[go: up one dir, main page]

US20100051470A1 - Process for producing metallic lithium - Google Patents

Process for producing metallic lithium Download PDF

Info

Publication number
US20100051470A1
US20100051470A1 US12/513,030 US51303007A US2010051470A1 US 20100051470 A1 US20100051470 A1 US 20100051470A1 US 51303007 A US51303007 A US 51303007A US 2010051470 A1 US2010051470 A1 US 2010051470A1
Authority
US
United States
Prior art keywords
lithium
lithium carbonate
chlorine gas
electrolysis
reacting
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.)
Abandoned
Application number
US12/513,030
Other languages
English (en)
Inventor
Eiji Nakamura
Hiroaki Takata
Yukihiro Yokoyama
Hiroshi Miyamoto
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.)
Santoku Corp
Original Assignee
Santoku Corp
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 Santoku Corp filed Critical Santoku Corp
Assigned to SANTOKU CORPORATION reassignment SANTOKU CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MIYAMOTO, HIROSHI, NAKAMURA, EIJI, TAKATA, HIROAKI, YOKOYAMA, YUKIHIRO
Publication of US20100051470A1 publication Critical patent/US20100051470A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • 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 method for producing lithium metal by molten salt electrolysis, in particular, a method for producing lithium metal which allows continuous operation of molten salt electrolysis along with the production of anhydrous lithium chloride as a raw material for the electrolysis.
  • Anhydrous lithium chloride is used as a raw material in molten salt electrolysis for production of lithium metal, or a desiccant.
  • Patent Publication 1 discloses reaction of lithium hydroxide with hydrochloric acid for producing a high purity product
  • Patent Publication 2 discloses reaction of lithium carbonate suspended in water with chlorine gas in the presence of an iron-nickel catalyst.
  • Both of these methods inevitably include dehydrating and drying of the resulting lithium chloride for obtaining anhydrous lithium chloride, which requires additional costs for operation and facility.
  • Patent Publication 3 discloses a method for producing anhydrous lithium chloride by reacting chlorine gas with lithium hydroxide.
  • the raw material lithium hydroxide which is strongly alkaline, irritates eyes, skin, and mucosa, and is easily stirred up when, in particular, the reaction is performed in a dry process, which causes difficulties in handling and additional costs for operation and facility.
  • Molten salt electrolysis has been employed for producing lithium metal, and attempts have conventionally been made to use inexpensive lithium carbonate as a lithium source.
  • lithium carbonate is not in use in commercial production at present because the graphite anode-consuming electrolytic reaction (2Li 2 CO 3 +C ⁇ 4Li+3CO 2 ) is the main reaction, and the lithium metal resulting from the electrolysis reacts with lithium carbonate (Li 2 CO 3 +4Li ⁇ 3Li 2 O+C) in the electrolyte to obstruct continuous electrolysis.
  • Patent Publication 4 discloses a method of molten salt electrolysis using anhydrous lithium chloride, wherein lithium carbonate is introduced onto the surface of the bath around the anode to cause the reaction 2Li 2 CO 3 +2Cl 2 ⁇ 4LiCl+2CO 2 +O 2 , to thereby generate anhydrous lithium chloride and allow continuous electrolysis.
  • Patent Publication 5 discloses a method of molten salt electrolysis using anhydrous lithium chloride, wherein lithium carbonate and charcoal or the like as a carbon source are simultaneously introduced into the anode compartment to cause the reaction 2Li 2 CO 3 +2Cl 2 +C ⁇ 4LiCl+3CO 2 , to thereby prevent consumption of the anode.
  • Patent Publications 4 and 5 do not solve the problem of reaction between the lithium metal resulting from electrolysis and lithium carbonate discussed above. Thus these methods have difficulties in the control of carbonate concentration and various problems in operation, such as declined current efficiency, black powder foam, and short circuit.
  • Patent Publication 6 discloses a method including the steps of extracting a part of a mixed molten salt of the electrolyte containing anhydrous lithium chloride outside the electrolytic cell, introducing the extracted molten salt into a chlorinating furnace, adding lithium carbonate and a chlorinating agent thereto, reacting the molten lithium carbonate and the chlorinating agent, and returning the resulting anhydrous lithium chloride to the electrolytic cell for use as a raw material.
  • This method has difficulties in controlling the concentration of the electrolyte, requires circulation facilities, and is not practical in view of safety.
