WO2022108006A1 - Reduction system and method for high-melting point metal oxides, using liquid metal crucible - Google Patents
Reduction system and method for high-melting point metal oxides, using liquid metal crucible Download PDFInfo
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- WO2022108006A1 WO2022108006A1 PCT/KR2021/003848 KR2021003848W WO2022108006A1 WO 2022108006 A1 WO2022108006 A1 WO 2022108006A1 KR 2021003848 W KR2021003848 W KR 2021003848W WO 2022108006 A1 WO2022108006 A1 WO 2022108006A1
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- 238000000034 method Methods 0.000 title claims abstract description 123
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 87
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 87
- 229910001338 liquidmetal Inorganic materials 0.000 title claims description 93
- 230000009467 reduction Effects 0.000 title description 14
- 238000002844 melting Methods 0.000 title description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 170
- 239000002184 metal Substances 0.000 claims abstract description 170
- 229910045601 alloy Inorganic materials 0.000 claims description 99
- 239000000956 alloy Substances 0.000 claims description 99
- 239000002994 raw material Substances 0.000 claims description 91
- 230000008569 process Effects 0.000 claims description 66
- 239000003792 electrolyte Substances 0.000 claims description 59
- 239000010410 layer Substances 0.000 claims description 52
- 239000007787 solid Substances 0.000 claims description 42
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 38
- 239000006227 byproduct Substances 0.000 claims description 33
- 239000012792 core layer Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 26
- 150000002739 metals Chemical class 0.000 claims description 21
- 230000005496 eutectics Effects 0.000 claims description 19
- 238000007670 refining Methods 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000011244 liquid electrolyte Substances 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229910052695 Americium Inorganic materials 0.000 claims description 4
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052685 Curium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052764 Mendelevium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052781 Neptunium Inorganic materials 0.000 claims description 4
- 229910052778 Plutonium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052774 Proactinium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052776 Thorium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052770 Uranium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052767 actinium Inorganic materials 0.000 claims description 4
- 229910000905 alloy phase Inorganic materials 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 description 28
- 230000009193 crawling Effects 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910010380 TiNi Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
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- 239000012467 final product Substances 0.000 description 7
- -1 Pm Inorganic materials 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- 230000007797 corrosion Effects 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
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- 239000012535 impurity Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000275031 Nica Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1277—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using other metals, e.g. Al, Si, Mn
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/14—Refining in the solid state
-
- 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
-
- 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
- C25C3/30—Electrolytic production, recovery or refining of metals by electrolysis of melts of manganese
-
- 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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- 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
- C25C7/06—Operating or servicing
Definitions
- the present invention relates to a system and method for reducing a high-melting-point metal oxide using a liquid metal crucible.
- the metal M can be obtained by reducing a raw material such as an oxide or halide.
- a raw material such as an oxide or halide.
- Kroll process the relatively well-known and most commonly used method in the art is a so-called Kroll process.
- the crawl process can be summarized as a process for reducing to titanium or zirconium by using molten magnesium as a reducing agent, and adding a chloride of the desired metal M, for example, titanium chloride or zirconium chloride.
- a chloride of the desired metal M for example, titanium chloride or zirconium chloride.
- this crawling process is a process using chloride as a raw material
- chlorine gas and magnesium chloride are produced as by-products during the process.
- chlorine gas is an environmental problem that causes fatal problems to the human body and is considered a representative problem of the crawler process
- magnesium chloride it causes a problem in the process of rapidly corroding the reaction vessel called, for example, an electrolyzer, a melting furnace, or a crucible. do.
- the crawling process requires an additional device for resolving environmentally acceptable regulations, and frequent replacement of the reaction vessel is accompanied, and thus the cost for operating the process is high.
- the crawling process is made in the form of a sponge in which the obtained metal contains a large number of pores, so that it is very difficult to control the oxygen that may be present in the metal.
- the crawling process has a limit in obtaining a metal of high purity.
- the reducing agent having a strong reducing power in the process system comes into direct contact with a part of the reactor, because of this, there is a problem of causing corrosion of the reaction vessel, like the crawling process.
- There is also a method to minimize the effect of the reducing agent by manufacturing the reaction vessel with W or Mo metal but since the unit cost of the reaction vessel itself is too high, it causes an increase in the overall manufacturing cost.
- CaO a by-product generated in the reduction reaction, must be removed, and a large amount of electrolyte is required to remove this. This also has a problem of causing an increase in the overall manufacturing cost.
- An object of the present invention is to provide a technique capable of solving the above-mentioned problems.
- the present invention provides a system optimized for obtaining a desired metal from a metal oxide and a method for preparing such a metal without using any metal chloride or chloride as an electrolyte. Therefore, the present invention can solve the environmental problem of the above-described crawling process and the cost problem due to corrosion of the electrolytic cell.
- the present invention provides a technique capable of obtaining a large amount of high-purity metal while facilitating the operation of the process according to the following aspects.
- the system and method provided by the present invention comprises using a liquid metal crucible containing a liquid metal alloy of a metal M 1 and a metal M 2 forming a eutectic phase with each other.
- a liquid alloy (M 1 and M 2 is a liquid metal alloy) is obtained as a liquid alloy by a eutectic reaction, and the metal alloy itself may be used as a final product.
- the final product derived from the liquid alloy has a significantly smaller specific surface area that can be in contact with oxygen compared to the sponge-type product of the crawling process, so the system and method of the present invention can minimize the problem of contamination of the product with oxygen. .
- metal M 1 may be obtained by electrolytic refining of the obtained metal alloy.
- the liquid alloy thus obtained can be thoroughly separated from an environment in which oxygen may exist, and thus contamination by oxygen can be remarkably prevented. That is, according to the above aspect, it is possible to obtain a high-purity metal alloy and metal M 1 .
- the raw material is, for example, an oxide including a target metal, a reducing agent, and a metal for an alloy forming a module as one component, and such raw material Features include using a module.
- the raw materials may be oxidized or contaminated with oxygen before being introduced, but the raw material module according to the present invention includes a configuration treated to prevent oxidation, Compared to the crawling process, it has a stronger oxygen barrier effect. Accordingly, the metal alloys and metals obtained according to the present invention may have remarkably low oxygen content, in other words, the present invention enables the implementation of high-purity metal alloys and metals having little oxygen.
- a system for reducing metal M 1 from a metal oxide is provided.
