EP0435382A1 - Electrolytic process for treating waste pickling solutions or product streams containing metallic ions - Google Patents
Electrolytic process for treating waste pickling solutions or product streams containing metallic ions Download PDFInfo
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- EP0435382A1 EP0435382A1 EP90203345A EP90203345A EP0435382A1 EP 0435382 A1 EP0435382 A1 EP 0435382A1 EP 90203345 A EP90203345 A EP 90203345A EP 90203345 A EP90203345 A EP 90203345A EP 0435382 A1 EP0435382 A1 EP 0435382A1
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- anode
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- pickling
- product streams
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Definitions
- the invention relates to an electrolysis process for the treatment of old stains or by-product streams containing at least two different metal ions and resulting from the surface treatment of metallic materials by means of aqueous pickling solutions by means of at least one anode and one cathode and one electrolyte.
- the conventional processes for the treatment of old pickles containing metal ions or by-product streams that arise during the surface treatment of metallic materials by means of aqueous pickling solutions include electrolysis, in which the metal or metals are deposited on the cathode either by regulating the cell voltage or the cell current and the anions be discharged at the anode.
- DE-A-1 558 711 describes an electrolysis process for the recovery of metals from pickling solutions containing impurities, in which the electrolyte containing ions of the metal in question is moved in a directed current onto the anode and then past the cathode in such a way that the cell voltage between the anode and cathode convert the metal ions into relatively pure metal.
- the solution to this problem is that the cathode and anode compartments of the electrolytic cell are separated by an anion exchange membrane, the anode compartment is filled with demetallized, oxidizable or non-oxidizable pickling solution, and the freely selectable potential of the cathode or anode is kept constant by means of a potential-controlled rectifier via a reference electrode.
- This arrangement makes it possible to process an old pickle or by-product stream containing metal ions, which contains metals which cannot be separated from aqueous solutions in addition to separable metals.
- the anions of the old pickle pass through the anion exchange membrane into the anode compartment, where they are concentrated.
- the metal ions remain in the cathode compartment so that a demetallized pickling solution can be supplied to the pickling bath or to production.
- the electrolysis is carried out until almost all of the metals which can be deposited are deposited on the cathode or until the old pickle or the by-product stream of anions is almost completely depleted.
- the non-separable metals remain in the pickling solution, which is depleted of anions.
- a preferred embodiment of the electrolysis process according to the invention consists in the use on old pickles containing iron (II) and / or iron (III) chloride or by-product streams which are used in the surface treatment of Iron-nickel alloys have emerged.
- the pickling solution depleted in metals is fed to the anode current and chlorine gas is developed at the anode until the iron (III) chloride-containing pickling solution has reached its initial concentration again.
- the chlorine gas oxidizes the iron (II) formed during the pickling process to iron (III).
- the iron (III) chloride concentration required for the pickling process can thus be kept constant over the entire pickling time.
- the cell voltage is 2.0 to 6.0 V, the current density 5 to 70 mA / cm2 and the potential of the cathode or anode to -2000 mV, preferably -100 to 1800 mV.
- metals with a plurality of oxidation levels can be deposited in succession or as alloy coatings by adjusting the specific potential and by changing the cathode.
- the demetallized pickling solution is fed into the anode compartment and, after electrolysis has been carried out, is fed to the pickling bath or the product stream.
- an Al3+ - and Cu2+ ion-containing old pickle based on sulfuric acid is fed via the line (25) to the cathode compartment (26) of the potential-controlled electrolysis cell (27).
- the copper is deposited on the cathode (28) to which the reference electrode (29) is assigned in a potential-controlled manner.
- the anions pass through the anion exchange membrane (30) into the anode space (31) with the anode (32) arranged therein, where they are concentrated.
- the largely demetallized pickling solution is fed via line (33) to a buffer tank (34) which is connected to the pickling bath (36) via line (35) and to the anode compartment (31) via line (37). connected is.
- the pickling solution containing copper-depleted Al3+ ions is withdrawn from the cathode compartment (21) via line (38).
