JPH0132317B2 - - Google Patents
Info
- Publication number
- JPH0132317B2 JPH0132317B2 JP2102385A JP2102385A JPH0132317B2 JP H0132317 B2 JPH0132317 B2 JP H0132317B2 JP 2102385 A JP2102385 A JP 2102385A JP 2102385 A JP2102385 A JP 2102385A JP H0132317 B2 JPH0132317 B2 JP H0132317B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- molten salt
- anode
- electrolyte
- electrolytic 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.)
- Expired
Links
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 57
- 229910052744 lithium Inorganic materials 0.000 claims description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 31
- 239000011833 salt mixture Substances 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCQWRNRRURULEY-UHFFFAOYSA-L lithium;potassium;dichloride Chemical group [Li+].[Cl-].[Cl-].[K+] HCQWRNRRURULEY-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、溶融塩混合物中の塩化リチウムを電
解し、次いでリチウムを分離することより成るリ
チウムの連続製造法、及びその製造に用いられる
装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a process for continuous production of lithium, which comprises electrolyzing lithium chloride in a molten salt mixture and then separating the lithium, and to an apparatus used for the production.
例えば、米国特許第3078218号及び第3163590号
では、シランの製造において、塩化リチウム及び
少くともアルカリ塩化物及び／又はアルカリ土類
塩化物を主成分とする溶融塩混合物中に含まれる
塩化リチウムから、電解によつてリチウムを製造
することが提案されている。この方法は下記の特
徴の少くとも１つを有する。
For example, in U.S. Pat. Nos. 3,078,218 and 3,163,590, in the production of silane, from lithium chloride and lithium chloride contained in a molten salt mixture based on at least alkali chlorides and/or alkaline earth chlorides, It has been proposed to produce lithium by electrolysis. The method has at least one of the following features.
(1) 半連続的方法−電解槽に電解性混合物を装入
し、この混合物に対して所望量の塩化リチウム
の電解を行い、次いでこの残留する混合物に新
たに塩化リチウムを供給する。(1) Semi-continuous process - an electrolytic cell is charged with an electrolytic mixture, the mixture is electrolyzed with the desired amount of lithium chloride, and the remaining mixture is then fed with fresh lithium chloride.
(2) 電解槽そのものの中で、溶融塩混合から生成
したリチウムを分離する一方で、リチウムと発
生するガス状塩素との再結合を防止するため
に、複雑で、面倒な装置を利用する。これは例
えば、リチウム層の上方の槽雰囲気を慎重に制
御するとか、陽極と陰極との間の浴中に隔膜を
用いるなどによつて行われる。(2) Within the electrolyzer itself, complex and cumbersome equipment is utilized to separate the lithium produced from the molten salt mixture while preventing recombination of the lithium with the gaseous chlorine produced. This is done, for example, by carefully controlling the bath atmosphere above the lithium layer, or by using a diaphragm in the bath between the anode and cathode.
［発明の目的］
本発明は溶融塩混合物中の塩化リチウムを電解
し、次いでリチウム生成物を分離する単純化され
たリチウム連続製造方法を提供することを目的と
する。OBJECTS OF THE INVENTION It is an object of the present invention to provide a simplified continuous process for producing lithium by electrolyzing lithium chloride in a molten salt mixture and then separating the lithium product.
［発明の要旨］
本発明の方法では、第１工程において溶融塩混
合物中で塩化リチウムを連続的に電気分解する。
この場合に、電解槽中では生成したリチウムは溶
融塩混合物から分離されず、金属リチウムと溶融
塩混合物とより成る混合物は電解槽から引出され
る。これは電解操作を大幅に単純化する。第２工
程において、電解槽から引出された金属リチウム
と溶融塩混合物とはデカンターに供給され、そこ
でリチウムは溶融塩から分離される。溶融塩は濾
過（必要ならば）の後に好ましくは電解槽への供
給物中へ循環させることができる。SUMMARY OF THE INVENTION In the method of the present invention, lithium chloride is continuously electrolyzed in a molten salt mixture in a first step.
In this case, the produced lithium is not separated from the molten salt mixture in the electrolytic cell, but the mixture of metallic lithium and molten salt mixture is drawn out of the electrolytic cell. This greatly simplifies electrolysis operations. In the second step, the lithium metal and molten salt mixture drawn from the electrolytic cell are fed to a decanter, where the lithium is separated from the molten salt. The molten salt can preferably be recycled into the feed to the electrolyzer after filtration (if necessary).
