EP0105896B1 - Einrichtung zum kontinuierlichen herstellen von elektroverzinktem blech - Google Patents

Einrichtung zum kontinuierlichen herstellen von elektroverzinktem blech Download PDF

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Publication number
EP0105896B1
EP0105896B1 EP83901324A EP83901324A EP0105896B1 EP 0105896 B1 EP0105896 B1 EP 0105896B1 EP 83901324 A EP83901324 A EP 83901324A EP 83901324 A EP83901324 A EP 83901324A EP 0105896 B1 EP0105896 B1 EP 0105896B1
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EP
European Patent Office
Prior art keywords
zinc
mercury
cell
compartment
layer
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.)
Expired
Application number
EP83901324A
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English (en)
French (fr)
Other versions
EP0105896A1 (de
Inventor
Joseph Alfred Hissel
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.)
Centre D'etude Et De Documentation De L'environnement(cebedeau)
Phenix Works SA
Original Assignee
Centre D'etude Et De Documentation De L'environnement(cebedeau)
Phenix Works SA
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
Priority claimed from BE0/207865A external-priority patent/BE892897A/fr
Application filed by Centre D'etude Et De Documentation De L'environnement(cebedeau), Phenix Works SA filed Critical Centre D'etude Et De Documentation De L'environnement(cebedeau)
Priority to AT83901324T priority Critical patent/ATE25859T1/de
Publication of EP0105896A1 publication Critical patent/EP0105896A1/de
Application granted granted Critical
Publication of EP0105896B1 publication Critical patent/EP0105896B1/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • 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 present invention relates to an industrial technique for the continuous production of electrogalvanized sheet from industrial zinciferous waste, for example steel.
  • industrial zinciferous waste is meant here any industrial residual product or solution obtained from industrial residues.
  • the treatment to which we turn instinctively when it comes to degalvanizing steel is the dissolution of zinc in an acid medium.
  • This technique is however far from satisfactory because if it rids the steel well of its annoying coating and thus makes it suitable for recycling in steelworks, it is accompanied on the other hand by the obligation to get rid of acid solutions charged with zinc and iron salts.
  • a neutralization treatment of these solutions is therefore necessary, for example using lime, to allow the discharge of waste water.
  • the acid used for the dissolution is not regenerated and that, in addition, a neutralization treatment gives rise to the formation of sludges which are difficult to recover without an expensive treatment due to the presence of zinc.
  • the neutralization treatment must be carefully monitored to avoid the discharge of zinc salts into the river.
  • a process for recovering metals by electrolysis in the presence of mercury is known from the publications DE-A 1 558763 and chemical Abstracts, volume 77, number 10, 1972, page 531, abbreviated 69255 u. This process uses a two-compartment electrolytic cell containing a sheet of mercury in the electrolyte. A cell as described in these publications allows the economic recovery of relatively pure zinc in a directly recoverable form.
  • the invention provides an attractive industrial solution to the problem of continuous production of electrogalvanized sheet by means of an installation comprising an electrolysis cell, which is characterized in that said cell comprises a bipolar liquid amalgam electrode consisting of a sheet of mercury disposed in the bottom of the cell divided into two compartments by a vertical partition arranged a short distance above the bottom of the cell, the two compartments each containing a separate electrolytic solution, in that the installation also includes a pump arranged to keep the sheet of mercury in forced circulation and to move it continuously between the first and second compartments of the cell, in that the anode of the cell consists of a member carrying zinciferous waste capable of move a predetermined distance above the layer of mercury in the electrolyte of the first compartment and in that the he cathode of the cell consists of the metal sheet to be coated positioned parallel to a predetermined distance above the sheet of mercury in the electrolyte, constituted by a galvanizing bath, of the second compartment.
  • anode of the cell consists of a member carrying zinc
  • the electrolyte contained in the anode compartment is, without this factor being limiting, preferably an alkaline solution, for example a solution of NaOH, and the electrolyte contained in the cathode compartment is an electrolytic galvanizing bath.
  • the electrodes can be electrically connected to the poles of the same electrical voltage source or to separate electrical voltage sources.
  • the technique according to the invention allows high-quality electrogalvanizing by recovering various industrial zinc-bearing waste: residual dust from electrical steelworks (which contains appreciable zinc contents of up to 20% and more), residual dust from blast furnaces, galvanizing and even zinc ores with soda. This technique thus gives significant added value to all this residual waste.
  • the technique according to the invention is based on the technology called amalgam metallurgy which consists in using a mercury electrode to extract a metal from an alloy or a compound.
  • This technique is implemented in an electrolysis cell as shown for example in the drawings.
  • the cell 10 comprises two compartments 1, 2 separated by a partition 3 and communicating with each other by an opening 4 formed in the lower part of the partition 3.
  • a sheet of mercury 5 which extends in the two compartments 1 and 2 through the opening 4 and which is maintained in forced circulation by a pump 11.
  • the first compartment 1 contains an electrolyte 6 in which is immersed an electrode 7 electrically connected to a source of positive electrical potential + V .
  • the electrode 7 consists of a conveyor chain circulating in the electrolytic bath at a certain distance above the sheet of mercury and is intended to carry the zinciferous waste to be treated.
  • the electrolyte 6 is preferably but without this factor being limiting, an alkaline solution, for example a NaOH solution.
  • the anode electrode 7 could also be a rotating basket for example, which would immerse the waste to be treated in the electrolyte 6. In other embodiments the anode electrode could be provided so as not to carry the zinciferous waste to be treated .
  • the zinciferous waste to be treated is immersed in the electrolyte 6 of the anode compartment 1.
  • the waste is either directly metallic waste (galvanized sheets, galvanizing mat) or a zinciferous solution obtained by chemical treatment of steelworks dust, high sludge - zinc furnaces or ores for example.
  • the sheet of mercury 5 functions as a cathode.
  • zinc is deposited cathodically and amalgamates with mercury.
  • the nature of the anodic reaction in compartment 1 can be judiciously selected by the arrangement of this compartment according to the nature of the waste to be treated.
  • an anodic steel electrode is chosen, immersed in a NaOH solution. Electrochemical dissolution of the zinc then takes place in the electrolyte.
  • the anodic reaction causes an evolution of oxygen.
  • the amalgam of zinc formed in compartment 1 passes into cathode compartment 2 with the sheet of mercury 5 in circulation.
  • the cathode compartment 2 constitutes an electrolytic galvanizing compartment.
  • a galvanizing bath is chosen for electrolyte 8 (alkaline cyanide bath or acid bath for example) and a steel sheet to be galvanized is used for example as cathode 9, electrically connected to a negative electrical potential - V.
  • the zinc is then deposited directly on the steel in the form of a galvanizing coating.
  • the electrolysis cell according to the invention thus makes it possible to constitute a particularly economical direct galvanizing station thanks to the use of zinc recovered from zinciferous waste. AT note that the electrolysis cell eliminates the presence of sludge in the cathode compartment.
  • a remarkable feature of the electrolysis cell according to the invention is that the sheet of mercury 5 plays the role of a bipolar electrode which is permeable to amalgamable elements such as zinc, lead, bismuth, tin for example contained in the anode compartment 1 and which is impermeable to ions and to solvent.
  • the sheet of mercury thus constitutes both a mechanical barrier preventing the mixing of the two electrolytic solutions 6 and 8 and a selective electrochemical barrier with respect to the ions to be separated.
  • the electrolytic solution 8 of the cathode compartment does not become contaminated with impurities and elements more electropositive than zinc which lower the hydrogenated overvoltage.
  • any impurities in the electrolytic bath dissolve in the mercury at the same time as the zinc, provided that they are more electropositive than the latter and that they are amalgamable with mercury. Otherwise, the impurities precipitate in the form of sludge or remain in solution without interfering: this is the case of aluminum for example.
  • the selective properties of the bipolar mercury electrode explain that the electrolysis cell according to the invention allows electro-refining of the zinc.
  • the mercury laden with amalgamated impurities can be regenerated continuously, for example by electrolysis in an auxiliary cell, in order to extract the amalgamated elements therefrom before being recycled.
  • the electrodes can be connected to the positive and negative poles of the same source of electrical voltage.
  • the two compartments can however also be connected to different sources of electrical potential, which makes it possible to regulate separately the operation of the two reactions in the anode and cathode compartments, the electrochemical yields of the two reactions not generally being equal.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (5)