- FIG. 2 A preferred embodiment of the electrolysis process according to the invention is shown in FIG. 2.
- Used line (39) is used stain of the composition Fe3+ 261 g / l, Fe2+ 5 g / l, Ni2+ 15 g / l, Cl - 521 g / l, free hydrochloric acid ⁇ 1 g / l to the cathode compartment (40) supplied to the potential-controlled electrolysis cell (41).
- a cell voltage of 4.5 V a current density of 50 mA / cm2 and a cathode potential of -1600 mV, iron and nickel are deposited together on the cathode (43) with an associated reference electrode (42).
- an anion exchange membrane (44) is arranged in the electrolysis cell (41). During the deposition of the metals on the cathode (43), due to the electric field, the Cl ⁇ ions migrate from the pickling solution through the anion exchange membrane (43) into the anode compartment (45), where oxidation by the anode (46) to chlorine gas takes place .
- the demetallized Fe (III) chloride pickling solution is fed from the cathode compartment (40) via line (47) to the anode compartment (45).
- the chlorine gas flows via line (48) and the Fe (III) chloride pickling solution via line (49) from the anode compartment (45) to the pickling bath (50).
- the Fe2+ ions contained in the pickling bath (5) due to the introduction of the anolyte after the electrolysis are oxidized to Fe3+ ions by the chlorine gas.
- the chemical analysis of the anolyte after electrolysis shows a composition of Fe3+ 57 g / l, Fe2+ ⁇ 10 mg / l, Ni2+ 1.2 g / l and Cl ⁇ 110.5 g / l.
- the advantage achieved with the invention is in particular that efficiencies of up to 95% can be achieved with the electrolysis process designed according to the invention.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Electrolytic Production Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
Die Erfindung betrifft ein Elektrolyseverfahren zur Aufbereitung mindestens zwei unterschiedliche Metallionen enthaltender, bei der Oberflächenbehandlung metallischer Werkstoffe mittels wäßriger Beizlösungen anfallender Altbeizen oder Nebenproduktströme mittels mindestens einer Anode und einer Kathode und einem Elektrolyten.The invention relates to an electrolysis process for the treatment of old stains or by-product streams containing at least two different metal ions and resulting from the surface treatment of metallic materials by means of aqueous pickling solutions by means of at least one anode and one cathode and one electrolyte.
Zu den herkömmlichen Verfahren zur Aufbereitung Metallionen enthaltender Altbeizen oder Nebenproduktströme, die bei der Oberflächenbehandlung metallischer Werkstoffe mittels wäßriger Beizlösungen entstehen, zählt die Elektrolyse, bei der das bzw. die Metalle entweder über die Regelung der Zellspannung oder des Zellstroms an der Kathode niedergeschlagen und die Anionen an der Anode entladen werden.The conventional processes for the treatment of old pickles containing metal ions or by-product streams that arise during the surface treatment of metallic materials by means of aqueous pickling solutions include electrolysis, in which the metal or metals are deposited on the cathode either by regulating the cell voltage or the cell current and the anions be discharged at the anode.
In der DE-A-1 558 711 ist ein Elektrolyseverfahren zur Gewinnung von Metallen aus Verunreinigungen enthaltenden Beizlösungen beschrieben, bei dem der Ionen des betreffenden Metalls enthaltende Elektrolyt in gerichtetem Strom auf die Anode und darauf an der Kathode so vorbeibewegt wird, daß die Zellspannung zwischen der Anode und Kathode eine Umwandlung der Metallionen in verhältnismäßig reines Metall bewirkt.DE-A-1 558 711 describes an electrolysis process for the recovery of metals from pickling solutions containing impurities, in which the electrolyte containing ions of the metal in question is moved in a directed current onto the anode and then past the cathode in such a way that the cell voltage between the anode and cathode convert the metal ions into relatively pure metal.