［好ましい特徴と作用効果］ 本発明は次の好ましい特徴を有する。[Preferred features and effects] The present invention has the following preferred features.
(1) 陽極と陰極との間に隔膜を用いることなく電
解が実行されるもので、陽極と陰極との間の空
間では電解質の自然な急速な循環が生じる。(1) Electrolysis is carried out without the use of a diaphragm between the anode and cathode, with natural rapid circulation of the electrolyte occurring in the space between the anode and cathode.
(2) 陽極を絶縁性耐火物質で電解質表面下まで被
覆することにより、電解質の表面に浮遊するリ
チウムによる陽極の攻撃を阻止し、陽極表面で
のリチウムの直接的な再酸化を防止する。(2) By coating the anode with an insulating refractory material down to the surface of the electrolyte, attack of the anode by lithium floating on the surface of the electrolyte is prevented, and direct re-oxidation of lithium on the anode surface is prevented.
(3) 一方、電解により発生する塩素は不活性ガス
で希釈することなく連続的に引出されるもので
あり、これによりその直接的な工業的利用を可
能にする。(3) On the other hand, chlorine generated by electrolysis can be drawn out continuously without being diluted with inert gas, which enables its direct industrial use.
(4) 最後に、電解槽からリチウム及び溶融塩を供
給されるデカンターは上澄み分離部（デカント
部）と引出用井部とから成つており、上澄み分
離部でリチウムは分離されて引出され、溶融塩
は井部で分離され、引出され、濾過の後に好ま
しくは電解槽へ再循環される。(4) Finally, the decanter to which lithium and molten salt are supplied from the electrolytic tank consists of a supernatant separation section (decant section) and a drawing well section, where the lithium is separated and drawn out, and the lithium is removed from the molten salt. The salt is separated in the well, withdrawn and, after filtration, preferably recycled to the electrolyzer.
［発明の具体的な説明］
電解質は塩化リチウム及び少なくとも他のアル
カリ及び／又はアルカリ土類元素の塩化物とを主
成分とする溶融塩混合物より成つており、塩化物
は塩化リチウムと共に約320〜360℃の温度で溶融
する共融混合物を形成する。使用しうる二元混合
物としては塩化リチウムと塩化カリウム、使用し
うる三元混合物としては塩化リチウム及び塩化カ
リウムの他に、塩化ナトリウム、塩化ルビジウ
ム、塩化ストロンチウム、塩化マグネシウム、塩
化カルシウム及び塩化バリウムから選ばれた塩化
物を挙げることができる。[Detailed Description of the Invention] The electrolyte is composed of a molten salt mixture consisting mainly of lithium chloride and a chloride of at least another alkali and/or alkaline earth element, and the chloride together with the lithium chloride Forms a eutectic mixture that melts at a temperature of 360 °C. Binary mixtures that can be used include lithium chloride and potassium chloride; ternary mixtures that can be used include lithium chloride and potassium chloride, as well as sodium chloride, rubidium chloride, strontium chloride, magnesium chloride, calcium chloride and barium chloride. Examples include chlorides.
いずれの場合にも電解は溶媒中で行われる。電
解は約400〜500℃の温度、好ましくは約500℃で
行われねばならないので、電解槽へ供給される溶
融塩の混合物は、電解にかけられる過剰な塩化リ
チウムと共に使用される混合物の共融組成に十分
近い組成を有するのが好都合である。このように
して、電解質として塩化リチウム及び塩化カリウ
ムの混合物を用いる場合には、約450℃でこの混
合物中の塩化リチウムは、溶融塩混合物中のLiCl
のモルで表わして、入口と出口とで約56〜69モル
％の間で変化しうる。この場合に入口濃度は出口
濃度よりも大きい。塩化リチウムは、塩化リチウ
ム−塩化カリウムの溶融塩混合物の共融組成に対
して10モル％までの過剰量で使用しうる。 In both cases the electrolysis is carried out in a solvent. Since the electrolysis has to be carried out at a temperature of about 400-500°C, preferably about 500°C, the mixture of molten salts fed to the electrolyzer has a eutectic composition of the mixture used with the excess lithium chloride subjected to electrolysis. It is advantageous to have a composition sufficiently close to . In this way, when using a mixture of lithium chloride and potassium chloride as an electrolyte, at about 450°C the lithium chloride in this mixture is reduced by the LiCl in the molten salt mixture.