- liquid metal crucible containing a liquid metal alloy of a metal M 1 and a metal M 2 that is received from the bottom of the electrolytic cell and forms an eutectic phase with each other;
- It may include a solid raw material module including the metal oxide, the metal M 2 and the reducing agent M 3 ,
- the metal oxide and the reducing agent metal M 3 react to reduce M 1 , and the reduced M 1 and M 2 form a liquid metal alloy while forming a liquid metal alloy. It can be continuously incorporated into a metal crucible.
- the system collects the liquid metal alloy formed by the reduced M 1 and M 2 and performs electrolytic refining to obtain the metal M 1 It may further include an electrolytic refining unit.
- the metal oxide may include at least one selected from the group consisting of M 1 x O z and M 1 x M 3 y O z , where x and y are each a real number of 1 to 3 and , z is a real number from 1 to 4.
- the solid raw material module may include a core layer including the metal oxide and the reducing agent metal M 3 ; and a shell layer surrounding the core layer and made of M 2 .
- the solid raw material module may include a core layer including the metal oxide; and a shell layer coated while enclosing the outer surface of the core layer, wherein the shell layer may include an alloy phase of the metal M 2 and the metal M 3 .
- the solid raw material module is configured to descend vertically in the electrolyzer until it reaches the liquid metal crucible through the electrolyte, at a distance/minute of 0.1% to 10% to the depth of the electrolyzer ( min) can descend.
- an oxide M 3 a O b is generated, and the M 3 a O b is added to the electrolyte.
- a and b are real numbers from 1 to 3, respectively.
- the M 3 a O b may float on the electrolyte due to a density difference to form a by-product layer.
- the liquid metal alloy is continuously obtained through the lower part of the electrolytic cell according to the process progress, and the by-product layer is continuously collected through the upper part of the electrolytic cell, so that a continuous process can be performed.
- a recycling device for collecting the by-product layer and mixing it with M 1 x O z to produce M 1 x M 3 y O z may be further included.
- the reaction of the metal oxide and the reducing metal may be performed in an inert gas and/or in the atmosphere.
- the core layer may be formed of a mixture of powder including the metal oxide powder and the reducing agent metal M 3 powder.
- the core layer may have a multilayer structure including a first core made of the metal oxide and a second core made of the metal M 3 , the first core being coated while enclosing an outer surface of the first core .
- the solid raw material module surrounds the shell layer, and may further include an antioxidant layer for preventing oxidation of the metal included in the core layer and/or the shell layer.
- the antioxidant layer is at least one selected from the group consisting of LiF, MgF 2 , CaF 2 , BaF 2 , CaCl 2 , MgCl 2 , MgO, CaO, BaO, Al 2 O 3 and SiO 2 .
- LiF, MgF 2 , CaF 2 , BaF 2 , CaCl 2 , MgCl 2 , MgO, CaO, BaO, Al 2 O 3 and SiO 2 may include
- M 1 is Ti, Zr, Hf, W, Fe, Ni, Zn, Co, Mn, Cr, Ta, Ga, Nb, Sn, Ag, La, Ce, Pr, Nd, Nb, Pm , Sm, Eu, Al, V, Mo, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md And may be one selected from the group consisting of No, M 2 may be one or more selected from Cu, Ni, Fe, Sn, Zn, Pb, Bi, Cd and alloys thereof, M 3 is Ca, Mg , Al, and may be at least one selected from alloys thereof.
- a method for refining a metal oxide by reducing it to a metal M 1 there is provided a method for refining a metal oxide by reducing it to a metal M 1 .
- the metal M 1 and the metal M 2 that form a eutectic phase with each other are added to the electrolytic cell to have a relatively high specific gravity compared to the electrolyte, and to form a layer in a state in which it is not mixed under the electrolyte, the electrolytic cell Preparing a liquid metal crucible accommodated in the;
- an oxide M 3 a O b as a by-product is produced, and the M 3 a O b is It has a relatively low specific gravity compared to the electrolyte,
- M 3 a O b forming a layer on the electrolyte is continuously collected, and M 1 x O z is added to and mixed with M 3 a O b , and the by-product M 3 a O b and added derived from M 1 x O z
- the method may further include preparing a metal oxide represented by M 1 x M 3 y O z .
- a metal alloy or metal obtained by the method according to the preceding embodiment wherein the metal alloy has a residual content of the reducing agent metal M 3 relative to its total weight of 0.1% by weight or less, specifically It may be 0.01 wt% or less, more specifically 0.001 wt% or less, and the oxygen content may be 1,200 ppm or less, specifically 1,000 ppm or less, and more specifically 990 ppm or less.
- the present invention provides a system optimized for obtaining a desired metal from a metal oxide and a method for preparing such a metal without using any metal chloride or chloride as an electrolyte. Therefore, the present invention can solve the environmental problem of the above-described crawling process and the cost problem due to corrosion of the electrolytic cell.
- the system and method provided in the present invention include using a liquid metal crucible containing a liquid metal alloy of a metal M 1 and a metal M 2 forming a eutectic phase with each other.
- a liquid metal crucible containing a liquid metal alloy of a metal M 1 and a metal M 2 forming a eutectic phase with each other.
- the use of such a liquid metal crucible is when the metal M 1 among the metal oxides contained in the raw material module is reduced, the melting point of the metal M 1 is lowered by the eutectic reaction, so that the electrolytic reduction can be effectively performed at a relatively low temperature. As a result, energy can be significantly saved, which can lead to cost savings.
- a liquid alloy (M 1 and M 2 is a liquid metal alloy) is obtained as a liquid alloy by a eutectic reaction, and the metal alloy itself may be used as a final product.
- the final product derived from the liquid alloy has a significantly smaller specific surface area that can be in contact with oxygen compared to the sponge-type product of the crawling process, so the system and method of the present invention can minimize the problem of contamination of the product with oxygen. .
- the liquid alloy thus obtained can be thoroughly separated from an environment in which oxygen may exist, and thus contamination by oxygen can be remarkably prevented. That is, it is possible to obtain a high-purity metal alloy and metal M 1 as described above.
- the raw material comprises, for example, an oxide containing a target metal, a reducing agent, and a metal for an alloy forming a module as one component, and using such a raw material module.
- the raw materials may be oxidized or contaminated with oxygen before being introduced, but the raw material module according to the present invention includes a configuration treated to prevent oxidation, Compared to the crawling process, it has a stronger oxygen barrier effect. Accordingly, the metal alloys and metals obtained according to the present invention may have remarkably low oxygen content, in other words, the present invention enables the implementation of high-purity metal alloys and metals having little oxygen.