Die Anwendung dieses herkömmlichen Elektrolyseverfahrens zur Aufbereitung wäßriger Metallionen enthaltender Altbeizen oder Nebenproduktströme ist nachteiligerweise nur mit Wirkungsgraden, die deutlich unter 90 % liegen, verbunden. Das ist im wesentlichen darauf zurückzuführen, daß entweder mehrere Metallionen mit unterschiedlichen Wasserstoffüberspannungen oder Metalle, die mehrere Oxidationsstufen besitzen, im Elektrolyten vorliegen. Weiterhin sind in Metallionen enthaltenden Altbeizen oder Nebenproduktströmen häufig Anionen enthalten, die aufgrund der relativ hohen Zellspannung an der Anode zu Schadgasen, z.B. Chlorgas, oxidiert werden.The use of this conventional electrolysis process for the treatment of aqueous pickles or by-product streams containing aqueous metal ions is disadvantageously associated only with efficiencies which are well below 90%. This is essentially due to the fact that either several metal ions with different hydrogen overvoltages or metals which have several oxidation states are present in the electrolyte. Furthermore, in old pickles containing metal ions or By-product streams often contain anions which, due to the relatively high cell voltage at the anode, are oxidized to harmful gases, eg chlorine gas.
Es ist die Aufgabe der vorliegenden Erfindung, den Wirkungsgrad der Metallabscheidung des eingangs beschriebenen Elektrolyseverfahrens wesentlich zu steigern, ohne die Beizlösungen oder die Nebenproduktströme chemisch zu verändern.It is the object of the present invention to significantly increase the efficiency of the metal deposition of the electrolysis process described at the outset without chemically changing the pickling solutions or the by-product streams.
Die Lösung dieser Aufgabe besteht darin, daß Kathoden- und Anodenraum der Elektrolysezelle durch eine Anionenaustauschermembrane getrennt, der Anodenraum mit entmetallisierter, oxidierbarer oder nicht oxidierbarer Beizlösung gefüllt und das frei wählbare Potential der Kathode oder Anode mittels potentialgeregeltem Gleichrichter über eine Bezugselektrode konstant gehalten wird.The solution to this problem is that the cathode and anode compartments of the electrolytic cell are separated by an anion exchange membrane, the anode compartment is filled with demetallized, oxidizable or non-oxidizable pickling solution, and the freely selectable potential of the cathode or anode is kept constant by means of a potential-controlled rectifier via a reference electrode.
Diese Anordnung ermöglicht eine Metallionen enthaltende Altbeize oder Nebenproduktstrom aufzuarbeiten, die neben abscheidbaren Metallen aus wäßrigen Lösungen nicht abscheidbare Metalle enthält. Die Anionen der Altbeize gelangen durch die Anionenaustauschermembrane in den Anodenraum, wo sie aufkonzentriert werden. Die Metallionen verbleiben im Kathodenraum, so daß eine entmetallisierte Beizlösung dem Beizbad oder der Produktion zugeführt werden kann. Die Elektrolyse wird solange durchgeführt, bis nahezu alle abscheidbaren Metalle an der Kathode niedergeschlagen sind oder bis die Altbeize bzw. der Nebenproduktstrom an Anionen nahezu vollkommen abgereichert ist. In der an Anionen verarmten Beizlösung verbleiben die nicht abscheidbaren Metalle.This arrangement makes it possible to process an old pickle or by-product stream containing metal ions, which contains metals which cannot be separated from aqueous solutions in addition to separable metals. The anions of the old pickle pass through the anion exchange membrane into the anode compartment, where they are concentrated. The metal ions remain in the cathode compartment so that a demetallized pickling solution can be supplied to the pickling bath or to production. The electrolysis is carried out until almost all of the metals which can be deposited are deposited on the cathode or until the old pickle or the by-product stream of anions is almost completely depleted. The non-separable metals remain in the pickling solution, which is depleted of anions.
