order to generate any additional hydrostatic pressure inside the electrodialysis cell as it flows through the anolyte 1.
  • the suspension device (18) Further firmly connected to the board is the suspension device (18) at the same time the power transmission from the anode rail to the electrodialysis cell is used.
  • the plastic body consists of a plastic foot cap, e.g. PVC (16) into which a plastic lattice tube, e.g. Polypropylene of defined length, e.g. 700 mm and defined diameter, e.g. 80 mm and cation exchange membrane (4) lying thereon and a second lattice tube piece of defined length, e.g. 640 mm and diameter, e.g. 100 mm with the anionic membrane lying on it (3) is hermetically sealed together, e.g. Pouring in synthetic resin.
  • the upper part of the two-chamber cylinder is also hermetically sealed in a plastic collar (17), so that both chambers have no connection to each other.
  • the tubular plastic collar (17) has an external thread at the top, e.g.
  • the anode (7) is inserted into the plastic body, below the board is a flat sealing ring (15) with a screw cap (8) made of plastic, which has an opening at the top, which is smaller than 10 mm in diameter the diameter of the board (14) and an internal thread, eg 2 1 ⁇ 2 ", has, the anode is screwed to the plastic body.
  • the passage to the outer Anolytehunt have. These are used to screw in two fittings (9), (10), eg angled threaded fittings with hose nozzles.
  • the outer anolyte chamber (5) is filled with sodium hydroxide solution (concentration eg 160 g / l), referred to in the following description as "Anolyte 2", via one of these two fittings, while venting takes place via the other fitting.
  • one of the two grommets is provided with a cap (12) to prevent later penetration of zinc / zinc alloy electrolyte into the anolyte 2 during the production process.
  • the drain fitting (10) for the overflowing Anolyte 2 in the working state the electrodialysis cell is for the same reason with a hose (11) or pipe bend (13) made of plastic with the opening facing down, provided.
  • the sodium hydroxide concentration continuously increases and osmosis sets in, counteracting the increase in the concentration gradient between the outer anolyte chamber and the zinc / zinc alloy electrolyte.
  • Water is withdrawn from the zinc / zinc alloy electrolyte via the anion exchange membrane (3) and reaches the outer anolyte chamber (5).
  • the volume of the anolyte 2 in the outer anolyte chamber thereby increases continuously.
  • the volume overhang is removed from the electrodialysis cell via the drainage device (10).
  • the overflowing amount of sodium hydroxide solution (Anolyt 2) should be recycled to 50% each in the zinc / zinc alloy electrolyte and the anolyte 1 to keep the concentration and volume ratios of zinc / zinc alloy electrolyte and anolyte 1 approximately constant, as the Charge carrier sodium ions and hydroxide ions in an equivalent amount of the anolyte 1 and the zinc / zinc alloy electrolyte in the Anolyte 2 chamber (5) have passed.
  • Fig. 4 The supply of required for the electrochemical oxidation at the anode anolyte 1 with a recommended concentration of about 160 g / l of sodium hydroxide is carried out as in Fig. 4 represented in the circulation system by means of a circulation pump (22) from a reservoir (23) via shut-off valves (20) and flow meter (21) for each individual electrodialysis cell.
  • FIG. 2 For better understanding with arrows, the anolyte flux of Anolyt 1 through the electrodialysis cell is shown.
  • the derivation of the excess volume of Anolyt 2 in the zinc / zinc alloy electrolyte is very easy by free overflow through the fitting with spout (10) and pipe bend (13), see Fig. 2 , half of the number of electrodialysis cells in the galvanic plant.
  • the dissipation of the overflowing Anolyte 2 - volume in the Anolyte 1 - reservoir is done by the other half of the number of located in the galvanic electrodialysis cells on the fitting with nozzle (10) a plastic tube (11) is plugged into a central return line to the Anolyte 1 tank opens, see Fig. 4 , (19).
  • the concentration of sodium hydroxide of the anolyte 1 should always be about 30 g / l greater than the sodium hydroxide concentration of the zinc / zinc alloy electrolyte. However, it must be smaller than the sodium hydroxide concentration of the Anolyte 2. Only then is it ensured that the osmosis water mainly from the zinc / zinc alloy electrolyte into the Anolyt 2 - chamber of the electrodialysis cell is "pushed" by osmotic pressure over the Anionenauleyermembran.
  • the starting concentrations of sodium hydroxide of Anolyte 1 and 2 may be equal before commissioning the electrodialysis cells, as shown in the list of reference in (5), (6), as the concentration of anolyte 2 increases after application of the electroplating current with operating time and the concentration of Anolyte 1 drops.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Description

Die Erfindung betrifft eine Anode in der galvanotechnischen Anwendung für den Einsatz in stark alkalischen, galvanischen Elektrolyten auf der Basis von Natriumhydroxid zum Abscheiden von Zink und Zinklegierungen auf Substraten von Stahl und Zink-Druckguss.The invention relates to an anode in the electroplating application for use in strongly alkaline, galvanic electrolytes based on sodium hydroxide for the deposition of zinc and zinc alloys on substrates of steel and zinc die-casting.

Stand der Technik ist, in alkalischen Verzinkungselektrolyten am häufigsten unlösliche Anoden aus Stahl, Edelstahl oder vernickeltem Stahl einzusetzen. Dabei werden verschiedene geometrische Formen gewählt, z.B. Platten in rechteckiger Form, Streckmetall in Rechteckform oder zylindrischer Form, Rundstäbe, Rohre und andere.The state of the art is to use most often insoluble anodes of steel, stainless steel or nickel-plated steel in alkaline galvanizing electrolytes. Different geometric shapes are selected, eg plates in rectangular shape, expanded metal in rectangular or cylindrical shape, Round rods, pipes and others.

Stark alkalische galvanische Verzinkungselektrolyte neigen je nach Elektrolytzusammensetzung nach relativ kurzer Betriebszeit von einigen Wochen zu teilweise starken Ablagerungen auf den Anodenoberflächen. Das hat den Nachteil der allmählichen Verschlechterung der kathodischen Stromausbeute und somit der Effizienz des galvanischen Prozesses sowie der galvanischen Anlage. Die Kosten an Elektroenergie pro Quadratmeter beschichteter Oberfläche steigen sukzessive an.Depending on the electrolyte composition, strongly alkaline galvanic galvanizing electrolytes tend to deposit strongly on the anode surfaces after a relatively short operating time of a few weeks. This has the disadvantage of the gradual deterioration of the cathodic current efficiency and thus the efficiency of the galvanic process and the galvanic plant. The cost of electrical energy per square meter of coated surface increases successively.

Diese Ablagerungen bestehen bei Natriumhydroxid basierten Elektrolyten zu großen Anteilen aus Natriumkarbonat und Natiumoxalat infolge von Oxydation an der Anodenoberfläche. Zusätzlich verändern organische Abbauprodukte die Ausgangseigenschaften der galvanischen Elektrolyte. Ein regelmäßiger, teilweise hoher Reinigungsaufwand ist notwendig. Der Karbonatgehalt solcher Elektrolyte muss oft mit Kristallisatoren unter zusätzlichem Elektroenergieverbrauch gesenkt werden. Alternativ werden die galvanischen Bäder neu angesetzt oder regelmäßig verdünnt. Die verbrauchten Elektrolyte werden entsorgt und erzeugen zusätzliche Chemikalien -, Entsorgungs-und Abwasserbehandlungskosten sowie Anlagenausfallzeiten.These deposits are large proportions of sodium carbonate and sodium oxalate due to oxidation at the anode surface in sodium hydroxide based electrolytes. In addition, organic degradation products alter the initial properties of the galvanic electrolytes. A regular, sometimes high cleaning effort is necessary. The carbonate content of such electrolytes often has to be lowered with crystallizers with additional electric energy consumption. Alternatively, the galvanic baths are recalculated or regularly diluted. The spent electrolytes are disposed of and generate additional chemicals, disposal and wastewater treatment costs, and equipment downtime.

