EP0156668A1 - Verfahren und Vorrichtung zur fortlaufenden Herstellung von Lithium - Google Patents

Verfahren und Vorrichtung zur fortlaufenden Herstellung von Lithium Download PDF

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Publication number
EP0156668A1
EP0156668A1 EP85400263A EP85400263A EP0156668A1 EP 0156668 A1 EP0156668 A1 EP 0156668A1 EP 85400263 A EP85400263 A EP 85400263A EP 85400263 A EP85400263 A EP 85400263A EP 0156668 A1 EP0156668 A1 EP 0156668A1
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EP
European Patent Office
Prior art keywords
lithium
mixture
electrolysis
cathode
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.)
Granted
Application number
EP85400263A
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English (en)
French (fr)
Other versions
EP0156668B1 (de
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 Specialites Chimiques
Rhone Poulenc Chimie SA
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Publication date
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Application filed by Rhone Poulenc Specialites Chimiques, Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Specialites Chimiques
Publication of EP0156668A1 publication Critical patent/EP0156668A1/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
    • 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 relates to a simplified process for the manufacture of lithium continuously by electrolysis of lithium chloride in a mixture of molten salts then separation of the lithium produced; this process comprises the following stages: in a first stage, the electrolysis of lithium chloride is continuously carried out in a mixture of molten salts; in the electrolyser, the lithium produced from the mixture of molten salts is not separated so that a mixture consisting of metallic lithium and the mixture of molten salts is removed from said electrolyser, which considerably simplifies the conduct of the electrolysis ; in a second step, the metallic lithium and the molten salts leaving the electrolyser feed a decanter in which the separation of lithium from molten salts, said salts being able to be recycled after optional filtration in the electrolyzer supply.
  • 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 procedure will be carried out in a liquid medium; the electrolysis having to be carried out at a temperature of between 400 and 500 ° C approximately and preferably around 450 ° C, the mixture of molten salts supplying the electrolyzer should have a composition fairly close to the eutectic composition of mixture used with an excess of lithium chloride which will be subjected to electrolysis.
  • the electrolysis medium it is considered that at approximately 450 ° C., the amount of lithium chloride in said mixture may vary for entry and exit between 56 and 69 7 mol of LiCl 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 repel the 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.
  • retractable material is meant a material which remains inert, at the electrolysis temperature, vis-à-vis 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 with lithium and the molten salts leaving the electrolyzer and comprises a decanting part and an evacuation well, said decanting part preferably having a surface S such that if Q is the feed rate of said decanter in m 3 / h and S the area in m "of said settling part; the supernatant light phase is the lithium which is withdrawn from the decanter and the remaining heavy phase constituted by the molten salts is, preferably, recycled after a possible filtratior. in the electrolyzer supply.
  • 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 similar, 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 mowed medium is circulated by a pump (17) which, for example, can be downstream of the tank (16).
  • the electrolysis cell (1) used has a diameter of O / 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 (1 /) 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 LiCl and KC1, 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 porous metal 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 Verfahren und Vorrichtung zur fortlaufenden Herstellung von Lithium Expired EP0156668B1 (de)

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 true EP0156668A1 (de) 1985-10-02
EP0156668B1 EP0156668B1 (de) 1987-11-04

Family

ID=9301368

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85400263A Expired EP0156668B1 (de) 1984-02-24 1985-02-15 Verfahren und Vorrichtung zur fortlaufenden Herstellung von Lithium

Country Status (5)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2591615A1 (fr) * 1985-12-13 1987-06-19 Rhone Poulenc Spec Chim Procede et appareillage pour la preparation en continu de lithium par electrolyse du chlorure de lithium

Families Citing this family (3)

* 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
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
US11280012B2 (en) 2016-06-07 2022-03-22 Research Institute Of Industrial Science & Technology Method for manufacturing metal lithium

Citations (4)

* 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
EP0054527A2 (de) * 1980-12-11 1982-06-23 Hiroshi Ishizuka Elektrolysezelle für Magnesiumchlorid
FR2532332A1 (fr) * 1982-08-31 1984-03-02 Rhone Poulenc Spec Chim Procede pour la preparation continue de lithium par electrolyse du chlorure de lithium dans un melange de sels fondus et appareillage pour la mise en oeuvre dudit procede

Patent Citations (4)

* 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
EP0054527A2 (de) * 1980-12-11 1982-06-23 Hiroshi Ishizuka Elektrolysezelle für Magnesiumchlorid
FR2532332A1 (fr) * 1982-08-31 1984-03-02 Rhone Poulenc Spec Chim Procede pour la preparation continue de lithium par electrolyse du chlorure de lithium dans un melange de sels fondus et appareillage pour la mise en oeuvre dudit procede

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2591615A1 (fr) * 1985-12-13 1987-06-19 Rhone Poulenc Spec Chim Procede et appareillage pour la preparation en continu de lithium par electrolyse du chlorure de lithium
EP0230171A1 (de) * 1985-12-13 1987-07-29 Rhone-Poulenc Chimie Verfahren und Vorrichtung zur kontinuierlichen Herstellung von Lithium durch Elektrolyse von Lithiumchlorid

Also Published As

Publication number Publication date
JPS60190587A (ja) 1985-09-28
DE3560911D1 (en) 1987-12-10
JPH0132317B2 (de) 1989-06-30
FR2560221A1 (fr) 1985-08-30
CA1250544A (fr) 1989-02-28
FR2560221B1 (fr) 1989-09-08
EP0156668B1 (de) 1987-11-04

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