Eine vorzugsweise Ausführungsform des erfindungsgemäßen Elektrolyseverfahrens besteht in der Anwendung auf Eisen(II)- und/oder Eisen(III)-chloridhaltige Altbeizen oder Nebenproduktströme, die bei der Oberflächenbehandlung von Eisen-Nickel-Legierungen entstanden sind. Hierbei wird nach erfolgter Metallabscheidung an der Kathode die an Metallen abgereicherte Beizlösung dem Anodenstrom zugeführt und an der Anode solange Chlorgas entwickelt, bis die Eisen(III)-chloridhaltige Beizlösung ihre Ausgangskonzentration wieder erreicht hat. Das Chlorgas oxidiert das während des Beizprozesses entstandene Eisen(II) zu Eisen(III). Die zum Beizvorgang erforderliche Eisen(III)-Chloridkonzentration kann somit über die gesamte Beizdauer konstant gehalten werden.A preferred embodiment of the electrolysis process according to the invention consists in the use on old pickles containing iron (II) and / or iron (III) chloride or by-product streams which are used in the surface treatment of Iron-nickel alloys have emerged. After the metal has been deposited on the cathode, the pickling solution depleted in metals is fed to the anode current and chlorine gas is developed at the anode until the iron (III) chloride-containing pickling solution has reached its initial concentration again. The chlorine gas oxidizes the iron (II) formed during the pickling process to iron (III). The iron (III) chloride concentration required for the pickling process can thus be kept constant over the entire pickling time.
Im Rahmen der zweckmäßigen Ausgestaltung des erfindungsgemäßen Elektrolyseverfahrens beträgt die Zellspannung 2,0 bis 6,0 V, die Stromdichte 5 bis 70 mA/cm² und das Potential der Kathode oder Anode bis -2000 mV, vorzugsweise -100 bis 1800 mV.In the context of the expedient embodiment of the electrolysis process according to the invention, the cell voltage is 2.0 to 6.0 V, the current density 5 to 70 mA / cm² and the potential of the cathode or anode to -2000 mV, preferably -100 to 1800 mV.
Auf diese Weise können mit hohem Wirkungsgrad Metalle mit mehreren Oxidationsstufen durch Einstellung des jeweils spezifischen Potentials und durch Kathodenwechsel nacheinander oder als Legierungsüberzüge abgeschieden werden. Die entmetallisierte Beizlösung wird in den Anodenraum geleitet und nach erfolgter Elektrolyse dem Beizbad oder dem Produktstrom zugeführt.In this way, metals with a plurality of oxidation levels can be deposited in succession or as alloy coatings by adjusting the specific potential and by changing the cathode. The demetallized pickling solution is fed into the anode compartment and, after electrolysis has been carried out, is fed to the pickling bath or the product stream.
Die Erfindung ist im folgenden anhand mehrerer Ausführungsbeispiele und schematischer Zeichnungen näher erläutert.The invention is explained in more detail below with the aid of several exemplary embodiments and schematic drawings.
Bei dem in Fig. 1 dargestellten Elektrolyseverfahren wird eine Al³⁺ - und Cu²⁺-Ionen enthaltende Altbeize auf Schwefelsäurebasis über die Leitung (25) dem Kathodenraum (26) der potentialgeregelten Elektrolysezelle (27) zugeführt. Das Kupfer wird an der Kathode (28), der die Bezugselektrode (29) zugeordnet ist, potentialgeregelt abgeschieden.In the electrolysis process shown in Fig. 1, an Al³⁺ - and Cu²⁺ ion-containing old pickle based on sulfuric acid is fed via the line (25) to the cathode compartment (26) of the potential-controlled electrolysis cell (27). The copper is deposited on the cathode (28) to which the reference electrode (29) is assigned in a potential-controlled manner.
Die Anionen gelangen durch die Anionenaustauschermembrane (30) in den Anodenraum (31) mit der darin angeordneten Anode (32), wo sie aufkonzentriert werden. Aus dem Anodenraum (31) wird die weitgehend entmetallisierte Beizlösung über die Leitung (33) einem Puffertank (34) aufgegeben, der über die Leitung (35) mit dem Beizbad (36) und über die Leitung (37) mit dem Anodenraum (31) verbunden ist. Die an Kupfer verarmte Al³⁺-Ionen enthaltende Beizlösung wird aus dem Kathodenraum (21) über die Leitung (38) abgezogen.The anions pass through the anion exchange membrane (30) into the anode space (31) with the anode (32) arranged therein, where they are concentrated. From the anode compartment (31), the largely demetallized pickling solution is fed via line (33) to a buffer tank (34) which is connected to the pickling bath (36) via line (35) and to the anode compartment (31) via line (37). connected is. The pickling solution containing copper-depleted Al³⁺ ions is withdrawn from the cathode compartment (21) via line (38).
Eine bevorzugte Ausführungsform des erfindungsgemäßen Elektrolyseverfahrens ist in Fig. 2 wiedergegeben. Über die Leitung (39) wird Altbeize der Zusammensetzung Fe³⁺ 261 g/l, Fe²⁺ 5 g/l, Ni²⁺ 15 g/l, Cl- 521 g/l, freie Salzsäure < 1 g/l dem Kathodenraum (40) der potentialgeregelten Elektrolysezelle (41) zugeführt. Bei einer Zellspannung von 4,5 V, einer Stromdichte von 50 mA/cm² und einem Kathodenpotential von -1600 mV werden Eisen und Nickel gemeinsam an der Kathode (43) mit zugeordneter Bezugselektrode (42) abgeschieden. Wegen der Gefahr der Oxidation von Fe²⁺- zu Fe³⁺ -Ionen ist in der Elektrolysezelle (41) eine Anionenaustauschermembrane (44) angeordnet. Während der Abscheidung der Metalle an der Kathode (43) wandern aufgrund des elektrischen Feldes die Cl⁻-Ionen aus der Beizlösung durch die Anionenaustauschermembrane (43) in den Anodenraum (45), wo eine durch die Anode (46) hervorgerufene Oxidation zu Chlorgas erfolgt. Aus dem Kathodenraum (40) wird die entmetallisierte Fe(III)-Chlorid-Beizlösung über Leitung (47) dem Anodenraum (45) zugeführt. Das Chlorgas strömt über Leitung (48) und die Fe(III)-Chlorid-Beizlösung über Leitung (49) vom Anodenraum (45) zum Beizbad (50). Die durch die Einleitung des Anolyts nach der Elektrolyse im Beizbad (5) enthaltenen Fe²⁺-Ionen werden durch das Chlorgas zu Fe³⁺-Ionen oxidiert.A preferred embodiment of the electrolysis process according to the invention is shown in FIG. 2. Used line (39) is used stain of the composition Fe³⁺ 261 g / l, Fe²⁺ 5 g / l, Ni²⁺ 15 g / l, Cl - 521 g / l, free hydrochloric acid <1 g / l to the cathode compartment (40) supplied to the potential-controlled electrolysis cell (41). At a cell voltage of 4.5 V, a current density of 50 mA / cm² and a cathode potential of -1600 mV, iron and nickel are deposited together on the cathode (43) with an associated reference electrode (42). Because of the risk of oxidation of Fe²⁺ to Fe³⁺ ions, an anion exchange membrane (44) is arranged in the electrolysis cell (41). During the deposition of the metals on the cathode (43), due to the electric field, the Cl⁻ ions migrate from the pickling solution through the anion exchange membrane (43) into the anode compartment (45), where oxidation by the anode (46) to chlorine gas takes place . The demetallized Fe (III) chloride pickling solution is fed from the cathode compartment (40) via line (47) to the anode compartment (45). The chlorine gas flows via line (48) and the Fe (III) chloride pickling solution via line (49) from the anode compartment (45) to the pickling bath (50). The Fe²⁺ ions contained in the pickling bath (5) due to the introduction of the anolyte after the electrolysis are oxidized to Fe³⁺ ions by the chlorine gas.
