JP2009529607A - Electrolytic production of metal and scouring method - Google Patents
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 175
- 239000002184 metal Substances 0.000 title claims abstract description 175
- 238000000034 method Methods 0.000 title claims abstract description 95
- 238000009991 scouring Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 174
- 239000000956 alloy Substances 0.000 claims abstract description 174
- 239000003792 electrolyte Substances 0.000 claims abstract description 147
- 239000010703 silicon Substances 0.000 claims abstract description 69
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 68
- 238000002844 melting Methods 0.000 claims abstract description 32
- 230000008018 melting Effects 0.000 claims abstract description 32
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000007670 refining Methods 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 64
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 62
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 150000004820 halides Chemical class 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910017758 Cu-Si Inorganic materials 0.000 claims description 5
- 229910017931 Cu—Si Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- 229910017082 Fe-Si Inorganic materials 0.000 claims description 3
- 229910017133 Fe—Si Inorganic materials 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 3
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 description 13
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052732 germanium Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910005347 FeSi Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- -1 silicon Chemical class 0.000 description 4
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000927 Ge alloy Inorganic materials 0.000 description 1
- 229910018594 Si-Cu Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004028 SiCU Inorganic materials 0.000 description 1
- 229910008465 Si—Cu Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- GGJOARIBACGTDV-UHFFFAOYSA-N germanium difluoride Chemical compound F[Ge]F GGJOARIBACGTDV-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910021422 solar-grade silicon Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/33—Silicon
-
- 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
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
- C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
-
- 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
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Silicon Compounds (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本発明は約100℃以上の融点を有する金属、特にケイ素の電解製造及び精練方法に関し、その際第1の電解質よりなる上部溶融電解質層と、精練すべき金属の合金よりなる下部溶融合金層と、精練すべき金属よりも貴重な少なくとも1つの金属とを有する第1の電解槽が設けられる。下方の合金層は第1の電解槽におけるカソードであり、アノードは上方の溶融電解質層に定置される。第2の電解槽はまた、精練すべき金属と同じ金属よりなる上部溶融金属層であって、カソードを構成する金属層と、アノードを構成する下部溶融合金層であって、精練すべき金属よりも高い密度を有する合金の下部層と、上部溶融層と下部溶融層との密度同志間の密度を有する中間の溶融電解質層とを備えている。両方の電解質共、精練すべき金属の酸化物を含有する酸化物基質の電解質であり、電解質は溶融状態にありしかも本法の操作温度以下の融点を有する。精練すべき金属の酸化物を包含する原料を第1の電解槽に添加し、精練すべき金属がアノードから移動し、カソードで溶融状態で沈着されるように直流をアノードを通してカソードに通電する。２つの電解槽は、２つの別個の工程で操作でき、合金を製造する１つの工程と合金から金属を精練する別の工程よりなる。 The present invention relates to a method for electrolytic production and scouring of metals having a melting point of about 100 ° C. or more, particularly silicon, wherein an upper molten electrolyte layer made of a first electrolyte and a lower molten alloy layer made of an alloy of the metal to be scoured A first electrolytic cell is provided having at least one metal that is more valuable than the metal to be refined. The lower alloy layer is the cathode in the first electrolytic cell, and the anode is placed on the upper molten electrolyte layer. The second electrolytic cell is also an upper molten metal layer made of the same metal as the metal to be refined, the metal layer constituting the cathode, and the lower molten alloy layer constituting the anode, the metal layer being refined. A lower layer of an alloy having a high density and an intermediate molten electrolyte layer having a density between the upper molten layer and the lower molten layer. Both electrolytes are oxide-based electrolytes containing the oxide of the metal to be refined, and the electrolyte is in a molten state and has a melting point below the operating temperature of the process. A raw material containing an oxide of the metal to be refined is added to the first electrolytic cell, and direct current is passed through the anode to the cathode so that the metal to be refined moves from the anode and is deposited in a molten state at the cathode. The two electrolyzers can be operated in two separate steps, consisting of one step for producing the alloy and another step for refining the metal from the alloy.
Description
本発明は約1000℃以上の高い融点を有する金属特にケイ素（シリコン）の電解製造及び精練方法に関する。 The present invention relates to an electrolytic production and scouring method for metals having a high melting point of about 1000 ° C. or more, particularly silicon.
高純度の金属、特に太陽電池品位及び電子部品品位の高純度ケイ素については要求が増大している。太陽電池用の太陽品位のケイ素補給は半導体産業から生ずる電子品位のケイ素からのスクラップ／廃棄物に基づいていた。電子品位のケイ素は、冶金ケイ素からのシランの製造及びシランのケイ素への気相還元により製造される。然しながらこの方法はきわめて高価である。更には、半導体産業からのスクラップ／廃棄物の入手可能性は今や余りにも少量すぎて迅速に増大する太陽電池の市場に供給することができない。 There is an increasing demand for high-purity metals, particularly high-purity silicon of solar cell quality and electronic component quality. Solar grade silicon replenishment for solar cells was based on scrap / waste from electronic grade silicon arising from the semiconductor industry. Electronic grade silicon is produced by the production of silane from metallurgical silicon and the gas phase reduction of silane to silicon. However, this method is very expensive. Furthermore, the availability of scrap / waste from the semiconductor industry is now too small to supply the rapidly growing solar cell market.
米国特許第3,219,561号からは、ケイ素又はゲルマニウムのフッ化物及び酸化物を含有する溶融塩浴と接触しているアノードと、フッ化物を含有する別の溶融塩浴と接触しているカソードとの間に直流を通電し、その際両浴はケイ素又はゲルマニウムと別の金属との溶融合金によって分離されてケイ素又はゲルマニウムの酸化物をケイ素又はゲルマニウムに還元し且つこれをカソード上に沈着させることにより精練したケイ素又はゲルマニウムを製造する方法は知られている。この電解方法においては、ケイ素又はゲルマニウムはカソード上に固体として沈着する。固体金属はカソードから取出さねばならず且つ破砕しなければならず且つ酸で処理してカソード上に沈着した金属中に捕捉された不純物を除去しなければならない。 From U.S. Pat.No. 3,219,561 between an anode in contact with a molten salt bath containing silicon or germanium fluoride and oxide and a cathode in contact with another molten salt bath containing fluoride. In this case, both baths are separated by a molten alloy of silicon or germanium and another metal to reduce silicon or germanium oxide to silicon or germanium and deposit it on the cathode. Processes for producing such silicon or germanium are known. In this electrolysis method, silicon or germanium is deposited as a solid on the cathode. The solid metal must be removed from the cathode and must be crushed and treated with acid to remove impurities trapped in the metal deposited on the cathode.
