EP1099782A1 - Vorrichtung und Verfahren zur elektrolytischen Auflösung durch Oxidation eines Metalles - Google Patents

Vorrichtung und Verfahren zur elektrolytischen Auflösung durch Oxidation eines Metalles Download PDF

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Publication number
EP1099782A1
EP1099782A1 EP00403078A EP00403078A EP1099782A1 EP 1099782 A1 EP1099782 A1 EP 1099782A1 EP 00403078 A EP00403078 A EP 00403078A EP 00403078 A EP00403078 A EP 00403078A EP 1099782 A1 EP1099782 A1 EP 1099782A1
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EP
European Patent Office
Prior art keywords
bath
anode
cathode
metal
cell
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Withdrawn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
EP00403078A
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English (en)
French (fr)
Inventor
Bernard Fritzinger
Marc Sardoy
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.)
USINOR SA
Original Assignee
USINOR SA
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Filing date
Publication date
Application filed by USINOR SA filed Critical USINOR SA
Publication of EP1099782A1 publication Critical patent/EP1099782A1/de
Withdrawn legal-status Critical Current

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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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • 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

Definitions

  • the document EP 0 550 002 describes an installation and a method of this type, which are used to supply electro-tinning solution to an electro-deposition cell with an insoluble anode and a metal surface material serving as a cathode intended to be coated with tin; the electro-dissolution cell of the electro-tinning solution production facility and the cell of electro-deposition are connected in a closed or quasi-closed loop so that the enriched electro-tinning solution is taken from the electro-dissolution cell to be brought into the electroplating cell, and that, at conversely, the electro-tinning solution to be enriched is taken from the cell electro-deposition to be brought into the electro-dissolution cell.
  • the electro-dissolution installation does not have an interposed membrane between the soluble anode and the cathode.
  • a means for strengthening the hydrogen production reaction on this cathode is to increase the current density at this cathode, for example by reducing the surface of this cathode below that of the soluble anode.
  • this installation and this process make it possible to enrich a wide variety of electrolyte baths, such as acid baths sulfuric, ferrostannate baths, methane sulfonate baths, cresol sulfonate baths, halide baths, fluosilicate baths, and fluoborate baths.
  • electrolyte baths such as acid baths sulfuric, ferrostannate baths, methane sulfonate baths, cresol sulfonate baths, halide baths, fluosilicate baths, and fluoborate baths.
  • the invention aims to significantly improve yields electroplating processes and installations of the aforementioned type.
  • this difference in density essentially corresponds to a difference in ion concentration of the oxidized metal; preferably, if C1 is the ion concentration of this metal near the cathode and if C2 is the ion concentration of this metal in the vicinity of the most active part anode, C1 ⁇ 10,000 x C2; preferably C1 remains below the threshold of concentration above which a deposit of said metal forms on the cathode.
  • the most active part of the anode as that grouping the points of the anode where the current densities are highest and represent 90% of the current flowing between anode and cathode; this precision is important in the case where the anode is formed of granules of said metal and where only part of the immersed granules directly contributes to the electrodissolution.
  • the main advantage of the invention is that, like the ion concentration metallic remains weak in the vicinity of the cathode, one avoids or at least one limits metal deposition on the cathode, which improves overall efficiency electro-dissolution of the installation.
  • new bath does not contain ions of the oxidized metal, the “virgin” electrolyte in which no addition of ions of the oxidized metal has been performed.
  • the invention will be described in the case of its application for the enrichment in stannous ions (Sn 2+ ) of spent electro-tinning solutions.
  • the electrolytic tin dissolution system comprises a cell 1 electrolysis provided with a soluble tin anode 2 and an insoluble cathode 3; no membrane is interposed between the anode 2 and the cathode 3; the cathode 3 is made of a conductive material chosen in a suitable manner to resist electrolyte and to present a hydrogen release overvoltage also as low as possible; in a conventional way, we take here a steel cathode stainless.
  • the cathode 3 is arranged in the cell above anode 2.
  • the installation includes an enriched bath sampling line opening into the bottom of the cell, at or below the anode (not shown in Figure 1); preferably, as illustrated in FIGS. 2 to 4, the bottom of the cell has a conical shape flared upwards opening out down, at the top of the cone, in the bath sampling line enriched.