Expressed in moles, the inlet and outlet may vary between about 56 and 69 mole percent. In this case the inlet concentration is greater than the outlet concentration. Lithium chloride may be used in an excess of up to 10 mol % relative to the eutectic composition of the lithium chloride-potassium chloride molten salt mixture.
本発明の方法の第１の特徴は連続性にある。す
なわち、電解槽には電解可能な物質として塩化リ
チウムを含有する溶融塩混合物より成る液体が連
続供給され、電解生成物である塩素、金属リチウ
ム及び溶解塩が電解槽から連続的に引出される。 The first feature of the method of the invention is its continuity. That is, the electrolytic cell is continuously supplied with a liquid consisting of a molten salt mixture containing lithium chloride as an electrolyzable substance, and the electrolytic products chlorine, metallic lithium, and dissolved salt are continuously drawn from the electrolytic cell.
本発明の方法の他の特徴は、電解槽で溶融塩混
合物からリチウムを分離しないという点にある。
この特徴は、以下でより詳しく説明する自然な循
環と相まつて、溶融塩がその表面に上昇して来る
リチウムと電解質表面上の雰囲気を形成する塩素
との再結合を阻止する結果を生じる。従つて、電
解質を塩素雰囲気から分離するのに特に注意する
必要は無くなるのである。しかも、電解質の急速
な自然循環のお陰で、隔膜を用いることなく電解
を行うことができる。自然循環は、単に陽極で発
生する塩素気泡による電解質表面への連行作用に
より得られるので自然と呼ぶことができる。この
自然循環以外の循環手段を用いても良いが、その
必要はない。電解質は陽極と陰極との間の空間で
塩素気泡による上昇運動により垂直に連行される
から、電解質が陰極の裏側の空間を降下し、適当
に配置された開口を通つて陽極と陰極との間の空
間へ侵入するように、電解槽中に電解質の再循環
手段を設けると好都合である。電解質の循環速度
は大きい。何故ならば自然循環がない場合の陽極
と陰極の間を流れる電解質の速度をV0で表わす
と、自然循環によつて現実に得られる速度Ｖは
V0の約100倍となる（行われた実験の平均は0.5〜
５cm／秒であつた）。 Another feature of the process of the invention is that lithium is not separated from the molten salt mixture in an electrolytic cell.
This feature, together with the natural circulation described in more detail below, results in the molten salt preventing the recombination of the lithium rising to its surface with the chlorine forming the atmosphere above the electrolyte surface. Therefore, there is no need to be particularly careful in separating the electrolyte from the chlorine atmosphere. Moreover, thanks to the rapid natural circulation of the electrolyte, electrolysis can be carried out without using a diaphragm. Natural circulation can be called natural because it is obtained simply by the entrainment action of chlorine bubbles generated at the anode to the electrolyte surface. Circulation means other than this natural circulation may be used, but are not necessary. Since the electrolyte is vertically entrained in the space between the anode and cathode by the upward movement of the chlorine bubbles, the electrolyte descends through the space behind the cathode and passes between the anode and cathode through appropriately placed openings. It is advantageous to provide electrolyte recirculation means in the electrolytic cell so as to penetrate into the space of the electrolyte. The circulation rate of electrolytes is high. This is because if the velocity of the electrolyte flowing between the anode and cathode in the absence of natural circulation is expressed as V 0 , the velocity V actually obtained by natural circulation is
V is about 100 times 0 (the average of the experiments conducted is 0.5~
5cm/sec).
電解質の自然循環を行なわせるには、陰極の頂
部は浸漬され、好ましくは広口形にされる。 To allow for natural circulation of the electrolyte, the top of the cathode is immersed, preferably wide-mouthed.
電解質の上昇運動は、陰極のこの好ましい広口
形状と相俟つて、リチウムを電解槽の壁に押しや
り、溢流により自然にこれを除去して塩素との再
結合を最小にする。 The upward motion of the electrolyte, combined with this preferred wide-mouthed geometry of the cathode, drives lithium to the walls of the electrolyzer, where overflow naturally removes it and minimizes recombination with chlorine.