Die chemische Analyse des Anolyts nach der Elektrolyse ergibt eine Zusammensetzung aus Fe³⁺ 57 g/l, Fe²⁺ < 10 mg/l, Ni²⁺ 1,2 g/l und Cl⁻ 110,5 g/l.The chemical analysis of the anolyte after electrolysis shows a composition of Fe³⁺ 57 g / l, Fe²⁺ <10 mg / l, Ni²⁺ 1.2 g / l and Cl⁻ 110.5 g / l.
Der mit der Erfindung erzielte Vorteil besteht insbesondere darin, daß sich mit dem erfindungsgemäß gestalteten Elektrolyseverfahren Wirkungsgrade bis 95 % erzielen lassen.The advantage achieved with the invention is in particular that efficiencies of up to 95% can be achieved with the electrolysis process designed according to the invention.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3943142 | 1989-12-28 | ||
| DE3943142A DE3943142A1 (en) | 1989-12-28 | 1989-12-28 | ELECTROLYSIS PROCESS FOR PROCESSING METALION-CONTAINING OLD Stains or Product Streams |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0435382A1 true EP0435382A1 (en) | 1991-07-03 |
| EP0435382B1 EP0435382B1 (en) | 1994-06-15 |
Family
ID=6396535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90203345A Expired - Lifetime EP0435382B1 (en) | 1989-12-28 | 1990-12-17 | Electrolytic process for treating waste pickling solutions or product streams containing metallic ions |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0435382B1 (en) |
| DE (2) | DE3943142A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4218915A1 (en) * | 1992-06-10 | 1993-12-16 | Heraeus Elektrochemie | Method and device for regenerating an aqueous solution containing metal ions and sulfuric acid, and use |
| EP0638664A1 (en) * | 1993-08-11 | 1995-02-15 | Heraeus Elektrochemie GmbH | Process and apparatus for regenerating solutions containing metal ions and sulfuric acid |
| WO1995023880A1 (en) * | 1994-03-04 | 1995-09-08 | Spunboa Pty. Limited | Treatement of electrolyte solutions |
| WO1995024518A1 (en) * | 1994-03-07 | 1995-09-14 | Mib Metallurgie Und Oberflächentechnik Und Innovation In Berlin Gmbh & Co. | Electrolysis process for regenerating a ferric chloride or sulphate solution, in particular for spray etching steel |
| WO1998038353A1 (en) * | 1997-02-25 | 1998-09-03 | Centro Sviluppo Materiali S.P.A. | Method for pickling products of a metal alloy in absence of nitric and for recovering exhausted pickling solutions and apparatus therefore |
| ES2172479A1 (en) * | 2001-03-13 | 2002-09-16 | Fundacion Cidetec | Metal electrodeposition via constant potential reference electrode comprises D.C. processing, with dissolving of anode metal and optimization of potential |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| WO2015000002A1 (en) * | 2013-07-04 | 2015-01-08 | Pureox Industrieanlagenbau Gmbh | Process for the electrochemical oxidation of fe2+ chloride solutions |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829592C1 (en) * | 1998-07-02 | 1999-12-09 | Umweltanalytisches Zentrum Gro | Mineral acids containing metals from pickling plants are processed and recovered |
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|---|---|---|---|---|
| US2810686A (en) * | 1954-11-09 | 1957-10-22 | Rohm & Haas | Electrolytic treatment of waste sulfate pickle liquor |
| DE1155610B (en) * | 1961-05-18 | 1963-10-10 | Ionics | Method and cell for the electrolytic deposition of metals, in particular iron |
| FR2273082A1 (en) * | 1974-05-28 | 1975-12-26 | Seprac | |
| US4149946A (en) * | 1978-03-21 | 1979-04-17 | Davis Walker Corporation | Recovery of spent pickle liquor and iron metal |
| EP0075882A2 (en) * | 1981-09-25 | 1983-04-06 | Hitachi, Ltd. | Process for regenerating cleaning fluid |
