EP0224400A1 - Elektrolyseapparat zur Gewinnung eines Stoffes aus einem elektrolytischen Bad - Google Patents

Elektrolyseapparat zur Gewinnung eines Stoffes aus einem elektrolytischen Bad Download PDF

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Publication number
EP0224400A1
EP0224400A1 EP86402334A EP86402334A EP0224400A1 EP 0224400 A1 EP0224400 A1 EP 0224400A1 EP 86402334 A EP86402334 A EP 86402334A EP 86402334 A EP86402334 A EP 86402334A EP 0224400 A1 EP0224400 A1 EP 0224400A1
Authority
EP
European Patent Office
Prior art keywords
cathode
substance
electrolyser
bath
anode
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Withdrawn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
EP86402334A
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English (en)
French (fr)
Inventor
Robert Bernard
Georges Lonchampt
Robert Tinti
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.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
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 Commissariat a lEnergie Atomique CEA filed Critical Commissariat a lEnergie Atomique CEA
Publication of EP0224400A1 publication Critical patent/EP0224400A1/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Withdrawn legal-status Critical Current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
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts

Definitions

  • the present invention relates to an electrolyser for extracting a substance from an electrolytic bath. It applies in particular to the manufacture of alkali metals such as lithium, sodium and potassium or alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium, for example from chlorides of these metals.
  • alkali metals such as lithium, sodium and potassium or alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium, for example from chlorides of these metals.
  • An electrolyzer which makes it possible to manufacture lithium from an electrolytic bath containing lithium chloride.
  • This known electrolyser shown diagrammatically in FIG. 1a, essentially comprises, in the body 2 of the electrolyser intended to be filled with the electrolytic bath 3, an anode 4, a metal cathode 6 surrounding the anode, a metal collector 8 in the form of an inverted gutter, surmounting the upper end of the cathode, and a metal diaphragm 10 which, placed between the anode and the cathode, is electrically insulated therefrom and extends downwards from the internal edge of the gutter 8.
  • this diaphragm The function of this diaphragm is to prevent the lithium formed at the cathode from being entrained by the convection currents of the bath, outside the space delimited by the diaphragm, the cathode and the collector 8.
  • a conduit 12 forming an overflow passes through the body 2 to open into the gutter and allows the evacuation of the lithium formed by electrolysis and accumulated in this gutter (because its density is lower than that of the electrolytic bath).
  • An outlet 14 for the chlorine formed during the electrolysis is provided at the upper part of the body 2 and a conduit 16 which opens into this body 2 also at the upper part thereof, is provided for the introduction of an inert gas such as argon or helium into the body 2 in order to prevent the recombination of chlorine and lithium and to allow the evacuation of chlorine by means of an appropriate pressure of inert gas.
  • the electrolyser shown in FIG. 1a may further comprise (FIG. 1b) an auxiliary anode 18 provided for polarizing the diaphragm 10 with respect to the electrolytic bath in order to reduce the corrosion of this diaphragm and of the manifold 8 which are brought to the same potential.
  • the known electrolyser which has just been described has the following drawback: the diaphragm 10 and the cathode 6 are very often short-circuited during electrolysis, by the pushing, on the cathode, of lithium dendrites which end up by reaching the diaphragm. Lithium then forms on the latter which is under these conditions at the same potential as the cathode. As a result, lithium can detach from the diaphragm in the space defined by the latter and the anode and gain the surface of the electrolytic bath where it partly recombines with chlorine.
  • the object of the present invention is to remedy this drawback.
  • this electrolyser for the extraction, of an electrolytic bath, of a substance less dense than this bath, this electrolyser comprising an anode and a cathode which plunge into the bath, the cathode, to which the substance is formed.
  • the electrolyser further comprising means for confining the substance in the vicinity of the cathode and for guiding this substance along and towards the end upper part of the cathode, and means for collecting the substance at this end, electrolyser characterized in that the confinement and guide means comprise at least one layer of a mesh made of a material resistant to bathing and to products electrolysis, each layer being disposed in the vicinity of the cathode, between the latter and the anode, and extending along the cathode.
  • the substance for example lithium in the case of electrolysis of lithium chloride
  • the substance is thus maintained in the vicinity of the cathode and led to the collecting means from where it can be evacuated. This prevents the substance from reaching the surface of the bath: in the case of the electrolysis of an alkali metal chloride, it prevents the surface formed by the metal formed and therefore the recombination of the latter with chlorine .
  • the layer or layers of mesh form a sort of internal lining of the cathode.
  • Each layer can be electrically conductive (for example in a stainless metal such as stainless steel) and electrically connected to the cathode, which occurs when the substance is electrically conductive (case of alkali metals which are liquids in the electrolytic bath) and that the upper end of the layers soak in this substance accumulated in the collection means.
  • the substance formed at the cathode or on the mesh is thus confined in and between the layers of mesh and then conducted by the latter to the collection means where it accumulates.
  • the respective heights of the lower ends of the layers, counted from the bottom of the cathode, may increase from the layer closest to the cathode, to take account of 'an accumulation of substance, increasing from bottom to top of the cathode.