一方、陽極は電解浴中に延びる絶縁性耐火物質
より成る外被により表面に浮遊するリチウムから
の攻撃に対して十分に保護される。耐火物質とし
ては、電解温度において、該耐火物質が接触する
生成物、すなわち主に溶融塩、塩素及びリチウム
に対して不活性な物質を用いる。この物質は電気
絶縁性でなければならない。このような陽極被覆
材としては、アルミナ、石英、シリカ、トリア、
ジルコニアまたはベリウム酸化物等が使用でき
る。 On the other hand, the anode is well protected against attack from lithium floating on the surface by a jacket of insulating refractory material extending into the electrolytic bath. The refractory material used is a material that is inert to the products with which it comes into contact at the electrolysis temperature, ie mainly molten salts, chlorine and lithium. This material must be electrically insulating. Such anode coating materials include alumina, quartz, silica, thoria,
Zirconia or beryum oxide can be used.
本発明の他の特徴は、電解槽から出たリチウム
生成物と溶融塩がデカンターで分離される工程を
有することである。デカンターは上澄み分離部
（デカント部）と排気井とから成つており、上澄
み分離部は好ましくは0.1＜Ｓ／Ｑ＜0.3で表わさ
れる面積Ｓを有する。ここにＱはデカンターへの
供給流量m3／ｈであり、Ｓは上澄み分離部の面積
m2である。軽い表面相はデカンターで分離される
リチウムであり、溶融塩により構成される残りの
重い相は必要ならば濾過の後に好ましくは電解槽
の供給流へと循環される。この再循還を行うに当
り、塩化リチウムを電解槽への供給流へ追加して
その濃度を上記の範囲内に維持するが、追加され
る塩化リチウムの量は電解で消費された量に対応
させることが好ましい。 Another feature of the invention is that it includes a step in which the lithium product and molten salt exiting the electrolytic cell are separated in a decanter. The decanter consists of a supernatant separation section (decant section) and an exhaust well, the supernatant separation section preferably having an area S expressed as 0.1<S/Q<0.3. Here, Q is the supply flow rate to the decanter m 3 /h, and S is the area of the supernatant separation section.
m2 . The light surface phase is the lithium which is separated off in a decanter, and the remaining heavy phase constituted by the molten salt is preferably recycled to the electrolyser feed stream after filtration if necessary. In performing this recirculation, lithium chloride is added to the feed stream to the electrolyzer to maintain its concentration within the above range, with the amount of lithium chloride added corresponding to the amount consumed in electrolysis. It is preferable to let
溶融塩混合物の濾過は好ましくは例えばフリツ
ト化したステンレス鋼などの多孔質金属材料など
を通過させて行う。 The molten salt mixture is preferably filtered through a porous metal material such as fritted stainless steel.
デカンターの温度は好ましくは電解槽の温度と
同一または近接したものである。 The temperature of the decanter is preferably the same as or close to the temperature of the electrolyzer.
本発明の方法は、電解槽とデカンターとの組合
を用い、次の好ましい特徴を有しうる。 The method of the present invention uses a combination of an electrolytic cell and a decanter and may have the following preferred features.
(1) 電解槽は被覆された陽極とそれを取囲む陰極
とを有する。陰極の上部は浴中に浸されてお
り、好ましくは広口形をなし、開口が陰極の下
部に形成されている。(1) An electrolytic cell has a coated anode and a surrounding cathode. The upper part of the cathode is immersed in the bath and is preferably wide-mouthed, with an opening formed in the lower part of the cathode.
(2) 電解槽への供給は好ましくは溶融塩混合物を
電解槽底部へ導入することにより行われる。(2) The electrolytic cell is preferably fed by introducing the molten salt mixture into the bottom of the electrolytic cell.
(3) 電解槽は一方では溶融塩混合物と金属リチウ
ムとをデカンターへ引き出し、他方では塩素ガ
スを引出すための出口手段を備えている。この
出口手段はデカンターへ流通する溢流口、及び
電解質上部の気相の排気口とから成る。(3) The electrolyzer is provided with outlet means for drawing off the molten salt mixture and metallic lithium on the one hand into the decanter and on the other hand for drawing off the chlorine gas. This outlet means consists of an overflow opening into the decanter and an outlet for the gas phase above the electrolyte.
(4) 電解槽から混合物を流量Ｑで供給されるデカ
ンターは、
(a) 表面積Ｓの上澄み分離領域と、
(b) 溢流による軽質相（リチウム）の引出し手
段と、
(c) 井部及び堰口より成る重質相（溶融塩混合
物）の引出手段と、より成る。(4) The decanter to which the mixture is supplied from the electrolytic cell at a flow rate Q consists of (a) a supernatant separation area with a surface area S, (b) a means for drawing out the light phase (lithium) by overflow, and (c) a well and a means for withdrawing the heavy phase (molten salt mixture) consisting of a weir;
［実施例の説明］
以下に添付図面を参照して本発明の好ましい実
施例を説明する。[Description of Embodiments] Preferred embodiments of the present invention will be described below with reference to the accompanying drawings.