  • Patent Publication 7 discloses an electrolysis method wherein the anode compartment is separated from the cathode compartment with a porous electrically nonconductive partition, lithium carbonate is introduced into the anode compartment, and only the lithium ions are delivered to the cathode compartment to deposite lithium metal. This method requires a high temperature, the current efficiency is low, and the corrosion resistance of the nonconductive partition should be attended to.
  • Patent Publication 1 U.S. Pat. No. 4,980,136-A1
  • Patent Publication 2 RU-2116251-C1
  • Patent Publication 3 U.S. Pat. No. 2,968,526-A1
  • Patent Publication 4 U.S. Pat. No. 3,344,049-A1
  • Patent Publication 5 JP-59-200731-A
  • Patent Publication 6 JP-1-152226-A
  • Patent Publication 7 U.S. Pat. No. 4,988,417-A1
  • Non-patent Publication 1 “Youyuen Netsugijutsu no Kiso (Basics of Molten Salt Thermal Technology)”, written and edited by The Society of Molten-Salt Thermal Technology, published by Agne Gijutsu Center (1993), p 97
  • Non-patent Publication 2 “Youyuen no Ouyou (Applications of Molten Salt)”, written and edited by Yasuhiko ITO, published by Industrial Publishing & consulting, Inc. (2003), p 305
  • a method for producing lithium metal comprising the steps of:
  • step (B) subjecting a raw material for electrolysis comprising said anhydrous lithium chloride obtained from step (A) to molten salt electrolysis under such conditions as to produce lithium metal;
  • step (B) wherein chlorine gas generated by said molten salt electrolysis in step (B) is used as said chlorine gas in step (A) to continuously perform steps (A) and (B).
  • step (A) efficient production of anhydrous lithium chloride is facilitated without causing corrosion of the system materials by the chlorine gas and the molten lithium carbonate.
  • step (B) lithium metal is produced by molten salt electrolysis of the anhydrous lithium chloride obtained from step (A) as a raw material, while the chlorine gas generated by the molten salt electrolysis is used for producing the raw material anhydrous lithium chloride without discharging the chlorine gas outside the system.
  • the method of the present invention is excellently safe and efficient in producing anhydrous lithium chloride and lithium metal.
  • FIG. 1 is a graph showing the relationship between the reaction temperature and the chlorination ratio of the lithium carbonate in powder form at various particle sizes (D90).
  • FIG. 2 is a sectional pattern diagram of an example of a system that may be used for the production of anhydrous lithium chloride in step (A) of the present invention.
  • FIG. 3 is a sectional pattern diagram of an example of a system that may be used for practicing the method for producing lithium metal according to the present invention.
  • the method of the present invention includes step (A) of contacting and reacting lithium carbonate and chlorine gas in a dry process to produce anhydrous lithium chloride.
  • This step (A) allows efficient production of anhydrous lithium chloride, so that this step alone may be a method for producing anhydrous lithium chloride.
  • step (A) The reaction between the lithium carbonate and the chlorine gas in step (A) is effected in a dry process, i.e., by contacting solid lithium carbonate and chlorine gas without a solvent, such as water. Chlorine gas generated by the molten salt electrolysis in step (B) to be discussed later may be used here.
  • step (A) alone is carried out to produce anhydrous lithium chloride, chlorine gas supplied from a gas cylinder or the like may be used.
  • the chlorine gas may preferably be at 100% concentration, but may alternatively be mixed with inert gas, such as argon or helium.
  • the lithium carbonate may be in any form without limitation, and preferably in the form of powder, which may further be granulated.
  • the optimum particle size range of the powdered lithium carbonate for efficient reaction with the chlorine gas in step (A) was determined through an experiment.
  • reactivity of lithium carbonate powders having D90's of 0.02 to 0.82 mm with chlorine gas was determined in the temperature range of 250 to 550° C.
  • D90 represents the particle size at which the cumulative volume fraction is 90% as measured with a laser diffraction particle size analyzer (Microtrac IISRA manufactured by NIKKISO CO., LTD.).
  • a vertical furnace having a cylindrical alumina pipe of 50 mm inner diameter was used.
  • a perforated alumina dish having 5 mm diameter pores at not less than 50% porosity was disposed in the soaking area in the cylindrical pipe, and an air permeable silica cloth was placed on the dish.
  • argon gas was blown up into the cylindrical pipe at 1.0 L/min, 10 g of lithium carbonate was placed on the cloth and held in the pipe.
  • the argon gas was replaced with chlorine gas (3N, 1.0 L/min), and held for 20 minutes. Then the chlorine gas was replaced with argon gas, and the pipe was cooled.