1. Eine Elektrolysezelle enthaltende Vorrichtung zur kontinuierlichen Herstellung von elektroverzinktem Blech, dadurch gekennzeichnet, dass die Elektrolysezelle eine bipolare Flüssigamalgamelektrode aufweist, die aus einer Quecksilberschicht (5) besteht, die am Boden der Zelle vorgesehen ist, die durch eine in geringem Abstand (4) oberhalb des Bodens der Zelle vorgesehene vertikale Trennwand (3) in zwei Abteile (1, 2) geteilt ist, wobei die beiden Abteile jeweils eine andere elektrolytische Lösung (6, 8) enthalten, dass die Vorrichtung auch eine angetriebene Pumpe aufweist, um die Quecksilberschicht (5) in Zwangsumlauf zu halten und um sie kontinuierlich zwischen dem ersten und dem zweiten Abteil der Zelle zu bewegen, dass die Anode der Zelle aus einem Tragorgan für zinkhaltige Abfälle (7) besteht, das geeignet ist, sich in einem vorherbestimmten Abstand oberhalb der Quecksilberschicht im Elektrolyten des ersten Abteils (1) zu bewegen, und dass die Kathode der Zelle aus dem zu beschichtenden Metallblech (9) besteht, das in einem vorherbestimmten Abstand oberhalb der Quecksilberschicht in dem aus einem Galvanisierbad bestehenden Elektrolyten des zweiten Abteils (2) positioniert ist.
2. Vorrichtung nach Anspruch 1, in der die Anodenelektrode (7) eine Transportkette ist, die die zu behandelnden zinkhaltigen Abfälle trägt und die geeignet ist, in der ersten elektrolytischen Lösung (6) in einem bestimmten Abstand oberhalb der Quecksilberschicht (5) zu zirkulieren.
3. Vorrichtung nach Anspruch 1, in der die Anodenelektrode (7) ein angetriebener Drehkorb ist, um die zu behandelnden zinkhaltigen Abfälle in die erste elektrolytische Lösung (6) zu tauchen.
4. Vorrichtung nach einem der Ansprüche 1 bis 3, in der die Elektroden (7, 9) elektrisch mit den Polen von ein- und derselben elektrischen Spannungsquelle verbunden sind.
5. Vorrichtung nach einem der Ansprüche 1 bis 3, in der die Elektroden (7, 9) elektrisch mit verschiedenen elektrischen Spannungsquellen verbunden sind.
EP83901324A 1982-04-19 1983-04-15 Einrichtung zum kontinuierlichen herstellen von elektroverzinktem blech Expired EP0105896B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83901324T ATE25859T1 (de) 1982-04-19 1983-04-15 Einrichtung zum kontinuierlichen herstellen von elektroverzinktem blech.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
BE0/207865A BE892897A (fr) 1982-04-19 1982-04-19 Procede et appareil de recuperation des composants d'objets en acier galvanise.
BE207865 1982-04-19
BE210551 1983-04-14
BE210551 1983-04-14