電解槽１はステンレス鋼から構成し、陰極２は
同様にステンレス鋼から円筒形に形成する。陰極
２は電解槽１の底に溶接され、またその下部には
電解槽中の電解質の循環を許容する開口３が設け
てある。陰極２の上部４は電解質の表面（電解槽
が運転されている際に形成される表面）よりも下
に保たれるように位置づけられ、また広口となつ
ている。 The electrolytic cell 1 is constructed from stainless steel, and the cathode 2 is likewise formed from stainless steel in a cylindrical shape. The cathode 2 is welded to the bottom of the electrolytic cell 1, and an opening 3 is provided in its lower part to allow circulation of the electrolyte in the electrolytic cell. The upper part 4 of the cathode 2 is positioned so as to be kept below the surface of the electrolyte (the surface formed when the cell is in operation) and has a wide mouth.
陽極６は陰極２の内側に配置された円筒形のグ
ラフアイトより成り、電解質よりも上になる部分
から電解質の表面（同じく運転時の表面）よりも
或る距離だけ下方となる位置までアルミナ被覆１
０で覆われている。 The anode 6 consists of a cylindrical graphite placed inside the cathode 2, and is coated with alumina from the part above the electrolyte to the part below the surface of the electrolyte (also the surface during operation) by a certain distance. 1
Covered with 0.
溶融塩混合物の供給は陽極６と陰極１の間に位
置する場所の直下で電解槽１の底に開口した導管
５により行われる。 The supply of the molten salt mixture takes place by a conduit 5 opening into the bottom of the electrolytic cell 1 directly below the location located between the anode 6 and the cathode 1 .
ガス（塩素）の引出しは電解槽１の頂部に設け
た導管９により行う。電解から得た混合物の引出
しは導管７によつて行われるもので、その高さは
電解槽１内の電解質のレベルにより決まる。 Gas (chlorine) is drawn out through a conduit 9 provided at the top of the electrolytic cell 1. The withdrawal of the mixture obtained from the electrolysis takes place by means of a conduit 7, the height of which is determined by the level of electrolyte in the electrolytic cell 1.
電解中に生じる塩素ガスは例えば不活性ガスで
希釈されることなく電解槽１から抜出されること
が分る。この特徴は塩素ガスが工業的にそのまま
使用しうる場合に重要となる。 It can be seen that the chlorine gas generated during electrolysis is extracted from the electrolytic cell 1 without being diluted with, for example, an inert gas. This feature becomes important when chlorine gas can be used industrially as it is.
デカンター８は導管７を通して電解槽から流量
Ｑの混合物を受入れる。デカンター８は表面積Ｓ
の上澄み分離部１１と、溢流口１２による軽質相
（金属リチウム）の引出手段と、井部１３、堰出
口１４及び有利にはさらに緩衝溜め１６とより成
る重質相引出手段とを含んでいる。重質相は主と
して溶融塩混合物であり、濾過装置１５及び導管
５を経て電解槽１へ再循環される。 Decanter 8 receives a flow rate Q of the mixture from the electrolytic cell through conduit 7. Decanter 8 has a surface area of S
It comprises a supernatant separation section 11, light phase (metallic lithium) withdrawal means by an overflow port 12, and heavy phase withdrawal means consisting of a well 13, a weir outlet 14 and advantageously also a buffer reservoir 16. There is. The heavy phase is mainly a molten salt mixture and is recycled to the electrolytic cell 1 via the filtration device 15 and the conduit 5.
電解質中の塩化リチウムの量は、電解で消費さ
れた分量の塩化リチウムを有利には緩衝溜め１６
へ補給することにより調整される。一方、溶融塩
の循環は溜め１６の出口に設置しうるポンプ１７
により行うことができる。 The amount of lithium chloride in the electrolyte is such that the amount of lithium chloride consumed in the electrolysis is preferably stored in a buffer reservoir 16.
It is adjusted by supplying to. On the other hand, circulation of the molten salt is carried out by a pump 17 that can be installed at the outlet of the reservoir 16.
This can be done by
次に、本発明の実施例を説明する。 Next, examples of the present invention will be described.
