EP0018592A1 - Procédé de régénération de solutions ammoniacales de décapage destinées au décapage de cuivre métallique - Google Patents

Procédé de régénération de solutions ammoniacales de décapage destinées au décapage de cuivre métallique Download PDF

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Publication number
EP0018592A1
EP0018592A1 EP80102194A EP80102194A EP0018592A1 EP 0018592 A1 EP0018592 A1 EP 0018592A1 EP 80102194 A EP80102194 A EP 80102194A EP 80102194 A EP80102194 A EP 80102194A EP 0018592 A1 EP0018592 A1 EP 0018592A1
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EP
European Patent Office
Prior art keywords
etching
copper
ammoniacal
regeneration
poorly soluble
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.)
Withdrawn
Application number
EP80102194A
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German (de)
English (en)
Inventor
Efthimios Dr. Konstantouros
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP0018592A1 publication Critical patent/EP0018592A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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

Definitions

  • the invention relates to a method for regenerating ammoniacal etching solutions for etching metallic copper, in particular for etching galvanized printed circuit boards.
  • Atmospheric oxygen is meant as 0 2 .
  • Air oxidation from Gu + to Cu ++ takes place spontaneously in the spray etching machine. A separate air supply is not necessary.
  • mixtures of NH 4 Cl and (NH 4 ) 2 CO 3 are preferably used as NH 4 salts.
  • the overall reaction for example with chloride, looks as follows:
  • the metallic copper is oxidized to [Cu (NH 3 ) 4 ] ++ ion using ammonia, ammonium salts and atmospheric oxygen.
  • the chemicals NH 3 and NH 4 salts are metered into the etching machine as aqueous solutions, so-called “supplementary solutions", during the etching process.
  • the resulting highly copper-containing etching concentrates are collected as an overflow and given to a relevant copper processing company, where, to our knowledge, the NH 3 is destroyed with chlorine and the copper is cemented with scrap iron (Fe). The transfer of the overflow to this company is associated with transport and processing costs.
  • the invention has for its object to provide a method for the regeneration of the ammoniacal etching solutions with which the NH 3 and NH 4 salts and the etched copper can be recovered in a relatively simple manner.
  • the recycling- developed to solve the task Veriahren consists in that with the help of a metal that is less noble than copper and forms a poorly soluble hydroxide in the pH range of the etching medium, the Cu ++ ion is reduced to metallic copper and the etching chemicals are re-formed, the metal itself becoming one poorly soluble hydroxide is oxidized.
  • Al is preferably used, since it does not form soluble amine complexes and does not release any toxic ions. The following reactions take place:
  • the decoupled solution is separated from the Cu and Al (OH) 3 sludge by filtration and reused as a supplementary solution for the etching process.
  • the cement copper is a heavy powder and is relatively easy to separate from the lighter hydroxide.
  • the ammonia property of dissolving some Al (OH) 3 as aluminate is completely prevented by the presence of the NH 4 salts.
  • the copper cementation is carried out in the form of an internal electrolysis, the deposited materials copper and aluminum hydroxide being obtained separately. This facilitates the regeneration process.
  • the anode compartment 3 is filled with supplementary solution and the cathode compartment 4 with a mixture of supplementary solution and etching solution.
  • An Al plate 5 is immersed in the anode compartment 3 as a base electrode as a soluble anode and a Cu plate 6 is immersed in the cathode compartment 4 as a nobler electrode.
  • electrolysis without an external power source internal electrolysis
  • the Al plate 5 emits electrons to the Cu plate 6 and decays itself into Al (OH) 3 after the following reaction:
  • the liquid in the cathode compartment 4 is completely decoupled, pure supplementary solution is formed. Part of it is removed and replaced with an etching solution.
  • the supplementary solution removed is metered into the etching machine for the etching process.
  • the overflow of the etching machine is decoupled in batches in the cathode space 4 and converted into supplementary solution.
  • the cathode liquid preferably consists of approx. 95% supplementary solution and 5% etching solution. This is necessary because of the difference in density (1.05 g / ml for the supplementary solution and 1.2 g / ml for the etching solution with approx.
  • the supplementary solution in the anode compartment 3 is separated from the Al (OH) 3 sludge by filtration and used again as the anode liquid.
  • the deposited Al (OH) 3 can be discarded.
EP80102194A 1979-04-30 1980-04-23 Procédé de régénération de solutions ammoniacales de décapage destinées au décapage de cuivre métallique Withdrawn EP0018592A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792917597 DE2917597A1 (de) 1979-04-30 1979-04-30 Verfahren zur regenerierung ammoniakalischer aetzloesungen zum aetzen von metallischem kupfer
DE2917597 1979-04-30

Publications (1)

Publication Number Publication Date
EP0018592A1 true EP0018592A1 (fr) 1980-11-12

Family

ID=6069704

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80102194A Withdrawn EP0018592A1 (fr) 1979-04-30 1980-04-23 Procédé de régénération de solutions ammoniacales de décapage destinées au décapage de cuivre métallique

Country Status (4)

Country Link
US (1) US4280887A (fr)
EP (1) EP0018592A1 (fr)
JP (1) JPS55148772A (fr)
DE (1) DE2917597A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0393270A1 (fr) * 1989-04-21 1990-10-24 Ming-Hsing Lee Procédé de décapage de cuivre à l'aide d'une solution de gravure ammoniacale et reconditionnement de la solution usée