In der EP 1 344 850 A1 wird beschrieben, wie diese genannten Nachteile bei der Zink-Nickel-Legierungsbeschichtung beseitigt oder verringert werden können. Der Zink-Nickel - Elektrolyt wird hierbei durch eine perfluorierte Kationenaustauscher-membran von der Anode getrennt. Als Anolyt wird verdünnte Schwefelsäure verwendet, als Anodenmaterial platiniertes Titan.In the EP 1 344 850 A1 It is described how these mentioned disadvantages in the zinc-nickel alloy coating can be eliminated or reduced. The zinc-nickel electrolyte is separated from the anode by a perfluorinated cation exchange membrane. Diluted sulfuric acid is used as the anolyte, and platinum-plated titanium as the anode material.

Die Bauformen solcher Membrananoden, die in den galvanischen Bädern zum Einsatz kommen, sind meist Kästen, wobei die Seite, die zur Galvanisierware zeigt, von der Kationenaustauschermembran gebildet wird. Als Anode findet meist platiniertes Streckmetall Anwendung.The designs of such membrane anodes used in the galvanic baths are mostly boxes, with the side facing the electroplating product being formed by the cation exchange membrane. As anode finds mostly platinized expanded metal application.

Als Nachteile der großtechnischen Anwendung des Patentes EP 1 344 850 A1 können genannt werden:

  1. a) Verdünnung des Zink-Nickel-Elektrolyten während des galvanischen Prozesses infolge Neutralisation des Natriumhydroxides durch positiv geladene Wasserstoff - Ionen (Protonen) des Schwefelsäure - Anolyten, die über die Kationenaustauscher-Membran "transportiert" werden und mit negativ geladenen Hydroxidionen zu Wasser reagieren:

            H+ Anolyt + OH- Katholyt → H2OKatholyt

    Dieser Prozess läuft in einer Richtung ab und führt zu der erwähnten permanenten, langsamen Verdünnung des Zink-Nickel-Elektrolyten.
  2. b) Volumenanstieg des Zink-Nickel-Elektrolyten:
    Die im Punkt a) beschriebene Verdünnung und die daraus resultierende notwendige Zugabe von Natriumhydroxid zur Wiederherstellung der für die Legierungsabscheidung erforderlichen Natriumhydroxid - Konzentration im Zink-Nickel-Elektrolyten trägt zum Volumenanstieg des Elektroyten bei, wenn die lonenaktivität des Zink-Nickel-Elektrolyten größer ist als die des Schwefelsäure-Anolyten. Dann steigt der osmotische Druck und es wird zusätzlich Wasser über die Kationenaustauschermembran in den Zink-Nickel-Elektrolyten gedrückt. Die Folge ist zusätzliche Verdünnung und Volumenanstieg des Zink-Nickel-Elektrolyten.
  3. c) Aus a) und b) folgend wird ein zusätzlicher, erheblicher technischer und energetischer Aufwand betrieben, um den permanent entstehenden, schwach verdünnten Elektrolyt-Volumenzuwachs mittels Vakuumverdampfer einzuengen und diskontinuierlich wieder in den Zink-Nickel-Elektrolyten zurückzuführen.
As disadvantages of the large-scale application of the patent EP 1 344 850 A1 can be named:
  1. a) Dilution of the zinc-nickel electrolyte during the galvanic process due to neutralization of the sodium hydroxide by positively charged hydrogen ions (protons) of the sulfuric acid anolyte, which are "transported" through the cation exchange membrane and react with negatively charged hydroxide ions to form water:

    H + anolyte + OH - catholyte → H 2 O catholyte

    This process is unidirectional and leads to the mentioned slow dilution of the zinc-nickel electrolyte.
  2. b) Volume increase of the zinc-nickel electrolyte:
    The dilution described in point a) and the consequent necessary addition of sodium hydroxide to restore the sodium hydroxide concentration in the zinc-nickel electrolyte required for the alloy deposition contributes to the volume increase of the electrolyte when the ion activity of the zinc-nickel electrolyte is greater than that of sulfuric acid anolyte. Then the osmotic pressure increases and water is additionally forced into the zinc-nickel electrolyte via the cation exchange membrane. The result is additional dilution and volume increase of the zinc-nickel electrolyte.
  3. c) From a) and b) following, an additional, considerable technical and energetic effort is operated to narrow the permanently arising, weakly diluted electrolyte volume increase by means of a vacuum evaporator and discontinuously returned to the zinc-nickel electrolyte.

In der WO 2001/096631 A1 und WO 2004/108995 A1 wird anstelle von Schwefelsäure als Anolyt eine Natriumhydroxidlösung angewendet, die den Vorteil bietet, dass keine Wasserstoffionen (Protonen) aus dem Anolyt über die Kationenaustauschermembran in den beschriebenen Zink-Nickel-Elektrolyt gelangen und diesen durch Umsetzung mit Hydroxidionen zu Wasser verdünnen können oder bei Vorhandensein von Cyanid-Ionen im Zink-Nickel-Elektrolyten beim Durchtritt durch die Membran zu gefährlichem Cyanwasserstoff reagieren können.In the WO 2001/096631 A1 and WO 2004/108995 A1 Instead of sulfuric acid as anolyte, a sodium hydroxide solution is used, which offers the advantage that no hydrogen ions (protons) from the anolyte on the cation exchange membrane in the zinc-nickel electrolyte described and can dilute this by reaction with hydroxide ions to water or in the presence of Cyanide ions in the zinc-nickel electrolyte can react when passing through the membrane to dangerous hydrogen cyanide.

Als Nachteil der Verwendung von Natriumhydroxidlösung als Anolyt muss allerdings die kontinuierlich steigende Konzentration von Natriumhydroxid und die permanente Volumenvergrößerung des Zink-Nickel-Elektrolyten angesehen werden, da Natrium-Ionen als positive Ladungsträger aus dem Anolyten über die Kationenaustauschermembran zur Kathode wandern und mit den "frei" werdenden Hydroxid-Ionen der Wasserspaltung als Co-Reaktion der Metallabscheidung an der Kathode die Natriumhydroxidkonzentration erhöhen:

        Na+ Anolyt + OH- Katholyt → NaOH

However, the disadvantage of the use of sodium hydroxide solution as the anolyte is the continuously increasing concentration of sodium hydroxide and the permanent increase in volume of the zinc-nickel electrolyte, since sodium ions migrate as positive charge carriers from the anolyte over the cation exchange membrane to the cathode and with the "free "As the co-reaction of the metal deposition at the cathode, hydroxide ions of the water splitting increase the sodium hydroxide concentration:

Na + anolyte + OH - catholyte → NaOH

Dieser Effekt führt zu wachsenden Konzentrationsunterschieden zwischen Anolyt und Zink-Nickel-Elektrolyt in dem Sinne, dass die Anolytkonzentration sinkt und die Zink-Nickel-Elektrolyt-Konzentration steigt. In der Folge setzt Osmose über die Kationenaustauschermembran vom Anolyt in den Katholyt ein, wodurch dem Anolyt Wasser entzogen und dem Zink-Nickel-Elektrolyt zugeführt wird. Dieser Fakt führt nunmehr zu der erwähnten kontinuierlichen Vergrößerung des Zink-Nickel-Elektrolytvolumens und des Sinkens des Anolytvolumens. In der großtechnischen Anwendung bedeutet das, Maßnahmen zur Entsorgung des Zink-Nickel-Elektrolyt-Volumenüberhanges zu treffen sowie in bestimmten Zeitabständen Verdünnungen des Zink-Nickel-Elektrolyten vorzunehmen, was sich negativ auf die Verfahrenskosten auswirkt.This effect leads to increasing concentration differences between anolyte and zinc-nickel electrolyte in the sense that the anolyte concentration decreases and the zinc-nickel electrolyte concentration increases. As a result, osmosis enters the catholyte via the cation exchange membrane from the anolyte, whereby water is removed from the anolyte and supplied to the zinc-nickel electrolyte. This fact now leads to the mentioned continuous increase in the zinc-nickel electrolyte volume and the sinking of the anolyte volume. In large-scale application, this means taking measures to dispose of the zinc-nickel-electrolyte volume overhang and at certain intervals dilutions of the zinc-nickel electrolyte which has a negative effect on the costs of the procedure.

Die US 2005/189231 A1 betrifft Bäder, Verfahren und Systeme zur Galvanisierung von Zink-Nickel ternären und höheren Legierungen, wobei das System eine Trennwand zur Ausbildung einer Kathodenkammer und einer Anodenkammer aufweisen kann, wobei das Galvanisierungsbad nur in der Kathodenkammer lokalisiert ist. Die DE 690 13 825 T2 offenbart ein Verfahren zur kontinuierlichen Entfernung und Rückgewinnung von EthylendiaminTetraessigsäure (EDTA) aus dem Prozesswasser der stromlosen Kupferplattierung und Vorrichtungen zur Ausführung dieses Verfahrens. Die DE 40 16 000 A1 offenbart eine Vorrichtung zur Aufbereitung von insbesondere metallhaltigen Flüssigkeiten durch lonenaustausch und gleichzeitige oder periodische Regenerierung des Ionenaustauscherharzes durch Elektrodialyse. Die US 5 162 079 A offenbart ein Verfahren und eine Vorrichtung zum Galvanisieren von Metallen, bei denen die Metallsalzkonzentration innerhalb des Galvanisierbades durch Vorsehen einer unlöslichen Anodenanordnung im Bad verringert wird.The US 2005/189231 A1 relates to baths, processes and systems for galvanizing zinc-nickel ternary and higher alloys, the system having a partition wall for forming a cathode chamber and an anode chamber, the plating bath being located only in the cathode chamber. The DE 690 13 825 T2 discloses a process for the continuous removal and recovery of ethylenediaminetetraacetic acid (EDTA) from the process water of electroless copper plating and apparatuses for carrying out this process. The DE 40 16 000 A1 discloses an apparatus for the treatment of particular metal-containing liquids by ion exchange and simultaneous or periodic regeneration of the ion exchange resin by electrodialysis. The US 5,162,079 A discloses a method and apparatus for plating metals in which the metal salt concentration within the plating bath is reduced by providing an insoluble anode assembly in the bath.

Ausgehend von den beschriebenen Nachteilen der Anwendung von Membrananoden mit Kationenaustauschermembranen in galvanischen Elektrolyten liegt dem Anspruch 1 der angegebenen Erfindung das Problem zugrunde, eine Elektrodialysezelle zu schaffen und zur industriellen Anwendung in galvanischen Zink-und Zinklegierungsanlagen zur Verfügung zu stellen, die die im vorhergehenden Text erläuterten Nachteile

  • Konzentrationsanstieg von Natriumhydroxid im Zink-oder Zinklegierungselektrolyt
  • Volumenanstieg des Zink-oder Zinklegierungselektrolyten
  • Salzablagerungen an der Anodenoberfläche oder der lonenaustauschermembran
  • Volumenverlust von Anolyt durch Osmose
in der Prozessführung nicht mehr aufweist und deren Herstellungskosten sich im Rahmen von Elektrodialysezellen mit Kationenaustauschermembranen entsprechend dem Stand der Technik bewegen.Based on the described disadvantages of the use of membrane anodes with cation exchange membranes in galvanic electrolytes is the claim 1 of the invention indicated the problem to provide an electrodialysis cell and to provide for industrial application in galvanic zinc and zinc alloy facilities, which explained in the preceding text disadvantage
  • Increasing the concentration of sodium hydroxide in the zinc or zinc alloy electrolyte
  • Volume increase of zinc or zinc alloy electrolyte
  • Salt deposits on the anode surface or ion exchange membrane
  • Volume loss of anolyte by osmosis
in the litigation no longer has and their manufacturing costs in the context of electrodialysis cells with cation exchange membranes according to the prior art move.

Die Vorteile der Anwendung von Membrananoden mit Kationenaustauschermembranen, wie in den zitierten Patentschriften beschrieben, bleiben bei der Anwendung der hier beschriebenen Erfindung bestehen.The advantages of using membrane anodes with cation exchange membranes, as described in the cited patents, remain with the use of the invention described herein.

Der Erfindung liegen umfangreiche Laboruntersuchungen zugrunde, deren Ergebnisse die Grundlage für die Beschreibung des konstruktiven Aufbaus und der Funktion der Zweikammer-Elektrodialysezelle bilden.The invention is based on extensive laboratory investigations, the results of which form the basis for the description of the structural design and the function of the two-chamber electrodialysis cell.

Die erläuterten Probleme werden mit den im Anspruch 1 aufgeführten Merkmalen gelöst.The problems explained are solved with the features listed in claim 1.

Erfindungsgemäß wird eine galvanische Anlage mit einer Zweikammer - Elektrodialysezelle als Anode in einem alkalischen Zink-und Zinklegierungselektrolyten bereitgestellt, dadurch gekennzeichnet, dass die Zweikammer - Elektrodialysezelle eine Anode enthält, die durch eine Kationen- und eine Anionenaustauschermembran von einem alkalischen Zink-oder Zinklegierungselektrolyten getrennt ist, wobei die Kationenaustauschermembran und Anionenaustauschermembran zwei getrennte Anolytkammern bilden, wobei eine innere Anolytkammer, in der sich die Anode befindet, von einem ersten Anolyt durchströmbar ist und eine äußere Anolytkammer Öffnungen mit Zufluss- und Abflusseinrichtungen zum Befüllen mit einem zweiten Anolyt bzw. Überlaufen von einem zweiten Anolyt aufweist.According to the invention, a galvanic plant with a two-chamber electrodialysis cell as anode in an alkaline zinc and zinc alloy electrolyte is provided, characterized in that the two-chamber electrodialysis cell contains an anode which is separated from an alkaline zinc or zinc alloy electrolyte by a cation and an anion exchange membrane in which the cation exchange membrane and the anion exchange membrane form two separate anolyte chambers, wherein an inner anolyte chamber in which the anode is located is permeable by a first anolyte and an outer anolyte chamber has openings with inflow and outflow means for filling with a second anolyte or overflowing one having second anolyte .