  • the installation comprises at least one bath introduction pipe to enrich or virgin electrolyte opening into the cell at or at above the cathode (not shown in Figure 1).
  • the installation comprises conventional means 4 for circulating a direct current between the soluble anode 2 and the cathode 3, suitable for dissolve the tin from anode 2, otherwise avoiding limiting the release oxygen.
  • the installation includes means for regulating the temperature of the cathode so as to limit its heating.
  • the installation comprises means 5 for cooling the bath in the vicinity of the anode at a temperature T2 lower than the temperature T1 of the bath near the cathode; in FIG. 1, these means correspond to a double tank containing a coolant in which the bottom of cell 1 is immersed.
  • an electro-tinning bath is introduced to enrich with stannous ions in cell 1 until submerging the cathode 3.
  • a continuous electric current is passed between anode 2 and cathode 3 so as to dissolve the tin from the anode while avoiding releasing oxygen to the anode; thus, the current density should remain, at all points of the anode, lower than the limit current density (J lim. ) beyond which, under the conditions of electro-dissolution, one would begin to give off oxygen; these electro-dissolution conditions include in particular the concentration of Sn 2+ , the temperature in the vicinity of the anode, and the composition of the bath.
  • the flow of current therefore causes the formation of Sn 2+ ions in the vicinity of the anode and the evolution of hydrogen at the cathode.
  • the bath sampling line By the bath sampling line, the bath is then continuously sampled in the vicinity of the anode (see arrow pointing downwards starting from the bottom of the cell in FIGS. 2 and 3); because of the formation of Sn 2+ ions, the bath taken is therefore enriched in Sn 2+ ions so as to be able to serve as an electrolyte for a conventional electro-tinning operation.
  • the bath is continuously introduced electro-tinning or virgin electrolyte to be enriched with stannous ions in the cell at a flow corresponding approximately to that of sample, so as to keep the bath level constant in the cell 1.
  • T1 is the bath temperature in the vicinity of the cathode and if T2 is the temperature of the bath bath in the vicinity of the most active part of the anode, T1> T2; of preferably T1-T2> 15 ° C.
  • the temperature gradient further accentuates this density gradient, since the bath temperature is higher at the level cathode (T1) than anode (T2).
  • the operating conditions of the cell carrying especially on the vertical distance separating the anode from the cathode, on the sampling and bath introduction rates, on the temperature gradient are adapted in a manner known per se so that the concentration in Sn2 + ions in the vicinity of cathode 3, which is at least 10,000 times lower than in the vicinity of the anode.
  • the concentration of Sn 2+ ions in the vicinity of the cathode should remain below 10 -2 g / l, preferably of the order of 10 -6 g / l.
  • the ion concentration metal near the cathode is even weaker and almost zero, which. reduces metal deposition on the cathode accordingly and improves again the overall yield of electro-dissolution.
  • the cell comprises both a cathode compartment and an anode compartment
  • the "new” bath is then introduced into the cathode compartment 6 ', 6 "and the" used "bath into the anode compartment 7'A, 7'B, 7".
  • the bottom of the cell is then lined with a grid 8 'of retention of the granules, to avoid their entrainment in the sampled bath.
  • FIGS. 3 and 4 represent an electro-dissolution cell used, according to the invention, for the dissolution of tin; the anode 2 "is formed of granules tin; the 3 "cathode is hollow to allow water circulation of cooling; there is no diaphragm between the anode and the cathode.
  • the cell has a conical bottom, the top of the cone 9 corresponding at the bath sampling point; above the sampling point, we has a mesh grid (not shown) adapted to prevent driving the tin granules from the 2 "anode.
  • the cell has an opposite lateral cathode compartment 6 "whose bulkhead extends down to immediately below the level of the 3 "cathode.
  • the means of cooling the bath near the active surface 2 " of the anode are formed by 5 "pipes passing through the bath, cooled by coolant circulation.
  • C "1 is the concentration of Sn 2+ ions in the vicinity of the cathode and if C" 2 is the concentration of Sn 2+ ions in the vicinity of the most active part of the anode, it is appropriate, in the absence of temperature difference (T1-T2), that C "1 ⁇ 10 000 x C" 2, which makes it possible to prevent any deposit of tin on the cathode.
  • the invention is applicable as soon as (D "2 -D" 1) ⁇ 100 g / l approximately, that the difference in density comes from the difference in concentration of Sn2 + ions or, as is the case here, of the temperature difference (T1 - T2).
  • Example 2 the same cell is operated under the same conditions as in Example 1, except that we shake the bath vigorously so as to maintain the same level of stannous ion concentration and the same temperature level throughout the bath, unlike the invention.
  • the temperature of the bath at the cathode is then identical to the bath temperature at the anode: 50 ° C.

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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)
EP00403078A 1999-11-12 2000-11-07 Vorrichtung und Verfahren zur elektrolytischen Auflösung durch Oxidation eines Metalles Withdrawn EP1099782A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9914186A FR2801062B1 (fr) 1999-11-12 1999-11-12 Installation et procede de dissolution electrolytique par oxydation d'un metal
FR9914186 1999-11-12

Publications (1)

Publication Number Publication Date
EP1099782A1 true EP1099782A1 (de) 2001-05-16

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EP00403078A Withdrawn EP1099782A1 (de) 1999-11-12 2000-11-07 Vorrichtung und Verfahren zur elektrolytischen Auflösung durch Oxidation eines Metalles

Country Status (7)

Country Link
US (1) US6361677B1 (de)
EP (1) EP1099782A1 (de)
JP (1) JP2001159000A (de)
KR (1) KR20010051603A (de)
BR (1) BR0005371A (de)
CA (1) CA2325890A1 (de)
FR (1) FR2801062B1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1816237A1 (de) * 2006-02-02 2007-08-08 Enthone, Inc. Verfahren und Vorrichtung zur Beschichtung von Substratoberflächen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1226658A (de) * 1967-08-03 1971-03-31
EP0398735A2 (de) * 1989-05-19 1990-11-22 Sun Industrial Coatings Private Limited Plattierungsverfahren
EP0770708A1 (de) * 1994-05-17 1997-05-02 Daiwa Fine Chemicals Co., Ltd. Elektrolytisches Verfahren zur Herstellung von Blei-Sulfonat und Zinn-Sulfonat mit Verwendung für Weichlötenbeschichtung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19719020A1 (de) * 1997-05-07 1998-11-12 Km Europa Metal Ag Verfahren und Vorrichtung zum Regenerieren von Verzinnungslösungen
US6251255B1 (en) * 1998-12-22 2001-06-26 Precision Process Equipment, Inc. Apparatus and method for electroplating tin with insoluble anodes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1226658A (de) * 1967-08-03 1971-03-31
EP0398735A2 (de) * 1989-05-19 1990-11-22 Sun Industrial Coatings Private Limited Plattierungsverfahren
EP0770708A1 (de) * 1994-05-17 1997-05-02 Daiwa Fine Chemicals Co., Ltd. Elektrolytisches Verfahren zur Herstellung von Blei-Sulfonat und Zinn-Sulfonat mit Verwendung für Weichlötenbeschichtung

Also Published As

Publication number Publication date
BR0005371A (pt) 2001-08-07
FR2801062A1 (fr) 2001-05-18
CA2325890A1 (fr) 2001-05-12
KR20010051603A (ko) 2001-06-25
JP2001159000A (ja) 2001-06-12
FR2801062B1 (fr) 2001-12-28
US6361677B1 (en) 2002-03-26

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