実施例
用いた電解槽１は直径0.7ｍ、高さ１ｍであり、
陰極２は内径0.34ｍを有し、陽極６は直径0.3ｍ
でその頂部分がアルミナ管で被覆されたグラフア
イトであつた。Example The electrolytic cell 1 used had a diameter of 0.7 m and a height of 1 m,
Cathode 2 has an inner diameter of 0.34 m and anode 6 has a diameter of 0.3 m.
The top part was made of graphite covered with an alumina tube.
デカンター８は直径0.5ｍ、高さ0.5ｍの円筒状
であり、上澄み分離部の表面積は0.2m2であり、
供給流量は１m3／ｈのものを用いた。 The decanter 8 has a cylindrical shape with a diameter of 0.5 m and a height of 0.5 m, and the surface area of the supernatant separation part is 0.2 m2 .
A supply flow rate of 1 m 3 /h was used.
緩衝溜め１６の次にはポンプ１７が配置され、
フリツト処理したステンレス鋼製のフイルター１
５により溶融塩の加圧濾過を行わせた。 A pump 17 is arranged next to the buffer reservoir 16,
Fritted stainless steel filter 1
5, the molten salt was filtered under pressure.
実験流量（管路５）は１m3／ｈであり、電解電
流は5000Aであつた。次の結果が得られた。 The experimental flow rate (line 5) was 1 m 3 /h, and the electrolytic current was 5000 A. The following results were obtained.
電解層入口（管路５）
KClの流量＝11111モル／ｈ
LiClの流量＝18518モル／ｈ（62.5モル／溶融塩
100）
電解槽出口（管路７）
KClの流量＝11111モル／ｈ
LiClの流量＝18351モル／ｈ（62.3モル／溶融塩
100）
Liの流量＝167モル／ｈ
電解槽のガス出口（管路９）
Cl2の流量＝83.5モル／ｈ
流れ７はデカンター８で２つに分かれ、最初の
流れ１４は溶融したLiCl及びKClの均一な重質相
から成り、第２の流れ１２は電解生成物に対応す
るLiの軽質相より成る。Electrolyte layer inlet (pipe 5) KCl flow rate = 11111 mol/h LiCl flow rate = 18518 mol/h (62.5 mol/molten salt
100) Electrolyzer outlet (pipe 7) KCl flow rate = 11111 mol/h LiCl flow rate = 18351 mol/h (62.3 mol/molten salt
100) Li flow rate = 167 mol/h Electrolyzer gas outlet (pipe 9) Cl 2 flow rate = 83.5 mol/h Stream 7 is divided into two by decanter 8, the first stream 14 is molten LiCl and KCl The second stream 12 consists of a light phase of Li corresponding to the electrolysis product.
溜め１６で回収された塩は連続的にフイルター
１５で多孔金属により濾過された後に電解槽へ再
循環される。 The salt recovered in the reservoir 16 is continuously filtered through porous metal in the filter 15 and then recycled to the electrolytic cell.
上記の実験において、167モル／ｈのLiCl不足
分が緩衝溜め１６で補給された。 In the above experiment, a LiCl deficit of 167 mol/h was made up in buffer reservoir 16.
第１図は本発明に用いる装置の概念図である。
図中主な部分は次の通りである。
１：電解槽、２：陰極、３：開口、４：陰極上
部、６：陽極、７：導管、８：デカンター、９：
導管、１０：アルミナ被覆、１１：上澄み分離部
（デカント部）、１２：溢流口、１３：井部、１
４：堰出口、１５：濾過装置、１６：緩衝溜め、
１７：ポンプ。
FIG. 1 is a conceptual diagram of an apparatus used in the present invention.
The main parts in the figure are as follows. 1: Electrolytic cell, 2: Cathode, 3: Opening, 4: Upper part of cathode, 6: Anode, 7: Conduit, 8: Decanter, 9:
Conduit, 10: Alumina coating, 11: Supernatant separation section (decant section), 12: Overflow port, 13: Well, 1
4: Weir outlet, 15: Filtration device, 16: Buffer reservoir,
17: Pump.