| DE3719604A1 (en) * | 1987-06-12 | 1988-12-22 | Markus Maria Dipl In Bringmann | Pickling of semifinished articles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1124222A (en) * | 1966-02-25 | 1968-08-21 | Continental Copper & Steel Ind | Electrolytic metal extraction |
-
1989
- 1989-12-28 DE DE3943142A patent/DE3943142A1/en not_active Withdrawn
-
1990
- 1990-12-17 DE DE59006142T patent/DE59006142D1/en not_active Expired - Lifetime
- 1990-12-17 EP EP90203345A patent/EP0435382B1/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2810686A (en) * | 1954-11-09 | 1957-10-22 | Rohm & Haas | Electrolytic treatment of waste sulfate pickle liquor |
| DE1155610B (en) * | 1961-05-18 | 1963-10-10 | Ionics | Method and cell for the electrolytic deposition of metals, in particular iron |
| FR2273082A1 (en) * | 1974-05-28 | 1975-12-26 | Seprac | |
| US4149946A (en) * | 1978-03-21 | 1979-04-17 | Davis Walker Corporation | Recovery of spent pickle liquor and iron metal |
| EP0075882A2 (en) * | 1981-09-25 | 1983-04-06 | Hitachi, Ltd. | Process for regenerating cleaning fluid |
| DE3719604A1 (en) * | 1987-06-12 | 1988-12-22 | Markus Maria Dipl In Bringmann | Pickling of semifinished articles |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4218915A1 (en) * | 1992-06-10 | 1993-12-16 | Heraeus Elektrochemie | Method and device for regenerating an aqueous solution containing metal ions and sulfuric acid, and use |
| EP0575699A2 (en) * | 1992-06-10 | 1993-12-29 | Heraeus Elektrochemie Gmbh | Process and apparatus for regenerating metal ions and sulfuric acid containing aqueous solutions and use thereof |
| EP0575699A3 (en) * | 1992-06-10 | 1994-06-01 | Heraeus Elektrochemie | Process and apparatus for regenerating metal ions and sulfuric acid containing aqueous solutions and use thereof |
| EP0638664A1 (en) * | 1993-08-11 | 1995-02-15 | Heraeus Elektrochemie GmbH | Process and apparatus for regenerating solutions containing metal ions and sulfuric acid |
| US5478448A (en) * | 1993-08-11 | 1995-12-26 | Heraeus Elektrochemie Gmbh | Process and apparatus for regenerating an aqueous solution containing metal ions and sulfuric acid |
| WO1995023880A1 (en) * | 1994-03-04 | 1995-09-08 | Spunboa Pty. Limited | Treatement of electrolyte solutions |
| WO1995024518A1 (en) * | 1994-03-07 | 1995-09-14 | Mib Metallurgie Und Oberflächentechnik Und Innovation In Berlin Gmbh & Co. | Electrolysis process for regenerating a ferric chloride or sulphate solution, in particular for spray etching steel |
| WO1998038353A1 (en) * | 1997-02-25 | 1998-09-03 | Centro Sviluppo Materiali S.P.A. | Method for pickling products of a metal alloy in absence of nitric and for recovering exhausted pickling solutions and apparatus therefore |
| US6221234B1 (en) | 1997-02-25 | 2001-04-24 | Acciai Speciali Terni S.P.A. | Method for pickling products of a metal alloy in absence of nitric acid and for recovering exhausted pickling solutions and apparatus therefore |
| ES2172479A1 (en) * | 2001-03-13 | 2002-09-16 | Fundacion Cidetec | Metal electrodeposition via constant potential reference electrode comprises D.C. processing, with dissolving of anode metal and optimization of potential |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| WO2015000002A1 (en) * | 2013-07-04 | 2015-01-08 | Pureox Industrieanlagenbau Gmbh | Process for the electrochemical oxidation of fe2+ chloride solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59006142D1 (en) | 1994-07-21 |
| EP0435382B1 (en) | 1994-06-15 |
| DE3943142A1 (en) | 1991-07-04 |
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