Publications (2)

Publication Number Publication Date
EP0105896A1 EP0105896A1 (de) 1984-04-25
EP0105896B1 true EP0105896B1 (de) 1987-03-11

Family

ID=25653104

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83901324A Expired EP0105896B1 (de) 1982-04-19 1983-04-15 Einrichtung zum kontinuierlichen herstellen von elektroverzinktem blech

Country Status (5)

Country Link
EP (1) EP0105896B1 (de)
JP (1) JPS59500871A (de)
DE (1) DE3370166D1 (de)
IT (1) IT1194207B (de)
WO (1) WO1983003627A1 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE746852C (de) * 1940-04-04 1944-08-28 Duisburger Kupferhuette Verfahren zur Aufarbeitung von Zinkabfaellen
DE1558763A1 (de) * 1967-11-06 1970-07-16 Schoelzel Dr Karl Verfahren zur elektrochemischen Abscheidung von Metallen aus Loesungen ihrer Verbindungen
US4056450A (en) * 1975-06-30 1977-11-01 M & T Chemicals Inc. Continuous detinning system
FR2397472A2 (fr) * 1977-07-13 1979-02-09 Seprez Perfectionnements aux procedes de traitement des residus des bains de galvanisation pour la recuperation du zinc

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Journal Officiel des Communautés européennes No. C27/23(29-1-1985) *

Also Published As

Publication number Publication date
IT1194207B (it) 1988-09-14
IT8320679A0 (it) 1983-04-19
WO1983003627A1 (fr) 1983-10-27
JPS59500871A (ja) 1984-05-17
DE3370166D1 (en) 1987-04-16
EP0105896A1 (de) 1984-04-25

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