EP0115791A1 - Process and apparatus for regenerating a copper-containing etching solution - Google Patents
Process and apparatus for regenerating a copper-containing etching solution Download PDFInfo
- Publication number
- EP0115791A1 EP0115791A1 EP84100326A EP84100326A EP0115791A1 EP 0115791 A1 EP0115791 A1 EP 0115791A1 EP 84100326 A EP84100326 A EP 84100326A EP 84100326 A EP84100326 A EP 84100326A EP 0115791 A1 EP0115791 A1 EP 0115791A1
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- EP
- European Patent Office
- Prior art keywords
- copper
- cathode
- anode
- chloride
- etching solution
- 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
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000010949 copper Substances 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 30
- 238000005530 etching Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000001172 regenerating effect Effects 0.000 title 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 4
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910001369 Brass Inorganic materials 0.000 claims abstract 2
- 229910000994 Tombac Inorganic materials 0.000 claims abstract 2
- 239000010951 brass Substances 0.000 claims abstract 2
- 230000008929 regeneration Effects 0.000 claims description 12
- 238000011069 regeneration method Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 239000012777 electrically insulating material Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
Definitions
- the invention is based on a method for the regeneration of a copper-containing etching solution according to the preamble of claim 1 and on an apparatus for carrying out the method according to claim 5.
- a copper (II ) it is known to etch a copper (II ) to use chloride-containing etching solution which contains an alkali chloride, in particular potassium chloride, as complexing agent.
- chloride-containing etching solution which contains an alkali chloride, in particular potassium chloride, as complexing agent.
- Such an etching solution which is used in particular in the manufacture of printed circuit boards, has the advantage over the conventional etching solutions which contain hydrochloric acid as a complexing agent that it has a higher etching speed, that no hydrochloric acid mist in the exhaust air and no signs of corrosion occur on the machines.
- the method according to the invention with the characterizing features of the main claim has the advantage that the composition of the CuCl 2 / KCl etching solution is kept optimally constant with the aid of an electrolysis cell, ie in principle only the etched metal is removed from the solution removed while keeping the CuI / II redox potential constant. There is no consumption of chemicals, the regeneration system can be built very compactly and is therefore very well suited for inclusion in a production line.
- the device according to the invention for carrying out the above-mentioned method with the characteristic features Cathode surface on carbon brushes, also not shown, on the rotating copper shaft and from there on the insulated copper disk on the end face made of titanium.
- the anode 4 which consists of titanium, niobium or tantalum and is coated with platinum, iridium or non-stoichiometric platinum metal oxide compounds, is arranged parallel to the end face of the disk 3 and at a short distance from the end face, wherein either solid material or expanded metal can be used .
- the partition Between the copper disk 3 serving as the cathode and the anode 4 there is a porous intermediate wall 5 made of electrically non-conductive material such as a coarse-pored plastic material made of polypropylene or polyethylene, which serves to keep the strong bath movement caused by the circulation pump 16 away from the cathode 3, without hindering the electrolyte exchange, the partition therefore has no diaphragm function, but only serves as a flow stabilizer.
- the disc 3 rotates, the copper sludge deposited on the cathode is stripped off and slips into a collecting container (not shown) with the aid of a water spray.
- the spray rinse water is used in the circuit. After reaching a predetermined amount of copper sludge and a certain salt concentration in the rinsing water, the contents of the collecting container are pumped on for solid-liquid separation (decanter, filter).
- the etching solution to be regenerated is fed from the etching system via the inlet 14 to the regeneration system and flows back in via the outlet 15 of the etching system.
- In Painting of claim 5 has the advantage that it can be built in a compact unit and that the type of execution of the cathode, the metal powder that is deposited on this cathode, can be removed continuously from the circuit.
- FIG. 1 shows a perspective view of the regeneration system and FIG. 2 shows a partial section through the disk-shaped cathode.
- the regeneration system consists of a container 1 made of plastic or insulated metal with an inlet 14 and an outlet 15 to the etching system as well as two connections 7 and 8 for a circulating pump 16.
- the container 1 there is a circular, fixed with a serving as cathodic power supply Copper shaft 2 connected copper disc 3, which serves as a cathode.
- the copper disk 10 has a copper ring 12 on its circumference, the whole is covered with PVC insulation 11 and a titanium ring 13 as contact material for the etching solution has been shrunk onto the non-insulated end face. Copper cannot serve as a contact material here because it dissolves in the etching medium.