米国特許第3,254,010号には、電流を、フッ化物を含有する溶融塩電解質に通してカソードとアノードとの間に通電し、アノードは不純なケイ素又はゲルマニウムあるいは不純なケイ素又はゲルマニウムとケイ素又はゲルマニウムよりも貴重な金属との合金から形成されてカソード上に精練したケイ素又はゲルマニウムを沈着させることからなる、不純なケイ素又はゲルマニウムを精練する別の方法が開示されている。この方法でもまた、固体の精練したケイ素又は固体の精練したゲルマニウムがカソード上に沈着される。電解質は氷晶石であるのが好ましい。かくして米国特許第3,254,010号の方法は米国特許第3,219,561号の方法と同じ欠点を有する。 In U.S. Pat.No. 3,254,010, current is passed between a cathode and an anode through a molten salt electrolyte containing fluoride, the anode being impure silicon or germanium or impure silicon or germanium and silicon or germanium. Another method of scouring impure silicon or germanium is disclosed, comprising depositing scoured silicon or germanium formed from an alloy with a precious metal. This method also deposits solid refined silicon or solid refined germanium on the cathode. The electrolyte is preferably cryolite. Thus, the method of US Pat. No. 3,254,010 has the same disadvantages as the method of US Pat. No. 3,219,561.
最後に、アルミニウムの如き比較的低い融点をもつ金属については、電解精練（electrolytic refining）は慣用の方法であり、米国特許第1,534,318号に記載される。該米国特許においては、アノードとしてアルミニウム含有溶融金属の下方層と、カソードとして溶融アルミニウムの上方層と、溶融アルミニウムよりも大きな密度の溶融電解質の中間層とが確立され、電解質が実質的に塩化物を含有せず本質的にフッ化物である、アルミニウムの電解精練方法が記載されている。電流はアノード金属から電解質を通ってアルミニウムカソードに通電し、その際アルミニウムはアノード金属から取出され、溶融状態でカソードに沈着される。溶融電解質はフッ化アルミニウムとフッ化ナトリウムと80より大きい原子量を有するアルカリ土類金属のフッ化物例えばフッ化バリウムの20％〜60％とを含有する。 Finally, for metals with relatively low melting points such as aluminum, electrolytic refining is a conventional method and is described in US Pat. No. 1,534,318. In the U.S. patent, an aluminum-containing molten metal lower layer as an anode, a molten aluminum upper layer as a cathode, and an intermediate layer of molten electrolyte having a density greater than molten aluminum are established, the electrolyte being substantially chloride. A process for the electrolytic scouring of aluminum, which is essentially a fluoride and does not contain any is described. Current is passed from the anode metal through the electrolyte to the aluminum cathode, where aluminum is withdrawn from the anode metal and deposited in the molten state on the cathode. The molten electrolyte contains aluminum fluoride, sodium fluoride, and an alkaline earth metal fluoride having an atomic weight greater than 80, such as 20% to 60% of barium fluoride.
然しながら米国特許第1,534,318号に開示される前記の方法は、1000℃以上の高い融点を有する金属の電解精練には用い得ない。何故ならば電解質の特性を破壊するかかる高温では沢山のフッ化物蒸気がフッ化物基質の溶融電解質で生成するからである。 However, the method disclosed in US Pat. No. 1,534,318 cannot be used for the electrolytic scouring of metals having a high melting point of 1000 ° C. or higher. This is because at such high temperatures that destroy the properties of the electrolyte, a lot of fluoride vapor is generated in the molten electrolyte of the fluoride substrate.
それ故、ケイ素の如き高純度、高融点の金属が電解精練法によって精練できる方法に対する必要性がある。 Therefore, there is a need for a method in which a high purity, high melting point metal such as silicon can be refined by electrolytic scouring.
精練した金属が溶融状態にある、約1000℃以上の高融点の金属特にケイ素の製造及び精練の電解方法を提供するのが本発明の目的である。 It is an object of the present invention to provide a process for the production and scouring of smelted metals, particularly silicon, having a high melting point above about 1000 ° C., in which the smelted metal is in a molten state.
かくして本発明は約1000℃以上の高融点の金属特にケイ素の製造及び精練用電解方法に関し、該方法は次の点を特徴とする；
（a）第１の電解槽に対して、精練すべき金属の酸化物を含有する第１の酸化物基質の電解質よりなる上部溶融電解質層であって第１の電解質が溶融状態にありしかも本法の操作温度以下の融点を有するものとし、即ち上部溶融電解層に定置させたアノードよりなる上部溶融電解質層と、精練すべき金属と精練すべき金属よりも貴重な少なくとも１つの金属との合金よりなる下部溶融合金層であって該合金が第１の電解槽においてカソードを成す下部溶融合金層とを設け、前記の第1の電解質は合金の密度よりも小さい密度を有するものとし；
（b）精練すべき金属の金属酸化物よりなる原料を前記の上部溶融電解質層に添加し；
（c）直流をアノードに通してカソードに通電して金属酸化物を還元してより高濃度の精練すべき金属を有する合金を製造し；
（d）第1の電解槽の下部溶融合金層の合金を第2の電解槽に移送して第2の電解槽に合金よりなる下部溶融合金層を設け、該合金は第2の電解槽でアノードを成すものとし；
（e）第2の電解槽に対して、精練すべき金属と同じ金属の金属よりなる上部溶融金属層であってカソードを構成する上部溶融金属層と、精練すべき金属の酸化物を含有する第2の酸化物基質の電解質よりなる中間の溶融電解質層とを設け、その際第2の電解質は溶融状態にありしかも本法の操作温度以下の融点を有し、前記の第2の電解質は上部溶融金属層と下部溶融合金層との密度同志間の密度を有するものとし；
（f）直流を第2の電解槽のアノードに通してカソードに通電し、これによって精練すべき金属はアノード合金から上部溶融金属層に移動する。
Thus, the present invention relates to a method for the production and scouring of metals with a high melting point above about 1000 ° C., especially silicon, characterized by the following points:
(A) An upper molten electrolyte layer made of an electrolyte of a first oxide substrate containing an oxide of a metal to be refined with respect to the first electrolytic cell, where the first electrolyte is in a molten state and An alloy of an upper molten electrolyte layer composed of an anode placed in the upper molten electrolytic layer and at least one metal that is more valuable than the metal to be scoured; A lower molten alloy layer comprising a lower molten alloy layer, the alloy forming a cathode in a first electrolytic cell, wherein the first electrolyte has a density less than that of the alloy;
(B) adding a raw material comprising a metal oxide of the metal to be refined to the upper molten electrolyte layer;
(C) reducing the metal oxide by passing a direct current through the anode and passing through the cathode to produce an alloy having a higher concentration of metal to be refined;
(D) The lower molten alloy layer alloy of the first electrolytic cell is transferred to the second electrolytic cell, and the lower molten alloy layer made of the alloy is provided in the second electrolytic cell. Shall form the anode;
(E) For the second electrolytic cell, an upper molten metal layer made of the same metal as the metal to be scoured and containing an upper molten metal layer constituting the cathode and an oxide of the metal to be scoured An intermediate molten electrolyte layer made of an electrolyte of a second oxide substrate, wherein the second electrolyte is in a molten state and has a melting point below the operating temperature of the method, the second electrolyte is Have a density between the upper molten metal layer and the lower molten alloy layer;
(F) Direct current is passed through the anode of the second electrolytic cell to the cathode, whereby the metal to be refined moves from the anode alloy to the upper molten metal layer.
本発明の２つの電解槽を用いると、第１の電解槽は原料から合金を製造し、第２の電解槽は合金を精練して金属を製造する。 When the two electrolytic cells of the present invention are used, the first electrolytic cell produces an alloy from raw materials, and the second electrolytic cell refines the alloy to produce a metal.
第１の電解槽において、直流はアノード、第１の電解質及びカソードに通電して、原料から合金層中により高濃度の精練すべき金属を有する合金を製造する。 In the first electrolytic cell, direct current is passed through the anode, first electrolyte and cathode to produce an alloy having a higher concentration of metal to be refined in the alloy layer from the raw material.
第２の電解槽において、直流はアノード合金、第２の電解質及び金属に通電して、合金を金属に精練する。 In the second electrolytic cell, direct current passes through the anode alloy, the second electrolyte, and the metal to refine the alloy into metal.
２つの電解槽は互いに独立して操作できる。即ち本発明の方法は２工程法として定義できる。第１の工程は１つの電解槽で原料から合金を製造するものであり；第２の工程は合金を精練して金属を形成するものである。 The two electrolytic cells can be operated independently of each other. That is, the method of the present invention can be defined as a two-step method. The first step is to produce the alloy from the raw materials in one electrolytic cell; the second step is to refine the alloy to form the metal.
合金は第１の電解槽から第２の電解槽に流動状態で移送されるのが好ましいが、合金は第１の電解槽からタップすることができ、固化させ、第２の電解槽に固体状態で供給できる。 The alloy is preferably transferred from the first electrolytic cell to the second electrolytic cell in a fluidized state, but the alloy can be tapped from the first electrolytic cell, solidified, and solidified in the second electrolytic cell. Can be supplied at.
広義には、本発明によると、第１の金属と第２の金属とを含有する合金を電解的に製造する方法は次の点を特徴とする；
（a）第１の電解槽に対して、第１の金属の酸化物を含有する第１の酸化物基質の電解質よりなる上部溶融電解質層であって第１の電解質が溶融状態にありしかも本法の操作温度以下の融点を有するものとし、上部溶融電解槽に定置させたアノードよりなる上部溶融電解質層と、第１の金属と第2の金属との合金よりなる下部溶融合金層であって第2の金属が第１の金属よりも貴重な金属であり、該合金が第１の電解槽においてカソードを成す下部溶融合金層とを設け、前記の第１の電解質は合金の密度よりも小さい密度を有するものとし；
（b）第１の金属の金属酸化物よりなる原料を前記の上部溶融電解質層に添加し；
（c）直流を第１の電解槽においてアノードからカソードに通電して高濃度の第１の金属を有する合金を製造する。
In a broad sense, according to the present invention, a method for electrolytically producing an alloy containing a first metal and a second metal is characterized by the following points;
(A) An upper molten electrolyte layer made of an electrolyte of a first oxide substrate containing an oxide of a first metal with respect to the first electrolytic cell, wherein the first electrolyte is in a molten state and An upper molten electrolyte layer made of an anode placed in an upper molten electrolytic cell, and a lower molten alloy layer made of an alloy of a first metal and a second metal. The second metal is a more valuable metal than the first metal, and the alloy is provided with a lower molten alloy layer forming a cathode in the first electrolytic cell, and the first electrolyte is smaller than the density of the alloy. Shall have a density;
(B) adding a raw material comprising a metal oxide of a first metal to the upper molten electrolyte layer;
(C) Direct current is passed from the anode to the cathode in the first electrolytic cell to produce an alloy having a high concentration of the first metal.
原料は精練すべき金属即ち第１の金属を含有する金属酸化物の何れか慣用の供給源例えばケイ素用の石英又はチタン用のルチルである。 The raw material is any conventional source of the metal to be refined, ie the metal oxide containing the first metal, for example quartz for silicon or rutile for titanium.
本発明の精練方法は本発明の第１工程とは異なるプロセスから形成した合金を用い得る。 The scouring method of the present invention can use an alloy formed from a process different from the first step of the present invention.
広義には、本発明により合金を金属に電解的に精練する方法は次の点を特徴とする；
（a）第２の電解槽に対して、精練すべき金属と同じ金属の金属よりなる上部溶融金属層であってカソードを構成する上部溶融金属層と、精練すべき金属と精練すべき金属よりも貴重な少なくとも１つの金属との合金よりなる下部溶融合金層であってアノードを構成する下部溶融合金層と、精練すべき金属の酸化物を含有する第２の酸化物基質の電解質よりなる中間の溶融電解質層とを設け、その際第２の電解質は溶融状態にありしかも本法の操作温度以下の融点を有し、前記の第２の電解質は上部溶融金属層と下部溶融合金層との密度同志間の密度を有するものとし；
（b）直流をアノード合金から第２の電解質に通してカソードに通電し、これによって精練すべき金属は合金から移動し、溶融状態でカソードに沈着する。
In a broad sense, the method of electrolytically refining an alloy into a metal according to the present invention is characterized by the following points:
(A) For the second electrolytic cell, an upper molten metal layer made of the same metal as the metal to be scoured and constituting the cathode, and a metal to be scoured and a metal to be scoured A lower molten alloy layer made of an alloy with at least one precious metal, the lower molten alloy layer constituting the anode, and an intermediate made of an electrolyte of a second oxide substrate containing an oxide of the metal to be scoured A molten electrolyte layer, wherein the second electrolyte is in a molten state and has a melting point not higher than the operating temperature of the present method, and the second electrolyte is composed of an upper molten metal layer and a lower molten alloy layer. Shall have a density between comrades;
(B) Direct current is passed from the anode alloy through the second electrolyte to the cathode, whereby the metal to be refined moves from the alloy and deposits in the molten state on the cathode.
製造且つ精練すべき金属は、ケイ素に加えて、チタン及びスカンジウムである。 In addition to silicon, the metals to be produced and refined are titanium and scandium.
精練方法において、合金並びに精練すべき金属の純度の低い金属の両方を合金層に添加できる。例えば、冶金品位のケイ素を合金層に添加でき、これによって精練されるようになる。 In the scouring method, both the alloy and the low purity metal to be smelted can be added to the alloy layer. For example, metallurgical grade silicon can be added to the alloy layer so that it can be refined.
本発明の独特の観点の１つは種々の原料を第１の電解槽で用い得ることである。金属の通常の炭熱製造では用いた金属の型式に制約があり、特に炭素源を介して金属中に不純物を導入する。何れか粒状形の原料を第１の電解槽に添加でき、炭素源からの不純物は解消される。何故ならば炭素源は必要としないからである。これは合金が慣用の合金よりも純粋であることができしかも本発明の精練法を助力することを意味する。 One unique aspect of the present invention is that a variety of raw materials can be used in the first cell. In the normal charcoal production of metals, the type of metal used is limited, and impurities are introduced into the metal through a carbon source. Any granular material can be added to the first electrolytic cell, and impurities from the carbon source are eliminated. This is because no carbon source is needed. This means that the alloy can be more pure than conventional alloys and also assists the refining process of the present invention.
前記の如く、精練で用いた合金は本発明により形成した合金である必要はない。 As described above, the alloy used for scouring need not be an alloy formed according to the present invention.
本法を先ず開始する時、合金層は、精練すべき金属と、第２の金属と呼ばれる、精練すべき金属よりも貴重な１つ又はそれ以上の金属との合金あるいは第２の金属単独よりなり得る。本法の操作中に精練すべき金属として合金それ自体が形成し又は第１の金属は合金層に移動する。 When the process is first started, the alloy layer consists of an alloy of the metal to be refined and one or more metals, called the second metal, which is more valuable than the metal to be refined, or the second metal alone. Can be. During the operation of the method, the alloy itself forms as the metal to be refined or the first metal moves into the alloy layer.
精練すべき金属即ち第１の金属と、精練すべき金属よりも貴重な少なくとも１つの金属即ち第２の金属との合金よりなる下部溶融合金層は、次の要件に適合する組成を有しなければならない；
（イ）溶融第１の電解質及び第２の電解質の密度よりも大きい密度；
（ロ）精練すべき金属の融点に近いか又はそれより低い融点、こうして該合金は溶融され、本法の操作温度で流動し得る。
The lower molten alloy layer consisting of an alloy of the metal to be refined or first metal and at least one metal or second metal more valuable than the metal to be refined must have a composition that meets the following requirements: Must;
(A) a density greater than the density of the molten first electrolyte and second electrolyte;
(B) a melting point close to or below the melting point of the metal to be refined, thus the alloy can be melted and flow at the operating temperature of the process.
特にケイ素の精練については、下部溶融合金層は例えばSi−Cu合金、FeSi合金又は、Cu−Fe−Si合金よりなり得る。これらの合金はケイ素の融点より十分に低い融点を有し、従ってまた第１の電解質及び第２の電解質の融点以下の融点を有する。 Particularly for silicon refining, the lower molten alloy layer can be made of, for example, a Si—Cu alloy, a FeSi alloy, or a Cu—Fe—Si alloy. These alloys have melting points well below the melting point of silicon, and therefore also have melting points below the melting points of the first electrolyte and the second electrolyte.
第１の酸化物基質の電解質は次の要件に適合する組成を有しなければならない；
（イ）精練すべき金属を含有する合金の下部合金層の密度よりも低い密度を操作温度で有しなければならない；
（ロ）操作温度よりも低い融点を有しなければならない；
（ハ）精練すべき金属のイオンに対する溶解度を有しなければならない；
（ニ）酸化物基質の電解質の主成分は精練すべき金属よりも余り貴重であってはならない；
（ホ）精練すべき金属の酸化物例えばケイ素についてはSiO2を含有しなければならない。
The electrolyte of the first oxide substrate must have a composition that meets the following requirements:
(B) It must have a density at the operating temperature that is lower than the density of the lower alloy layer of the alloy containing the metal to be refined;
(B) must have a melting point lower than the operating temperature;
(C) It must have solubility in the ions of the metal to be refined;
(D) The main component of the oxide-based electrolyte must not be more precious than the metal to be refined;
(E) The oxide of the metal to be refined, for example silicon, must contain SiO 2 .
第2の酸化物基質の電解質は第1の酸化物基質の電解質の要件に適合する組成を有しなければならず、しかも精練すべき金属の密度よりも大きい密度を操作温度で有しなければならない。 The electrolyte of the second oxide substrate must have a composition that meets the requirements of the electrolyte of the first oxide substrate, and must have a density at the operating temperature that is greater than the density of the metal to be scoured. Don't be.
酸化物基質の電解質は更に、酸化物が無毒であり低い蒸気圧を有するという利点がある。別の利点は、用いた酸化物基質の電解質が無毒であり、特別な廃物として沈着させねばならないことでないことである。電解質の無毒性は酸化バリウムを含有する電解質を除いては真実である。何故なら酸化バリウムは有毒と考えられるからである。 The oxide-based electrolyte further has the advantage that the oxide is non-toxic and has a low vapor pressure. Another advantage is that the oxide-based electrolyte used is non-toxic and does not have to be deposited as a special waste. The non-toxicity of the electrolyte is true except for the electrolyte containing barium oxide. This is because barium oxide is considered toxic.
本発明について特にケイ素について、次の酸化物基質の電解質が適当である；
（1）CaO−SiO2、好ましくは40〜75重量％のSiO2を含有する
（2）40%以下のMgO含量を有するCaO−MgO−SiO2
（3）50%以下のAl2O3含量を有するCaO−Al2O3−SiO2
（4）Al2O3−CaO−SiO2−TiO2
（5）BaO−SiO2、好ましくは25〜60重量%のSiO2を含有する
（6）BaO−TiO2−SiO2、好ましくは約10〜50重量%のBaO、約10〜50重量%のTiO2及び約10〜50重量%のSiO2
（7）CaO−TiO2−SiO2、好ましくは約10〜50重量%のCaO、約10〜50重量%のTiO2及び約10〜50重量%のSiO2
（8）MgO−TiO2−SiO2、好ましくは約10〜50重量%のMgO、約10〜50重量%のTiO2及び約10〜50重量%のSiO2
（9）Al2O3−CaO−MgO−SiO2及び
（10）CaO−MgO−SiO2−TiO2
更に、ハライド特にアルカリ及びアルカリ土類フッ化物は酸化物基質の電解質に添加して電解質の粘度、密度、融点及び電導度を改質できる。酸化物基質の電解質に添加したハライドの量は20重量%以下であるのが好ましく、7重量%以下であるのがより好ましい。
For the present invention, particularly for silicon, the following oxide-based electrolytes are suitable;
(1) CaO—SiO 2 , preferably containing 40 to 75% by weight of SiO 2 (2) CaO—MgO—SiO 2 having a MgO content of 40% or less
(3) CaO—Al 2 O 3 —SiO 2 having an Al 2 O 3 content of 50% or less
(4) Al 2 O 3 -CaO -SiO 2 -
(5) BaO—SiO 2 , preferably containing 25-60 wt% SiO 2 (6) BaO—TiO 2 —SiO 2 , preferably about 10-50 wt% BaO, about 10-50 wt% TiO 2 and about 10-50 wt% SiO 2
(7) CaO—TiO 2 —SiO 2 , preferably about 10-50 wt% CaO, about 10-50 wt% TiO 2 and about 10-50 wt% SiO 2
(8) MgO—TiO 2 —SiO 2 , preferably about 10-50 wt% MgO, about 10-50 wt% TiO 2 and about 10-50 wt% SiO 2
(9) Al 2 O 3 —CaO—MgO—SiO 2 and (10) CaO—MgO—SiO 2 —TiO 2
In addition, halides, particularly alkali and alkaline earth fluorides, can be added to the oxide matrix electrolyte to modify the viscosity, density, melting point and conductivity of the electrolyte. The amount of halide added to the oxide-based electrolyte is preferably 20% by weight or less, and more preferably 7% by weight or less.
特にケイ素については酸化物基質の電解質は、ケイ素の融点で溶融ケイ素の密度である約2.57g／cm3以上の密度を有するべきであり、75%のFeSiを合金として用いるならば約3.37g／cm3以下及び50%FeSiを合金として用いるならば約5.5g／cm3以下の密度を有するべきである。ケイ素については酸化物基質の電解質は、1414℃であるケイ素の融点に近い又はそれ以下の融点を有しなければならない。 Particularly for silicon, the oxide-based electrolyte should have a density of about 2.57 g / cm 3, which is the density of molten silicon at the melting point of silicon, and about 3.37 g / if 75% FeSi is used as the alloy. If cm 3 or less and 50% FeSi are used as the alloy, they should have a density of about 5.5 g / cm 3 or less. For silicon, the oxide-based electrolyte must have a melting point close to or below that of silicon, which is 1414 ° C.
ケイ素について特に適当な酸化物基質の電解質は40〜75%のSiO2を含有するCaO−SiO2電解質である。この電解質は約2.5g／cm3と約2.7g／cm3との間の密度を有し且つSi−イオンの高い溶解度とSiの低い溶解度とケイ素の融点以上の操作温度で低い揮発性とを有する。 A particularly suitable oxide-based electrolyte for silicon is a CaO—SiO 2 electrolyte containing 40-75% SiO 2 . The electrolyte has a density between about 2.5 g / cm 3 and about 2.7 g / cm 3 and has high Si-ion solubility, low Si solubility, and low volatility at operating temperatures above the melting point of silicon. Have.
第1の電解質及び第2の電解質は同じ組成を有し得るか又は異なる組成を有し得る。第2の電解質は溶融状態で、それが中間の溶融電解質層を形成し且つ上部溶融金属層と下部溶融合金層との間にそれ自体位置するような密度を有しなければならない。第1の電解質はこのようには制約されない。第1の電解質は溶融状態で、それが下部溶融合金層の頂部に浮遊するような密度を有しなければならず、即ち溶融合金よりも小さい密度を有する。然しながら、第1の電解質は溶融状態で溶融状態の金属より大きい密度を有する必要はない。 The first electrolyte and the second electrolyte can have the same composition or can have different compositions. The second electrolyte must be in a molten state and have a density such that it forms an intermediate molten electrolyte layer and is itself located between the upper molten metal layer and the lower molten alloy layer. The first electrolyte is not so limited. The first electrolyte must be in a molten state and have a density such that it floats on top of the lower molten alloy layer, i.e. has a lower density than the molten alloy. However, the first electrolyte need not have a higher density in the molten state than the molten metal.
本発明の合金の製造又は精練方法の何れも、アルミナ、マグネシア、窒化ケイ素、炭化ケイ素又は黒鉛の如き耐熱性の耐火内張りを有する適当な慣用の容器で実施し得る。該容器の側壁は蒸発冷却部材の如き慣用の冷却システムを備えて該容器の側壁の内部で冷凍内張りを生じ得るのが好都合である。 Any of the methods for producing or scouring the alloys of the present invention can be carried out in a suitable conventional container having a heat-resistant refractory lining such as alumina, magnesia, silicon nitride, silicon carbide or graphite. Conveniently, the side wall of the container may be provided with a conventional cooling system such as an evaporative cooling member to produce a refrigeration lining inside the side wall of the container.
本発明においては、別個の容器を用いる際に本法が製造と精練とを同時に伴なう時には、該容器は両容器の側壁中の管体を通しての如く互いに流体連通し得る。両側壁における管体用の開口は底部溶融合金層の高さよりも下方に位置しなければならず、換言すれば、溶融合金層の頂部は両容器間に流体連通を与える管体用の開口の高さよりも上方であるべきである。かかる設計においては、１つの容器は合金を製造する第１の電解槽として作用し、別の容器は精練用の第２の電解槽として作用する。 In the present invention, when the process involves manufacturing and scouring simultaneously when using separate containers, the containers can be in fluid communication with each other, such as through tubes in the side walls of both containers. The opening for the tube in the side walls must be located below the height of the bottom molten alloy layer, in other words, the top of the molten alloy layer is the opening for the tube that provides fluid communication between both vessels. Should be above the height. In such a design, one container acts as a first electrolytic cell for producing the alloy and another container acts as a second electrolytic cell for scouring.
同時に合金を製造し且つ金属を精練するのに単一の容器を用いるのが好ましく、その際該容器は第１の電解槽と第２の電解槽とに分割されており、２つの電解槽は合金層を介して互いに流体連通している。かかる設計は1965年11月23日発行の米国特許第3,219,561号に示されており、その内容を参考のため本明細書に組入れてある。 It is preferable to use a single container for producing the alloy and refining the metal at the same time, the container being divided into a first electrolytic cell and a second electrolytic cell, They are in fluid communication with each other through an alloy layer. Such a design is shown in US Pat. No. 3,219,561 issued November 23, 1965, the contents of which are incorporated herein by reference.
同時に合金を製造し且つ金属を精練する設計では、２つの電解質は互いに分離されており、互いに汚染しない。 In designs that simultaneously produce alloys and refine metal, the two electrolytes are separated from each other and do not contaminate each other.
何れかの設計においても、アノード及びカソードは慣用の仕方で直流電源に接続されていて本法に直流を供給する。 In either design, the anode and cathode are connected to a DC power source in a conventional manner to supply DC to the method.
直流を１つ又はそれ以上の電解槽に通電する時は、合金中の精練すべき金属例えばケイ素は、ケイ素よりも電気化学的に余り貴重でない合金中の何れかの不純物のイオンと共に第２の酸化物基質の電解質に入来する。ケイ素は第２の電解質の最も貴重な元素であるので、ケイ素イオンはカソードで還元され、溶融した純ケイ素を形成するものであり、これを溶融ケイ素カソードで収集する。かくしてケイ素よりも貴重な不純物は合金層中に捕捉され、然るにケイ素よりも余り貴重でない不純物は第２の電解質に捕捉される。 When direct current is applied to one or more electrolyzers, the metal to be refined in the alloy, such as silicon, together with the ions of any impurities in the alloy that are less electrochemically valuable than silicon is the second. Coming into the oxide matrix electrolyte. Since silicon is the most valuable element of the second electrolyte, the silicon ions are reduced at the cathode to form molten pure silicon, which is collected at the molten silicon cathode. Thus, impurities that are more valuable than silicon are trapped in the alloy layer, while impurities that are less valuable than silicon are trapped in the second electrolyte.
本発明の精練方法は回分法として及び連続法として実施できる。 The scouring method of the present invention can be carried out as a batch method and as a continuous method.
精練法を回分法として行なう時は、合金を連続的に又は間欠的に合金層に添加する。結局電解質及び合金は不純物が余りにも高くなる。次いで本法を停止し、電解質及び合金の残留部分を電解槽から取出す。新たな合金及び新たな酸化物基質の電解質を精練すべき金属の開始カソードと共に添加し、その後に電流を電解槽に再び通電する。 When the scouring method is performed as a batch method, the alloy is added to the alloy layer continuously or intermittently. Eventually electrolytes and alloys are too high in impurities. The process is then stopped and the remaining electrolyte and alloy are removed from the electrolytic cell. A new alloy and a new oxide-based electrolyte are added along with the starting cathode of the metal to be scoured, after which current is again passed through the cell.
２つの別個の電解槽、即ち合金を製造する第１の電解槽と精練用の第２の電解槽とを用いる時は、精練すべき金属が涸渇された第２の電解槽からの合金を断続的にタップし、第１の電解槽に添加する。 When using two separate electrolyzers, a first electrolyzer producing an alloy and a second electrolyzer for scouring, the alloy from the second electrolyzer depleted of the metal to be scoured is interrupted. Tapped and added to the first electrolytic cell.
本発明の精練法を連続法として実施する時は、合金を連続的又は間欠的に供給する手段と、酸化物基質の電解質を連続的又は間欠的に取出す手段と、新鮮な酸化物基質の電解質を連続的又は間欠的に供給する手段とを設ける。最後に、上部溶融金属層から精練した金属を連続的に又は間欠的にタップする（tapping）手段を設ける。合金を除去する理由は、合金が電解中に精練すべき金属よりも貴重な不純物元素を増大した含量で得ることである。また、電解中に、電解質は精練すべき金属よりも余り貴重でない元素を増大した含量で得るものであり、この不純物元素の含量を低減するのに、電解質の一部を取出し且つ精練後に電解槽の電解質層に返送できあるいは沈着させ得る。 When the scouring method of the present invention is carried out as a continuous method, means for continuously or intermittently supplying the alloy, means for continuously or intermittently taking out the oxide-based electrolyte, and fresh oxide-based electrolyte Means for continuously or intermittently supplying. Finally, a means for tapping the smelted metal from the upper molten metal layer continuously or intermittently is provided. The reason for removing the alloy is that the alloy obtains an increased content of impurity elements that are more valuable than the metal to be refined during electrolysis. Also, during electrolysis, the electrolyte is obtained with an increased content of elements that are less valuable than the metal to be scoured. To reduce this impurity element content, a portion of the electrolyte is taken out and after scouring the electrolytic cell Can be returned to or deposited on the electrolyte layer.
同様な要領で、合金を形成し金属を精練する両方についての方法は回分法又は連続法の何れかとして実施できる。 In a similar manner, the method for both forming the alloy and refining the metal can be carried out as either a batch process or a continuous process.
かくして本発明により、純粋な形の金属特にケイ素を取得する簡単で経費の有効な方法が提供される。精練すべき金属と、精練すべき金属よりも貴重な金属との低経費合金は合金として用い得る。ケイ素については、FeSi合金及びCu−Si合金の如きケイ素合金は合金として用い得る。かかる合金は本発明により又は何れか慣用の手段を用いて何れか慣用の要領で製造し得る。 Thus, the present invention provides a simple and cost effective way to obtain a pure form of metal, especially silicon. Low cost alloys of the metal to be refined and the metal more valuable than the metal to be refined can be used as an alloy. For silicon, silicon alloys such as FeSi alloys and Cu-Si alloys can be used as alloys. Such alloys may be made in any conventional manner according to the present invention or using any conventional means.
添附図面を参照するに、図１は本発明の精練方法で用いる電解槽の断面図解図である。図２は本発明により合金を製造し且つ金属を精練する方法で用いる電解槽の断面図解図である。図３は合金を製造する方法で用いる電解槽の断面図解図である。 Referring to the attached drawings, FIG. 1 is a schematic sectional view of an electrolytic cell used in the scouring method of the present invention. FIG. 2 is a schematic sectional view of an electrolytic cell used in a method for producing an alloy and refining a metal according to the present invention. FIG. 3 is a cross-sectional view of an electrolytic cell used in the method for producing an alloy.
図１においては、ケイ素を精練する本発明の方法を実施する電解槽の図解図が示されている。電解槽は耐火層２を有する容器１よりなる。電解槽においては、電解槽中でアノードとして作用する、ケイ素とケイ素よりも貴重な金属との合金例えばCu−Si合金の下方層がある。下方のアノード層３の上方には、アノード合金３の密度よりも低い密度であって溶融ケイ素の密度よりも高い密度を有する酸化物基質の電解質４がある。適当な電解質４は50重量%のCaOと50重量%のSiO2との混合物である。電解質層4の頂部には、カソードとして作用する純粋なケイ素金属の層５がある。アノード4及びカソード５はそれぞれ接触部６及び７を介して、電解槽に電流を導通するための直流電源（図示せず）に接続されている。直流を電解槽に通電する時、アノード合金３中のケイ素は、ケイ素よりも電気化学的に余り貴重でないアノード合金３中の何れかの不純物のイオンと共に酸化物基質の電解質４に入来する。ケイ素は電解質４の最も貴重な元素であるので、ケイ素イオンはカソード５で還元され、溶融した純粋なケイ素を形成し、これを溶融したケイ素カソード５で収集する。かくしてケイ素よりも貴重な不純物はアノード層３に捕捉され然るにケイ素よりも余り貴重でない不純物は電解質４に捕捉される。純粋な精練したケイ素は時々溶融カソード層５からタップされる。追加の固体又は溶融アノード合金又は固体又は溶融未精練品位の精練すべき金属は、アノード合金供給流路８を介して溶融アノード層３に連続的に又は間欠的に供給する。
FIG. 1 shows a schematic diagram of an electrolytic cell in which the method of the invention for scouring silicon is carried out. The electrolytic cell comprises a container 1 having a
電解槽を操作した或る時間後にアノード層はケイ素よりも貴重な金属の不純物を増大した含量で有し、電解質はケイ素よりも余り貴重でない元素を増大した含量で得るものである。それ故電解槽は停止させねばならず、純粋なアノード合金及び新たな汚染されていない電解質を用いて再始動させねばならない。 After a certain time of operation of the electrolytic cell, the anode layer has an increased content of metal impurities that are more valuable than silicon, and the electrolyte is obtained with an increased content of elements that are less valuable than silicon. The electrolytic cell must therefore be shut down and restarted with a pure anode alloy and new uncontaminated electrolyte.
図２においては、容器10は耐火層11を有する。合金層12は合金を含有し、電解質層13は第２の電解質を含有し、電解質層14は第１の電解質を含有する。層15は純粋な金属であり、カソードとして作用する。アノード16及びカソード17は慣用の接触部を介して、図示してない直流電源に接続される。壁面18は２つの電解槽即ち第１の電解槽19と第２の電解槽20を分離する。合金層12は壁面18の下方で２つの電解槽同志間で流動する。第１の電解槽19では、原料例えば石英SiO2を金属状態例えばケイ素に電解還元して合金層12中に精練すべき金属の濃度を増大させ、次いで第2の電解槽20では、ケイ素合金の如き精練すべき金属をアノード層から第2の電解質層13を通して純粋な金属像15に移動させる。合金層12は壁面18の下方端部より上方の高さまで電解槽を充填し、これによって２つの電解槽の２つの電解質を分離する。アノード16は電解質層14に浸漬され、カソード17は金属層15に浸漬されるが、両者とも合金層12と直接接触していない。合金層12は共通の電極として作用する。
In FIG. 2, the
電解質層14の第1の電解質にある精練すべき金属及び精練すべき金属よりも貴重な元素は、合金上に沈着し溶融合金と共に沈澱する。
The metal to be refined and the elements more valuable than the metal to be refined in the first electrolyte of the
アノード16は不活性又は消費可能なアノード例えば焼成カーボン又は黒鉛であり得る。
The
図３において、黒鉛ルツボである容器30において、電解質層31は55重量%のCaOと45重量%のSiO2との組成を有する。SiO2、石英の原料を電解質層31に度々添加して電解質組成を維持し且つ本法に原料供給源を与える。4.5Vの電圧を黒鉛アノード32とカソード35との間に印加して大体1A／cm2のカソード電流密度を与える。槽の温度は1650℃で一定に保持する。電解槽は銅製の液体カソード34で始動する。この槽では第1の金属はケイ素であり、第2の金属は銅である。
In FIG. 3, in the
電流が電解槽に流れるにつれて、酸化ケイ素イオンはカソードに運搬されそこでケイ素に還元される。12時間の電解後に、銅カソードは約20重量%のSiを含有し、約40%の電流効率を与える。かくしてSiCuの合金が製造された。 As current flows through the electrolytic cell, silicon oxide ions are transported to the cathode where they are reduced to silicon. After 12 hours of electrolysis, the copper cathode contains about 20% by weight Si, giving a current efficiency of about 40%. Thus, an alloy of SiCu was produced.
前記から見られる通り、この電解槽は合金層中の純粋な第2の金属で始動し、電解槽の操作によって合金が合金層に形成される。 As can be seen from the foregoing, this electrolytic cell starts with a pure second metal in the alloy layer, and the operation of the electrolytic cell forms an alloy in the alloy layer.
１ 容器、 ２ 耐火層、 ３ アノードとして作用する下方合金層、 ４ 電解質層、 ５ カソードとして作用する金属層、 ６，７ 接触部、 １０ 容器、 １１ 耐火層、 １２ 合金層、１３ 第２の電解質を含有する電解質層、１４ 第１の電解質を含有する電解質層、１５ カソードとして作用する純粋金属層、 １６ アノード、 １７ カソード、 １８ 壁面、１９ 第１の電解槽、 ２０ 第２の電解槽、 ３０ 黒鉛ルツボ、 ３１ 電解質層、 ３２ アノード、 ３３ カソード、 ３４ 銅製のカソード
DESCRIPTION OF SYMBOLS 1 Container, 2 Refractory layer, 3 Lower alloy layer which acts as anode, 4 Electrolyte layer, 5 Metal layer which acts as cathode, 6,7 Contact part, 10 Container, 11 Refractory layer, 12 Alloy layer, 13
Claims (44)
第１の電解槽に対して、精錬すべき金属の酸化物を含有する第１の酸化物基質の電解質よりなる上部溶融電解質層であって第１の電解質が溶融状態にありしかも本法の操作温度以下の融点を有し、上部溶融電解層に定置させたアノードよりなる上部溶融電解質槽と、精練すべき金属と精練すべき金属よりも貴重な少なくとも１つの金属との合金よりなる下部溶融合金層であって該合金が第１の電解槽においてカソードを成す下部溶融合金層とを設け、その際前記の第１の電解槽は合金の密度より小さい密度を有するものとし；
精練すべき金属の金属酸化物よりなる原料を前記の上部溶融電解質層に添加し；
直流をアノードに通してカソードに通電して金属酸化物を還元してより高濃度の精練すべき金属の合金を製造し；
第１の電解槽の下部溶融合金層の合金を第２の電解槽に移送して第２の電解槽に合金よりなる下部溶融合金層を設け、該合金は第２の電解槽でアノードを成すものとし；
第２の電解槽に対して、精練すべき金属と同じ金属の金属よりなる上部溶融金属層であってアノードを構成する上部溶融金属層と、精練すべき金属の酸化物を含有する第２の酸化物基質の電解質よりなる中間の溶融電解質層とを設け、その際第２の電解質は溶融状態にありしかも本法の操作温度以下の融点を有し、前記の第２の電解質は上部溶融金属層と下部溶融合金層との密度同志間の密度を有するものとし；
直流を第２の電解槽のアノードに通してカソードに通電し、これによって精練すべき金属はアノード合金から、上部溶融金属層に移動することを特徴とする、金属の電解製造及び精練方法。 In a method of producing and scouring a metal by an electrolytic method,
Operation of the present method for an upper molten electrolyte layer comprising an electrolyte of a first oxide substrate containing an oxide of a metal to be refined relative to a first electrolytic cell, wherein the first electrolyte is in a molten state A lower molten alloy comprising an upper molten electrolyte tank having an anode having a melting point equal to or lower than a temperature and made of an anode placed on the upper molten electrolytic layer, and an alloy of a metal to be refined and at least one metal more valuable than the metal to be refined A lower molten alloy layer wherein the alloy forms a cathode in a first electrolytic cell, wherein the first electrolytic cell has a density less than that of the alloy;
Adding a raw material comprising a metal oxide of the metal to be refined to the upper molten electrolyte layer;
Passing a direct current through the anode and energizing the cathode to reduce the metal oxide to produce a higher concentration of the metal alloy to be refined;
An alloy of the lower molten alloy layer of the first electrolytic cell is transferred to the second electrolytic cell, and a lower molten alloy layer made of the alloy is provided in the second electrolytic cell, and the alloy forms an anode in the second electrolytic cell. Shall be;
A second electrolytic cell containing an upper molten metal layer made of the same metal as the metal to be scoured, the upper molten metal layer constituting the anode, and an oxide of the metal to be scoured An intermediate molten electrolyte layer made of an oxide-based electrolyte, wherein the second electrolyte is in a molten state and has a melting point below the operating temperature of the method, said second electrolyte being the upper molten metal Having a density between the layers and the lower molten alloy layer;
A method for electrolytic production and refining of metals, characterized in that a direct current is passed through the anode of the second electrolytic cell and the cathode is energized, whereby the metal to be refined moves from the anode alloy to the upper molten metal layer.