- FIG. 1 is a schematic diagram of a system according to an embodiment of the present invention.
- FIG. 2 is a photograph of a process of manufacturing a raw material module according to an embodiment of the present invention including MgTiO 3 as a metal oxide.
- FIG. 3 is a graph showing the results of XRD analysis of the raw material prepared in FIG. 2 .
- FIG. 4 is a vertical cross-sectional schematic view of a raw material module according to an embodiment of the present invention.
- FIG. 5 is a vertical cross-sectional schematic view of a raw material module according to another embodiment of the present invention.
- FIG. 6 is a vertical cross-sectional schematic view of a raw material module according to another embodiment of the present invention.
- EDS 10 is a table of results of elemental analysis using an energy dispersive spectrometer (EDS) inside the alloy after cutting the alloy prepared in Examples.
- EDS energy dispersive spectrometer
- 11 is a table of results of measuring the oxygen content present in the alloy using ELTRA ONH2000.
- the term “loading” may be used interchangeably with “introduction”, “introduction”, “introduction”, and “injection” in the present specification, and refers to introducing or putting any material, such as a raw material, into a necessary place. can be understood to mean
- FIG. 1 a system for reducing metal M 1 from a metal oxide according to the present invention is schematically shown in FIG. 1 .
- the system according to the present invention Referring to Figure 1, the system according to the present invention,
- the liquid electrolyte 200 is layered in a state not to be mixed on the liquid metal crucible 100 and accommodated in the electrolytic cell;
- the metal oxide and the reducing agent metal M 3 react to reduce M 1 , and the reduced M 1 and M 2 are liquid metal alloys. It may be continuously mixed in the liquid metal crucible 100 while forming.
- the target metal M 1 in the system of the present invention is not particularly limited, but specifically Ti, Zr, Hf, W, Fe, Ni, Zn, Co, Mn, Cr, Ta, Ga, Nb, Sn, Ag, La, Ce, Pr, Nd, Nb, Pm, Sm, Eu, Al, V, Mo, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ac, Th, Pa, U, Np, Pu, Am, It may be one selected from the group consisting of Cm, Bk, Cf, Es, Fm, Md and No, and more specifically, Ti, Zr, W, Fe, Ni, Zn, Co, Mn, Cr, Ta, Er and It may be one selected from the group consisting of No, and more specifically, may be one selected from the group consisting of Ti, Zr, W, Fe, Ni, Zn, Co, Mn, and Cr, and in particular, Ti, Zr or W.
- the metal M 2 is not particularly limited as long as it can form a liquid metal alloy through a eutectic reaction with the metal M 1 , and specifically, Cu, Ni, Fe, Sn, Zn, Pb, Bi, Cd And it may be at least one selected from alloys thereof, and more specifically, may be Cu, Ni, or alloys thereof.
- the metal M 3 is not particularly limited as long as it can reduce a metal oxide to M 1 , but among such materials, at least one selected from Ca, Mg, Al and alloys thereof may be preferable, and more Specifically, it may be Ca or Mg, and in particular, it may be Mg.
- the metal oxide may include at least one selected from the group consisting of M 1 x O z and M 1 x M 3 y O z , wherein x and y are each a real number of 1 to 3 and , z is a real number from 1 to 4.
- Non-limiting examples of the metal oxide for better understanding include ZrO 2 , TiO 2 , MgTiO 3 , HfO 2 , Nb 2 O 5 , Dy 2 O 3 , Tb 4 O 7 , WO 3 , Co 3 O 4 , MnO,
- One selected from the group consisting of Cr 2 O 3 , MgO, CaO, Al 2 O 3 , Ta 2 O 5 , Ga 2 O 3 , Pb 3 O 4 , SnO, NbO and Ag 2 O, or a combination of two or more thereof may include
- the system according to the present invention is different from the conventional crawling process in that it uses a metal oxide instead of a metal chloride as a raw material.
- Raw materials usually found in nature include oxides of M 1 , and in order to use them in the crawling process, a pretreatment process of replacing these metal oxides with chlorides is involved. If it goes through such a pretreatment process, it itself causes an increase in process cost.
- hydrochloric acid is used in the pretreatment process of replacing the metal oxide with chloride, which promotes corrosion of manufacturing equipment due to strong acidity, and toxic chlorine gas may be generated during the process, which may cause environmental problems. Since the system according to the present invention does not require a pretreatment process for replacing the metal oxide with a chloride, the process cost is lower than the crawling process and does not cause environmental problems.
- the electrolytic cell 400 has a high melting point in terms of durability. Materials that do not cause side reactions with electrolyte and liquid metal crucibles are preferred.
- the material of the electrolyzer is, but not limited to, MgO, Cr 2 O 3 , Al 2 O 3 , SiO 2 , CaO, SiC, WO 3 , W, C, and may include one or more selected from the group consisting of Mo have.
- the electrolytic bath 400 may include a tapping hole 410 for continuously tapping the liquid metal alloy generated at the lower end thereof.
- liquid metal crucible means that at least one metal is fluid in a molten state, and is accommodated in, for example, the electrolytic cell of the present invention to form a layer, and within it And on the layer surface thereof, it may mean a reaction region in which the raw material module of the present invention is melted to create an environment in which metal oxide can be reduced.
- the system according to the invention has the advantage of using such a liquid metal crucible.
- the system of the present invention uses a liquid metal crucible containing a liquid metal alloy of a metal M 1 and a metal M 2 that forms a eutectic phase with each other, thereby reducing the metal M 1 of the metal oxide of the raw material module and simultaneously reducing the eutectic phase.
- the melting point of the metal M 1 is lowered by the reaction (Eutectic reaction), so that the electrolytic reduction can be effectively performed at a relatively low temperature. That is, in the system of the present invention, it is possible to obtain a liquid metal alloy while operating a liquid metal crucible in which the metal is a molten liquid, but it is possible to operate the process at a temperature lower than the melting point of the metal M 1 , thereby significantly reducing energy can do.
- This temperature may vary depending on the type of M 1 and M 2 , but preferably may be 900 °C to 1,600 °C.
- the liquid metal crucible based on the eutectic reaction induced in the system of the present invention, it is obtained in the state of a liquid alloy (M 1 and M 2 are liquid metal alloy), so that the metal alloy itself can be used as a final product.
- M 1 is often used in the form of an alloy industrially.
- a post-treatment process of forming an alloy with other metals may be required.
- the present invention has high process efficiency in that a final product can be obtained in the form of a metal alloy of M 1 and M 2 at the same time as reduction without such a post-treatment process.
- the ratio of M 1 and M 2 can be adjusted, and the ratio of the metal oxide and M 2 can be adjusted in the module as well.
- the metal alloy, M 1 and M 2 There is also the advantage of being able to adjust the ratio.
- the metal M 1 may be obtained by electrolytic refining of the obtained metal alloy. Of course, this electrolytic refining may use a method known in the art.
- the liquid alloy obtained according to the present invention can be thoroughly separated from an environment in which oxygen may exist, and thus contamination by oxygen can be remarkably prevented. That is, according to the above aspect, it is possible to obtain a high-purity metal alloy and metal M 1 .
- the use of a liquid metal crucible containing a liquid metal alloy of a metal M 1 and a metal M 2 that form a eutectic phase with each other is advantageous in that the metal oxide contained in the raw material is a material that is difficult to be electrolytically reduced to a metal, but the liquid metal alloy and It has the advantage of being able to more easily reduce the metal oxide of the raw material module by using the standard redox potential difference of the desired metal M 1 . That is, when using a metal M 2 having a positive standard reduction potential than the standard reduction potential of the metal M 1 , the standard reduction potential value of M 1 is moved in a positive direction by the liquid metal crucible, so that the electrolytic reduction of the metal is It can be done more easily.
- the system of the present invention does not introduce a metal oxide as a raw material, another metal and other additive metals as a reducing agent, but they form a raw material module as one component, and the raw material module Based on this, it is possible to obtain the desired metal alloy and metal of better quality.
- the raw material module according to the present invention includes a configuration treated to prevent oxidation. , has a more enhanced oxygen barrier effect compared to the crawling process. Accordingly, the metal alloys and metals obtained according to the present invention can have a significantly low oxygen content.
- the system of the present invention includes a configuration in which the electrolyte acts as a barrier film for blocking oxygen, and the raw material module itself can also block oxygen, so that oxygen is double blocked. Accordingly, the system of the present invention can operate the reaction of the metal oxide and the reducing metal under an atmosphere of an inert gas conventionally recognized in the art, as well as operating the reaction of the metal oxide and the reducing metal in the atmosphere. It has significant advantages. Even when the system of the present invention is operated in the atmosphere, the metal alloys and metals thus produced are of high purity with little oxygen. This will be clearly demonstrated through the following examples. In some cases, in the system of the present invention, the reaction of the metal oxide and the reducing metal may be performed in combination with a method of proceeding in an atmosphere of an inert gas and a method of proceeding in a conventional atmosphere.
- the system of the present invention uses a raw material module in which raw materials necessary for the reaction are aggregated, there is an advantage in that it is easy to induce the reaction in the most optimal position among the electrolytic cells.
- FIG. 2 A photograph of a process of manufacturing a raw material module according to the present invention is shown in FIG. 2
- FIG. 4 is a schematic diagram of a raw material module according to an embodiment of the present invention.
- the photograph shown in FIG. 2 is only for helping understanding of the raw material module manufacturing as a non-limiting example, and the scope of the present invention is not limited thereto.
- the solid raw material module 300 includes a core layer 310 including a metal oxide 10 and a reducing metal M 3 30 ; And surrounding the core layer 310 may include a shell layer 320 composed of M 2 (20). As shown in FIG. 4 , the core layer 310 is coated while enclosing the outer surfaces of the first core 311 and the first core 311 made of the metal oxide 10, and the reducing agent metal M 3 (30) It may have a multi-layered structure including the second core 312 made of
- the raw material module 300a as shown in FIG. 5 in which the core layer is shown as another example of the present invention may be used.
- the core layer 310a of the raw material module 300a may be made of a mixture of powder including the metal oxide powder 10a and the reducing agent metal M 3 powder 30a.
- the structure shown in FIG. 6 may also be preferred as a raw material module.
- the raw material module 300b is similar to the example described above in terms of a multi-layer structure, but while surrounding the outer surface of the core layer 310b and the core layer 310b including the metal oxide 10b. It includes a coated shell layer 320b, but the shell layer 320b is different in that it is a coating layer including the alloy phase 330b of the metal M 2 (20b) and the metal M 3 (30b).
- the solid raw material modules described above enclose the shell layer and further include an anti-oxidation layer (330 in FIG. 4) for preventing oxidation thereof by blocking contact between the metal and oxygen included in the core layer and/or the shell layer.
- the antioxidant layer 330 may include at least one selected from the group consisting of LiF, MgF 2 , CaF 2 , BaF 2 , CaCl 2 , MgCl 2 , MgO, CaO, BaO, Al 2 O 3 and SiO 2 .
- the scope of the present invention is not limited thereto.
- the antioxidant layer is illustrated only in FIG. 4 , of course, it may be applied to FIGS. 5 and 6 according to another exemplary embodiment.
- This solid raw material module is configured to descend vertically in the electrolyzer until it reaches the liquid metal crucible through the electrolyte, and descends at a rate of distance/min (min) of 0.1% to 10% with respect to the depth of the electrolyzer. can do.
- the descending direction of the solid raw material module is set as an imaginary axis, it may be preferable in terms of stirring the liquid metal crucible and improving the reactivity thereof to rotate about this axis. Said rotation may be made during the descent after being introduced into the electrolyzer and/or when the descent is complete and no longer descends.
- system according to the present invention may further include a rotation unit to which the solid raw material module is mounted and rotates it.
- the solid raw material module descends to the liquid metal crucible and melts, and at the same time or partially simultaneously, the metal oxide and the reducing agent metal M 3 react to reduce M 1 from the metal oxide, and the reduced M 1 is the solid raw material module It forms a liquid metal alloy with M 2 contained in it.
- the metal oxide (M 1 x O z ) is TiO 2
- M 2 is Ni
- M 3 is Mg
- the metal Ti is reduced according to the following Reaction Schemes 1-1 and 1-2
- the oxide (M 3 a O b ) of M 3 can be separated while the liquid metal alloy TiNi is obtained.
- the metal oxide (M 1 x M 3 y O z ) is MgTiO 3
- M 2 is Ni
- M 3 is Mg
- a metal according to Scheme 2-1 and Scheme 2-2 Ti is reduced, and then an oxide of M 3 (M 3 a O b ) may be separated while obtaining a liquid metal alloy TiNi.
- M 3 a O b generated according to the above reaction may have a relatively low specific gravity compared to the electrolyte of the present invention as a kind of by-product.
- the M 3 a O b may float on the electrolyte due to a density difference with the electrolyte to form a by-product layer. Therefore, the by-product M 3 a O b is not mixed with the liquid metal crucible and the liquid metal alloy formed layered under the electrolyte.
- the by-product layer may serve to prevent the electrolyte from being vaporized and lost while being positioned on top of the electrolyte, and to prevent oxygen in the atmosphere from penetrating into the reactor.
- the system according to the present invention may be configured to enable a continuous process by utilizing these by-products.
- the system of the present invention continuously collects layered by-products floating on the electrolyte through the upper part of the electrolyzer, for example, by mixing with M 1 x O z , and M 1 x as a metal oxide. It may further include a recycling device for manufacturing M 3 y O z . In this case, when the prepared M 1 x M 3 y O z is used, the reduction reaction rate may be further improved compared to the case where M 1 x O z is used.
- the electrolyte preferably has an intermediate specific gravity so that the liquid metal crucible and the by-product M 3 a O b do not mix with each other, and at the same time is preferably insoluble in the by-product M 3 a O b .
- the electrolyte can also prevent oxygen from penetrating into the liquid metal crucible and the liquid metal alloy containing the desired metal M 1 , but a material that does not cause environmental problems, for example, a material that is not a chlorine-based material is preferred .
- Such an electrolyte may include a molten salt of a halide of one or two or more metals selected from the group of alkali metals and alkaline earth metals, but is not a chloride. More specifically, in the system of the present invention, the electrolyte is a halide of one or more metals selected from the group consisting of alkali metals including Li, Na, K, Rb and Cs and alkaline earth metals including Mg, Ca, Sr and Ba. This may be molten molten salt.
- the halide may include fluoride, bromide, iodide, or a mixture thereof.
- the electrolyte is also 10% to 50% by weight, specifically 10% by weight, based on the metal oxide involved in the entire reduction reaction, that is, the metal oxide that can be reduced to the target metal M 1 contained in the raw material module. It may be weight % to 20 weight %, more specifically 10 weight % to 15 weight %, and even more specifically 12 weight % to 13 weight %.
- the electrolyte may further include an oxide of one or two or more metals selected from the group of alkali metals and alkaline earth metals as additives.
- the content of the additive may be 0.1 to 25% by weight based on the total weight of the electrolyte.
- Additives may include, but are not limited to, Li 2 O, Na 2 O, SrO, Cs 2 O, K 2 O, CaO, BaO, or mixtures thereof.
- the additives contained in the electrolyte may enable easier reduction of the metal oxide contained in the raw material module.
- the system according to the present invention continuously obtains and collects a liquid metal alloy formed by M 1 and M 2 through the lower part of the electrolytic cell according to the process progress, and electrolytic refining to obtain metal M 1 It may further include an electrolytic refining unit.
- the electrolytic refining unit may solidify the obtained liquid metal alloy to obtain a solid metal alloy, and electrolytically refining the solid metal alloy to recover metal M 1 from the metal alloy.
- the electrolyte that may remain in the liquid metal alloy may be removed before electrolytic refining of the solidified alloy.
- the distillation temperature heat treatment temperature
- the distillation temperature is not particularly limited as long as the temperature is higher than the melting point of the electrolyte used in the system of the present invention, and may be, for example, 780 to 1,000°C.
- the electrolytic refining unit may include an electrolyte including a molten salt in which a halide of one or more metals selected from the group consisting of alkali metals and alkaline earth metals is molten independently of the electrolyte used for the above-described reduction reaction.
- the method according to the present invention comprises:
- the metal M 1 and the metal M 2 that form a eutectic phase with each other are added to the electrolytic cell to have a relatively high specific gravity compared to the electrolyte, and to form a layer in a state in which it is not mixed under the electrolyte, the electrolytic cell Preparing a liquid metal crucible accommodated in the;
- the metal oxide and the reducing agent metal M 3 may react to reduce M 1 , and the reduced M 1 and M 2 may be continuously mixed into the liquid metal crucible while forming a liquid metal alloy.
- the target metal M 1 is not particularly limited, but specifically Ti, Zr, Hf, W, Fe, Ni, Zn, Co, Mn, Cr, Ta, Ga, Nb, Sn, Ag, La, Ce, Pr, Nd, Nb, Pm, Sm, Eu, Al, V, Mo, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ac, Th, Pa, U, Np, Pu, Am, It may be one selected from the group consisting of Cm, Bk, Cf, Es, Fm, Md and No, and more specifically, Ti, Zr, W, Fe, Ni, Zn, Co, Mn, Cr, Ta, Er and It may be one selected from the group consisting of No, and more specifically, may be one selected from the group consisting of Ti, Zr, W, Fe, Ni, Zn, Co, Mn, and Cr, and in particular, Ti, Zr or W.
- the metal M 2 is not particularly limited as long as it can form a liquid metal alloy through a eutectic reaction with the metal M 1 , and specifically Cu, Ni, Fe, Sn, Zn, Pb, Bi, Cd And it may be at least one selected from alloys thereof, and more specifically, may be Cu, Ni, or alloys thereof.
- the metal M 3 is not particularly limited as long as it can reduce the metal oxide to M 1 , but among such materials, at least one selected from Ca, Mg, Al, and alloys thereof may be preferable, and more Specifically, it may be Ca or Mg, and in particular, it may be Mg.
- the metal oxide may include at least one selected from the group consisting of M 1 x O z and M 1 x M 3 y O z , where x and y are each a real number of 1 to 3 and , z is a real number from 1 to 4.
- Non-limiting examples of the metal oxide for better understanding include ZrO 2 , TiO 2 , MgTiO 3 , HfO 2 , Nb 2 O 5 , Dy 2 O 3 , Tb 4 O 7 , WO 3 , Co 3 O 4 , MnO,
- One selected from the group consisting of Cr 2 O 3 , MgO, CaO, Al 2 O 3 , Ta 2 O 5 , Ga 2 O 3 , Pb 3 O 4 , SnO, NbO and Ag 2 O, or a combination of two or more thereof may include
- the method according to the present invention is different from the conventional crawling process in that a metal oxide is used instead of a metal chloride as a raw material.
- Raw materials usually found in nature include oxides of M 1 , and in order to use them in the crawling process, a pretreatment process of replacing these metal oxides with chlorides is involved. If it goes through such a pretreatment process, it itself causes an increase in process cost.
- hydrochloric acid is used in the pretreatment process of replacing the metal oxide with chloride, which promotes corrosion of manufacturing equipment due to strong acidity, and toxic chlorine gas may be generated during the process, which may cause environmental problems. Since the method according to the present invention does not require a pretreatment process for replacing the metal oxide with a chloride, the process cost is lower than that of the crawling process and does not cause environmental problems.
- the raw material module used in the method of the present invention includes a core layer comprising a metal oxide and a reducing agent metal M 3 ; and a shell layer surrounding the core layer and composed of M 2 .
- the core layer may have a multilayer structure including a first core made of a metal oxide and a second core made of a reducing agent metal M 3 , which is coated while enclosing the outer surface of the first core.
- the core layer may be formed of a mixture of a powder including a metal oxide powder and a reducing agent metal M 3 powder.
- a raw material module as shown in FIG. 6 may also be used, and such a module includes a core layer including a metal oxide and a shell layer coated while enclosing the outer surface of the core layer, wherein the shell layer includes a metal M 2 and it may be a coating layer comprising an alloy phase of the metal M 3 .
- the solid raw material module may further include an anti-oxidation layer surrounding the shell layer and preventing oxidation thereof by blocking contact between oxygen and metal included in the core layer and/or the shell layer.
- the antioxidant layer may include at least one selected from the group consisting of LiF, MgF 2 , CaF 2 , BaF 2 , CaCl 2 , MgCl 2 , MgO, CaO, BaO, Al 2 O 3 and SiO 2 , These are not intended to limit the scope of the present invention.
- the solid raw material module may be lowered at a rate of a distance/minute (min) of 0.1% to 10% with respect to the depth of the electrolytic cell until it reaches the liquid metal crucible through the electrolyte. .
- the metal oxide and the reducing agent metal M 3 react to reduce M 1 from the metal oxide, and the reduction M 1 may be a step of forming a liquid metal alloy with M 2 contained in the solid raw material module.
- the metal oxide (M 1 x O z ) is TiO 2
- M 2 is Ni
- M 3 is Mg
- the metal Ti is reduced according to the following Reaction Schemes 1-1 and 1-2
- the oxide (M 3 a O b ) of M 3 can be separated while the liquid metal alloy TiNi is obtained.
- the metal oxide (M 1 x M 3 y O z ) is MgTiO 3
- M 2 is Ni
- M 3 is Mg
- a metal according to Scheme 2-1 and Scheme 2-2 Ti is reduced, and then an oxide of M 3 (M 3 a O b ) may be separated while obtaining a liquid metal alloy TiNi.
- M 3 a O b generated according to the above reaction may have a relatively low specific gravity compared to the electrolyte of the present invention as a kind of by-product.
- the M 3 a O b may float on the electrolyte due to a density difference with the electrolyte to form a by-product layer. Therefore, the by-product M 3 a O b is not mixed with the liquid metal crucible and the liquid metal alloy formed layered under the electrolyte.
- the by-product layer may serve to prevent the electrolyte from being vaporized and lost while being positioned on top of the electrolyte, and to prevent oxygen in the atmosphere from penetrating into the reactor.
- the method according to the present invention may be configured to utilize these by-products.
- the method of the present invention continuously collects, through the upper part of the electrolytic cell, a by-product floating on the electrolyte and layered, that is, M 3 a O b , and in the M 3 a O b , for example, By adding and mixing M 1 x O z , the by-product M 3 a O b and added
- the method may further include preparing M 1 x M 3 y O z which is a metal oxide derived from M 1 x O z .
- the reduction reaction rate can be further improved compared to the case of using M 1 x O z .
- the manufacturing of the M 1 x M 3 y O z may be performed at a temperature of 1,000°C to 1,500°C, specifically 1,200°C to 1,400°C, and more specifically 1,250°C to 1,350°C.
- the type of the electrolyte is not particularly limited unless it is a chlorine-based material, and is preferably as defined in the previous embodiment.
- the method according to the present invention may further comprise the step of electrolytic refining an alloy comprising metals M 1 and M 2 obtained after obtaining an alloy comprising metals M 1 and M 2 to obtain metal M 1 .
- the electrolytic refining to obtain the metal M 1 may be a step of solidifying the obtained liquid metal alloy to obtain a solid alloy, and electrolytically refining the solid alloy to recover the metal M 1 from the alloy.
- a system as shown in FIG. 1 was used.
- the electrolyte MgF 2 (0.2 kg)-BaF 2 (1.5 kg) was weighed, put into the electrolytic cell, and heated to about 1,200° C. to form an electrolyte layer.
- the prepared raw material module is charged into the electrolyzer, and it is vertically lowered at a speed of about 6 cm/min until it reaches the layer of the liquid metal crucible, and the module is rotated for 10 minutes to agitate the electrolyte and the liquid metal crucible.
- the melting and reduction reaction was carried out for 2 hours, and a CuTi liquid metal alloy as a reaction product was obtained through an outlet provided at the bottom of the electrolytic cell and solidified to finally obtain a CuTi alloy as shown in FIG. 9 .
- the reaction was completed, it was cooled at -10°C/min to prevent damage to the crucible.
- ELTRA ONH2000 was used to measure the oxygen content present in the alloy.
- FIG. 10 shows the result of cutting the alloy prepared in Example and checking the residual impurity content using the energy dispersion spectrum inside the alloy. According to FIG. 10 , it can be seen that the alloy consists only of Ti and Cu, which are target metals, and Mg used as a reducing material does not exist at all.
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Abstract
Description
Claims (25)
- 금속 산화물로부터 금속 M1을 환원시키기 위한 시스템으로서,A system for reducing metal M 1 from a metal oxide comprising:전해조;electrolyzer;상기 전해조의 저면으로부터 수용되고, 서로 공융상(eutectic phase)을 형성하는 금속 M1과 금속 M2의 액상 금속 합금을 포함하는 액상 금속 도가니;a liquid metal crucible containing a liquid metal alloy of a metal M 1 and a metal M 2 that is received from the bottom of the electrolytic cell and forms an eutectic phase with each other;상기 액상 금속 도가니의 위에 혼입되지 않는 상태로 층을 이루면서, 상기 전해조에 수용되는 액상의 전해질; 및a liquid electrolyte accommodated in the electrolytic cell while forming a layer in a state not to be mixed on the liquid metal crucible; and상기 금속 산화물, 금속 M2 및 환원제 금속 M3을 포함하는 고체 원료 모듈을 포함하고,A solid raw material module comprising the metal oxide, metal M 2 and reducing metal M 3 ,상기 고체 원료 모듈이 상기 액상 금속 도가니에 도달하여 용융되면서 상기 금속 산화물과 환원제 금속 M3이 반응하여 M1을 환원시키고, 환원된 M1과 M2가 액상 금속 합금을 형성하면서 액상 금속 도가니에 연속적으로 혼입되는, 시스템.As the solid raw material module reaches the liquid metal crucible and melts, the metal oxide and the reducing agent metal M 3 react to reduce M 1 , and the reduced M 1 and M 2 are continuously in the liquid metal crucible while forming a liquid metal alloy. incorporated into the system.
- 제1항에 있어서, According to claim 1,상기 환원된 M1과 M2가 형성한 액상 금속 합금을 수거하고 전해 정련하여 금속 M1을 수득하는 전해 정련부를 더 포함하는, 시스템. Collecting the liquid metal alloy formed by the reduced M 1 and M 2 and electrolytic refining to obtain a metal M 1 The system further comprising an electrolytic refining unit.
- 제1항에 있어서,According to claim 1,상기 금속 산화물은 M1 xOz 및 M1 xM3 yOz로 이루어진 군에서 선택된 적어도 하나를 포함하는, 시스템:Wherein the metal oxide comprises at least one selected from the group consisting of M 1 x O z and M 1 x M 3 y O z , the system:여기서, x, y는 각각 1 내지 3의 실수이고, z는 1 내지 4의 실수이다.Here, x and y are real numbers from 1 to 3, respectively, and z is a real number from 1 to 4.
- 제1항에 있어서,According to claim 1,상기 고체 원료 모듈은 상기 금속 산화물 및 상기 환원제 금속 M3을 포함하는 코어 층; 및 상기 코어 층을 감싸며 M2로 구성된 쉘 층을 포함하는, 시스템.The solid raw material module may include: a core layer including the metal oxide and the reducing agent metal M 3 ; and a shell layer surrounding the core layer and comprised of M 2 .
- 제1항에 있어서, According to claim 1,상기 고체 원료 모듈은 상기 금속 산화물을 포함하는 코어 층; 및 상기 코어 층의 외곽 표면을 감싸면서 코팅된 쉘 층을 포함하는 다층 구조이고,The solid raw material module may include a core layer including the metal oxide; and a multi-layered structure including a coated shell layer while surrounding the outer surface of the core layer,상기 쉘 층은 상기 금속 M2 및 상기 금속 M3의 합금상을 포함하는, 시스템.wherein the shell layer comprises an alloy phase of the metal M 2 and the metal M 3 .
- 제1항에 있어서,According to claim 1,상기 고체 원료 모듈이 전해질을 통해 상기 액상 금속 도가니에 도달할 때까지 상기 전해조 내에서 수직으로 하강하도록 구성되며, and the solid raw material module is configured to descend vertically in the electrolyzer until it reaches the liquid metal crucible through the electrolyte;상기 전해조의 깊이에 대해 0.1% 내지 10%인 거리/분(min)의 속도로 하강하는, 시스템.descending at a rate of distance/minute (min) that is between 0.1% and 10% of the depth of the electrolyzer.
- 제1항에 있어서, According to claim 1,상기 고체 원료 모듈이 용융되면서 금속 산화물과 환원제 금속 M3이 반응하여 M1을 환원시킬 때, 산화물 M3 aOb가 생성되고, 상기 M3 aOb는 상기 전해질에 비해 상대적으로 낮은 비중을 갖는, 시스템:When the solid raw material module is melted and the metal oxide and the reducing agent metal M 3 react to reduce M 1 , the oxide M 3 a O b is generated, and the M 3 a O b has a relatively low specific gravity compared to the electrolyte. Having, the system:여기서, a 및 b는 각각 1 내지 3의 실수이다.Here, a and b are real numbers from 1 to 3, respectively.
- 제7항에 있어서, 8. The method of claim 7,상기 M3 aOb는 밀도 차에 의해 상기 전해질 위로 부상하여 부산물 층을 형성하는, 시스템.wherein the M 3 a O b floats over the electrolyte due to a density difference to form a by-product layer.
- 제8항에 있어서,9. The method of claim 8,공정 진행도에 따라 상기 전해조의 하부를 통해 상기 액상 금속 합금을 연속적으로 수득하고, 상기 전해조의 상부를 통해 상기 부산물 층을 연속적으로 수거하여, 연속 공정이 가능하도록 하는, 시스템.A system for continuously obtaining the liquid metal alloy through the lower part of the electrolytic cell according to the process progress, and continuously collecting the by-product layer through the upper part of the electrolytic cell, thereby enabling a continuous process.
- 제9항에 있어서,10. The method of claim 9,상기 부산물 층을 수거하고 M1 xOz와 혼합하여, M1 xM3 yOz를 제조하는 재활용 장치를 더 포함하는, 시스템.and a recycling device for collecting the by-product layer and mixing it with M 1 x O z to produce M 1 x M 3 y O z .
- 제1항에 있어서,According to claim 1,상기 금속 산화물과 환원제 금속의 반응은 불활성 기체 중에서 및/또는 대기 중에서 이루어지는, 시스템.wherein the reaction of the metal oxide with the reducing metal occurs in an inert gas and/or in an atmosphere.
- 제4항에 있어서, 5. The method of claim 4,상기 코어 층이 상기 금속 산화물 분말 및 상기 환원제 금속 M3 분말을 포함하는 분말의 혼합물로 이루어진 시스템.A system in which the core layer consists of a mixture of powders comprising the metal oxide powder and the reducing agent metal M 3 powder.
- 제4항에 있어서, 5. The method of claim 4,상기 코어 층이 상기 금속 산화물로 이루어진 제1 코어 및 상기 제1 코어의 외곽 표면을 감싸면서 코팅되어 있으며, 상기 금속 M3으로 이루어진 제2 코어를 포함하는 다층 구조인, 시스템.The system of claim 1, wherein the core layer has a multi-layer structure including a first core made of the metal oxide and a second core made of the metal M 3 , the second core being coated while enclosing an outer surface of the first core.
- 제4항에 있어서,5. The method of claim 4,상기 고체 원료 모듈이 상기 쉘 층을 감싸고 있고, 상기 코어 층 및/또는 상기 쉘 층에 포함된 금속의 산화를 방지하기 위한 산화 방지 층을 더 포함하는, 시스템.The system according to claim 1, wherein the solid raw material module surrounds the shell layer, and further comprising an anti-oxidation layer for preventing oxidation of the core layer and/or the metal included in the shell layer.