Claims (1)
物中の塩化リチウムを連続的に電解し、生成リチ
ウムを電解槽中で溶融塩混合物から分離しないで
生成リチウム及び溶融塩混合物より成る混合物を
電解槽から引出す第１工程と、前記引出された混
合物をデカンターに供給してリチウムを溶融塩か
ら分離し、リチウムを分離された溶融塩を電解槽
へ再循環させるリチウムの連続製造方法。 ２ 陽極と陰極との間には隔膜を用いないで混合
物の急速な自然循環を生じさせる、前記第１項記
載の製造方法。 ３ 陽極は、電解質の表面に浮んで来るリチウム
による攻撃から保護するために、及び陽極表面で
のリチウムの再酸化を防止するために、電解質の
表面下まで絶縁性耐化物で被覆されている前記第
１項記載の製造方法。 ４ 電解で生成される塩素は不活性ガスで希釈す
ることなくそのまま引出される前記第１項または
第２項記載の製造方法。 ５ デカンターは上澄み分離部（デカント部）と
引出井部とから成り、上澄み分離部中の分離され
たリチウムはそこから引出され、一方井部中に分
離された溶融塩は濾過後に電解槽に再循環される
前記第１項記載の製造方法。 ６ 電解質は塩化リチウム及び塩化カリウムより
成り、塩化リチウムの量は溶融塩混合物中のモル
で表わして入出口に対して56〜69％LiClの範囲に
あり、入口側の方が出口側よりも大きい濃度とな
つている前記第１項記載の製造方法。 ７ 上澄み分離部は0.1＜Ｓ／Ｑ＜0.3で表わされ
る表面積Ｓ（ただしＱは流量）を有する前記第１
項記載の製造方法。 ８ 電解槽と、デカンターとより成り、前記槽は
陽極と、それを取囲む陰極とを有し、前記陰極の
上側部分は電解質中に浸された広口形を有し、下
側部分は開口を有しており、槽はさらに底部に溶
融塩混合物の導入口と、溶融塩及び金属リチウム
引出用の溢流出口と、塩素ガスの出口とを有して
おり、前記デカンターは前記溢流出口へ結合され
ており且つ軽相（リチウム）引出用のオーバフロ
ー上澄み分離部と、重質相（溶融塩混合物）引出
用の井部より成つており、さらに前記井部から引
出される重質相を前記導入口へ循環する手段が設
けられているリチウムの製造装置。 ９ 槽はステンレス鋼製であり、陰極はステンレ
ス鋼製で円筒形をなし且つ底部が槽底へ固定され
ており、陽極はグラフアイト製で円柱形をなし且
つ頂部が電解質表面上方からその表面化のところ
（槽の運転中）までアルミナで覆われており、溶
融塩混合物の導入口は陽極と陰極との間の空間の
直下に開口しており、塩素ガスの出口は槽の頂部
に設けられており、溢流出口は槽中の電解質の高
さで定まるレベルにあり、デカンターの井部は堰
状出口とそれにつながる緩衝溜めとを有している
前記第８項記載の製造装置。[Claims] 1. Lithium chloride in a molten salt mixture is continuously electrolyzed between the cathode and anode of an electrolytic cell, and the lithium produced and the molten lithium are not separated from the molten salt mixture in the electrolytic cell. a first step of drawing a mixture consisting of a salt mixture from the electrolytic cell, feeding said drawn mixture to a decanter to separate lithium from the molten salt, and recycling the lithium-separated molten salt to the electrolytic cell; Continuous manufacturing method. 2. The manufacturing method according to item 1 above, wherein rapid natural circulation of the mixture is caused without using a diaphragm between the anode and the cathode. 3. The anode is coated with an insulating material up to below the surface of the electrolyte in order to protect it from attack by lithium floating on the surface of the electrolyte and to prevent re-oxidation of lithium on the surface of the anode. The manufacturing method according to item 1. 4. The manufacturing method according to item 1 or 2, wherein the chlorine generated by electrolysis is extracted as is without being diluted with an inert gas. 5 The decanter consists of a supernatant separation section (decant section) and a withdrawal well section, from which the separated lithium in the supernatant separation section is drawn out, while the molten salt separated in the well section is returned to the electrolytic cell after filtration. The manufacturing method according to item 1 above, which is recycled. 6 The electrolyte consists of lithium chloride and potassium chloride, and the amount of lithium chloride, expressed in moles in the molten salt mixture, is in the range of 56 to 69% LiCl relative to the inlet and outlet, with the inlet side being greater than the outlet side. The manufacturing method according to item 1 above, wherein the concentration is 7 The supernatant separation section has a surface area S expressed by 0.1<S/Q<0.3 (where Q is the flow rate).