Die Erfindung betrifft ferner die Verwendung einer Zweikammer - Elektrodialysezelle mit Anionen- und Kationenaustauschermembran als Anode in einem alkalischen Zink- und Zinklegierungselektrolyten einer galvanischen Anlage zum Zweck der Metallabscheidung, dadurch gekennzeichnet, dass die Zweikammer-Elektrodialysezelle eine Anode enthält, die durch die Kationen- und eine Anionenaustauschermembran von dem alkalischen Zink-oder Zinklegierungselektrolyten getrennt ist, wobei die Kationenaustauschermembran und Anionenaustauschermembran zwei getrennte Anolytkammern bilden, wobei eine innere Anolytkammer, in der sich die Anode befindet, von einem ersten Anolyt durchströmbar ist und eine äußere Anolytkammer Öffnungen mit Zufluss- und Abflusseinrichtungen zum Befüllen mit einem zweiten Anolyt bzw. Überlaufen von einem zweiten Anolyt aufweist.The invention further relates to the use of a two-chamber electrodialysis cell with anion and cation exchange membrane as an anode in an alkaline zinc and zinc alloy electrolyte of a galvanic plant for the purpose of metal deposition, characterized in that the two-chamber electrodialysis cell contains an anode, which by the cation and an anion exchange membrane is separated from the alkaline zinc or zinc alloy electrolyte, wherein the cation exchange membrane and anion exchange membrane form two separate anolyte chambers, wherein an inner anolyte chamber, in which the anode is located, is permeable by a first anolyte and an outer anolyte chamber openings with inflow and outflow means for filling with a second anolyte or overflow of a second anolyte .

Bei der galvanotechnischen Anwendung von Elektrodialysezellen mit einer Anolyt-Kammer, wo die Anode durch eine Kationenaustauschermembran vom stark alkalischen, aminhaltigen Zink-Nickel-Elektrolyten und der Kathode (Galvanisiergut) getrennt ist, um eine anodische Oxydation der organischen Elektrolytzusätze und ein Absinken der kathodischen Stromausbeute zu vermeiden, werden bei Anlegen des Galvanisierstromes die positiv geladenen Ionen (Natrium-Ionen, Patent WO2001096631 A1 ) oder Protonen (Patent DE19834353 A1 ) aus der Anolyt-Kammer in den Zink-Nickel-Elektrolyten "transportiert". Dies führt zu irreversiblen Konzentrations- und Volumenänderungen des Zink-Nickel-Elektrolyten und hat Zusatzkosten für Chemikalien und Entsorgung zur Folge.In the electroplating application of electrodialysis cells with an anolyte chamber, where the anode is separated by a cation exchange membrane from the strongly alkaline, amine-containing zinc-nickel electrolyte and the cathode (electroplating) to anodic oxidation of the organic To avoid electrolyte additives and a decrease in the cathodic current efficiency, the positively charged ions (sodium ions, patent WO2001096631 A1 ) or protons (Patent DE19834353 A1 ) "transported" from the anolyte chamber in the zinc-nickel electrolyte. This results in irreversible concentration and volume changes of the zinc-nickel electrolyte and results in additional costs for chemicals and disposal.

Durch die Anwendung der Zweikammer-Elektrodialysezelle werden diese Nachteile beseitigt.By using the two-chamber electrodialysis cell, these disadvantages are eliminated.

Die Funktion der Zweikammer-Elektrodialysezelle verhindert ein Ansteigen der Natriumhydroxid-Konzentration und des Volumens des Zink-Nickel-Elektrolyten.The function of the two-compartment electrodialysis cell prevents an increase in the sodium hydroxide concentration and the volume of the zinc-nickel electrolyte.

Sie besteht aus einer inneren (6) und einer äußeren Anolyt-Kammer (5). Die innere Kammer mit der Anode (7) ist durch eine Kationenaustauschermembran (4) von der äußeren Kammer getrennt. Diese wiederum ist durch eine Anionenaustauschermembran (3) vom Zink-Nickel-Elektrolyten abgegrenzt. Die innere Anolyt-Kammer ist über Armaturen (1), (2) mit einem Anolyt-Kreislauf verbunden. Durch die anodische Reaktion sinkt die Natriumhydroxid-Konzentration im Anolyt-Kreislaufsystem. Die Natriumhydroxid-Konzentration in der äußeren Kammer steigt infolge der "lonen-Zuwanderung" von Na+ Anolyt und OH- Zink-Nickel bis auf Werte größer 300 g/l. Osmose entzieht dem Zink-Nickel-Elektrolyt Wasser über die Anionenaustauschermembran.It consists of an inner (6) and an outer anolyte chamber (5). The inner chamber with the anode (7) is separated from the outer chamber by a cation exchange membrane (4). This in turn is separated from the zinc-nickel electrolyte by an anion exchange membrane (3). The inner anolyte chamber is connected via fittings (1), (2) with an anolyte circuit. The anodic reaction reduces the sodium hydroxide concentration in the anolyte circulatory system. The sodium hydroxide concentration in the outer chamber increases due to the "ion inflow" of Na + anolyte and OH - zinc-nickel to values greater than 300 g / l. Osmosis deprives the zinc-nickel electrolyte of water via the anion exchange membrane.

Infolge des osmotischen Druckes steigt das Natronlauge-Volumen in der äußeren Kammer und kann über die Armatur (10) mit Schlauch (11) in den Anolyt-Kreislauf oder Zink-Nickel-Elektrolyt zurückgeführt werden. Die Konzentrationen und Volumina von Anolyt und Zink-Nickel-Elektrolyt können somit stabil gehalten werden.As a result of the osmotic pressure, the sodium hydroxide volume in the outer chamber increases and can be returned via the fitting (10) with hose (11) in the anolyte circuit or zinc-nickel electrolyte. The concentrations and volumes of anolyte and zinc-nickel electrolyte can thus be kept stable.

Die Zweikammer-Elektrodialysezelle eignet sich bevorzugt für den Einsatz in stark alkalischen, galvanischen Zink-Nickel-Elektrolyten, die auf der Basis von Natriumhydroxid und aminhaltigen Zusätzen aufgebaut sind, da hier die Effizienz des Abscheideprozesses besonders stark positiv beeinflusst wird.The two-chamber electrodialysis cell is preferably suitable for use in strongly alkaline, galvanic zinc-nickel electrolytes, which are based on sodium hydroxide and amine-containing additives, since the efficiency of the deposition process is particularly strongly influenced positively.

Die kathodische Stromausbeute bleibt auf hohem Niveau. Die Prozesssicherheit wird gesteigert. Zusätzliche Entsorgungskosten entfallen. Prozesschemikalien werden eingespart.The cathodic current efficiency remains at a high level. Process reliability is increased. Additional disposal costs are eliminated. Process chemicals are saved.

Eine vorteilhafte Gestaltungsform der vorliegenden Offenbarung ist in den Figuren 1, 2 und 3 dargestellt und wird der weiteren Beschreibung zugrunde gelegt.
Andere Bauformen, wie in Anspruch 12 genannt und in Figur 5 grafisch dargestellt, sind technisch möglich.An advantageous design form of the present disclosure is disclosed in U.S. Patent Nos. 4,378,359 FIGS. 1 . 2 and 3 and will be used as the further description.
Other types as recited in claim 12 and in FIG. 5 shown graphically, are technically possible.