  • the temperature suitable for the reaction is not lower than 350° C. and lower than 506° C., preferably not lower than 400° C. and lower than 506° C.
  • X-ray diffraction analysis of the products produced at temperatures below 506° C. detected nothing other than lithium carbonate.
  • the D90 of the powdered lithium carbonate suitable for the reaction may be not more than 0.70 mm, preferably not more than 0.40 mm, more preferably not more than 0.10 mm.
  • the reaction discussed above is performed in a solid system without molten lithium carbonate being involved, and at a temperature lower than 506° C. Thus the problem of corrosion of the apparatus may be avoided, and even stainless steel, which is a general-purpose material, may be used for manufacturing the system with sufficient corrosion resistance.
  • step (A) the reaction of the lithium carbonate with the chlorine gas may be effected in a fixed, moving, or fluidized bed, and either in a continuous or batch system.
  • anhydrous lithium chloride may be produced continuously as a moving bed, which may be continuously drawn out or supplied to step (B) to be discussed later.
  • step (A) continuous introduction of the lithium carbonate, reaction with the chlorine gas, and recovery of the resulting anhydrous lithium chloride may be achieved by stirring the lithium carbonate in apparatus of a rotary kiln type while the chlorine gas is blown in a counterflow, or by introducing the lithium carbonate down into a vertical reaction vessel equipped with stirring means while the chlorine gas is blown up in a counterflow. In the latter case, hermetical sealing of the facility may be secured more easily.
  • lithium carbonate of a smaller particle size is advantageous in view of the reaction speed, but may cause declined air permeability to obstruct introduction of the chlorine gas into the center of the lithium carbonate bed, which may inhibit progress of the reaction.
  • the particle size distribution of the granulated lithium carbonate may preferably be in the range of 0.1 to 5 mm.
  • the effect of granulation may not be exhibited sufficiently, and at more than 5 mm, not only the granulation per se but also introduction of the chlorine gas into the center of the resulting granules becomes hard.
  • the particle size distribution may be controlled by means of a sieve after the granulation.
  • the granulation may be carried out by self-granulation, such as rolling, fluidized-bed, or stirring granulation, or by forced granulation, such as loosening, compression, extrusion, or dissolving granulation, among which extrusion granulation is preferred.
  • the granulation may be carried out with an organic binder.
  • the residual carbon will act as an additive for reduction reaction.
  • the binder may alternatively be water, and then moisture needs to be removed sufficiently after the granulation.
  • the moisture content of the lithium carbonate in powder or granular form used as a raw material for step (A) may usually be not higher than 1 mass %, preferably not higher than 0.3 mass %.
  • the anhydrous lithium chloride powder generated in step (A) may be agglomerated and solidified into bulks as the temperature rises to some extent, even lower than the melting point. The bulks may cause hanging or decline of gas permeability in the reaction vessel, which may withhold the progress of reaction at a low chlorination ratio.
  • step (A) alone may be performed for producing anhydrous lithium chloride will be explained.
  • FIG. 2 is a sectional pattern diagram of an example of a system in which step (A) may be performed for producing anhydrous lithium chloride.
  • the system 10 includes a reaction vessel (chlorinating furnace) 11 for contacting and reacting lithium carbonate and chlorine gas in a dry process, a hopper 12 for reserving therein lithium carbonate 12 a as a raw material, and a chlorine gas cylinder 13 .
  • the reaction vessel 11 may be made of a material which is resistant to corrosion by hot chlorine gas, for example, Inconel (registered trademark), stainless steel, or mild steel lined with ceramics, such as alumina, silica, or mullite.
  • Inconel registered trademark
  • stainless steel or mild steel lined with ceramics, such as alumina, silica, or mullite.
  • the hopper 12 is equipped with a rotary valve 14 for supplying the lithium carbonate into the reaction vessel 11 , and is connected from above to the reaction vessel 11 .
  • the chlorine gas cylinder 13 is connected from below to the reaction vessel 11 via a duct 15 made of, for example, stainless steel and equipped with a valve 15 a , for supplying the chlorine gas up into the reaction vessel 11 .
  • the reaction vessel 11 is provided with an electric furnace 16 arranged therearound for controlling the reaction temperature, and a shaft 17 a arranged therein having a plurality of stirring bars 17 b for effecting the reaction under stirring, with the shaft 17 a being connected to an external motor 17 c .
