EP1006213A2 - Verfahren zum Regenerieren einer Prozesslösung - Google Patents
Verfahren zum Regenerieren einer Prozesslösung Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- chamber
- solution
- anode
- hypophosphite
- exchange membrane
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 85
- 230000001172 regenerating effect Effects 0.000 title claims description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 26
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000909 electrodialysis Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 15
- 230000008929 regeneration Effects 0.000 claims abstract description 13
- 238000011069 regeneration method Methods 0.000 claims abstract description 13
- 238000005341 cation exchange Methods 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000010959 steel Substances 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- -1 hypophosphite ions Chemical class 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 238000007747 plating Methods 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 238000007792 addition Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 abstract 2
- 229940005631 hypophosphite ion Drugs 0.000 abstract 2
- 230000037427 ion transport Effects 0.000 abstract 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 50
- 229910052759 nickel Inorganic materials 0.000 description 24
- 229910001453 nickel ion Inorganic materials 0.000 description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 10
- 238000000151 deposition Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000454 electroless metal deposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
Description
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.
- 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.
- 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.
- Verfahren nach einem der Anspprüche 1 bis 3, dadurch gekennzeichnet, daß Beschichtungsmetall zu dessen Nachdosierung der ersten Kammer (5) aufgegeben wird.
- 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.
- Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Prozeßlösung (PL) der weiteren Kammer (10) aufgegeben und von dort der ersten Kammer (5) zugeleitet wird.
- Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß ein Teilstrom (TL) der Prozeßlösung (PL) durch die weitere Kammer (10) geleitet wird.
- 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.
- Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Anodenkammer (2) Ionen des Beschichtungsmetalls zugeführt werden.
- Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß eine lösliche, aus dem Beschichtungsmetall bestehende Anode (2) verwendet wird.
- Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß eine Elektrodialysezelle (EZ) mit einer Mehrfachanordnung der Kammern eingesetzt wird.
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)
Publication Number | Publication Date |
---|---|
EP1006213A2 true EP1006213A2 (de) | 2000-06-07 |
EP1006213A3 EP1006213A3 (de) | 2000-08-09 |
EP1006213B1 EP1006213B1 (de) | 2004-12-15 |
Family
ID=7886899
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99120998A Expired - Lifetime EP1006213B1 (de) | 1998-11-06 | 1999-11-04 | Verfahren zum Regenerieren einer Prozesslösung |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1006213B1 (de) |
AT (1) | ATE284980T1 (de) |
DE (2) | DE19851180C1 (de) |
Cited By (1)
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 |
Families Citing this family (4)
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 |
EP1726683B1 (de) | 2005-05-25 | 2008-04-09 | Enthone Inc. | Verfahren und Vorrichtung zur Einstellung der Ionenkonzentration in Elektrolyten |
Citations (3)
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 |
-
1998
- 1998-11-06 DE DE19851180A patent/DE19851180C1/de not_active Expired - Fee Related
-
1999
- 1999-11-04 DE DE59911270T patent/DE59911270D1/de not_active Expired - Lifetime
- 1999-11-04 EP EP99120998A patent/EP1006213B1/de not_active Expired - Lifetime
- 1999-11-04 AT AT99120998T patent/ATE284980T1/de not_active IP Right Cessation
Patent Citations (3)
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 |
Cited By (3)
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 (de) | 2010-04-16 | 2011-10-20 | Atotech Deutschland Gmbh | Membranelektrolysestapel, diesen enthaltende Elektrodialyseeinrichtung sowie Verfahren zum Regenerieren eines außenstromlos arbeitenden Bades zur Metallabscheidung |
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
Publication number | Publication date |
---|---|
EP1006213A3 (de) | 2000-08-09 |
DE59911270D1 (de) | 2005-01-20 |
EP1006213B1 (de) | 2004-12-15 |
DE19851180C1 (de) | 2000-04-20 |
ATE284980T1 (de) | 2005-01-15 |
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