Es zeigen:

Fig. 1
den Prinzipaufbau der Elektrodialysezelle mit den funktionsrelevanten Bestandteilen,
Fig. 2
die detaillierte Darstellung des Aufbaus einer zylindrischen Elektrodialysezelle,
Fig. 3
die Anordnung der lonenaustauschermembranen und des Anodenrohres im Querschnitt,
Fig. 4
das technische Aufbauschema eines galvanischen Bades mit den Elektrodialysezellen und der notwendigen technischen Peripherie,
Fig. 5
die grafische Darstellung einer möglichen Bauform in Kastenbauweise.
Show it:
Fig. 1
the basic structure of the electrodialysis cell with the function-relevant components,
Fig. 2
the detailed representation of the construction of a cylindrical electrodialysis cell,
Fig. 3
the arrangement of the ion exchange membranes and the anode tube in cross section,
Fig. 4
the technical structure of a galvanic bath with the electrodialysis cells and the necessary technical periphery,
Fig. 5
the graphic representation of a possible design in box construction.

Entsprechend dem Anspruch 1 werden anstelle von einer lonenaustauschermembran zwei lonenaustauschermembranen zu einem festen Elektrodialysemodul, wie in den Figuren 1 und 2 dargestellt, zusammengefügt, so dass zwei Anolytkammern (5) und (6) entstehen.According to claim 1, instead of an ion exchange membrane, two ion exchange membranes become a solid electrodialysis module, as in US Pat FIGS. 1 and 2 shown, joined together so that two anolyte chambers (5) and (6) arise.

Das Elektrodialysemodul setzt sich aus zwei miteinander verschraubten Baukomponenten zusammen:

  1. a) Anode(7) mit Schraubkappe (8), Fig. 1 und 2
  2. b) Kunststoffkörper
The electrodialysis module is composed of two structural components bolted together:
  1. a) anode (7) with screw cap (8), Fig. 1 and 2
  2. b) plastic body

Die Anode kann aus einem Edelstahlrohr (7), dessen Durchmesser und Länge je nach Anwendungsfall unterschiedlich sein können und das an einer Seite verjüngt ist und einer kreisrunden Edelstahl-Platine (14), die mit dem Anodenrohr fest verbunden ist (z.B. verschweißt), aufgebaut sein. Ein gebräuchlicher Rohrdurchmesser für den Anwendungsfall wäre z.B. 2 Zoll. Zwei Bohrungen von unterschiedlichem Durchmesser in der Platine dienen zum Einschrauben oder Verschweißen der Zu-und Ablaufarmaturen (1), (2) für den Anolyt Natronlauge (Konzentration ca. 160 g/l), in der weiteren Beschreibung als "Anolyt 1" bezeichnet. Die Zu-und Ablaufarmaturen können Schlauchtüllen von unterschiedlichem Durchmesser sein, wobei der kleinere Durchmesser für den Zulauf zu verwenden ist, um keinen zusätzlichen hydrostatischen Druck im Inneren der Elektrodialysezelle beim Durchströmen des Anolyt 1 zu erzeugen. Weiterhin fest verbunden mit der Platine ist die Aufhängevorrichtung (18), die gleichzeitig der Stromübertragung von der Anodenschiene auf die Elektrodialysezelle dient.The anode can be made of a stainless steel tube (7) whose diameter and length can be different depending on the application and which is tapered on one side and a circular stainless steel board (14) which is firmly connected to the anode tube (eg welded) constructed his. A common pipe diameter for the application would be eg 2 inches. Two holes of different diameter in the board are used for screwing or welding the inlet and outlet fittings (1), (2) for the Anolyte sodium hydroxide solution (concentration about 160 g / l), hereinafter referred to as "Anolyte 1". The inlet and outlet fittings may be hose nozzles of different diameter, wherein the smaller diameter is to be used for the inlet, in order to generate any additional hydrostatic pressure inside the electrodialysis cell as it flows through the anolyte 1. Further firmly connected to the board is the suspension device (18) at the same time the power transmission from the anode rail to the electrodialysis cell is used.

Der Kunststoffkörper besteht aus einer Kunststoff-Fußkappe, z.B. PVC (16), in die ein Gitterrohrstück aus Kunststoff, z.B. Polypropylen, von definierter Länge, z.B. 700 mm und definiertem Durchmesser, z.B. 80 mm und darauf liegender Kationenaustauschermembran (4) sowie ein zweites Gitterrohrstück von definierter Länge, z.B. 640 mm und Durchmesser, z.B. 100 mm mit darauf liegender_Anionenaustauschermembran (3) hermetisch dicht zusammengefügt wird, z.B. Eingießen in Kunstharz. Der obere Teil des aus zwei Kammern bestehenden Zylinders ist in einem Kunststoffkragen (17) ebenfalls hermetisch dicht eingebaut, so dass beide Kammern keine Verbindung zueinander haben. Der röhrenförmige Kunststoffkragen (17) besitzt am oberen Ende ein Außengewinde, z.B. 2 ½". Die Anode (7) wird in den Kunststoffkörper eingesetzt. Unter der Platine befindet sich ein Flachdichtungsring (15). Mit einer Schraubkappe (8) aus Kunststoff, die oben eine Öffnung hat, welche ca. 10 mm im Durchmesser kleiner als der Durchmesser der Platine (14) sein muss und ein Innengewinde, z.B. 2 ½", aufweist, wird die Anode mit dem Kunststoffkörper verschraubt.The plastic body consists of a plastic foot cap, e.g. PVC (16) into which a plastic lattice tube, e.g. Polypropylene of defined length, e.g. 700 mm and defined diameter, e.g. 80 mm and cation exchange membrane (4) lying thereon and a second lattice tube piece of defined length, e.g. 640 mm and diameter, e.g. 100 mm with the anionic membrane lying on it (3) is hermetically sealed together, e.g. Pouring in synthetic resin. The upper part of the two-chamber cylinder is also hermetically sealed in a plastic collar (17), so that both chambers have no connection to each other. The tubular plastic collar (17) has an external thread at the top, e.g. The anode (7) is inserted into the plastic body, below the board is a flat sealing ring (15) with a screw cap (8) made of plastic, which has an opening at the top, which is smaller than 10 mm in diameter the diameter of the board (14) and an internal thread, eg 2 ½ ", has, the anode is screwed to the plastic body.

Im Kunststoffkragen sind gegenüberliegend zwei Gewindebohrungen vorhanden, die Durchgang zur äußeren Anolytkammer haben. Diese dienen zum Einschrauben von zwei Armaturen (9), (10), z.B. gewinkelte Gewindefittings mit Schlauchtüllen. Über eine dieser beiden Armaturen wird die äußere Anolytkammer (5) mit Natronlauge (Konzentration z.B. 160 g/l), in der weiteren Beschreibung als "Anolyt 2" bezeichnet, gefüllt, während über die andere Armatur die Entlüftung stattfindet. Danach wird eine der beiden Tüllen mit einer Abdeckkappe (12) versehen, um später ein Eindringen von Zink-/Zinklegierungselektrolyt in den Anolyt 2 während des Produktionsprozesses zu verhindern. Die Ablaufarmatur (10) für den überlaufenden Anolyt 2 im Arbeitszustand der Elektrodialysezelle ist aus dem gleichen Grund mit einem Schlauch (11) oder Rohrbogen (13) aus Kunststoff mit der Öffnung nach unten zeigend, versehen.In the plastic collar opposite two threaded holes are present, the passage to the outer Anolytekammer have. These are used to screw in two fittings (9), (10), eg angled threaded fittings with hose nozzles. The outer anolyte chamber (5) is filled with sodium hydroxide solution (concentration eg 160 g / l), referred to in the following description as "Anolyte 2", via one of these two fittings, while venting takes place via the other fitting. Thereafter, one of the two grommets is provided with a cap (12) to prevent later penetration of zinc / zinc alloy electrolyte into the anolyte 2 during the production process. The drain fitting (10) for the overflowing Anolyte 2 in the working state the electrodialysis cell is for the same reason with a hose (11) or pipe bend (13) made of plastic with the opening facing down, provided.