  • the stirring bars 17 b may be of any shape, such as rod, plate, or vane, as long as the stirring may be effected.
  • a stainless steel rotary valve 18 is disposed below the reaction vessel 11 for discharging the generated anhydrous lithium chloride out of the system.
  • a duct 19 equipped with a valve 19 a and a blower 19 b is disposed above the reaction vessel 11 for discharging the carbon dioxide gas and oxygen gas generated by the reaction out of the system.
  • the duct 19 may be made of, for example, stainless steel, nickel-based alloys, or vinyl chloride.
  • Step (A) may be performed in the system 10 by supplying the lithium carbonate 12 a in the hopper 12 down into the reaction vessel 11 while the chlorine gas from the chlorine gas cylinder 13 is supplied up into the reaction vessel 11 , with the shaft 17 a being rotated by the motor 17 c and the temperature inside the reaction vessel 11 being controlled with the electric furnace 16 , to thereby mix and react the lithium carbonate 12 a and the chlorine gas under stirring.
  • the lithium carbonate 12 a contacts and reacts with the chlorine gas in a counter flow manner in the reaction vessel 11 , and the resulting anhydrous lithium chloride is sequentially discharged out of the system via the rotary valve 18 .
  • the supply rate of the lithium carbonate 12 a into the reaction vessel 11 is controlled by the rotary valve 14
  • the supply rate of the chlorine gas is controlled by the valve 15 a .
  • Carbon dioxide gas and oxygen gas resulting from the reaction in the reaction vessel 11 are sucked by the blower 19 b with the discharge rate being controlled with the valve 19 a , and discharged out of the system.
  • the method of the present invention includes step (B) of subjecting the raw material for electrolysis including the anhydrous lithium chloride obtained from step (A) to molten salt electrolysis under such conditions as to produce lithium metal.
  • step (B) the specific constructions of the electrolytic cell, the electrodes, and the electrolyte, as well as the specific operating conditions, such as cell voltage and current density, for the molten salt electrolysis, are conventionally well known, and may suitably be selected with reference to the conventional methods. In the Examples to be discussed later, an example of the conditions will be presented.
  • chlorine gas is generated by the molten salt electrolysis in step (B).
  • steps (A) and (B) may be carried out continuously. That is, the chlorine gas generated by the molten salt electrolysis in step (B) is used in carrying out step (A) to generate anhydrous lithium chloride, which is in turn used in supplementing the electrolyte, which decreases with the progress of the electrolysis in step (B). In this way, steps (A) and (B) may be performed continuously.
  • lithium carbonate having the lithium weight equivalent to that of the anhydrous lithium chloride to be electrolyzed in step (B) is converted to anhydrous lithium chloride in step (A), which is then used as the raw material for the electrolysis in step (B)
  • nominal electrolysis of lithium carbonate is achieved.
  • the present system may flexibly respond to the change in operation by employing, as a part of the anhydrous lithium chloride to be supplemented to the system, anhydrous lithium chloride that has been prepared by a dry or wet method outside the electrolytic system, or by introducing additional chlorine gas from outside the electrolytic system to produce more anhydrous lithium chloride than that is consumed in the electrolysis.
  • the present invention allows in principle to form a closed system, so that costs for environmental protection may be reduced.
  • the continuous electrolysis allows safe and efficient production of lithium metal without discharging the chlorine gas outside the system.
  • the anhydrous lithium chloride prepared in a dry process in step (A) is used as the raw material anhydrous lithium chloride for the electrolysis.
  • anhydrous lithium chloride prepared in step (A) of the present invention has an extremely low moisture content, and accordingly the electrolysis may be effected without the drawbacks mentioned above.
  • FIG. 3 an example of a system with which the method of the present invention may be performed by continuously carrying out steps (A) and (B), will now be discussed below.
  • steps (A) and (B) will now be discussed below.
  • members already appeared in FIG. 2 are referred to by the same numbers as in FIG. 2 , and further discussion is eliminated.
  • FIG. 3 is a sectional pattern diagram of an example of a system that may be used for continuously carrying out steps (A) and (B) to produce lithium metal.
  • the system 20 is basically composed of the system 10 for carrying out step (A) as discussed with reference to FIG. 2 , and a cell for lithium electrolysis 21 connected thereto.
