EP0156668B1 - Procédé et dispositif pour la fabrication de lithium en continu - Google Patents

Procédé et dispositif pour la fabrication de lithium en continu Download PDF

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Publication number
EP0156668B1
EP0156668B1 EP85400263A EP85400263A EP0156668B1 EP 0156668 B1 EP0156668 B1 EP 0156668B1 EP 85400263 A EP85400263 A EP 85400263A EP 85400263 A EP85400263 A EP 85400263A EP 0156668 B1 EP0156668 B1 EP 0156668B1
Authority
EP
European Patent Office
Prior art keywords
electrolysis
lithium
mixture
molten salts
cathode
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
EP85400263A
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German (de)
English (en)
French (fr)
Other versions
EP0156668A1 (fr
Inventor
Jean-Michel Verdier
Serge Jacubert
Jean Grosbois
Jean-Yves Dumousseau
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.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie 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.)
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Publication date
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Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0156668A1 publication Critical patent/EP0156668A1/fr
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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
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals

Definitions

  • the present invention relates to a process for the manufacture of lithium continuously by electrolysis of lithium chloride in a mixture of molten salts then separation of the lithium produced; it also relates to an apparatus used for the implementation of said method.
  • the present invention consists in an improvement of the process described in the European application cited above, an improvement which consists in carrying out after electrolysis the separation of lithium from the molten salts.
  • the molten salts which feed the decanter preferably are recycled after possible filtration in the supply to the electrolyser.
  • the electrolysis medium consists of a mixture of molten salts based on lithium chloride and at least one other alkali and / or alkaline earth chloride which, with lithium chloride, form a eutectic mixture melting at a temperature between 320 and 360 ° C approximately.
  • binary mixture which can be used, mention may be made of lithium chloride and potassium chloride; as ternary mixtures which can be used, mention may be made of mixtures containing, in addition to lithium chloride and potassium chloride, a chloride chosen from sodium, rubidium, strontium, magnesium, calcium and barium chlorides.
  • the electrolysis having to be carried out at a temperature between 400 and 500 ° C approximately and preferably around 450 ° C, the mixture of molten salts should supplying the electrolyser has a composition fairly close to the eutectic composition of the mixture used with an excess of lithium chloride which will be subjected to electrolysis.
  • the amount of lithium chloride in said mixture may vary for entry and exit between 56 and 69 mol% of LiCI in the mixture of molten salts, the concentration at the entry being greater than the concentration at the exit.
  • the lithium chloride may be in an excess of up to 10 mol% relative to the eutectic composition of the mixture of molten lithium chloride-potassium chloride salts.
  • the first characteristic of the process is that it is carried out continuously; that is to say that the electrolysis cell is continuously supplied with a fluid constituted by the mixture of molten salts containing, as the electrolysable material, lithium chloride and that the products are also continuously removed from the electrolyser electrolysis, that is to say chlorine on the one hand and the mixture of metallic lithium and molten salts on the other hand.
  • Electrolysis is moreover carried out without the use of a diaphragm by the organization of a rapid natural circulation of the electrolysis medium.
  • Said circulation will be said to be natural because it is obtained simply by the entrainment effect on the electrolysis medium of the chlorine bubbles which are released at the anode; it is therefore not necessary, but not impossible to use a means of circulation independent of this natural means.
  • the upper part of the cathode is immersed and preferably has a flared shape.
  • the upward movement of the electrolysis medium linked to the preferably flared shape of the cathode makes it possible to push lithium towards the walls of the cell and thus facilitate its natural elimination by overflow while minimizing recombination with chlorine.
  • the anode is advantageously protected against possible attack by the supernatant lithium by a sheath of insulating refractory material which plunges into the electrolysis bath.
  • refractory material means a material which remains inert, at the electrolysis temperature, with respect to the products with which said refractory material is in contact, that is to say essentially the mixture of molten salts, the chlorine and lithium. This material must be electrically insulating.
  • the sheathing of the anode will therefore be used with a material such as alumina, quartz, silica, thorine, zirconia or beryllium oxide.
  • the decanter is supplied by lithium and the molten salts leaving the electrolyser and comprises a decanting part and an evacuation well, said decanting part preferably having an area S such that 0.1 ⁇ 8 ⁇ 0.3 if Q is the feed rate of said decanter in m 3 / h and S is the area in m 2 of said settling part; the supernatant light phase is lithium which is withdrawn from the decanter and the remaining heavy phase constituted by the molten salts is preferably recycled after possible filtration in the supply to the electrolyser.
  • lithium chloride should be added to the electrolyzer supply so that its concentration remains within the limits which have been indicated above, the amount of lithium chloride added preferably corresponding to that which was consumed due to electrolysis.
  • the optional filtration of the mixture of molten salts is preferably carried out through a porous metallic material such as sintered stainless steel for example.
  • the temperature in the decanter is preferably close to, if not identical to that in the electrolyser.
  • the amount of lithium chloride in the electrolysis medium is adjusted to replace that consumed due to the electrolysis by adding it advantageously in the buffer tank (16). Furthermore, the circulation of the molten medium is carried out by a pump (17) which for example may be downstream of the tank (16).
  • the electrolysis cell (1) used has a diameter of 0./m for a height of one meter, the cathode (2) has an internal diameter of 0.34 m and the graphite anode a diameter of 0.3 m, its upper part being sheathed by an alumina tube.
  • the decanter (8) has a cylindrical shape of 0.5 m in diameter for a height of 0.5 m and has an area of 0.2 m 2 , the feed rate being 1 m 3 / h.
  • the buffer tank (16) is followed by a pump (17) making it possible to filter the salts under pressure on a filter (15) made of sintered stainless steel.
  • Stream 7 is separated into two streams by the decanter (8), the first stream (14) being constituted by a heavy homogeneous phase of molten salts LiCI and KCI, the second (12) being a light lithium phase corresponding to the production electrolysis.
  • the salts recovered in the tank (16) are pumped continuously to be recycled to the electrolyser after filtration on the metallic porous material contained in the identified device (15).