Mit der Erfindung wird erreicht, dass bei Stromfluss im galvanischen Bad die an der Anode frei gesetzten positiv geladenen Natrium - Ionen von der inneren Anolytkammer (6) über die Kationenaustauschermembran (4) in die äußere Anolytkammer (5) gelangen und dort von der Anionenaustauschermembran (3) für den weiteren "Transport" in den Zink-oder Zinklegierungselektrolyt blockiert werden. Im Gegenzug "wandern" äquivalente Ladungsmengen negativ geladener Hydroxidionen aus dem Zink-oder Zinklegierungselektrolyt in Richtung Anode (7) und passieren die Anionenaustauschermembran (3) in die äußere Anolytkammer (5) der Elektrodialysezelle. Hier werden sie am Weitertransport zur Anode durch die Kationenaustauschermembran (4) gehindert.With the invention it is achieved that, when there is current flow in the galvanic bath, the positively charged sodium ions released at the anode pass from the inner anolyte chamber (6) via the cation exchange membrane (4) into the outer anolyte chamber (5), where they are separated from the anion exchange membrane (5). 3) for further "transport" into the zinc or zinc alloy electrolyte. In turn, equivalent charge amounts of negatively charged hydroxide ions "migrate" from the zinc or zinc alloy electrolyte toward the anode (7) and pass the anion exchange membrane (3) into the outer anolyte chamber (5) of the electrodialysis cell. Here they are prevented from further transport to the anode by the cation exchange membrane (4).

In der Folge des elektrochemischen Metallabscheidungsprozesses steigt in der äußeren Anolytkammer (5) die Natriumhydroxidkonzentration kontinuierlich an und Osmose setzt ein, die dem Anwachsen des Konzentrationsgradienten zwischen äußerer Anolytkammer und Zink-/Zinklegierungselektrolyt entgegenwirkt. Dem Zink-/Zinklegierungselektrolyt wird dabei über die Anionenaustauschermembran (3) Wasser entzogen und gelangt in die äußere Anolytkammer (5). Das Volumen des Anolyt 2 in der äußeren Anolytkammer vergrößert sich dadurch kontinuierlich. Der Volumenüberhang wird über die Ablaufeinrichtung (10) aus der Elektrodialysezelle abgeführt. In der praktischen Anwendung soll die überlaufende Menge Natronlauge (Anolyt 2) zu je 50% in den Zink-/Zinklegierungselektrolyt und den Anolyt 1 rückgeführt werden, um die Konzentrations- und Volumenverhältnisse von Zink-/Zinklegierungselektrolyt und Anolyt 1 annähernd konstant zu halten, da die Ladungsträger Natrium-Ionen und Hydroxid-Ionen in äquivalenter Menge aus dem Anolyt 1 und dem Zink-/Zinklegierungselektrolyt in die Anolyt 2 -Kammer (5) gelangt sind.As a result of the electrochemical metal deposition process, in the outer anolyte chamber (5), the sodium hydroxide concentration continuously increases and osmosis sets in, counteracting the increase in the concentration gradient between the outer anolyte chamber and the zinc / zinc alloy electrolyte. Water is withdrawn from the zinc / zinc alloy electrolyte via the anion exchange membrane (3) and reaches the outer anolyte chamber (5). The volume of the anolyte 2 in the outer anolyte chamber thereby increases continuously. The volume overhang is removed from the electrodialysis cell via the drainage device (10). In practical application, the overflowing amount of sodium hydroxide solution (Anolyt 2) should be recycled to 50% each in the zinc / zinc alloy electrolyte and the anolyte 1 to keep the concentration and volume ratios of zinc / zinc alloy electrolyte and anolyte 1 approximately constant, as the Charge carrier sodium ions and hydroxide ions in an equivalent amount of the anolyte 1 and the zinc / zinc alloy electrolyte in the Anolyte 2 chamber (5) have passed.

Die Zuführung des für die elektrochemische Oxydation an der Anode benötigten Anolyt 1 mit einer empfohlenen Konzentration von ca. 160 g/l Natiumhydroxid erfolgt, wie in Fig. 4 dargestellt, im Kreislaufsystem mittels einer Umwälzpumpe (22) aus einem Vorratsbehälter (23) über Absperrventile (20) und Durchflussmengenmesser (21) für jede einzelne Elektrodialysezelle.The supply of required for the electrochemical oxidation at the anode anolyte 1 with a recommended concentration of about 160 g / l of sodium hydroxide is carried out as in Fig. 4 represented in the circulation system by means of a circulation pump (22) from a reservoir (23) via shut-off valves (20) and flow meter (21) for each individual electrodialysis cell.

Die Ableitung des Anolyt 1 aus den Elektrodialysezellen muss ohne zusätzlichen Gegendruck in den Anolyt 1-Vorratsbehälter (23)erfolgen, um die lonenaustauschermembranen nicht zu überdehnen, wodurch Mikrorisse und Undichtheiten entstehen können. Eine praktische Realisierungsmöglichkeit ist das Einbinden der Rücklaufschläuche von Anolyt 1 in freiem Auslauf nach Fig.4, (24) in eine zentrale Rücklaufleitung, Fig.4, (25), von entsprechend großem Fassungsvermögen und leichtem Gefälle zum Anolyt 1-Vorratsbehälter.The removal of the anolyte 1 from the electrodialysis cells must be carried out without additional back pressure in the Anolyte 1 reservoir (23) so as not to overstretch the ion exchange membranes, whereby microcracks and leaks may occur. A practical realization possibility is the integration of the return hoses of Anolyt 1 in the free outlet Figure 4 , (24) into a central return line, Figure 4 , (25), of correspondingly large capacity and slight slope to the Anolyte 1 reservoir.

In Figur 2 ist zum besseren Verständnis mit Pfeilen der Anolytfluss von Anolyt 1 durch die Elektrodialysezelle dargestellt.In FIG. 2 For better understanding with arrows, the anolyte flux of Anolyt 1 through the electrodialysis cell is shown.

Das Ableiten des Überhangvolumens von Anolyt 2 in den Zink-/Zinklegierungselektrolyten erfolgt sehr einfach durch freies Überlaufen über die Armatur mit Tülle (10) und Rohrbogen (13), siehe Fig. 2, bei der Hälfte der Anzahl der in der galvanischen Anlage befindlichen Elektrodialysezellen. Das Ableiten des überlaufenden Anolyt 2 - Volumens in den Anolyt 1 - Vorratsbehälter geschieht, indem bei der anderen Hälfte der Anzahl der sich in der galvanischen Anlage befindlichen Elektrodialysezellen auf die Armatur mit Tülle (10) ein Kunststoffschlauch (11) gesteckt wird, der in eine zentrale Rücklaufleitung zum Anolyt 1 - Behälter mündet, siehe Fig. 4, (19).The derivation of the excess volume of Anolyt 2 in the zinc / zinc alloy electrolyte is very easy by free overflow through the fitting with spout (10) and pipe bend (13), see Fig. 2 , half of the number of electrodialysis cells in the galvanic plant. The dissipation of the overflowing Anolyte 2 - volume in the Anolyte 1 - reservoir is done by the other half of the number of located in the galvanic electrodialysis cells on the fitting with nozzle (10) a plastic tube (11) is plugged into a central return line to the Anolyte 1 tank opens, see Fig. 4 , (19).