含有するCaO−Al2O3−SiO2、BaO−SiO2、BaO−TiO2−SiO2、CaO−TiO2−SiO2、MgO−TiO2−SiO2、Al2O3−CaO−MgO−SiO2、40重量%以下のMgOを含有するAl2O3−CaO−SiO2−TiO2及びCaO−MgO−SiO2−TiO2から選ばれることを特徴とする請求項２０記載の方法。 To refine silicon, the oxide-based electrolyte is CaO—Al 2 O 3 —SiO 2 , BaO—SiO 2 , BaO—TiO 2 —SiO 2 , CaO containing 50 wt% or less of Al 2 O 3. -TiO 2 -SiO 2, MgO-TiO 2 -SiO 2, Al 2 O 3 -CaO-MgO-SiO 2, 40 containing wt% MgO Al 2 O 3 -CaO-SiO 2 -TiO 2 and CaO the method of claim 20, wherein the selected from -MgO-SiO 2 -TiO 2.
第１の金属の金属酸化物よりなる原料を上部溶融電解質層に添加し；
第１の電解槽においてアノードからカソード合金に直流を通電してより高濃度の第１の金属を有する合金を製造することを特徴とする合金の電解製造方法。 In an electrolytic production method of an alloy containing a first metal and a second metal, the upper part made of an electrolyte of a first oxide substrate containing an oxide of the first metal with respect to the first electrolytic cell An upper molten electrolyte layer placed as an anode, a first electrolyte and a second metal, wherein the first electrolyte is in a molten state and has a melting point below the operating temperature of the method; A lower molten alloy layer made of an alloy with the second molten metal, the second metal being more valuable than the metal to be scoured, and the alloy comprising a lower molten alloy layer comprising a cathode in the first electrolytic cell. Providing, wherein the first electrolyte has a density less than or equal to that of the alloy;
Adding a raw material comprising a metal oxide of a first metal to the upper molten electrolyte layer;
An alloy electrolytic production method comprising producing an alloy having a higher concentration of a first metal by applying a direct current from an anode to a cathode alloy in a first electrolytic cell.
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- 2007-03-08 WO PCT/US2007/063555 patent/WO2007106709A2/en active Application Filing
- 2007-03-08 JP JP2008558531A patent/JP5183498B2/en active Active
- 2007-03-08 ES ES07758136.1T patent/ES2633113T3/en active Active
- 2007-03-08 BR BRPI0708603A patent/BRPI0708603B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012165017A1 (en) * | 2011-05-30 | 2012-12-06 | 国立大学法人京都大学 | Process for producing silicon |
| JP2013011012A (en) * | 2011-05-30 | 2013-01-17 | Kyoto Univ | Process for producing silicon |
| WO2018016778A1 (en) * | 2016-07-20 | 2018-01-25 | 충남대학교산학협력단 | Method for refining metal by using electrolytic reduction and electrolytic refining processes |
| CN111094631A (en) * | 2017-08-01 | 2020-05-01 | 波士顿电冶公司 | Electrolytic production of active metals |
| JP2020529517A (en) * | 2017-08-01 | 2020-10-08 | ボストン エレクトロメタラジカル コーポレイションＢｏｓｔｏｎ Ｅｌｅｃｔｒｏｍｅｔａｌｌｕｒｇｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ | Electrolytic formation of reactive metals |
| JP2022058350A (en) * | 2017-08-01 | 2022-04-12 | ボストン エレクトロメタラジカル コーポレイション | Electrolytic preparation of reactive metal |
| CN111094631B (en) * | 2017-08-01 | 2022-11-18 | 波士顿电冶公司 | Electrolytic production of active metals |
| JP7486199B2 (en) | 2017-08-01 | 2024-05-17 | ボストン エレクトロメタラジカル コーポレイション | Electrochemical generation of reactive metals |
| WO2021090546A1 (en) * | 2019-11-07 | 2021-05-14 | 三菱重工業株式会社 | Electrolytic smelting furnace and electrolytic smelting method |
| JP7373361B2 (en) | 2019-11-07 | 2023-11-02 | 三菱重工業株式会社 | Electrolytic smelting furnace and electrolytic smelting method |
| KR20210116351A (en) * | 2020-03-17 | 2021-09-27 | 서울대학교산학협력단 | Electrolysis device and method for production of hydrogen peroxide |
| KR102498338B1 (en) | 2020-03-17 | 2023-02-10 | 서울대학교산학협력단 | Electrolysis device and method for production of hydrogen peroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0708603B1 (en) | 2016-05-17 |
| JP5183498B2 (en) | 2013-04-17 |
| NO20083970L (en) | 2008-09-17 |
| ES2633113T3 (en) | 2017-09-19 |
| NO344829B1 (en) | 2020-05-18 |
| EP1999286B1 (en) | 2017-04-19 |
| AU2007226754B2 (en) | 2011-01-20 |
| WO2007106709A9 (en) | 2008-01-03 |
| CA2645161C (en) | 2011-11-22 |
| AU2007226754A1 (en) | 2007-09-20 |
| EP1999286A4 (en) | 2011-09-07 |
| CA2645161A1 (en) | 2007-09-20 |
| WO2007106709A2 (en) | 2007-09-20 |
| BRPI0708603A2 (en) | 2011-06-07 |
| WO2007106709A3 (en) | 2007-11-29 |
| EP1999286A2 (en) | 2008-12-10 |
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