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3031567A1 (de) * 1980-08-21 1982-04-29 Elochem Ätztechnik GmbH, 7758 Meersburg Verfahren zum regenerieren einer ammoniakalischen aetzloesung
DE3237246A1 (de) * 1982-10-07 1984-04-12 Gosudarstvennyj naučno-issledovatel'skij i proektnyj institut po obogaščeniju rud cvetnych metallov KAZMECHANOBR, Alma-Ata Verfahren zur reinigung von abwaessern und loesungen und apparat zur durchfuehrung desselben
US4655895A (en) * 1982-10-07 1987-04-07 Gosudarstvenny Nauchno-Issledovatelsky I Proektny Institut Po Obogascheniju Rud Tsvetnykh Metallov "Kazmekhanobr" Apparatus for purifying effluents and liquids
DE3324450A1 (de) * 1983-07-07 1985-01-17 ELO-CHEM Ätztechnik GmbH, 7758 Meersburg Ammoniumsulfathaltige aetzloesung sowie verfahren zur regeneration der aetzloesung
US4490224A (en) * 1984-04-16 1984-12-25 Lancy International, Inc. Process for reconditioning a used ammoniacal copper etching solution containing copper solute
JPH01190907A (ja) * 1988-01-25 1989-08-01 Nissan Motor Co Ltd 再溶融チルカムシャフト
US5348629A (en) * 1989-11-17 1994-09-20 Khudenko Boris M Method and apparatus for electrolytic processing of materials
US5133873A (en) * 1991-02-22 1992-07-28 Miles Inc. Process for removal of copper ions from aqueous effluent
US5417818A (en) * 1993-11-24 1995-05-23 Elo-Chem Atztechnik Gmbh Process for the accelerated etching and refining of metals in ammoniacal etching systems
DE69530984D1 (de) * 1994-07-19 2003-07-10 Corus Staal Bv Verfahren zum elektrochemischen Lösen eines Metalles, wie z. B. Zink oder Zinn
US5524780A (en) * 1995-01-31 1996-06-11 Applied Electroless Concepts Inc. Control of regeneration of ammoniacal copper etchant
US5626736A (en) 1996-01-19 1997-05-06 Shipley Company, L.L.C. Electroplating process
US6086779A (en) * 1999-03-01 2000-07-11 Mcgean-Rohco, Inc. Copper etching compositions and method for etching copper
US6869519B2 (en) * 2001-09-27 2005-03-22 National Institute Of Advanced Industrial Science And Technology Electrolytic process for the production of metallic copper and apparatus therefor
US20050082172A1 (en) * 2003-10-21 2005-04-21 Applied Materials, Inc. Copper replenishment for copper plating with insoluble anode
CN100378014C (zh) * 2005-02-03 2008-04-02 黄伟君 污水处理及资源回收的系统和方法
US20060193750A1 (en) * 2005-02-28 2006-08-31 Medis El Ltd. Electrochemical detection of explosives in air
CN113200635B (zh) * 2021-06-17 2022-05-10 徐鸿顺 一种电路板蚀刻废水处理装置及方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2072986A5 (fr) * 1969-12-09 1971-09-24 Didier Werke Ag
US3761369A (en) * 1971-10-18 1973-09-25 Electrodies Inc Process for the electrolytic reclamation of spent etching fluids
AT313671B (de) * 1971-03-08 1974-02-25 Hoellmueller Maschbau H Verfahren zum Regenerieren von Ätzlösungen für Kupfer und Kupferlegierungen, Regenerationsanlage zur Durchführung dieses Verfahrens sowie Meß- und Steuereinrichtung für diese Regenerationsanlage
GB1416637A (en) * 1972-09-09 1975-12-03 Loewe Opta Gmbh Treatment of used copper etching solutions
AT326973B (de) * 1973-03-03 1976-01-12 Hoellmueller Maschbau H Verfahren und vorrichtung zum reinigen von kupferhaltigen ammoniakalischen losungen
DE2651675A1 (de) * 1976-01-09 1977-07-14 C Paul Pesek Anordnung zur kontinuierlichen wiedergewinnung von aetzmaterial und geaetztem material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6603696A (fr) * 1965-04-28 1966-10-31
US4035269A (en) * 1971-04-23 1977-07-12 Snam Progetti, S.P.A. Process for the galvanic purification of the waste waters
US3766036A (en) * 1972-03-06 1973-10-16 Occidental Petroleum Corp Process for the removal of ionic metallic impurities from water
US4152229A (en) * 1978-04-19 1979-05-01 London Laboratories Limited Apparatus and method for removal of soluble metal ions from aqueous effluent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2072986A5 (fr) * 1969-12-09 1971-09-24 Didier Werke Ag
AT313671B (de) * 1971-03-08 1974-02-25 Hoellmueller Maschbau H Verfahren zum Regenerieren von Ätzlösungen für Kupfer und Kupferlegierungen, Regenerationsanlage zur Durchführung dieses Verfahrens sowie Meß- und Steuereinrichtung für diese Regenerationsanlage
US3761369A (en) * 1971-10-18 1973-09-25 Electrodies Inc Process for the electrolytic reclamation of spent etching fluids
GB1416637A (en) * 1972-09-09 1975-12-03 Loewe Opta Gmbh Treatment of used copper etching solutions
AT326973B (de) * 1973-03-03 1976-01-12 Hoellmueller Maschbau H Verfahren und vorrichtung zum reinigen von kupferhaltigen ammoniakalischen losungen
DE2651675A1 (de) * 1976-01-09 1977-07-14 C Paul Pesek Anordnung zur kontinuierlichen wiedergewinnung von aetzmaterial und geaetztem material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0393270A1 (fr) * 1989-04-21 1990-10-24 Ming-Hsing Lee Procédé de décapage de cuivre à l'aide d'une solution de gravure ammoniacale et reconditionnement de la solution usée

Also Published As

Publication number Publication date
DE2917597A1 (de) 1980-11-13
JPS55148772A (en) 1980-11-19
US4280887A (en) 1981-07-28

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Effective date: 19821022

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Inventor name: KONSTANTOUROS, EFTHIMIOS, DR.