Für eine sichere Funktion der beschriebenen Erfindung muss die folgende chemische Grundvoraussetzung erfüllt sein, die durch regelmäßige Analysentätigkeit zu gewährleisten ist:
Die Konzentration von Natriumhydroxid des Anolyt 1 soll stets ca. 30 g/l größer sein als die Natriumhydroxidkonzentration des Zink-/Zinklegierungselektrolyten. Sie muss aber kleiner sein als die Natriumhydroxid- Konzentration des Anolyt 2. Nur dann ist gewährleistet, dass das Osmose-Wasser hauptsächlich aus dem Zink-/Zinklegierungselektrolyten in die Anolyt 2 - Kammer der Elektrodialysezelle durch osmotischen Druck über die Anionenautauschermembran "gedrückt" wird.For a safe operation of the described invention, the following basic chemical requirement must be met, which is to be ensured by regular analysis activity:
The concentration of sodium hydroxide of the anolyte 1 should always be about 30 g / l greater than the sodium hydroxide concentration of the zinc / zinc alloy electrolyte. However, it must be smaller than the sodium hydroxide concentration of the Anolyte 2. Only then is it ensured that the osmosis water mainly from the zinc / zinc alloy electrolyte into the Anolyt 2 - chamber of the electrodialysis cell is "pushed" by osmotic pressure over the Anionenautauschermembran.

Die Ausgangskonzentrationen von Natriumhydroxid der Anolyte 1 und 2 können vor der Inbetriebnahme der Elektrodialysezellen gleich groß sein, wie in der Bezugszeichenliste unter (5), (6) ersichtlich ist, da sich die Konzentration von Anolyt 2 nach Anlegen des Galvanisierstromes mit laufender Betriebszeit erhöht und die Konzentration von Anolyt 1 sinkt.The starting concentrations of sodium hydroxide of Anolyte 1 and 2 may be equal before commissioning the electrodialysis cells, as shown in the list of reference in (5), (6), as the concentration of anolyte 2 increases after application of the electroplating current with operating time and the concentration of Anolyte 1 drops.

Mit der Anwendung der beschriebenen Erfindung sind folgende Nutzeffekte zu erreichen:

  1. 1. Einsparung von Prozesschemikalien, da eine oxydative Umsetzung, vor allem von organischen Zusätzen wie Glanzzusatzlösungen und Komplexbildnern an der Anode unterbunden wird.
  2. 2. Deutlich weniger Natriumkarbonatbildung im Zink-/Zinklegierungselektrolyten.
  3. 3. Steigerung der kathodischen Stromausbeute.
  4. 4. Steigerung des Warendurchsatzes an der galvanischen Anlage.
  5. 5. Einsparung von Elektroenergie pro Quadratmeter galvanisierter Oberfläche.
  6. 6. Regenerierung von Alt-Elektrolyten, indem keine neuen Abbauprodukte durch anodische Oxydation mehr entstehen und die vorhandenen mit der beschichteten Ware nach und nach ausgeschleppt werden.
  7. 7. Einsparung von Zusatzgeräten zum Eindampfen von Volumenüberhang, z.B. Vakuumverdampfer.
  8. 8. Einsparung von Entsorgungskosten für Volumenüberhang von Zink-/Zinklegierungs-elektrolyt.
With the application of the described invention, the following benefits can be achieved:
  1. 1. Saving of process chemicals, as an oxidative conversion, especially of organic additives such as brightener solutions and complexing agents is prevented at the anode.
  2. 2. Significantly less sodium carbonate formation in the zinc / zinc alloy electrolyte.
  3. 3. Increase in cathodic current efficiency.
  4. 4. Increasing the throughput of the galvanic plant.
  5. 5. Saving of electrical energy per square meter of galvanized surface.
  6. 6. Regeneration of old electrolytes by no new degradation products caused by anodic oxidation and the existing with the coated goods are gradually removed.
  7. 7. Saving of additional equipment for evaporation of volume surplus, eg vacuum evaporator.
  8. 8. Saving disposal costs for volume overhang of zinc / zinc alloy electrolyte.

BezugszeichenlisteLIST OF REFERENCE NUMBERS

Fig. 1, 2, 3, 4, 5

1
Zulaufarmatur für Anolyt 1
2
Ablaufarmatur für Anolyt 1
3
Gitterrohr / Kunststoffgitter mit Anionenaustauschermembran
4
Gitterrohr/Kunststoffgitter mit Kationenaustauschermembran
5
Äußere Anolytkammer mit Anolyt 2 (Natronlauge, Ausgangskonzentration 160g/l)
6
Innere Anolytkammer mit Anolyt 1 (Natronlauge, Ausgangskonzentration 160 g/l)
7
Anode (Rohr)
8
Kunststoff-Schraubkappe mit Innengewinde
9
Armatur mit Zu-/Ablauftülle für Anolyt 2 (Natronlauge, Ausgangskonzentration 160 g/l)
10
Armatur mit Zu-/Ablauftülle für Anolyt 2 (Natronlauge, Ausgangskonzentration 160 g/l)
11
Ablaufschlauch für Anolyt 2 zur zentralen Rücklaufleitung in den Anolyt 1-Vorratsbehälter
12
Abdeckkappe für Ablauftülle von Anolyt 2
13
Rohrbogen für Ablauftülle von Anolyt 2
14
Angeschweißte Platine am Anodenrohr mit Zulauf-und Ablauftülle für Anolyt 1
15
Flachdichtung
16
Kunststoff-Fußkappe
17
Kunststoff-Kragen
18
Aufhänge-und Stromzuführung
19
Zentrale Rücklaufleitung von Anolyt 2 in den Vorratsbehälter von Anolyt 1
20
Absperrventil in der Zulaufleitung von Anolyt 1
21
Durchflussmengenmesser
22
Umwälzpumpe für Anolyt 1
23
Vorratsbehälter für Anolyt 1
24
Rücklaufleitung von Anolyt 1 von der Elektrodialyszelle in eine zentrale Rücklaufleitung
25
Zentrale Rücklaufleitung in den Anolyt 1-Vorratsbehälter
Fig. 1 . 2 . 3 . 4 . 5
1
Inlet fitting for Anolyt 1
2
Drain fitting for Anolyt 1
3
Grid pipe / plastic grid with anion exchange membrane
4
Grid pipe / plastic grid with cation exchange membrane
5
Outer anolyte chamber with anolyte 2 (sodium hydroxide solution, initial concentration 160g / l)
6
Inner anolyte chamber with Anolyte 1 (sodium hydroxide solution, initial concentration 160 g / l)
7
Anode (tube)
8th
Plastic screw cap with internal thread
9
Fitting with inlet / outlet grommet for Anolyt 2 (caustic soda, initial concentration 160 g / l)
10
Fitting with inlet / outlet grommet for Anolyt 2 (caustic soda, initial concentration 160 g / l)
11
Drain hose for Anolyte 2 to the central return line in the Anolyte 1 storage tank
12
Drain cap of Anolyt 2
13
Pipe bend for drainage nozzle of Anolyt 2
14
Welded board on anode tube with inlet and drainage nozzle for Anolyt 1
15
gasket
16
Plastic foot cap
17
Plastic collar
18
Hanging and power supply
19
Central return line of Anolyt 2 in the storage tank of Anolyt 1
20
Shut-off valve in the supply line of Anolyt 1
21
Flow meters
22
Circulation pump for Anolyt 1
23
Storage tank for Anolyt 1
24
Return line of Anolyte 1 from the electrodialysis cell into a central return line
25
Central return line in the Anolyte 1 storage tank

