DE3115436A1 - Method for reprocessing copper-etching waste solutions involving precipitation of the copper fraction as copper oxide and recovery of ammonia - Google Patents
Method for reprocessing copper-etching waste solutions involving precipitation of the copper fraction as copper oxide and recovery of ammoniaInfo
- Publication number
- DE3115436A1 DE3115436A1 DE19813115436 DE3115436A DE3115436A1 DE 3115436 A1 DE3115436 A1 DE 3115436A1 DE 19813115436 DE19813115436 DE 19813115436 DE 3115436 A DE3115436 A DE 3115436A DE 3115436 A1 DE3115436 A1 DE 3115436A1
- Authority
- DE
- Germany
- Prior art keywords
- copper
- mol
- ammonia
- precipitation
- recovery
- 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- Withdrawn
Links
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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/10—Separation of ammonia from ammonia liquors, e.g. gas liquors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Aufar-The invention relates to a method for Aufar-
beitung von Kupferätzabfallösungen mit Ausfällung des Kupferanteils als Kupferoxid und Rückgewinnung von Ammoniak.Processing of copper etching waste solutions with precipitation of the copper content as copper oxide and recovery of ammonia.
Bei der galvanotechnischen Merstellung von gedruckten Schaltungen unter Einsatz der in der Ätztechnik üblichen Ätzmedien fallen Kupferätzabfallösungen an, die einer Aufarbeitung bedürfen, um den Forderungen der Rohstoffwiedergewinnung und des Umweltschutzes gerecht zu werden. In der bT-PS 25 24 546 beispielsweise wird ein vergleichbares Verfahren beschrieben, das jedoch auf Kupferätzlösungen mit niedrigerem Kupfergehalt eingeschränkt ist, das eine sehr aufwendige möglichst vollständige Abtrennung des NH3 anstrebt und das eine Sonderabtrennung von Kupfer- und Zinkionen miteinschließt, um ein die Umwelt nicht belastendes Abwasser zu erhalten.In the electroplating production of printed circuits Using the etching media customary in etching technology, copper etching waste solutions are produced that require reconditioning to meet the demands of raw material recovery and environmental protection. In bT-PS 25 24 546 for example a comparable method is described, but it is based on copper etching solutions is limited with a lower copper content, which is a very expensive possible strives for complete separation of the NH3 and that a special separation of copper and includes zinc ions in order to obtain a non-polluting waste water.
Der Erfindung liegt die Aufgabe zugrunde, diese Nachteile zu vermeiden und ein für die in der heutigen Galvanotechnik anfallenden Kupferätzabfallösungen mit höheren Kupferionenkonzentrationen von ca 150 bi.s 200 g/l einsetzbares Verfahren vorzuschlagen, durch das neben Kupferoxid ausschließlich wiedereinsetzbare Produkte gewonnen werden.The invention is based on the object of avoiding these disadvantages and one for the copper etching waste solutions that arise in today's electroplating technology Process that can be used with higher copper ion concentrations of approx. 150 to 200 g / l to propose that, in addition to copper oxide, only reusable products be won.
Gelöst wird diese Aufgabe bei dem eingangs erwähnten Verfa@ren erfindungsgemäß durch Schaffung eines Mehrstoffsystems in Forrn einer Ammoniumchlorid-Natri umchloridlösung mit Kupfer- und Zinkionen (NaCl, NH4Cl, H2O, Cu2+, Zn2+), durch Vorneutralisieren einer noch H202-haltigen salzsauren Kupferätzlösung mit Natronlauge oder Kupferhydroxidaufschlämmung (Cu(OH)2) auf einen pH-Wert von 4-5, durch Einrühren dieser vorneutralisierten Kupferätzlösung in eine ammoniakalische Supferutzlösung, die zuvor mit konzentrierter kalter Alkalilösung umgesetzt worden ist, durch Einstellen eines Konzentrationsverhältnisses von mindestens 2 ; 4 : 4,25 Mol/l des Gesamtkupfers zum Gesamtammoniak und zum Gesamtalkali in den verrührten Kupferätzlösungen und durch Ausfällung von Kupferoxid und partielle NX3 - Verdampfung mittels langsamer Temperaturerhöhung des Reaktionsgemisches auf 80 - 950 C.This object is achieved according to the invention in the method mentioned at the beginning by creating a multicomponent system in the form of an ammonium chloride-sodium chloride solution with copper and zinc ions (NaCl, NH4Cl, H2O, Cu2 +, Zn2 +), by pre-neutralizing one more H202-containing hydrochloric copper etching solution with caustic soda or copper hydroxide slurry (Cu (OH) 2) to a pH of 4-5 by stirring in this pre-neutralized copper etching solution into an ammoniacal super-usable solution, which has previously been reacted with concentrated cold alkali solution by setting a concentration ratio of at least 2; 4: 4.25 mol / l of the total copper to total ammonia and total alkali in the stirred copper etching solutions and by precipitation of copper oxide and partial NX3 evaporation by means of slower Increase in temperature of the reaction mixture to 80 - 950 C.
Zweckmäßig wird nach Ausfällung des Kupferoxids (CuO) die überstehende filtrierte Reaktionslauge mit Waschwasser -etwa im Verhältnis von 1000 1 . 300 1- vereinigt und mit Salzsäure neutralisiert.After the copper oxide (CuO) has precipitated, the protruding one is expedient filtered reaction liquor with washing water -approximately in the ratio of 1000 1. 300 1- combined and neutralized with hydrochloric acid.
Vorteilhaft wird eine Reaktionslauge von mindestens 2 Mol Cu/l eingesetzt.A reaction liquor of at least 2 mol Cu / l is advantageously used.
-Die dabei erhaltene Salzlauge kennzeichnet sich durch folgende Konzentration NR4Cl 1 - 4 Mol/l NaCl 2 - 4,5 Mol/l Cu2+ 0,01 - 0,1 Mol/l Zn2+ 0,01 - 0,1 Mol/l PH = 5 -7.-The brine obtained is characterized by the following concentration NR4Cl 1 - 4 mol / l NaCl 2 - 4.5 mol / l Cu2 + 0.01 - 0.1 mol / l Zn2 + 0.01 - 0.1 mol / l PH = 5-7.
Durch die erfindungsgemäße vorgeschlagene und erreichte Schaffung eines Mehrstoffsystems in Form ener Ammoniumchlorid-Natriumchloridlösung mit Kupfer- und Zinkionen wird durch diese Art der Aufarbeitung ein wertvoller Rohstoff geschaffen, der in der Ziegelindustrie als Kalktöter und in der Spanplattenindustrie als Härterlösung für Harnstoff-Formaldehydharzsysteme eingesetzt werden kann. Bei der Verarbeitung dieser Lösung in der Spanplatten@@@dustrie wird darüber hinaus eine zusätzliche katalytische Wirkung njit einem fungiziden Effekt erzielt, welcher zur- Verbesserung der Konservierung der Spanplatte bei trägt.By the creation proposed and achieved according to the invention a multi-component system in the form of an ammonium chloride-sodium chloride solution with copper and zinc ions, this type of processing creates a valuable raw material, that in the brick industry as a lime killer and in the chipboard industry as a hardener solution for Urea-formaldehyde resin systems can be used. When processing this Solution in the chipboard industry is also an additional catalytic Effect achieved with a fungicidal effect, which improves the preservation the chipboard contributes.
Aufgrund der Gleichgewichtslage des Systems haben sich folgende Komponentenkonzentrationen gebildet: CuO: 150 - 250 g/l Rest-Cu1+/2+: bis 5 g/l Rest Zn2+ : 3 g/l Rest NH3 : bis 1 -4 Mol/l NaCl : 2 - 4,5 Mol/l NaOlI : 0,25 Mol/l Das gebildete CuO setzt sich gut ab, die überstehende, zum Teil blaue Flüssigkeit wird abdekantiert. Das Trennen und Wachen des CuO wird zweckmäßigerweise in einem Vakuumdruckfilteraggregat vorgenommen.Due to the equilibrium position of the system, the following component concentrations have been found formed: CuO: 150 - 250 g / l remainder Cu1 + / 2 +: up to 5 g / l remainder Zn2 +: 3 g / l remainder NH3 : up to 1 -4 mol / l NaCl: 2 - 4.5 mol / l NaOlI: 0.25 mol / l The CuO formed sets off well, the protruding, partly blue liquid is decanted off. That Separation and monitoring of the CuO is expediently carried out in a vacuum pressure filter unit performed.