  • the system 10 has been modified by replacing the chlorine gas cylinder 13 with a chlorine gas transfer line 22 connecting the lower portion of the reaction vessel 11 and the cell for lithium electrolysis 21 , and by providing a transfer line 23 made of stainless steel for transferring the anhydrous lithium chloride generated in the reaction vessel 11 to the cell for lithium electrolysis 21 via a rotary valve 18 .
  • Other members of the system 10 are the same as shown in FIG. 2 .
  • the cell for lithium electrolysis 21 may be a generally used Downs-type cell or a conversion thereof.
  • the cell 21 is equipped with a graphite electrode as an anode 24 and an iron electrode as a cathode 25 , and electrolyte 26 is introduced therein.
  • Steps (A) and (B) may be carried out continuously in the system 20 by producing anhydrous lithium chloride in the reaction vessel 11 as in the system 10 , supplying the anhydrous lithium chloride through the rotary valve 18 and transfer line 23 into the electrolyte 26 in the cell for lithium electrolysis 21 , and effecting electrolysis.
  • the chlorine gas to be used in the reaction in the reaction vessel 11 the chlorine gas generated by the molten salt electrolysis in the cell for lithium electrolysis 21 is transferred to the reaction vessel 11 through the chlorine gas transfer line 22 during the reaction.
  • anhydrous lithium chloride was produced according to the following process.
  • the granulated powder was dried to the moisture content of 0.3 mass %, to thereby obtain lithium carbonate 12 a in granular form having the particle size distribution in the range of 0.8 to 1.2 mm.
  • the lithium carbonate 12 a was chlorinated with 3N chlorine gas supplied from the chlorine gas cylinder 13 .
  • the reaction vessel 11 was heated with the electric furnace 16 to create an area of 400° C. to 500° C. over about 1000 mm, wherein the chlorinating reaction was effected.
  • the velocity of the moving bed was adjusted so that the residence time of the lithium carbonate 12 a in this temperature area was not shorter than 2 hours.
  • the supply rate of the lithium carbonate 12 a from the hopper 12 was 3.5 kg/h in average, and the discharge rate of the anhydrous lithium chloride was 3.9 kg/h in average.
  • the exhaust gas from the reaction vessel 11 was mainly composed of carbon dioxide and oxygen gases.
  • the chlorination ratio from the carbonate to the chloride was maintained over 95%. Only slight hanging was occurred in the reaction vessel 11 , and continuous operation was permitted.
  • the resulting anhydrous lithium chloride had a moisture content of less than 0.1 mass %.
  • anhydrous lithium chloride was produced in accordance with the following process.
  • the lithium carbonate 12 a was produced in the same way as in Production Example 1.
  • molten salt electrolysis was performed at the current of 10 kA and at the temperature of 460° C., using an electrolyte composed of 35 to 45 mass % lithium chloride and 55 to 65 mass % potassium chloride, as the electrolyte 26 .
  • Production Example 1 was followed, except that the chlorine gas generated by the electrolysis was transferred to the reaction vessel 11 through the chlorine gas transfer line 22 , and the chlorination reaction of the lithium carbonate 12 a was carried out with the velocity of the moving bed being adjusted so that the residence time of the lithium carbonate 12 a in the area at 400° C. to 500° C. was not shorter than 4 hours.
  • the supply rate of the lithium carbonate 12 a from the hopper 12 was 11.5 kg/h in average
  • the discharge rate of the anhydrous lithium chloride was 12.9 kg/h in average
  • 2.1 kg/h in average of lithium metal was recovered from the cell for lithium electrolysis 21 .
  • the exhaust gas mainly detected from the reaction vessel 11 was carbon dioxide and oxygen gases, and the chlorination ratio from the carbonate to the chloride was maintained over 95%. Only slight hanging was occurred in the reaction vessel 11 , and continuous operation was permitted.
  • the electrolysis in the cell for lithium electrolysis 21 was effected in the same way as the ordinary chloride electrolysis, the formation of black powder foam, which is characteristic of direct electrolysis of carbonate, was not observed, and remarkable consumption of the anode 24 (graphite anode) was not observed.
  • lithium metal was used as an anode foil of lithium primary battery, with no problem being observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US12/513,030 2006-11-02 2007-11-02 Process for producing metallic lithium Abandoned US20100051470A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2006-298328 2006-11-02
JP2006298328 2006-11-02
PCT/JP2007/071374 WO2008053986A1 (fr) 2006-11-02 2007-11-02 Procédé de production de lithium métallique