Claims (12)

  1. An electroplating system comprising a two-chamber electrodialysis cell as an anode (7) in an alkaline zinc and zinc alloy electrolyte, said two-chamber electrodialysis cell containing an anode (7) separated from an alkaline zinc or zinc alloy electrolyte by a cation (4) and an anion exchange membrane (3), the cation exchange membrane (4) and the anion exchange membrane (3) forming two separate anolyte chambers (5, 6), wherein a first anolyte can flow through an inner anolyte chamber (6), in which the anode (7) is located, and an outer anolyte chamber (5) has openings with inflow (9) and outflow devices (10) for filling with a second anolyte or overflow of a second anolyte, respectively.
  2. The electroplating system according to claim 1, characterized in that the cation exchange membrane (4) is mounted towards the anode (7) and the anion exchange membrane (3) is mounted towards a cathode.
  3. The electroplating system according to one of the preceding claims, characterized in that the inner anolyte chamber (6) has an inflow device (1) via which the anolyte stream is conducted to the foot of the anode (7).
  4. The electroplating system according to one of the preceding claims, characterized in that the internal anolyte chamber (6) has a discharge device (2) via which the anolyte flow rising at the anode surface is conveyed into a discharge line (24), which opens into a collecting line (25), to an anolyte storage container (23).
  5. The electroplating system according to one of the preceding claims, characterized in that the first anolyte consists of sodium hydroxide solution or potassium hydroxide solution.
  6. The electroplating system according to one of the preceding claims, characterised in that the outer anolyte chamber (5) has angle fittings or hose nozzles for filling with second anolyte or overflowing of second anolyte.
  7. The electroplating system according to one of the preceding claims, characterized in that the second anolyte consists of sodium hydroxide solution or potassium hydroxide solution.
  8. The electroplating system according to one of the preceding claims, characterized in that the anode material is steel, stainless steel, nickel or nickel-plated steel.
  9. The electroplating system according to claim 8, characterized in that the anode is designed as a round tube, square tube, U-profile, T-profile, spiral both in solid material and expanded metal.
  10. The electroplating system according to one of the preceding claims, characterized in that the electrodialysis cell is of box design.
  11. The electroplating system according to one of the preceding claims, characterized in that the anode (7) is a membrane anode (7) provided with the cation exchange membrane (4) and adapted to be retrofitted with the outer anolyte chamber (5) based on the anion exchange membrane (3).
  12. A use of a two-chamber electrodialysis cell as an anode (7) in an alkaline zinc and zinc alloy electrolyte of an electroplating plant for the purpose of metal deposition, wherein the two-chamber electrodialysis cell contains an anode (7) separated from the alkaline zinc or zinc alloy electrolyte by a cation (4) and an anion exchange membrane (3), the cation exchange membrane (4) and the anion exchange membrane (3) forming two separate anolyte chambers (5, 6), wherein a first anolyte can flow through an inner anolyte chamber (6), in which the anode (7) is located, and an outer anolyte chamber (5) has openings with inflow (9) and outflow devices (10) for filling with a second anolyte or overflow of a second anolyte, respectively.
EP16711218.4A 2015-03-25 2016-03-16 Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc electrolytes and zinc alloy electrolytes for the purpose of deposition of metal in electroplating systems Active EP3274489B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE202015002289.8U DE202015002289U1 (en) 2015-03-25 2015-03-25 Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc and zinc alloy electrolytes for the purpose of metal deposition in electroplating plants
DE102015009379.7A DE102015009379A1 (en) 2015-03-25 2015-07-18 Two-compartment electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc and zinc alloy electrolytes for the purpose of metal deposition in galvanic plants
PCT/EP2016/055690 WO2016150793A2 (en) 2015-03-25 2016-03-16 Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc electrolytes and zinc alloy electrolytes for the purpose of deposition of metal in electroplating systems

Publications (2)

Publication Number Publication Date
EP3274489A2 EP3274489A2 (en) 2018-01-31
EP3274489B1 true EP3274489B1 (en) 2019-08-07

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EP16711218.4A Active EP3274489B1 (en) 2015-03-25 2016-03-16 Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc electrolytes and zinc alloy electrolytes for the purpose of deposition of metal in electroplating systems

Country Status (5)

Country Link
US (1) US10738391B2 (en)
EP (1) EP3274489B1 (en)
DE (2) DE202015002289U1 (en)
ES (1) ES2751633T3 (en)
WO (1) WO2016150793A2 (en)

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CN106550606B (en) 2015-07-22 2019-04-26 迪普索股份公司 Kirsite method for plating
CN105350063B (en) * 2015-11-09 2018-10-30 科文特亚环保电镀技术（江苏）有限公司 A kind of anode system of electroplate liquid separation
MX2021008925A (en) 2019-01-24 2021-08-24 Atotech Deutschland Gmbh Membrane anode system for electrolytic zinc-nickel alloy deposition.
EP4077771A1 (en) 2019-12-20 2022-10-26 Atotech Deutschland GmbH & Co. KG Method and system for depositing a zinc-nickel alloy on a substrate
EP3875642A1 (en) * 2020-03-04 2021-09-08 AT & S Austria Technologie & Systemtechnik Aktiengesellschaft Method for preparing rinsing water from printed circuit board and / or substrate production

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DE3929137C1 (en) 1989-09-01 1991-02-28 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung Ev, 8000 Muenchen, De
DE4016000C2 (en) 1990-05-18 1993-10-21 Hager & Elsaesser Device for the treatment of metal-containing liquids by ion exchange and simultaneous or periodic regeneration of the ion exchange resin by electrodialysis
US5162079A (en) * 1991-01-28 1992-11-10 Eco-Tec Limited Process and apparatus for control of electroplating bath composition
DE19834353C2 (en) 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkaline zinc-nickel bath
EP1292724B2 (en) 2000-06-15 2015-12-23 Coventya, Inc. Zinc-nickel electroplating
WO2004108995A1 (en) 2003-06-03 2004-12-16 Taskem Inc. Zinc and zinc-alloy electroplating
US7442286B2 (en) 2004-02-26 2008-10-28 Atotech Deutschland Gmbh Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys
DE102010044551A1 (en) 2010-09-07 2012-03-08 Coventya Gmbh Anode and their use in an alkaline electroplating bath

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Publication number Publication date
EP3274489A2 (en) 2018-01-31
DE202015002289U1 (en) 2015-05-06
US20180087177A1 (en) 2018-03-29
WO2016150793A3 (en) 2016-11-10
ES2751633T3 (en) 2020-04-01
US10738391B2 (en) 2020-08-11
WO2016150793A2 (en) 2016-09-29
DE102015009379A1 (en) 2016-09-29

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