- the copper shaft 2 is rotatably mounted on the container edge, as indicated in the figure.
- the disk is driven by a plastic gear (not shown) attached to the copper shaft as electrical insulation, while the power supply to the regeneration system was achieved with the etching solution described at cathodic current densities between 50 and 150 A / dm 2 and temperatures between 30 and 50 ° C current yields between 0.9 and 1.15 g / Ah copper in powder form.
- the regeneration system forms metallic copper as a very fine crystalline copper sludge when current flows through the cathode 3 by discharging the copper ions at very high current densities.
- Discharge of the chloride ions forms chlorine at the anode, which dissolves well in water and is quickly distributed throughout the container by the strong bath movement caused by the circulation pump 16.
- This chlorine oxidizes existing copper (I) chloride to copper (II) chloride.
- the electrochemical process is controlled by detecting the copper (I) ions with the aid of the redox potential and switching off the current at a limit value which is approximately 390 mV.
- the regeneration system as used here has a volume of 210 1, the cathode 3 has a disk diameter of 500 mm with an immersed cathode surface of 2 dm 2, while the anode surface is 25 dm 2 .
- the circulation pump 16 pumps the entire container volume 25 times an hour.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Es werden ein Verfahren und eine Vorrichtung angegeben, die zur Regenerierung einer kupferhaltigen Ätzlösung, die Kupfer(II)-Chlorid sowie Alkalichlorid als Komplexbildner enthält, dient. An einer Kathode bildet sich bei einer Stromdichte von 40-400 A/dm² Kupfer in Pulverform, während sich an einer Anode bei einer Stromdichte von 1-100 A/dm² Chlor bildet, das Kupfer(I)-Chlorid zu Kupfer (II)-Chlorid oxidiert. Nach diesem Verfahren können auch Ätzlösungen behandelt werden, die neben Kupfer noch Zinkdurch Ätzen von Messing oder Tombak enthalten, wobei ein Pulvergemisch aus Kupfer und Zink entsteht. - Die Vorrichtung weist eine rotierende, scheibenförmige Kathode auf, von deren Stirnfläche das Metallpulver durch eine Abstreifvorrichtung entfernt wird.A method and a device are specified which are used to regenerate a copper-containing etching solution which contains copper (II) chloride and alkali metal chloride as complexing agents. Copper forms in powder form on a cathode at a current density of 40-400 A / dm², while copper forms on an anode at a current density of 1-100 A / dm², the copper (I) chloride to copper (II) - Chloride oxidizes. This process can also be used to treat etching solutions which, in addition to copper, also contain zinc by etching brass or tombac, a powder mixture of copper and zinc being produced. - The device has a rotating, disk-shaped cathode, from the end face of which the metal powder is removed by a stripping device.
Description
Die Erfindung geht aus von einem Verfahren zur Regenerierung einer kupferhaltigen Ätzlösung nach der Gattung des Anspruchs 1 sowie von einer Vorrichtung zur Durchführung des Verfahrens nach Anspruch 5. Aus der DE-OS 29 42 504 ist es bekannt, zum Ätzen von Kupfer eine kupfer(II)-chloridhaltige Ätzlösung einzusetzen, die als Komplexbildner ein Alkalichlorid, insbesondere Kaliumchlorid, enthält. Eine solche Ätzlösung, die insbesondere bei der Leiterplattenfertigung eingesetzt wird, hat gegenüber den herkömmlichen Ätzlösungen, die Salzsäure als Komplexbildner enthalten, den Vorteil, daß sie eine höhere Ätzgeschwindigkeit aufweist, daß keinerlei Salzsäurenebel in der Abluft und keine Korrosionserscheinungen an den Maschinen auftreten. Sie läßt sich sowohl in einem Sprühautomaten als auch in einem Tauchprozeß, der in einen Galvanisierautomaten integriert ist, einsetzen. Eine solche Ätzlösung läßt sich zwar durch Einleiten von Luft regenerieren, was den sonst üblichen Einsatz von Wasserstoffperoxid überflüssig macht, jedoch erfordert diese Luftoxidation ein Filtrieren des dabei gebildeten Kupfer(Ii)-Hydroxids, aus dem schließlich durch Lösen in Säure und anschließende Elektrolyse Kupfer in metallischer Form gewonnen werden kann. Dieses Verfahren läßt sich indessen nicht in einem geschlossenen Kreislauf verwirklichen, da das in Form von Kupferhydroxid anfallende Kupfer aus der Ätzlösung schlecht filtrierbar ist.The invention is based on a method for the regeneration of a copper-containing etching solution according to the preamble of claim 1 and on an apparatus for carrying out the method according to
Das erfindungsgemäße Verfahren mit den kennzeichnenden Merkmalen des Hauptanspruchs hat demgegenüber den Vor- teil, daß die CuCl2/KCl-Ätzlösung mit Hilfe einer Elektrolysezelle in ihrer Zusammensetzung in optimaler Weise konstant gehalten wird, d. h. es wird im Prinzip nur das abgeätzte Metall aus der Lösung entfernt bei gleichzeitiger Konstanthaltung des CuI/II-Redoxpotentials. Es tritt kein Chemikalienverbrauch auf, die Regenerieranlage läßt sich sehr kompakt bauen und ist daher sehr gut für die Einbeziehung in eine Fertigungs- straße geeignet.In contrast, the method according to the invention with the characterizing features of the main claim has the advantage that the composition of the CuCl 2 / KCl etching solution is kept optimally constant with the aid of an electrolysis cell, ie in principle only the etched metal is removed from the solution removed while keeping the CuI / II redox potential constant. There is no consumption of chemicals, the regeneration system can be built very compactly and is therefore very well suited for inclusion in a production line.
Durch die in den Unteransprüchen aufgeführten Maßnahmen sind vorteilhafte Weiterbildungen und Verbesserungen des im Hauptanspruch angegebenen Verfahrens möglich.Advantageous further developments and improvements of the method specified in the main claim are possible through the measures listed in the subclaims.
Besonders vorteilhaft ist es, im Falle des Ätzens von Legierungen, die neben Kupfer unedlere Metalle wie z. B. Zink enthalten, wenn man die Regenerieranlage mit einer kathodischen Stromdichte zwischen 100 und 400 A/dm und bei einem pH-Wert über 1,0 betreibt, da in diesem Falle nicht nur das Kupfer in Pulverform, sondern gleichzeitig auch das Zink in Pulverform abgeschieden wird.It is particularly advantageous in the case of the etching of alloys which, in addition to copper, base metals such as. B. contain zinc if you operate the regeneration system with a cathodic current density between 100 and 400 A / dm and at a pH value above 1.0, since in this case not only the copper in powder form, but also the zinc in powder form is deposited.
Die erfindungsgemäße Vorrichtung zur Durchführung des obengenannten Verfahrens mit den kennzeichnenden Merk-Kathodenoberfläche über ebenfalls nicht dargestellte Kohlebürsten auf die sich drehende Kupferwelle und von da über die isolierte Kupferscheibe auf die Stirnfläche aus Titan erfolgt. In dem Behälter 1 ist parallel zur Stirnfläche der Scheibe 3 und mit geringem Abstand zur Stirnfläche die Anode 4 angeordnet, die aus Titan, Niob oder Tantal besteht, das mit Platin, Iridium oder nichtstöchiometrischen Platinmetalloxidverbindungen beschichtet ist, wobei entweder Vollmaterial oder Streckmetall eingesetzt werden kann. - Zwischen der als Kathode dienenden Kupferscheibe 3 und der Anode 4 befindet sich eine poröse Zwischenwand 5 aus elektrisch nicht leitendem Material wie einem grobporigen Kunststoffmaterial aus Polypropylen oder Polyäthylen, die dazu dient, die durch die Umwälzpumpe 16 verursachte starke Badbewegung von der Kathode 3 fernzuhalten, ohne den Elektrolytaustausch zu behindern, die Zwischenwand hat also keine Diaphragma-Funktion, sondern dient lediglich als Strömungsberuhiger. - Am Behälterrand befestigt, mit losem Kontakt zur Stirnfläche der Kathode 3 befindet sich eine Abstreifvorrichtung 6. Bei der drehenden Bewegung der Scheibe 3 wird so der an der Kathode abgeschiedene Kupferschlamm abgestreift und rutscht mit Hilfe einer Wasserspritzspülung in einen nicht dargestellten Auffangbehälter. Das Spritzspülwasser wird im Kreislauf eingesetzt. Nach Erreichen einer vorgegebenen Kupferschlamm-Menge und einer bestimmten Salzkonzentration-im Spülwasser wird der Inhalt des Auffangbehälters zur Fest-Flüssigabtrennung (Dekanter, Filter) weitergepumpt.The device according to the invention for carrying out the above-mentioned method with the characteristic features Cathode surface on carbon brushes, also not shown, on the rotating copper shaft and from there on the insulated copper disk on the end face made of titanium. In the container 1, the anode 4, which consists of titanium, niobium or tantalum and is coated with platinum, iridium or non-stoichiometric platinum metal oxide compounds, is arranged parallel to the end face of the disk 3 and at a short distance from the end face, wherein either solid material or expanded metal can be used . - Between the copper disk 3 serving as the cathode and the anode 4 there is a porous
Die zu regenerierende Ätzlösung wird aus der Ätzanlage über den Zulauf 14 der Regenerieranlage zugeführt und fließt über den Ablauf 15 der Ätzanlage wieder zu. In malen des Anspruchs 5 hat den Vorteil, daß sie sich in einer kompakten Einheit bauen läßt und daß durch die Art der Ausführung der Kathode sich das Metallpulver, das an dieser Kathode abgeschieden wird, kontinuierlich aus dem Kreislauf entfernen läßt.The etching solution to be regenerated is fed from the etching system via the
Ein Ausführungsbeispiel der Erfindung ist in der Zeichnung dargestellt und in der nachfolgenden Beschreibung näher erläutert. Es zeigen Figur 1 eine perspektivische Darstellung der Regenerieranlage und Figur 2 einen Teilschnitt durch die scheibenförmige Kathode.An embodiment of the invention is shown in the drawing and explained in more detail in the following description. 1 shows a perspective view of the regeneration system and FIG. 2 shows a partial section through the disk-shaped cathode.
Die Regenerieranlage besteht aus einem Behälter 1 aus Kunststoff oder isoliertem Metall mit einem Zulauf 14 und einem Ablauf-15 an die Ätzanlage sowie zwei Anschlüssen 7 und 8 für eine Umwälzpumpe 16. In dem Behälter 1 läuft eine kreisrunde, fest mit einer als kathodische Stromzuführung dienende Kupferwelle 2 verbundene Kupferscheibe 3, die als Kathode dient. Gemäß Figur 2 trägt die Kupferscheibe 10 an ihrem Umfang einen Kupferring 12, das Ganze ist mit einer Isolierung 11 aus PVC überzogen und auf die nicht isolierte Stirnfläche ein Titanreif 13 als Kontaktwerkstoff zur Ätzlösung aufgeschrumpft worden. Kupfer kann hier nicht als Kontaktwerkstoff dienen, da dieses sich in dem Ätzmedium auflöst. Die Kupferwelle 2 ist auf dem Behälterrand, wie in der Figur angedeutet, drehbar gelagert. Der Antrieb der Scheibe erfolgt über ein auf der Kupferwelle befestigtes, nicht dargestelltes Kunststoffzahnrad als elektrische Isolierung, während die Stromzuführung zur der Regenerieranlage wurden mit der beschriebenen Ätzlösung bei kathodischen Stromdichten zwischen 50 und 150 A/dm2 und Temperaturen zwischen 30 und 50 °C Stromausbeuten zwischen 0,9 und 1,15 g/Ah Kupfer in Pulverform erzielt.The regeneration system consists of a container 1 made of plastic or insulated metal with an
Im folgenden Beispiel wurde ein Ätzlösung regeneriert, die abgeätztes Zink neben Kupfer enthält:
- Cu: 50 g/l
- KC1: 100 g/l
- Zn: 20 g/1
- Temperatur: 22 °C
- pH-Wert: 1,5.
- Cu: 50 g / l
- KC1: 100 g / l
- Zn: 20 g / 1
- Temperature: 22 ° C
- pH: 1.5.
Bei einer kathodischen Stromdichte von 300 A/dm2 wurde ein Metallpulver erhalten, das zu 58 % aus Kupfer und zu 42 % aus Zink besteht.At a cathodic current density of 300 A / dm 2 , a metal powder was obtained which consists of 58% copper and 42% zinc.
der Regenerieranlage bildet.sich bei Stromdurchgang an der Kathode 3 durch Entladung der Kupferionen bei sehr hohen Stromdichten metallisches Kupfer als sehr feinkristalliner Kupferschlamm. An der Anode bildet sich durch Entladung der Chloridionen Chlor, das sich in Wasser gut löst und durch die von der Umwälzpumpe 16 verursachte starke Badbewegung schnell im ganzen Behälter verteilt wird. Dieses Chlor oxidiert vorhandenes Kupfer(I)- Chlorid zu Kupfer(II)-Chlorid. Um zu verhindern, daß mehr Chlor gebildet als für die Oxidation benötigt wird, erfolgt eine Steuerung des elektrochemischen Vorgangs durch Erfassen der Kupfer(I)-Ionen mit Hilfe des Redoxpotentials und Abschaltung des Stroms bei einem Grenzwert, der bei etwa 390 mV liegt.The regeneration system forms metallic copper as a very fine crystalline copper sludge when current flows through the cathode 3 by discharging the copper ions at very high current densities. Discharge of the chloride ions forms chlorine at the anode, which dissolves well in water and is quickly distributed throughout the container by the strong bath movement caused by the
Es folgen jetzt Beispiele zur Regenerierung einer Ätzlösung, die beim Sprühätzen mit den folgenden Parametern eingesetzt wird:
- Cu: 50g/l
- KCl: 150 g/l
- Redoxpotential: 390 mV
- Temperatur: 45 °C
- Druck: 2 bar
- Ätzgeschwindigkeit: 38 /um/min
- pH-Wert: 2,3
- Cu: 50g / l
- KCl: 150 g / l
- Redox potential: 390 mV
- Temperature: 45 ° C
- Pressure: 2 bar
- Etching speed: 38 / um / min
- pH: 2.3
Die Regenerieranlage, wie sie hier benutzt wurde, besitzt ein Volumen von 210 1, die Kathode 3 einen Scheibendurchmesser von 500 mm mit einer eingetauchten Kathodenoberfläche von 2 dm2 während die Anodenoberfläche 25 dm2 beträgt. Die Umwälzpumpe 16 pumpt das gesamte Behältervolumen 25mal in der Stunde um. InThe regeneration system as used here has a volume of 210 1, the cathode 3 has a disk diameter of 500 mm with an immersed cathode surface of 2 dm 2, while the anode surface is 25 dm 2 . The
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833303594 DE3303594A1 (en) | 1983-02-03 | 1983-02-03 | METHOD AND DEVICE FOR REGENERATING A copper-containing etching solution |
| DE3303594 | 1983-02-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0115791A1 true EP0115791A1 (en) | 1984-08-15 |
| EP0115791B1 EP0115791B1 (en) | 1988-06-01 |
Family
ID=6189908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84100326A Expired EP0115791B1 (en) | 1983-02-03 | 1984-01-13 | Process and apparatus for regenerating a copper-containing etching solution |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4508599A (en) |
| EP (1) | EP0115791B1 (en) |
| JP (1) | JPS59143072A (en) |
| DE (2) | DE3303594A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014801A1 (en) * | 1990-03-29 | 1991-10-03 | Hans Höllmüller Maschinenbau GmbH & Co. | Device for the electrolytic regeneration of an etching agent containing metal, especially copper |
| EP0539792A1 (en) * | 1991-10-28 | 1993-05-05 | Nittetsu Mining Co., Ltd. | Method for regenerating etchant |
| CN110306209A (en) * | 2019-08-09 | 2019-10-08 | 郑州金泉矿冶设备有限公司 | The equipment of electrolysis method production super fine silver powder |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4773978A (en) * | 1985-06-27 | 1988-09-27 | Cheminor A/S | Apparatus for the production of metals by electrolysis |
| DE3832674A1 (en) * | 1988-09-27 | 1990-03-29 | Kodak Ag | METAL RECOVERY DEVICE |
| GB2293390A (en) * | 1994-09-20 | 1996-03-27 | British Tech Group | Simultaneous etchant regeneration and metal deposition by electrodialysis |