Die Aufarbeitung der Reaktionslauge einschlieBlicll Waschwasser entfällt, da nach deren Neutralisation ein voll einsatzfähiges Wirtschaftsgut in entsprechend hochkonzentrierter Form anfällt.There is no need to work up the reaction liquor, including washing water, since after their neutralization a fully operational asset is accordingly highly concentrated form.
Damit ist es gelungen, ein Aufarbeitungsverfahren zu entwichen, das völlig indifferent gegenüber der Umwelt ist und bei dem alle Inhaltsstoffe der aufzuarbeitenden Lösungen einschließlich Waschwässer umformuliert werden.It was thus possible to escape a processing method that is completely indifferent to the environment and in which all ingredients of the processed Solutions including wash water can be reformulated.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813115436 DE3115436A1 (en) | 1981-04-16 | 1981-04-16 | Method for reprocessing copper-etching waste solutions involving precipitation of the copper fraction as copper oxide and recovery of ammonia |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813115436 DE3115436A1 (en) | 1981-04-16 | 1981-04-16 | Method for reprocessing copper-etching waste solutions involving precipitation of the copper fraction as copper oxide and recovery of ammonia |
Publications (1)
Publication Number | Publication Date |
---|---|
DE3115436A1 true DE3115436A1 (en) | 1982-12-16 |
Family
ID=6130303
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19813115436 Withdrawn DE3115436A1 (en) | 1981-04-16 | 1981-04-16 | Method for reprocessing copper-etching waste solutions involving precipitation of the copper fraction as copper oxide and recovery of ammonia |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE3115436A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2542325A1 (en) * | 1983-03-12 | 1984-09-14 | Didier Werke Ag | Combined etching soln. regeneration and metal recovery |
US5188703A (en) * | 1992-01-27 | 1993-02-23 | Diversified Recycling Technology | Method and apparatus for recovering copper and regenerating ammoniacal etchant from spent ammoniacal etchant |
RU2568225C1 (en) * | 2014-06-10 | 2015-11-10 | Акционерное общество "Калужский научно-исследовательский институт телемеханических устройств"(АО "КНИИТМУ") | Method of extracting copper (+2) from spent solutions |
RU2622072C1 (en) * | 2016-01-11 | 2017-06-09 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Пензенский государственный университет" (ФГБОУ ВПО "Пензенский государственный университет") | Method of utilisation of a processed copper-ammonium solution |
CN111547759A (en) * | 2020-05-19 | 2020-08-18 | 姚丰硕 | Preparation method of PS loaded copper oxide nanorod |
-
1981
- 1981-04-16 DE DE19813115436 patent/DE3115436A1/en not_active Withdrawn
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2542325A1 (en) * | 1983-03-12 | 1984-09-14 | Didier Werke Ag | Combined etching soln. regeneration and metal recovery |
US5188703A (en) * | 1992-01-27 | 1993-02-23 | Diversified Recycling Technology | Method and apparatus for recovering copper and regenerating ammoniacal etchant from spent ammoniacal etchant |
RU2568225C1 (en) * | 2014-06-10 | 2015-11-10 | Акционерное общество "Калужский научно-исследовательский институт телемеханических устройств"(АО "КНИИТМУ") | Method of extracting copper (+2) from spent solutions |
RU2622072C1 (en) * | 2016-01-11 | 2017-06-09 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Пензенский государственный университет" (ФГБОУ ВПО "Пензенский государственный университет") | Method of utilisation of a processed copper-ammonium solution |
CN111547759A (en) * | 2020-05-19 | 2020-08-18 | 姚丰硕 | Preparation method of PS loaded copper oxide nanorod |
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Legal Events
Date | Code | Title | Description |
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OAV | Applicant agreed to the publication of the unexamined application as to paragraph 31 lit. 2 z1 | ||
8139 | Disposal/non-payment of the annual fee |