- 제14항에 있어서, 상기 산화 방지 층이 LiF, MgF2, CaF2, BaF2, CaCl2, MgCl2, MgO, CaO, BaO, Al2O3 및 SiO2로 이루어진 군으로부터 선택되는 1종 이상을 포함하는, 시스템.15. The method of claim 14, wherein the antioxidant layer is at least one selected from the group consisting of LiF, MgF 2 , CaF 2 , BaF 2 , CaCl 2 , MgCl 2 , MgO, CaO, BaO, Al 2 O 3 and SiO 2 . comprising, a system.
- 제1항에 있어서, According to claim 1,M1은 Ti, Zr, Hf, W, Fe, Ni, Zn, Co, Mn, Cr, Ta, Ga, Nb, Sn, Ag, La, Ce, Pr, Nd, Nb, Pm, Sm, Eu, Al, V, Mo, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md 및 No로 이루어진 군으로부터 선택되는 1종인, 시스템. M 1 is Ti, Zr, Hf, W, Fe, Ni, Zn, Co, Mn, Cr, Ta, Ga, Nb, Sn, Ag, La, Ce, Pr, Nd, Nb, Pm, Sm, Eu, Al from the group consisting of , V, Mo, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md and No One of the choices, the system.
- 제1항에 있어서, According to claim 1,M2는 Cu, Ni, Fe, Sn, Zn, Pb, Bi, Cd 및 이들의 합금에서 선택되는 1종 이상인, 시스템.M 2 is at least one selected from Cu, Ni, Fe, Sn, Zn, Pb, Bi, Cd, and alloys thereof, the system.
- 제1항에 있어서, According to claim 1,M3은 Ca, Mg, Al 및 이들의 합금에서 선택되는 1종 이상인, 시스템.M 3 is at least one selected from Ca, Mg, Al, and alloys thereof, the system.
- 제1항에 있어서, According to claim 1,상기 전해질이 알칼리금속 및 알칼리토금속 군에서 하나 또는 둘 이상 선택되는 금속의 할로겐화물의 용융염을 포함하는, 시스템.The system, wherein the electrolyte comprises a molten salt of a halide of one or two or more metals selected from the group of alkali metals and alkaline earth metals.
- 금속 산화물로부터 금속 M1을 환원시키는 방법으로서,A method for reducing metal M 1 from a metal oxide comprising:전해조를 구비하는 단계;providing an electrolyzer;액상의 전해질을 상기 전해조에 투입하는 단계;introducing a liquid electrolyte into the electrolyzer;상기 전해조에 서로 공융상(eutectic phase)을 형성하는 금속 M1과 금속 M2를 투입하여 상기 전해질에 비해 상대적으로 높은 비중을 가지며, 상기 전해질의 아래에서 혼입되지 않는 상태로 층을 이루면서, 상기 전해조에 수용되는 액상 금속 도가니를 제조하는 단계;Metal M 1 and metal M 2 that form a eutectic phase with each other are added to the electrolytic cell to have a relatively high specific gravity compared to the electrolyte, and to form a layer in a state not to be mixed under the electrolyte, the electrolytic cell Preparing a liquid metal crucible accommodated in the;상기 전해조에 상기 금속 산화물, 금속 M2 및 환원제 금속 M3을 포함하는 고체 원료 모듈을 상기 전해질을 통해 상기 액상 금속 도가니에 도달할 때까지 이동시키는 단계; 및moving the solid raw material module including the metal oxide, the metal M 2 and the reducing metal M 3 to the electrolytic cell through the electrolyte until it reaches the liquid metal crucible; and상기 고체 원료 모듈의 금속 산화물로부터 유래된 금속 M1 및 M2를 포함하는 액상 금속 합금을 수득하는 단계를 포함하는, 방법.and obtaining a liquid metal alloy comprising metals M 1 and M 2 derived from the metal oxide of the solid raw material module.
- 제20항에 있어서, 21. The method of claim 20,수득된 금속 M1 및 M2를 포함하는 금속 합금을 전해 정련하여 금속 M1을 수득하는 단계를 더 포함하는, 방법.The method further comprising the step of electrolytic refining the metal alloy comprising the obtained metals M 1 and M 2 to obtain a metal M 1 .
- 제20항에 있어서, 21. The method of claim 20,상기 고체 원료 모듈 이동시키는 단계 및/또는 상기 액상 금속 합금을 수득하는 단계에서, 부산물인 산화물 M3 aOb가 생성되고, 상기 M3 aOb가 상기 전해질에 비해 상대적으로 낮은 비중을 갖고,In the step of moving the solid raw material module and / or obtaining the liquid metal alloy, an oxide M 3 a O b as a by-product is generated, and the M 3 a O b has a relatively low specific gravity compared to the electrolyte,전해질 위에서 층을 이루는 M3 aOb를 연속적으로 수거하고 상기 M3 aOb에 M1 xOz를 첨가 및 혼합하여, 상기 부산물인 M3 aOb 및 첨가된 M1 xOz로부터 유래되는 M1 xM3 yOz를로 표현되는 금속 산화물을 제조하는 단계를 더 포함하는, 방법.M 3 a O b that forms a layer on the electrolyte is continuously collected, and M 1 x O z is added to and mixed with M 3 a O b , and the by-product M 3 a O b and added derived from M 1 x O z The method further comprising the step of preparing a metal oxide represented by M 1 x M 3 y O z .
- 제20항에 따른 방법으로 수득된 금속 합금.A metal alloy obtained by the method according to claim 20 .
- 제21항에 따른 방법으로 수득된 금속.A metal obtained by the method according to claim 21 .
- 제23항에 있어서, 상기 금속 합금의 전체 중량 대비 환원제 금속 M3의 잔존 함량이 0.1 중량%이하이고, 산소 함유량이 1,000 ppm이하인, 금속 합금.The metal alloy according to claim 23, wherein the residual content of the reducing agent metal M 3 relative to the total weight of the metal alloy is 0.1 wt% or less, and the oxygen content is 1,000 ppm or less.
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JP2023529926A JP2023549557A (en) | 2020-11-17 | 2021-03-29 | System and method for reducing high melting point metal oxides using a liquid metal crucible |
US18/253,346 US20240026555A1 (en) | 2020-11-17 | 2021-03-29 | Reduction system and method for high-melting point metal oxides, using liquid metal crucible |
CA3200992A CA3200992A1 (en) | 2020-11-17 | 2021-03-29 | Reduction system and method for high-melting point metal oxides, using liquid metal crucible |
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