EP0354891A1 - Verfahren und Vorrichtung zur Regenerierung einer Lösung für das elektrolytische Abscheiden Eisens - Google Patents

Verfahren und Vorrichtung zur Regenerierung einer Lösung für das elektrolytische Abscheiden Eisens Download PDF

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Publication number
EP0354891A1
EP0354891A1 EP89870107A EP89870107A EP0354891A1 EP 0354891 A1 EP0354891 A1 EP 0354891A1 EP 89870107 A EP89870107 A EP 89870107A EP 89870107 A EP89870107 A EP 89870107A EP 0354891 A1 EP0354891 A1 EP 0354891A1
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EP
European Patent Office
Prior art keywords
solution
iron
electrolytic
electrolytic solution
temperature
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Withdrawn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
EP89870107A
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English (en)
French (fr)
Inventor
Marios Economopoulos
Nicole Lambert
Jean Crahay
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 de Recherches Metallurgiques CRM ASBL
Original Assignee
Centre de Recherches Metallurgiques CRM ASBL
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 Centre de Recherches Metallurgiques CRM ASBL filed Critical Centre de Recherches Metallurgiques CRM ASBL
Publication of EP0354891A1 publication Critical patent/EP0354891A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron

Definitions

  • the present invention relates firstly to a process for regenerating a solution intended for the electrolytic deposition of iron on a substrate, both in the form of a detachable film or "foil" and in the form of a permanent coating. It also relates to a device allowing the implementation of this process. Finally, it extends to a method and a device for the electrolytic deposition of iron on a substrate, which make use of the present method or of the present regeneration device.
  • sheet of iron simply called “sheet of iron” or “foil” for simplicity.
  • This iron sheet is obtained by electrolytic deposition of iron on a mobile substrate from an aqueous solution of ferrous chloride (FeCl2) followed by the separation of the substrate and the deposited film which thus constitutes the sheet of iron.
  • FeCl2 ferrous chloride
  • this reaction is favored by an elevated temperature of the solution. This temperature is therefore kept as high as possible while remaining below the boiling point; in this case, this temperature is around 105 degrees C.
  • the iron produced by this reaction is entrained out of the solution, since it constitutes the coating deposited on the mobile substrate.
  • the solution depletes in FeCl2.
  • it quickly enriches in FeCl3 since the deposition of 1 kg of iron leads to the formation of 2 kg of FeCl3. It is therefore necessary to reconstitute the solution to maintain the conditions of the deposit.
  • the solution poor in FeCl2, and enriched in FeCl3 will now be called “spent solution", as opposed to a "fresh solution” rich in FeCl2.
  • This fresh solution is preferably obtained by regeneration of the spent solution; for this reason, it can also be called “regenerated solution”.
  • a conventional process for regenerating this spent solution consists in reacting it with scrap, according to the following reduction reaction: 2 FeCl3 + Fe - 3 FeCl2 (2).
  • This iron reduction reaction requires an amount of iron which exactly corresponds to the amount of iron consumed by the deposition reaction (1). Reactions (1) and (2) therefore balance each other theoretically perfectly.
  • reaction (2) is carried out in a scrap dissolution reactor, in which it is however always accompanied by a corrosion reaction of the scrap with hydrochloric acid present in the solution.
  • This corrosion reaction is part of: Fe + 2 HCl - FeCl2 + H2
  • the reaction (3) here constitutes a parasitic reaction, because it per the equilibrium resulting from reactions (1) and (2). It indeed produces an excess amount of FeCl2 which it is necessary to evacuate for example by drainage, which leads to high costs and significant losses of materials, in particular Fe and Cl; it also gives rise to the release of hydrogen and therefore to the consumption of hydrochloric acid.
  • the object of the present invention is to propose a regeneration process of the aforementioned type, which does not require the cooling and reheating of the solution and which makes it possible to operate with low circulation speeds of the solution in the regeneration step.
  • a method of regenerating a solution intended for the electrolytic deposition of iron in which the electrolytic solution is regenerated by means of an iron source, is characterized in that the regeneration of said said is carried out.
  • the speed of circulation of the electrolytic solution in the regeneration stage is less than 1 m / s and preferably less than 0.3 m / s.
  • the other parameters of the electrolytic deposition are maintained essentially at their conventional values; these are in particular the concentrations of Fe++ and Fe+++ ions, the current density and the temperature of the solution, which is between 100 ° C. and 110 ° C.
  • the particular characteristics introduced by the present process are, on the one hand, that the temperature of the solution during regeneration is substantially equal to that which the solution exhibits during electrolytic deposition, and, on the other hand, that the pH of this solution is clearly increased from 1 in conventional methods to 2 - 3 in the present method.
  • Such an increase in pH corresponds to a decrease, by a factor of 20, in the concentration of H+ ions in the electrolytic solution.
  • the equalization of the electroplating and regeneration temperatures makes it possible to integrate these two operations into a common circuit, where the circulation of the solution is ensured by a single pump.
  • Another aspect of the present invention relates to a device for regenerating a solution intended for the electrolytic deposition of iron, which makes it possible to implement the process which has just been described.
  • FIG. 1 there is shown a cross section through the electrolytic deposition and regeneration device, along the line A-A of FIG. 2. It should be emphasized that this Fig. 2 is only a longitudinal view of the electrolytic deposition device, intended to facilitate understanding of the corresponding elements of FIG. 1; it does not include any element of the regeneration device.
  • the electrolytic cell 1 consists of two parts 1 ′, 1 ⁇ , arranged in parallel, corresponding respectively to the upper and lower strands of the movable cathode 2.
  • the two parts 1 ′ and 1 ⁇ of the electrolytic cell are supplied with electric current, in a manner known per se, from an appropriate source 3.
  • the device comprises a reactor 4, which is supplied with scrap 5 by a conveyor belt 6 which is not part of the invention.
  • a reservoir 7 for storing and homogenizing the electrolytic solution is also part of the device.
  • the circulation circuit of the electrolytic solution comprises a first pipe 8, which directly connects the reservoir 7 to the inlet of parts 1 ′ and 1 ⁇ of the electrolysis tank 1.
  • a second pipe 9 directly connects the outlet of these parts 1 ′ and 1 ⁇ to reactor 4.
  • a third pipe 10 directly connects reactor 4 to tank 7.
  • a pump 11, mounted for example in the first pipe 8, ensures the circulation of the electrolytic solution throughout the entire circuit.
  • the reservoir 7 can be provided with means, not shown, for adding water or hydrochloric acid.
  • the device of the invention therefore comprises only a single circuit for circulation of the electrolytic solution, which comprises in series the electrolysis tank 1, the regeneration reactor 4 and the storage tank 7.
  • the electrolytic solution sucked from the tank 7 by pump 11, successively passes through: - line 8, with pump 11, where the solution is "fresh” or regenerated; - the electrolysis tank 1, where the solution is consumed according to reaction (1); - Line 9, where it is a "used”solution; - reactor 4, where the "used” solution is regenerated by reaction (2); the line 10, which returns the "regenerated” solution to the storage tank 7.
  • This device thus proves to be particularly advantageous, because not only does it have only one circulation circuit with a single pump, but also it no longer has the slightest heat exchanger.

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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)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP89870107A 1988-07-25 1989-07-03 Verfahren und Vorrichtung zur Regenerierung einer Lösung für das elektrolytische Abscheiden Eisens Withdrawn EP0354891A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE8800842 1988-07-25
BE8800842A BE1002458A6 (fr) 1988-07-25 1988-07-25 Procede et dispositif de regeneration d'une solution destinee au depot electrolytique de fer.

Publications (1)

Publication Number Publication Date
EP0354891A1 true EP0354891A1 (de) 1990-02-14

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP89870107A Withdrawn EP0354891A1 (de) 1988-07-25 1989-07-03 Verfahren und Vorrichtung zur Regenerierung einer Lösung für das elektrolytische Abscheiden Eisens

Country Status (2)

Country Link
EP (1) EP0354891A1 (de)
BE (1) BE1002458A6 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3937765A1 (de) * 1989-11-14 1991-05-16 Bayerische Motoren Werke Ag Bauteil mit einer siliziumcarbidhaltigen verschleiss-schutzschicht

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1251650A (de) * 1968-03-28 1971-10-27

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1251650A (de) * 1968-03-28 1971-10-27

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PLATING AND SURFACE FINISHING, vol. 69, no. 2, février 1982, pages 48-52, Winterpark, Florida, US; P.K. SUBRAMANYAN et al.: "Electrolytic iron foil" *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3937765A1 (de) * 1989-11-14 1991-05-16 Bayerische Motoren Werke Ag Bauteil mit einer siliziumcarbidhaltigen verschleiss-schutzschicht

Also Published As

Publication number Publication date
BE1002458A6 (fr) 1991-02-19

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