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/071374 A-371-Of-International WO2008053986A1 (fr) 2006-11-02 2007-11-02 Procédé de production de lithium métallique

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/608,561 Continuation US8911610B2 (en) 2006-11-02 2012-09-10 Process for producing metallic lithium

Publications (1)

Publication Number Publication Date
US20100051470A1 true US20100051470A1 (en) 2010-03-04

Family

ID=39344325

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/513,030 Abandoned US20100051470A1 (en) 2006-11-02 2007-11-02 Process for producing metallic lithium
US13/608,561 Active US8911610B2 (en) 2006-11-02 2012-09-10 Process for producing metallic lithium

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/608,561 Active US8911610B2 (en) 2006-11-02 2012-09-10 Process for producing metallic lithium

Country Status (4)

Country Link
US (2) US20100051470A1 (ja)
JP (1) JP5336193B2 (ja)
CN (1) CN101573296B (ja)
WO (1) WO2008053986A1 (ja)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120073984A1 (en) * 2010-09-23 2012-03-29 Semiconductor Energy Laboratory Co., Ltd. Method for recovering metallic lithium
WO2014005878A1 (de) * 2012-07-05 2014-01-09 Siemens Aktiengesellschaft Verfahren zur gewinnung eines elektropositiven metalls aus einem metallcarbonat
CN104372383A (zh) * 2014-11-28 2015-02-25 陈小磊 一种锂电解槽上料装置及使用其的锂电解槽
WO2015121196A1 (de) * 2014-02-13 2015-08-20 Siemens Aktiengesellschaft Umwandlung von metallcarbonat in metallchlorid
WO2015121192A1 (de) * 2014-02-13 2015-08-20 Siemens Aktiengesellschaft Umwandlung von metallcarbonat in metallchlorid
CN113881975A (zh) * 2021-10-19 2022-01-04 杭州嘉悦智能设备有限公司 熔盐氯化电解炉及其控制方法

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5382117B2 (ja) 2009-06-19 2014-01-08 富士通株式会社 データ転送方法、コード変換回路及び装置
CN103205774A (zh) * 2013-05-02 2013-07-17 新疆骏强科技发展有限公司 锂盐一步法熔融电解制金属锂的方法
DE102014219274A1 (de) 2014-09-24 2016-03-24 Siemens Aktiengesellschaft Kraftwerk zur Herstellung von Energie und Ammoniak
DE102014219276A1 (de) 2014-09-24 2016-03-24 Siemens Aktiengesellschaft Gas und Dampfkraftwerksanlage (GUD) auf der Basis von elektropositiven Metallen mit optional angeschlossenem Fischer-Tropsch Prozess
CN104311499A (zh) * 2014-09-29 2015-01-28 奉新赣锋锂业有限公司 一种处理金属锂生产中产生的氯气的方法及其应用
DE102014222919A1 (de) 2014-11-11 2016-05-12 Siemens Aktiengesellschaft Verbrennung von elektropositivem Metall in einer Flüssigkeit
CN104404574B (zh) * 2014-11-28 2016-09-07 陈小磊 快速上料锂电解槽的上料装置及使用其的锂电解槽
WO2017213272A1 (ko) 2016-06-07 2017-12-14 재단법인 포항산업과학연구원 금속리튬의 제조 방법
CN109837561A (zh) * 2017-11-27 2019-06-04 中国科学院大连化学物理研究所 一种金属锂粉及其电化学制备方法
CN108264067A (zh) * 2018-03-22 2018-07-10 何朋飞 一种盐湖卤水生产氯化锂的新工艺及装备
CN110306052B (zh) * 2019-06-25 2020-09-15 中南大学 一种金属锂单质及其制备方法与应用
US20220267918A1 (en) * 2019-07-25 2022-08-25 Li-Metal Corp. Molten salt membrane electrolyzer
CN110668474B (zh) * 2019-10-15 2022-03-04 赣州有色冶金研究所有限公司 一种利用氯气制备氯化锂的方法
CN112048737A (zh) * 2020-08-28 2020-12-08 奉新赣锋锂业有限公司 一种通过控制水含量提高金属锂电解电流效率的方法
EP3964480A1 (en) * 2020-09-02 2022-03-09 AMG Lithium GmbH Process for preparing lithium salts
AU2022210740A1 (en) 2021-01-21 2023-08-10 Li-Metal Corp. Electrowinning cell for the production of a metal product and method of using same
AU2022211401A1 (en) 2021-01-21 2023-08-10 Li-Metal Corp. Process for production refined lithium metal
WO2022155752A1 (en) 2021-01-21 2022-07-28 Li-Metal Corp. Electrorefining apparatus and process for refining lithium metal