Manufacturing method described in section. 8 Consisting of an electrolytic cell and a decanter, said cell having an anode and a cathode surrounding it, the upper part of said cathode having a wide mouth shape immersed in the electrolyte, and the lower part having an opening. The tank further has an inlet for the molten salt mixture at the bottom, an overflow outlet for drawing out the molten salt and metallic lithium, and an outlet for chlorine gas, and the decanter is connected to the overflow outlet. It consists of an overflow supernatant separation section for drawing out the light phase (lithium) and a well section for drawing out the heavy phase (molten salt mixture), which are connected to each other, and the heavy phase drawn out from the well section is separated from the above-mentioned well section. Lithium production equipment that is provided with means for circulating it to the inlet. 9 The tank is made of stainless steel, the cathode is made of stainless steel, has a cylindrical shape, and the bottom part is fixed to the bottom of the tank, and the anode is made of graphite, has a cylindrical shape, and the top part is connected from above the electrolyte surface to The inlet for the molten salt mixture opens directly below the space between the anode and cathode, and the outlet for the chlorine gas is located at the top of the tank. 9. The manufacturing apparatus according to item 8, wherein the overflow outlet is at a level determined by the height of the electrolyte in the tank, and the well of the decanter has a weir-like outlet and a buffer reservoir connected thereto.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8402840A FR2560221B1 (en) | 1984-02-24 | 1984-02-24 | PROCESS AND DEVICE FOR THE CONTINUOUS MANUFACTURE OF LITHIUM |
| FR84.02840 | 1984-02-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60190587A JPS60190587A (en) | 1985-09-28 |
| JPH0132317B2 true JPH0132317B2 (en) | 1989-06-30 |
Family
ID=9301368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2102385A Granted JPS60190587A (en) | 1984-02-24 | 1985-02-07 | Lithium continuous manufacture and installation |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0156668B1 (en) |
| JP (1) | JPS60190587A (en) |
| CA (1) | CA1250544A (en) |
| DE (1) | DE3560911D1 (en) |
| FR (1) | FR2560221B1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3532956A1 (en) * | 1985-09-14 | 1987-03-19 | Metallgesellschaft Ag | METHOD AND DEVICE FOR PRODUCING HIGH PURE PURITY LITHIUM METAL BY MELTFLOW ELECTROLYSIS |
| FR2591615B1 (en) * | 1985-12-13 | 1988-02-19 | Rhone Poulenc Spec Chim | PROCESS AND APPARATUS FOR THE CONTINUOUS PREPARATION OF LITHIUM BY ELECTROLYSIS OF LITHIUM CHLORIDE |
| RU2135615C1 (en) * | 1997-12-25 | 1999-08-27 | Открытое акционерное общество "Новосибирский завод химконцентратов" | Method of lithium production |
| JP2007063585A (en) * | 2005-08-30 | 2007-03-15 | Sumitomo Titanium Corp | MOLTEN SALT ELECTROLYSIS METHOD, ELECTROLYTIC CELL, AND METHOD FOR PRODUCING Ti BY USING THE SAME |
| JP6772299B2 (en) * | 2016-06-07 | 2020-10-21 | リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー | Method of manufacturing metallic lithium |
Family Cites Families (4)
| 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 |
| CA1171384A (en) * | 1980-12-11 | 1984-07-24 | Hiroshi Ishizuka | Electrolytic cell for magnesium chloride |
| FR2532332B1 (en) * | 1982-08-31 | 1986-04-04 | Rhone Poulenc Spec Chim | PROCESS FOR THE CONTINUOUS PREPARATION OF LITHIUM BY ELECTROLYSIS OF LITHIUM CHLORIDE IN A MIXTURE OF MOLTEN SALTS AND APPARATUS FOR CARRYING OUT SAID PROCESS |
-
1984
- 1984-02-24 FR FR8402840A patent/FR2560221B1/en not_active Expired
-
1985
- 1985-02-07 JP JP2102385A patent/JPS60190587A/en active Granted
- 1985-02-15 EP EP85400263A patent/EP0156668B1/en not_active Expired
- 1985-02-15 DE DE8585400263T patent/DE3560911D1/en not_active Expired
- 1985-02-22 CA CA000474940A patent/CA1250544A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3560911D1 (en) | 1987-12-10 |
| EP0156668A1 (en) | 1985-10-02 |
| FR2560221A1 (en) | 1985-08-30 |
| FR2560221B1 (en) | 1989-09-08 |
| JPS60190587A (en) | 1985-09-28 |
| CA1250544A (en) | 1989-02-28 |
| EP0156668B1 (en) | 1987-11-04 |
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