| JP2941741B2 (en) * | 1997-06-03 | 1999-08-30 | 核燃料サイクル開発機構 | Dry reprocessing method and spent reprocessing device for spent nuclear fuel |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD45299A (en) * | ||||
| FR1213119A (en) * | 1957-10-28 | 1960-03-29 | Western Electric Co | Bath to corrode copper and regeneration of this bath |
| DE1223653B (en) * | 1960-01-11 | 1966-08-25 | Siemens Ag | Device for the continuous electro-lytic regeneration of copper chloride etching solutions |
| FR2156249A1 (en) * | 1971-10-12 | 1973-05-25 | Shipley Co | |
| US3825484A (en) * | 1971-04-29 | 1974-07-23 | N Fronsman | Electrolytic regenerator for chemical etchants including scraper means and rotating cathodes |
| DE2650912A1 (en) * | 1976-11-06 | 1978-05-18 | Hoellmueller Maschbau H | Electrolytic regeneration of copper etching reagent - contg. chloride and cuprous ion, with control of copper concn. in reagent and current density |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1959376A (en) * | 1930-09-26 | 1934-05-22 | Nichols Copper Co | Process for producing metal powders |
| JPS5124537A (en) * | 1974-08-26 | 1976-02-27 | Hitachi Ltd | Etsuchinguyokuno saiseihoho |
| SU548051A1 (en) * | 1975-03-17 | 1977-10-05 | Горьковский политехнический институт им.А.А.Жданова | Method of regeneration of ferrumcopper-chloride etching solutions |
| DE2641905C2 (en) * | 1976-09-17 | 1986-03-20 | Geb. Bakulina Galina Aleksandrovna Batova | Process for the regeneration of used etching solutions |
| DE2850564C2 (en) * | 1978-11-22 | 1982-12-23 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Method and device for regenerating an etching solution containing copper (II) chloride and / or iron (III) chloride in an electrolytic cell |
| JPS5629686A (en) * | 1979-08-17 | 1981-03-25 | Kazuo Ogawa | Electrolytic cathode plate for copper recovery |
| JPS5914097B2 (en) * | 1980-07-30 | 1984-04-03 | 新日本製鐵株式会社 | Ferritic heat-resistant steel with improved toughness |
-
1983
- 1983-02-03 DE DE19833303594 patent/DE3303594A1/en not_active Ceased
-
1984
- 1984-01-13 EP EP84100326A patent/EP0115791B1/en not_active Expired
- 1984-01-13 DE DE8484100326T patent/DE3471692D1/en not_active Expired
- 1984-01-30 US US06/575,043 patent/US4508599A/en not_active Expired - Fee Related
- 1984-02-02 JP JP59016199A patent/JPS59143072A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD45299A (en) * | ||||
| FR1213119A (en) * | 1957-10-28 | 1960-03-29 | Western Electric Co | Bath to corrode copper and regeneration of this bath |
| DE1223653B (en) * | 1960-01-11 | 1966-08-25 | Siemens Ag | Device for the continuous electro-lytic regeneration of copper chloride etching solutions |
| US3825484A (en) * | 1971-04-29 | 1974-07-23 | N Fronsman | Electrolytic regenerator for chemical etchants including scraper means and rotating cathodes |
| FR2156249A1 (en) * | 1971-10-12 | 1973-05-25 | Shipley Co | |
| DE2650912A1 (en) * | 1976-11-06 | 1978-05-18 | Hoellmueller Maschbau H | Electrolytic regeneration of copper etching reagent - contg. chloride and cuprous ion, with control of copper concn. in reagent and current density |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 98, Nr. 2, 10. Januar 1983, Seiten 160,161, Nr. 7189a, Columbus, Ohio, USA * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014801A1 (en) * | 1990-03-29 | 1991-10-03 | Hans Höllmüller Maschinenbau GmbH & Co. | Device for the electrolytic regeneration of an etching agent containing metal, especially copper |
| EP0539792A1 (en) * | 1991-10-28 | 1993-05-05 | Nittetsu Mining Co., Ltd. | Method for regenerating etchant |
| CN110306209A (en) * | 2019-08-09 | 2019-10-08 | 郑州金泉矿冶设备有限公司 | The equipment of electrolysis method production super fine silver powder |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3303594A1 (en) | 1984-08-09 |
| JPH0472910B2 (en) | 1992-11-19 |
| US4508599A (en) | 1985-04-02 |
| JPS59143072A (en) | 1984-08-16 |
| DE3471692D1 (en) | 1988-07-07 |
| EP0115791B1 (en) | 1988-06-01 |
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