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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)
EP85400263A 1984-02-24 1985-02-15 Procédé et dispositif pour la fabrication de lithium en continu Expired EP0156668B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8402840 1984-02-24
FR8402840A FR2560221B1 (fr) 1984-02-24 1984-02-24 Procede et dispositif pour la fabrication de lithium en continu

Publications (2)

Publication Number Publication Date
EP0156668A1 EP0156668A1 (fr) 1985-10-02
EP0156668B1 true EP0156668B1 (fr) 1987-11-04

Family

ID=9301368

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85400263A Expired EP0156668B1 (fr) 1984-02-24 1985-02-15 Procédé et dispositif pour la fabrication de lithium en continu

Country Status (5)

Country Link
EP (1) EP0156668B1 (enrdf_load_stackoverflow)
JP (1) JPS60190587A (enrdf_load_stackoverflow)
CA (1) CA1250544A (enrdf_load_stackoverflow)
DE (1) DE3560911D1 (enrdf_load_stackoverflow)
FR (1) FR2560221B1 (enrdf_load_stackoverflow)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3532956A1 (de) * 1985-09-14 1987-03-19 Metallgesellschaft Ag Verfahren und vorrichtung zur herstellung von lithiummetall hoher reinheit durch schmelzflusselektrolyse
FR2591615B1 (fr) * 1985-12-13 1988-02-19 Rhone Poulenc Spec Chim Procede et appareillage pour la preparation en continu de lithium par electrolyse du chlorure de lithium
RU2135615C1 (ru) * 1997-12-25 1999-08-27 Открытое акционерное общество "Новосибирский завод химконцентратов" Способ получения лития
JP2007063585A (ja) * 2005-08-30 2007-03-15 Sumitomo Titanium Corp 溶融塩電解方法および電解槽並びにそれを用いたＴｉの製造方法
CN109312483B (zh) * 2016-06-07 2021-06-22 浦项产业科学研究院 金属锂的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0107521A1 (fr) * 1982-08-31 1984-05-02 Rhone-Poulenc Chimie Procédé pour la préparation continue de lithium par électrolyse du chlorure de lithium dans un mélange de sels fondus et appareillage pour la mise en oeuvre dudit procédé

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2075150A (en) * 1932-11-07 1937-03-30 Justin F Wait Process for the producing of metals and utilization thereof
US3661738A (en) * 1970-06-29 1972-05-09 American Magnesium Co System for melting melt enriching solids utilizing excess heat from electrolysis cells
IL64372A0 (en) * 1980-12-11 1982-02-28 Ishizuka Hiroshi Electrolytic cell for magnesium chloride

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0107521A1 (fr) * 1982-08-31 1984-05-02 Rhone-Poulenc Chimie Procédé pour la préparation continue de lithium par électrolyse du chlorure de lithium dans un mélange de sels fondus et appareillage pour la mise en oeuvre dudit procédé

Also Published As

Publication number Publication date
JPH0132317B2 (enrdf_load_stackoverflow) 1989-06-30
FR2560221A1 (fr) 1985-08-30
JPS60190587A (ja) 1985-09-28
DE3560911D1 (en) 1987-12-10
CA1250544A (fr) 1989-02-28
EP0156668A1 (fr) 1985-10-02
FR2560221B1 (fr) 1989-09-08

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