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2752299A (en) * 1952-01-08 1956-06-26 Walter M Weil Electrolytic production of manganese and ferromanganese
US2968526A (en) * 1958-04-17 1961-01-17 Foote Mineral Co Manufacture of anhydrous lithium halide by direct halogenation of lithium hydroxide
US3024082A (en) * 1957-06-27 1962-03-06 Scient Design Co Lithium chloride production
US3344049A (en) * 1967-09-26 Method of producing lithium
US4487677A (en) * 1983-04-11 1984-12-11 Metals Production Research, Inc. Electrolytic recovery system for obtaining titanium metal from its ore
US4699704A (en) * 1985-02-13 1987-10-13 Hiroshi Ishizuka Electrolytic cell for a molten salt
JPH01152226A (ja) * 1987-12-08 1989-06-14 Nippon Soda Co Ltd 金属リチウムの製造法
US4980136A (en) * 1989-07-14 1990-12-25 Cyprus Foote Mineral Company Production of lithium metal grade lithium chloride from lithium-containing brine
US4988417A (en) * 1988-12-29 1991-01-29 Aluminum Company Of America Production of lithium by direct electrolysis of lithium carbonate
US5089094A (en) * 1989-03-16 1992-02-18 Osaka Titanium Company Limited Process for the electrolytic production of magnesium
US5665220A (en) * 1995-12-26 1997-09-09 General Motors Corporation Electrolytic magnesium production process
US20060219053A1 (en) * 2003-08-28 2006-10-05 Tadashi Ogasawara Method and apparatus for producing metal

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59200731A (ja) * 1983-04-28 1984-11-14 Nippon Soda Co Ltd 金属リチウムの製造法
JP3093421B2 (ja) * 1992-04-03 2000-10-03 旭テック株式会社 リチウムの生成方法
RU2116251C1 (ru) 1997-06-11 1998-07-27 Акционерное Общество Открытого Типа "Новосибирский завод Химконцентратов" Способ получения хлорида лития
DE69838575T2 (de) * 1997-11-28 2008-07-24 Maizuru Corp. Verfahren zur Oberflächenbehandlung von Eisenmaterial und Salzbadofen dafür verwendet
JP4763169B2 (ja) * 2001-08-06 2011-08-31 株式会社三徳 金属リチウムの製造方法
CN1230380C (zh) * 2003-07-28 2005-12-07 东北大学 一种氯化锂提纯的工艺方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344049A (en) * 1967-09-26 Method of producing lithium
US2752299A (en) * 1952-01-08 1956-06-26 Walter M Weil Electrolytic production of manganese and ferromanganese
US3024082A (en) * 1957-06-27 1962-03-06 Scient Design Co Lithium chloride production
US2968526A (en) * 1958-04-17 1961-01-17 Foote Mineral Co Manufacture of anhydrous lithium halide by direct halogenation of lithium hydroxide
US4487677A (en) * 1983-04-11 1984-12-11 Metals Production Research, Inc. Electrolytic recovery system for obtaining titanium metal from its ore
US4699704A (en) * 1985-02-13 1987-10-13 Hiroshi Ishizuka Electrolytic cell for a molten salt
JPH01152226A (ja) * 1987-12-08 1989-06-14 Nippon Soda Co Ltd 金属リチウムの製造法
US4988417A (en) * 1988-12-29 1991-01-29 Aluminum Company Of America Production of lithium by direct electrolysis of lithium carbonate
US5089094A (en) * 1989-03-16 1992-02-18 Osaka Titanium Company Limited Process for the electrolytic production of magnesium
US4980136A (en) * 1989-07-14 1990-12-25 Cyprus Foote Mineral Company Production of lithium metal grade lithium chloride from lithium-containing brine
US5665220A (en) * 1995-12-26 1997-09-09 General Motors Corporation Electrolytic magnesium production process
US20060219053A1 (en) * 2003-08-28 2006-10-05 Tadashi Ogasawara Method and apparatus for producing metal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
English Abstract of JP 01-152226 A *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120073984A1 (en) * 2010-09-23 2012-03-29 Semiconductor Energy Laboratory Co., Ltd. Method for recovering metallic lithium
US9085813B2 (en) * 2010-09-23 2015-07-21 Semiconductor Energy Laboratory Co., Ltd. Method for recovering metallic lithium
WO2014005878A1 (de) * 2012-07-05 2014-01-09 Siemens Aktiengesellschaft Verfahren zur gewinnung eines elektropositiven metalls aus einem metallcarbonat
CN104411843B (zh) * 2012-07-05 2018-06-29 西门子公司 由金属碳酸盐回收正电性金属的方法
CN104411843A (zh) * 2012-07-05 2015-03-11 西门子公司 由金属碳酸盐回收正电性金属的方法
US9624590B2 (en) 2012-07-05 2017-04-18 Siemens Aktiengesellschaft Method for recovering an electropositive metal from a metal carbonate
US20170001875A1 (en) * 2014-02-13 2017-01-05 Siemens Aktiengesellschaft Conversion of Metal Carbonate into Metal Chloride
CN105992748A (zh) * 2014-02-13 2016-10-05 西门子公司 金属碳酸盐向金属氯化物的转化
WO2015121192A1 (de) * 2014-02-13 2015-08-20 Siemens Aktiengesellschaft Umwandlung von metallcarbonat in metallchlorid
US20170050859A1 (en) * 2014-02-13 2017-02-23 Siemens Aktiengesellschaft Conversion of Metal Carbonate to Metal Chloride
WO2015121196A1 (de) * 2014-02-13 2015-08-20 Siemens Aktiengesellschaft Umwandlung von metallcarbonat in metallchlorid
RU2652635C2 (ru) * 2014-02-13 2018-04-28 Сименс Акциенгезелльшафт Преобразование карбоната металла в хлорид металла
KR101862342B1 (ko) 2014-02-13 2018-05-29 지멘스 악티엔게젤샤프트 금속 카보네이트의 금속 클로라이드로의 전환
US10099937B2 (en) * 2014-02-13 2018-10-16 Siemens Aktiengesellschaft Conversion of metal carbonate to metal chloride
US10280090B2 (en) 2014-02-13 2019-05-07 Siemens Aktiengesellschaft Conversion of metal carbonate into metal chloride
CN104372383A (zh) * 2014-11-28 2015-02-25 陈小磊 一种锂电解槽上料装置及使用其的锂电解槽
CN113881975A (zh) * 2021-10-19 2022-01-04 杭州嘉悦智能设备有限公司 熔盐氯化电解炉及其控制方法