  • the lower edge of the mesh has the shape of a helix wound on a cone which tapers upwards.
  • the collecting means comprise a downward-facing gutter, which is placed above the cathode and whose outer edge runs along the upper end of the latter, and the upper end of each layer of mesh is sufficiently close to the gutter to soak in the substance accumulated in this gutter when the electrolyser is in operation, so that the "pump" formed by each layer of mesh vis-à-vis the substance, has a good flow.
  • this electrolyser further comprises means for continuously supplying a component of the bath, which contains the substance.
  • the electrolyser according to the invention is for example intended for the manufacture of lithium from lithium chloride and comprises a tank 20 for example cylindrical, held in a tank support 21 and intended to contain a mixed bath of molten lithium chloride / potassium chloride, the tank being brought to an appropriate temperature by heating means such as heating collars 22 surrounding the tank 20.
  • the tank 20 is also open at its upper part (and closed at the bottom).
  • the electrolyser of FIG. 2 also comprises a cylindrical cathode 24, coaxial with the tank, arranged inside the latter and an anode 26 of elongated shape, arranged along the axis of the tank.
  • This cathode can be made of metal, for example nickel.
  • the tank is extended below by a conduit 28 closed at its lower end, arranged along the axis of the tank and opening into the latter.
  • the anode passes through this conduit to extend in the tank to halfway up the cathode for example. Part 29 of the anode, located in the tank, can be swollen.
  • the duct 28 is provided with cooling means 30 which consist, for example, of an air circulation, and also with heating means 32 such as heating collars arranged along the duct 28.
  • a pipe 34 intended for draining the bath is provided at the base of the conduit 28, communicates with the latter and includes a drain valve 36.
  • the anode 26 is provided with a ceramic sheath 38 the lower part of which covers the base or lower end of the duct 28.
  • the lower end of the anode is fi lined and protrudes from the base of the conduit 28.
  • An electrically insulating ring 40 is mounted on this end of the anode and a nut 42 screwed to the base of the anode keeps the ring 40 against the ceramic 38, by means of a metal washer 44.
  • the positive pole of a source of direct electric current (not shown) is connected to the lower end of the anode and the negative pole of this source is connected to the cathode, through an electrically insulating passage (not shown) passing through the tank 20, which is also electrically isolated from the anode and the cathode.
  • a conduit 48 forming an overflow passes through the support 21 and a sealed passage (not shown) provided on the tank to open, at one end, into the gutter 46.
  • the other end of the overflow 48 penetrates, through a bellows seal 50, in a sealed enclosure 52 such as a glove box, filled with a gas which does not react chemically with lithium, argon for example.
  • a container 54 is placed in the enclosure 52 under the other end of the overflow 48 and can rest on a continuous weighing device 56.
  • the enclosure 52 is provided with an airlock 58 making it possible to intervene in this enclosure and extract the container 54 therefrom.
  • cylindrical, coaxial grids 60 extend along and in the vicinity of the internal wall of the cathode situated opposite the anode, from the interior of the gutter 46 to the bottom of the cathode, the heights respective of the lower ends of the grids, counted from the bottom of the cathode, increasing from the grid closest to the cathode.
  • the grids touch, the interval between them being zero, and the grid closest to the cathode touches the latter, each grid having a thickness of 0.6 cm and being produced from wires. 0.25 cm in diameter, forming square meshes 0.5 cm side.
  • the upper part of the tank 20 is closed in a leaktight manner by a cover 62 in the form of a hood, the top of which is tightly connected to a duct 64.
  • the end of a pipe 66 which is provided for supplying the bath in a component thereof, containing the substance, and which passes through the hood 62 by a sealed passage, not shown, ends at the upper part of the tank, above the surface of the electrolytic bath which fills the tank by covering the anode, the cathode, the gutter and the part 68 of the overflow present in the tank.
  • the bath is animated by rising and falling convection currents respectively along the internal and external walls of the cathode, passages being provided between the latter and the bottom of the tank for the circulation of the bath.
  • the chlorine which is released at the anode is evacuated via the conduit 64.
  • the lithium (liquid) formed at the cathode rises along the latter and the grids 60 to accumulate in the gutter 46 from where it is evacuated by the overflow 48.
  • the lithium then falls into the container 54 which can be extracted from the enclosure 52 by the airlock 58 when a sufficient quantity of lithium, measured by the continuous weighing means 56 , is contained in container 54.
  • the tank 20, its support 21, the cover 62, the conduit 28, the cathode 24, the anode 26, the gutter 46 and the grids 60 are for example made of stainless steel.
  • the cathode, the collector 46 and the part 68 of the overflow which are constantly immersed in the bath, can be made of a less noble metal than the tank and the cover, this metal being for example ordinary steel.
  • the lithium layer present in the collector must not go too low in it, at the risk of escaping from it through the lower (open) part of this collector.
  • the height of the bath which depends on the position of the overflow and the apparent density of the bath at the collector 46, density depending on the amount of chlorine present at this level, does not vary by more than one centimeter approx Ron. It is therefore preferable to continuously supply the bath with dry lithium chloride through line 66.
  • the electrolyser according to the invention has an excellent overall yield of lithium, allows continuous production of this metal, preventing the formation of short circuits between the anode and the cathode. In this electrolyser, corrosion of the cathode, the grids and the collector 46 is greatly reduced. Finally, the marketing of chlorine produced at the same time as lithium is possible.

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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)
EP86402334A 1985-10-25 1986-10-17 Elektrolyseapparat zur Gewinnung eines Stoffes aus einem elektrolytischen Bad Withdrawn EP0224400A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8515885 1985-10-25
FR8515885A FR2589169B1 (fr) 1985-10-25 1985-10-25 Electrolyseur pour l'extraction d'une substance, notamment d'un metal alcalin, d'un bain electrolytique

Publications (1)

Publication Number Publication Date
EP0224400A1 true EP0224400A1 (de) 1987-06-03

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Family Applications (1)

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EP86402334A Withdrawn EP0224400A1 (de) 1985-10-25 1986-10-17 Elektrolyseapparat zur Gewinnung eines Stoffes aus einem elektrolytischen Bad

Country Status (3)

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US (1) US4744876A (de)
EP (1) EP0224400A1 (de)
FR (1) FR2589169B1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989009296A1 (en) * 1988-03-29 1989-10-05 Metallurg, Inc. Transporting a liquid past a barrier
WO1999005343A1 (en) * 1997-07-25 1999-02-04 E.I. Du Pont De Nemours And Company Fused chloride salt electrolysis cell
EP1811062A1 (de) * 2004-10-12 2007-07-25 Toho Titanium Co., Ltd. Verfahren und vorrichtung zur herstellung von metall durch schmelzflusselektrolyse
CN106958029A (zh) * 2017-04-07 2017-07-18 东莞市佳乾新材料科技有限公司 一种带取料装置的电解槽

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994028201A1 (fr) * 1993-05-24 1994-12-08 Maloe Nauchno-Proizvodstvennoe Predpriyatie 'mms' Procede de production d'un alliage d'aluminium-strontium
US5660710A (en) * 1996-01-31 1997-08-26 Sivilotti; Olivo Method and apparatus for electrolyzing light metals
US5855757A (en) * 1997-01-21 1999-01-05 Sivilotti; Olivo Method and apparatus for electrolysing light metals
GB9815169D0 (en) * 1998-07-13 1998-09-09 Eastman Kodak Co Electrolytic cell
CN112011803A (zh) * 2020-05-19 2020-12-01 金昆仑锂业有限公司 一种带有集锂室的熔盐电解槽
CN113549955B (zh) * 2021-07-08 2022-05-20 中南大学 一种粗镓的电解精炼装置及电解精炼方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092228A (en) * 1977-03-07 1978-05-30 E. I. Du Pont De Nemours And Company Electrolytic cell
GB2132634A (en) * 1982-12-30 1984-07-11 Alcan Int Ltd Electrolytic cell for metal production

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2111264A (en) * 1933-02-17 1938-03-15 Du Pont Electrolysis of fused salts
US2944950A (en) * 1957-09-24 1960-07-12 Ethyl Corp Operation and discharge of sodium cells
US3011964A (en) * 1958-09-29 1961-12-05 Ethyl Corp Diaphragm structure for electrolysis cells
US3248311A (en) * 1962-03-29 1966-04-26 Ethyl Corp Manufacture of sodium
US3776823A (en) * 1971-10-21 1973-12-04 S Crowther Process for starting operation of a fused salt electrolytic cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092228A (en) * 1977-03-07 1978-05-30 E. I. Du Pont De Nemours And Company Electrolytic cell
GB2132634A (en) * 1982-12-30 1984-07-11 Alcan Int Ltd Electrolytic cell for metal production

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989009296A1 (en) * 1988-03-29 1989-10-05 Metallurg, Inc. Transporting a liquid past a barrier
WO1999005343A1 (en) * 1997-07-25 1999-02-04 E.I. Du Pont De Nemours And Company Fused chloride salt electrolysis cell
EP1811062A1 (de) * 2004-10-12 2007-07-25 Toho Titanium Co., Ltd. Verfahren und vorrichtung zur herstellung von metall durch schmelzflusselektrolyse
EP1811062A4 (de) * 2004-10-12 2009-04-29 Toho Titanium Co Ltd Verfahren und vorrichtung zur herstellung von metall durch schmelzflusselektrolyse
CN106958029A (zh) * 2017-04-07 2017-07-18 东莞市佳乾新材料科技有限公司 一种带取料装置的电解槽
CN106958029B (zh) * 2017-04-07 2018-12-04 绍兴市华润铜业制造有限公司 一种带取料装置的电解槽

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Publication number Publication date
FR2589169B1 (fr) 1990-08-31
US4744876A (en) 1988-05-17
FR2589169A1 (fr) 1987-04-30

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