Also Published As

Publication number Publication date
US20130001097A1 (en) 2013-01-03
JPWO2008053986A1 (ja) 2010-02-25
JP5336193B2 (ja) 2013-11-06
CN101573296A (zh) 2009-11-04
WO2008053986A1 (fr) 2008-05-08
CN101573296B (zh) 2011-07-27
US8911610B2 (en) 2014-12-16

Similar Documents

Publication Publication Date Title
US8911610B2 (en) Process for producing metallic lithium
AU2002335251B2 (en) Method and apparatus for smelting titanium metal
CN103451682B (zh) 一种含钛可溶阳极熔盐电解提取金属钛的方法
US4563339A (en) Process for the preparation of magnesium chloride for use as an electrolyte in electrolytic production of magnesium metal
CA2698025C (en) Method for preparing metallic titanium by electrolyzing molten salt with titanium circulation
CN103298742B (zh) 一种制造氯化钛的工艺
US4919771A (en) Process for producing aluminum by molten salt electrolysis
CN102656287A (zh) 钛矿的处理
CN105200458B (zh) 一种制备碳化钛的方法
US3953574A (en) Process for purifying molten magnesium chloride
US11180863B2 (en) Device and method for preparing pure titanium by electrolysis-chlorination-electrolysis
JP4198434B2 (ja) 金属チタンの製錬方法
Martinez et al. New method for low-cost titanium production
US6733738B1 (en) Method and device for the continuous production of NaAlCl4 or NaFeCl4
CN113104870A (zh) 一种电解镁用熔盐电解质的连续制备方法
KR100522116B1 (ko) 비전도성 다공성 세라믹 용기를 이용한 리튬 전구체를포함하는 용융염에서의 리튬 회수장치 및 방법
JP2006274340A (ja) Ｔｉ又はＴｉ合金の製造方法
JPS63118089A (ja) チタン，チタン合金の製造方法
KR101966257B1 (ko) 전해환원 장치에 사용되는 양극 모듈, 이를 포함하는 전해환원 장치 및 그 방법
JP4243899B2 (ja) 半導体スクラップの分解法
Doughty et al. Use of sodium beta alumina in novel processes for the production of metals
CN115747889A (zh) 一种制备钛电解精炼用电解质的方法及电解提钛的方法
WO2024240610A2 (en) Process for the recovery of lithium
JPH03140492A (ja) Ａｌ―Ｌｉ合金の製造方法
RU1789569C (ru) Способ получени металлов

Legal Events

Date Code Title Description
AS Assignment

Owner name: SANTOKU CORPORATION,JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NAKAMURA, EIJI;TAKATA, HIROAKI;YOKOYAMA, YUKIHIRO;AND OTHERS;REEL/FRAME:022811/0534

Effective date: 20090428

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION