WO2022230403A1 - Metal titanium production method and metal titanium electrodeposit - Google Patents
Metal titanium production method and metal titanium electrodeposit Download PDFInfo
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- WO2022230403A1 WO2022230403A1 PCT/JP2022/011426 JP2022011426W WO2022230403A1 WO 2022230403 A1 WO2022230403 A1 WO 2022230403A1 JP 2022011426 W JP2022011426 W JP 2022011426W WO 2022230403 A1 WO2022230403 A1 WO 2022230403A1
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- 239000010936 titanium Substances 0.000 title claims abstract description 240
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 240
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000002659 electrodeposit Substances 0.000 title claims abstract description 107
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 67
- 239000002184 metal Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 114
- 238000004070 electrodeposition Methods 0.000 claims abstract description 102
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 70
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 54
- 150000003839 salts Chemical class 0.000 claims abstract description 54
- 239000004020 conductor Substances 0.000 claims abstract description 47
- 229910010052 TiAlO Inorganic materials 0.000 claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- 238000007670 refining Methods 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000012535 impurity Substances 0.000 description 39
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 9
- 229910001069 Ti alloy Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- -1 CaCl 2 Chemical compound 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229940102127 rubidium chloride Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/26—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
- C22B34/1277—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
- 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
- C22B34/1295—Refining, melting, remelting, working up of titanium
Definitions
- the present invention relates to a method for producing metallic titanium and a metallic titanium electrodeposit.
- the production of titanium metal is carried out by the Kroll method.
- the production involves many steps.
- Patent Literature 1 discloses a method of producing a titanium alloy by heat-treating a raw material containing titanium ore and aluminum and then subjecting the obtained raw material to molten salt electrolysis.
- a chloride bath composed of sodium chloride and potassium chloride is used to refine the titanium alloy.
- a refined titanium product with a predetermined aluminum content and oxygen content is obtained (see Table 3 of Patent Document 1).
- Such refined titanium products have at least a high aluminum content, which makes them unsuitable for the production of other titanium alloy products and titanium metal products, although they can be used as raw materials for aluminum-containing titanium alloy products.
- an object of the present invention is to provide a method for producing metallic titanium by molten salt electrolysis using a conductive material containing titanium, aluminum, oxygen and other impurities.
- the inventors of the present invention conducted various studies to reduce the impurity content (especially the oxygen content) by molten salt electrolysis to obtain a titanium alloy as disclosed in Patent Document 1, for example. It has been found that not only the oxygen content but also the aluminum content can be reduced depending on the composition of the chloride bath used in the molten salt electrolysis.
- molten salt electrolysis is sometimes carried out for the purpose of refining metals and alloys.
- molten salt electrolysis is performed in a chloride bath containing sodium chloride and potassium chloride, as in the production method described in Patent Document 1, the aluminum content cannot be sufficiently reduced.
- a method for producing titanium metal including a refining step of refining a TiAlO conductive material containing titanium, aluminum, and oxygen, wherein the refining step includes the TiAlO conductive material in a chloride bath.
- At least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refined electrodeposition step contains 50 mol % of the chloride bath. Contains more than magnesium chloride.
- the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refined electrodeposition step are magnesium chloride containing 30 mol % or more of magnesium chloride. respectively.
- the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refined electrodeposition step are magnesium chloride containing 50 mol % or more of magnesium chloride. respectively.
- the TiAlO conductive material is obtained by heat-treating a chemical blend containing a titanium ore containing titanium oxide, aluminum, and a separating agent before the refining step. Further includes an extraction step.
- the molar ratio of titanium oxide, aluminum and separating agent contained in the chemical blend is 3:4-7:2-6.
- the separating agent contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride.
- the metallic titanium has an aluminum content of 100 mass ppm or less and an oxygen content of 500 mass ppm or less.
- the metallic titanium has a nitrogen content of 0.03% by mass or less, a carbon content of 0.01% by mass or less, and an iron content of is 0.010% by mass or less, the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, the chromium content is 0.005% by mass or less, and silicon The content is 0.001% by mass or less, the manganese content is 0.05% by mass or less, and the tin content is 0.01% by mass or less.
- a metal titanium electrodeposit having an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less It is a titanium electrodeposit.
- the nitrogen content is 0.001% by mass or more and 0.03% by mass or less, and the carbon content is 0.0004% by mass or more and 0.01% by mass. % or less, the iron content is 0.010 mass % or less, the magnesium content is 0.05 mass % or less, the nickel content is 0.01 mass % or less, and the chromium content is 0.01 mass % or less. 005% by mass or less, a silicon content of 0.001% by mass or less, a manganese content of 0.05% by mass or less, and a tin content of 0.01% by mass or less.
- FIG. 1 A) to (D) are diagrams for explaining refining steps in an embodiment of the method for producing metallic titanium according to the present invention.
- FIG. 1 A) to (D) are diagrams for explaining refining steps in another embodiment of the method for producing metallic titanium according to the present invention.
- FIG. 1 A) to (D) are diagrams for explaining refining steps in another embodiment of the method for producing metallic titanium according to the present invention.
- FIG. 1 A) to (D) are diagrams for explaining refining steps in another embodiment of the method for producing metallic titanium according to the present invention.
- FIG. (A) is a photograph of the titanium-containing electrodeposit after the crude electrodeposition step obtained in Example 1
- (B) is a photograph of the titanium-containing electrodeposit after the crude electrodeposition step obtained in Example 1. It is the photograph obtained by SEM observation of a thing.
- (A) is a photograph of the titanium metal electrodeposit after the purification electrodeposition step obtained in Example 1
- (B) is a photograph of the metal titanium electrodeposit after the purification electrodeposition step obtained in Example 1. It is the photograph obtained by SEM observation of a thing.
- the present invention is not limited to the embodiments described below, and can be embodied by modifying the constituent elements without departing from the spirit of the present invention.
- various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in each embodiment.
- the invention may be formed by omitting some components from all the components shown in the embodiments.
- some members are shown schematically in order to facilitate understanding of the embodiments included in the invention, and the illustrated sizes, positional relationships, etc. may not necessarily be accurate.
- the "metallic titanium electrodeposit" is generally granular in appearance, and when microscopically observed, it often has a three-dimensional shape in which dendritic or polyhedral fine grains are linked (Fig. 9). (B)).
- One embodiment of the method for producing titanium metal according to the present invention includes a refining step to reduce the impurity content. Note that an extraction step may be further included before the refining step. An example of each step will be described below.
- the extraction step heat-treats a chemical blend containing, for example, a titanium ore containing titanium oxide, aluminum, and a separating agent to obtain a TiAlO conductive material. It is considered that the following reactions are utilized by the heat treatment. That is, in the extraction step, a thermite reaction is used to reduce titanium oxide, which is a metal oxide, with aluminum.
- a chemical blend is a raw material mixture for obtaining a TiAlO conductive material. Titanium oxide in titanium ore is not suitable for molten salt electrolysis due to its low electrical conductivity. Therefore, the TiAlO conductive material can be produced by performing the extraction step using titanium ore.
- the TiAlO conductive material Since the TiAlO conductive material has a relatively high electrical conductivity, it can be used in the later-described refining process for producing metallic titanium. In the extraction step, the TiAlO conductive material may be produced by appropriately referring to the known method described in Patent Document 1 (Japanese Patent Publication No. 2015-507696) or the like.
- titanium ore The content of titanium oxide in the titanium ore is not limited, but is, for example, 50% by mass or more, for example 80% by mass or more, for example 90% by mass or more. Titanium ore includes not only those obtained by mining, but also those that have been so-called upgraded. When the titanium oxide content in the titanium ore is low, appropriate treatment such as leaching may be performed to improve the titanium oxide content (that is, upgrade treatment).
- Separating agents are incorporated into the chemical blend for the purpose of separating TiAlO conductors and slag by-products in the extraction process. Those having such a function can be used as a separating agent, but the separating agent preferably contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride. From the viewpoint of morphology, it is more preferable to contain calcium fluoride. Therefore, the separating agent may be calcium fluoride alone.
- the temperature inside the container is, for example, 1500° C. or higher and 1800° C. or lower in an inert gas (eg, Ar) atmosphere.
- examples of materials for the inner wall of the container include carbon, ceramics, and the like.
- TiAlO conductive material The TiAlO conductive material obtained in the extraction step has, for example, a titanium content of 50% by mass or more and 80% by mass or less, an aluminum content of 3% by mass or more and 40% by mass or less, and an oxygen content of 0.5% by mass or more. It is 2% by mass or more and 40% by mass or less.
- the said titanium content is 60 mass % or more as a lower limit.
- the said aluminum content is 5 mass % or more as a lower limit.
- the upper limit of the aluminum content is, for example, 30% by mass or less, for example, 20% by mass or less.
- the lower limit of the oxygen content is, for example, 3% by mass or more, 5% by mass or more, or 8% by mass or more.
- the upper limit of the oxygen content is, for example, 30% by mass or less, for example, 20% by mass or less.
- the method for measuring the impurity content of each component of the TiAlO conductive material the measuring method described in the examples of this specification can be adopted.
- the upper limit of the specific resistance of the TiAlO conductive material may be, for example, 1 ⁇ 10 ⁇ 4 ⁇ m or less from the viewpoint of efficiently performing molten salt electrolysis in the refining process described later for producing metallic titanium.
- the lower limit of the specific resistance may be, for example, 1 ⁇ 10 ⁇ 8 ⁇ m or more.
- the lower limit of the specific resistance may be, for example, 1 ⁇ 10 ⁇ 7 ⁇ m or more, for example, 5 ⁇ 10 ⁇ 7 ⁇ m or more.
- the method for measuring the resistivity of the TiAlO conductive material the measuring method described in the examples of this specification can be adopted.
- the refining process uses an electrolytic device to refine the TiAlO conductive material in order to reduce the impurity content. That is, in the refining process, metallic titanium with high purity is obtained by reducing the contents of mainly aluminum and oxygen in the TiAlO conductive material, as well as other ore-derived elements.
- the refining process includes a crude electrodeposition step and one or more refinement electrodeposition steps in which molten salt electrolysis is performed using an electrode containing the titanium-containing electrodeposit obtained in the crude electrodeposition step.
- electrolytic apparatus 100 In one embodiment, various electrolytic devices can be used.
- An example of the electrolysis apparatus 100 shown in FIG. 1A is of a batch type, and includes an electrolytic bath 110 in the form of a sealed container that stores a chloride bath Bf, and an anode 120 and a cathode 130 that are immersed in the chloride bath Bf. and a power source (not shown) connected to the anode 120 and the cathode 130 via conductive wires to energize the anode 120 and the cathode 130 .
- the electrolytic device 100 usually has a structure that can be opened and closed in order to install or take out the anode and cathode.
- the electrolysis apparatus 100 has an opening for gas supply and exhaust in order to make the space above the chloride bath Bf an inert gas atmosphere.
- the electrolysis apparatus 100 is provided with a heater at an appropriate location so that the chloride bath Bf can be maintained in a molten state by heating.
- the material of the electrolytic bath 110 is not particularly limited as long as it has heat resistance and corrosion resistance.
- the electrodes may further include a bipolar electrode.
- the molten salt that constitutes the chloride bath may contain, for example, 70 mol % or more, such as 80 mol % or more, such as 90 mol % or more of alkali metal chlorides and alkaline earth metal chlorides.
- reasons for not using a fluoride bath, a bromide bath and an iodide bath in place of the chloride bath include high corrosiveness, high environmental load and high cost.
- At least one chloride bath Bf of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step reduces not only the oxygen content but also the aluminum content to produce metallic titanium From the viewpoint of manufacturing, it contains 30 mol% or more of magnesium chloride.
- Using a chloride bath with a high magnesium chloride content can increase the effect of reducing the aluminum content.
- only the chloride bath used in the crude electrodeposition step may contain the predetermined amount of magnesium chloride, or at least Only one chloride bath may contain the predetermined amount of magnesium chloride.
- at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step which is performed one or more times contains the predetermined amount of magnesium chloride.
- the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement step performed one or more times At least one chloride bath of the baths may each contain the amount of magnesium chloride described above.
- the above chloride bath containing a predetermined amount of magnesium chloride is effective in reducing the aluminum content and oxygen content in the electrodeposit, and the lower limit of the magnesium chloride content is preferably 30 mol % or more. , more preferably 50 mol % or more, still more preferably 80 mol % or more, still more preferably 85 mol % or more, still more preferably 90 mol % or more.
- the chloride bath contains lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsCl), beryllium chloride (BeCl 2 ), calcium chloride (CaCl 2 ) one or more metal chlorides selected from strontium chloride (SrCl 2 ) and barium chloride (BaCl 2 ), for example 70 mol% or less, for example 50 mol% or less, for example 20 mol% or less, or for example 15 mol% or less , and may further contain, for example, 10 mol % or less. Further, the chloride bath may optionally contain lower titanium chloride, such as titanium dichloride and titanium trichloride.
- the content of the lower titanium chloride may be appropriately adjusted.
- the specific salt type and content can be appropriately determined in consideration of the operating temperature and the like.
- the content on a molar basis is measured by ICP emission spectrometry and atomic absorption spectrometry.
- the content on a molar basis is calculated as follows. After solidifying a molten salt sample collected from the chloride bath, the components of the sample are subjected to ICP emission spectrometry and atomic absorption spectrometry to calculate the content of each metal ion on a molar basis in the chloride bath Bf. do.
- the metal ion content was determined by atomic absorption spectroscopy for Na and K and ICP emission spectroscopy for the others.
- Mm is obtained by adding the content of magnesium ions, the content of sodium ions, the content of potassium ions, the content of calcium ions, the content of lithium ions, and the content of titanium ions.
- the molar content of each component contained in the chloride bath is calculated by dividing the metal ion content of each component by the total metal ion content (Mm) and expressing it as a percentage. can be done.
- the content of chloride is determined based on the content of metal ions contained in the chloride bath.
- Each of the anode 120 and the cathode 130 can be, for example, rod-shaped, a long band that is used while being moved, a cylinder, a plate-shaped, a cylinder or other columnar shape, or a block-shaped shape.
- a TiAlO conductive material as the anode 120 can be melted and cast to form the anode. If the inter-electrode distance between the anode 120 and the cathode 130 is to be set within a specific range, it is preferable that the shapes of the opposing portions of the anode 120 and the cathode 130 are similar in vertical cross section.
- the anode 120 may also be cylindrical. In this case, since the cylindrical anode 120 surrounds the cathode 130, the area where the electrodeposits are produced can be increased.
- a rod-shaped or column-shaped cathode 130 that is rotatable with a fixed axial position may be used, and a plate-shaped anode 120 having an arc-shaped cross section may be used at the opposed portion. Even in this case, the opposing portions of the anode 120 and the cathode 130 can maintain substantially the same inter-electrode distance.
- the anode 120 may be formed by placing the TiAlO conductive material obtained in the above-described extraction process in the form of granules or powder in a metal basket (for example, made of nickel) having a lower ionization tendency than titanium.
- a metal basket for example, made of nickel
- the basket BK has many through holes, and the shape of the basket BK can be treated as the shape of the anode 120 . Further, even if the cage is electrically connected, the cage BK is less likely to elute into the chloride bath Bf, and mainly the TiAlO conductive material is eluted.
- the portion where the TiAlO conductive material or the like is eluted is sometimes described with the symbol of anode.
- the shape of the cathode 130 at least part of the surface of the cathode 130 on which metallic titanium is deposited may be curved.
- metal titanium can be electrodeposited on the surface of the cathode 130 while rotating the cathode 130, which contributes to miniaturization of the apparatus during continuous production.
- the chloride bath used in the crude electrodeposition step has a bath composition containing the aforementioned predetermined amount of magnesium chloride
- the chloride bath used in the refined electrodeposition step contains the above-mentioned predetermined amount of magnesium chloride. composition, or another bath composition that does not contain the predetermined amount of magnesium chloride.
- the chloride bath used in the refinement electrodeposition step has a bath composition containing a predetermined amount of magnesium chloride as described above, the chloride bath used in the crude electrodeposition step contains the above-mentioned predetermined amount of magnesium chloride.
- 1A to 1D to 5A to 5D can be connected to a power supply (not shown), and a control mechanism for the power supply (not shown). is capable of appropriately switching conductive lines for supplying current according to each anode and each cathode.
- molten salt electrolysis is performed in a chloride bath Bf using an electrode containing a TiAlO conductive material to obtain a titanium-containing electrodeposit.
- a nickel cage BK in which a TiAlO conductive material as an anode 120 is placed and a titanium cathode 130 are placed in a chloride bath Bf.
- the control mechanism then supplies current to the anode 120 and the cathode 130 via the conductive line EL connected to the cage BK and the cathode 130, thereby performing molten salt electrolysis.
- the anodes 120 are placed in separate baskets BK, but the anodes may be placed in, for example, ring-shaped nickel baskets (see FIGS. 6A and 7).
- a rod-shaped or plate-shaped anode obtained by casting a TiAlO conductive material may be directly connected to the conductive wire without using a cage.
- the temperature of the chloride bath Bf may be appropriately changed depending on the components in the chloride bath Bf. That is, the temperature of the chloride bath Bf may be appropriately determined from the viewpoints of maintaining the molten state of the chloride bath and eliminating energy loss due to excessive heating. At this time, it is also possible to appropriately determine the temperature of the chloride bath Bf with reference to the melting point of each metal chloride. To give a specific example, the temperature of the chloride bath Bf is controlled within a range of, for example, 450° C. or higher and 900° C. or lower. Also, the current density of the cathode 130 is not particularly limited and may be determined as appropriate.
- the current density of the cathode 130 may be, for example, 0.01 A/cm 2 or more and 5 A/cm 2 or less.
- a pulse current may be used in which an energization stop period is provided in which the current value is set to zero (that is, no energization), and the energization period and the energization stop period are alternately repeated. good.
- the inside of the electrolytic cell 110 is controlled to an inert atmosphere such as argon, for example, from the viewpoint of suppressing an increase in the content of impurities in the titanium-containing electrodeposit due to the contamination of moisture and the like in the air.
- an inert atmosphere such as argon
- the titanium-containing electrodeposit TC formed on the surface of the cathode 130 taken out from the electrolytic cell 110 is recovered by peeling it off with a cutting tool or the like.
- the titanium-containing electrodeposit TC may be washed and dried as described below. Washing and drying may be performed together with the cathode 130 or may be performed after recovery from the cathode 130 .
- the cathode 130 is removed from the electrolytic cell 110, and the cathode 130 and the titanium-containing electrodeposit TC are washed with an acid and/or water to dissolve and remove the molten salt adhering thereto.
- the titanium-containing electrodeposit TC is peeled off from the surface of the cathode 130 with a cutting tool or the like. Then, the titanium-containing electrodeposit TC is placed in a container and vacuum-dried to evaporate moisture.
- ⁇ Purification electrodeposition step> In the refinement electrodeposition step, after the crude electrodeposition step, molten salt electrolysis is performed in a chloride bath Bf using an electrode containing titanium-containing electrodeposits TC. Thus, by further purifying the titanium-containing electrodeposit TC obtained in the crude electrodeposition step, a metal titanium electrodeposit TP having a further reduced impurity content can be obtained.
- the refining electrodeposition step can be performed one or more times, and from the second time onwards, the metallic titanium electrodeposit obtained last time is used as an electrode. For example, as shown in FIG.
- Molten salt electrolysis is then performed by the control mechanism supplying current to the anode 122 and the cathode 130 via the conductive line EL connected to the cage BK and the cathode 130 .
- the cathode 130 may be the same as the cathode 130 used in the crude electrodeposition step, or may be replaced with a new cathode.
- composition of the chloride bath Bf, the temperature of the chloride bath, and the current density in the refinement electrodeposition step are the same as in the crude electrodeposition step, so the explanation is omitted.
- the titanium-containing anode 122 is exhausted as it is eluted into the chloride bath Bf, and a metallic titanium electrode having a reduced impurity content is deposited on the surface of the cathode 130 .
- a precipitate TP is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
- the metal titanium electrodeposit TP formed on the surface of the cathode 130 taken out from the electrolytic cell 110 is recovered by peeling it off with a cutting tool or the like.
- the titanium metal electrodeposit TP may be subjected to the washing and drying described above in the crude electrodeposition step. Washing and drying may be performed together with the cathode 130 or may be performed after recovery from the cathode 130 . This yields titanium metal with reduced aluminum and oxygen content.
- the purification electrodeposition step is performed once, but in order to further reduce the impurity content and further improve the purity of metallic titanium, the purification electrodeposition step is performed.
- a step may be performed multiple times. More specifically, the obtained metal titanium electrodeposit TP is placed in a nickel cage BK in the electrolytic bath 110, and the control mechanism controls the flow between the metal titanium electrodeposit TP as an anode and the titanium cathode 130. Molten salt electrolysis is performed by supplying a current to . Every time such an operation is repeated, it becomes possible to recover titanium metal in which the aluminum content and the oxygen content are more reliably reduced. However, from the viewpoint of manufacturing cost, the number of repetitions may be appropriately selected.
- the purification electrodeposition step is, for example, one or more and five or less times, and for example, one or more and three or less times.
- composition of metallic titanium According to the refining process described above, it is possible to obtain metallic titanium having an aluminum content of 100 mass ppm or less, an oxygen content of 500 mass ppm or less, and a balance of titanium and unavoidable impurities. These unavoidable impurities are often ore-derived impurities and chloride bath-derived components.
- the composition of metallic titanium here corresponds to the titanium purity of so-called industrial pure titanium, and metallic titanium has a low impurity content, for example, the total impurity content is 3000 mass ppm or less.
- the said aluminum content is 50 mass ppm or less as an upper limit.
- the lower limit of the aluminum content is, for example, 10 mass ppm or more, for example 20 mass ppm or more.
- the upper limit of the oxygen content is, for example, 450 mass ppm or less, for example, 400 mass ppm or less.
- the lower limit of the oxygen content is, for example, 100 mass ppm or more, for example 200 mass ppm or more.
- the nitrogen content is 0.03% by mass or less
- the carbon content is 0.01% by mass or less
- the iron content is 0.010% by mass or less
- magnesium content of 0.05% by mass or less nickel content of 0.01% by mass or less
- chromium content of 0.005% by mass or less silicon content of 0.001% by mass or less
- metallic titanium in which the manganese content is further controlled to 0.05% by mass or less and the tin content is controlled to 0.01% by mass or less.
- the lower limit of the nitrogen content is, for example, 0.002% by mass or more, for example 0.003% by mass or more.
- the upper limit of the nitrogen content is, for example, 0.009% by mass or less, for example, 0.008% by mass or less.
- the lower limit of the carbon content is, for example, 0.0006% by mass or more, for example, 0.0008% by mass or more.
- the upper limit of the carbon content is, for example, 0.008% by mass or less, for example, 0.004% by mass or less.
- the upper limit of the iron content is, for example, 0.005% by mass or less, for example 0.003% by mass or less.
- the lower limit of the magnesium content is, for example, 0.001% by mass or more, for example 0.005% by mass or more.
- the upper limit of the nickel content is, for example, 0.008% by mass or less, for example, 0.004% by mass or less.
- the chromium content is, as a lower limit, 0.0005% by mass or more, for example 0.001% by mass or more.
- the upper limit of the silicon content is, for example, 0.0005% by mass or less.
- the manganese content is, as a lower limit, for example 0.001% by mass or more, for example 0.005% by mass or more.
- the upper limit of the manganese content is, for example, 0.03% by mass or less.
- the upper limit of the tin content is, for example, 0.005% by mass or less, for example 0.003% by mass or less. It is presumed that various pure titanium products and titanium alloy products can be obtained at low cost by using metallic titanium produced according to one embodiment of the present invention.
- FIGS. 1(A) to 1(D) Another embodiment is described below.
- the points that are different from the above-described embodiments will be mainly described. That is, the configurations described in the above embodiments can be appropriately applied to the following embodiments.
- the anode and the cathode are arranged at approximately the same height, but the crude electrodeposition step and the refinement electrodeposition step can be performed even if the arrangement of the anode and the cathode is changed. It is possible.
- an embodiment in which the cathode is arranged on the upper side and the anode is arranged on the lower side will be described below. As shown in FIG.
- an electrolytic device 200 for example, a nickel base BS is placed on the bottom of an electrolytic bath 210, and a TiAlO conductive material as an anode 220 is placed on the base BS. A titanium cathode 230 is placed at a higher position.
- the control mechanism supplies current to the anode 220 and the cathode 230 through the conductive line EL connected to the base BS and the cathode 230, thereby performing molten salt electrolysis (rough electrodeposition step).
- the control mechanism stops the current supply to end the molten salt electrolysis.
- the titanium-containing electrodeposit TC formed on the surface of the cathode 230 taken out from the electrolytic bath 210 is recovered by peeling it off with a cutting tool or the like. Note that the titanium-containing electrodeposit TC may be washed and dried as described above. Next, as shown in FIG.
- a nickel-made base BS and a titanium-containing electrodeposit TC as an anode 222 are placed on the base BS at the bottom of the electrolytic cell 210.
- a titanium cathode 230 is placed at a higher position.
- the control mechanism supplies current to the anode 222 and the cathode 230 through the conductive line EL connected to the base BS and the cathode 230, thereby performing molten salt electrolysis (refining electrodeposition step).
- the control mechanism stops the current supply to end the molten salt electrolysis.
- the cathode 230 is taken out from the electrolytic cell 210, and the metal titanium electrodeposit TP formed on the surface of the cathode 230 is washed, peeled off and dried to obtain metal titanium.
- the embodiment shown in FIG. 3 is an embodiment in which at least part of the electrolytic cell is made of nickel and the part made of nickel is used as the cathode.
- metallic titanium can be produced without taking out the titanium-containing electrodeposit TC from the chloride bath Bf.
- a nickel basket BK in which a TiAlO conductive material as an anode 320 is placed is arranged in the electrolytic device 300 . At this time, by making the material of at least the inner wall of the electrolytic cell 310 nickel, the inner wall serves as the cathode 330 during the molten salt electrolysis.
- the control mechanism supplies current to the anode 320 and the cathode 330 via the conductive wire EL connected to the cage BK and the cathode 330, thereby performing molten salt electrolysis (rough electrodeposition step).
- the control mechanism stops the current supply to end the molten salt electrolysis.
- the nickel basket BK is removed from the chloride bath Bf.
- a titanium cathode 335 is placed in the chloride bath Bf.
- the titanium-containing electrodeposit TC formed on the inner wall surface of the nickel electrolytic bath 310 is used as the anode 322 .
- the control mechanism supplies a current to the anode 322 and the cathode 335 via the conductive wire EL connected to the inner wall of the electrolytic cell 310 and the cathode 335 to perform molten salt electrolysis (refining electrodeposition step). .
- the anode 322 is consumed as the anode 322 is eluted into the chloride bath Bf, and a metallic titanium electrodeposit TP having a reduced impurity content is formed on the surface of the cathode 335. is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis. Next, the cathode 335 is taken out from the electrolytic bath 310, and the metal titanium electrodeposit TP formed on the surface of the cathode 335 is washed, peeled off and dried to obtain metal titanium.
- metallic titanium can be produced without removing the titanium-containing electrodeposit TC from the chloride bath Bf.
- a nickel basket BK in which a TiAlO conductive material as an anode 420 is placed is placed in an electrolysis device 400 .
- two titanium cathodes 430 and 435 are arranged side by side toward the center from the position where the cage BK is arranged.
- the titanium cathode 430 preferably has a large number of holes having openings on the anode 420 side and the titanium cathode 435 side.
- this hole is not particularly limited, and it may be a through hole with a linear cross section, or a hole with a complicated shape such as that of a porous body.
- molten salt electrolysis is carried out by supplying electric current to the anode 420 and the cathode 430 through the conductive wire EL to the basket BK and the cathode 430 to which the control mechanism is connected (crude electrodeposition step).
- the anode 420 is eluted into the chloride bath Bf, the anode 420 is exhausted, and a titanium-containing electrodeposit TC having a reduced impurity content is deposited on the surface of the cathode 430. is formed.
- the control mechanism stops the current supply to end the molten salt electrolysis.
- the cathode 430 (see FIG. 4(B)) having the titanium-containing electrodeposit TC formed on the surface is switched to the anode 424, and the anode whose control mechanism has been switched.
- Molten salt electrolysis is performed by supplying current to 424 and cathode 435 near the center (refining electrodeposition step). At this time, the titanium-containing electrodeposit TC becomes the anode 422 .
- FIG. 4(C) the cathode 430 (see FIG. 4(B)) having the titanium-containing electrodeposit TC formed on the surface is switched to the anode 424, and the anode whose control mechanism has been switched.
- Molten salt electrolysis is performed by supplying current to 424 and cathode 435 near the center (refining electrodeposition step). At this time, the titanium-containing electrodeposit TC becomes the anode 422 .
- the anode 422 and possibly also the anode 424 are depleted as they are eluted into the chloride bath Bf, leaving metal with reduced impurity content on the surface of the cathode 435.
- a titanium electrodeposit TP is formed.
- the control mechanism stops the current supply to end the molten salt electrolysis.
- the cathode 435 is taken out from the electrolytic bath 410, and the metal titanium electrodeposit TP formed on the surface of the cathode 435 is washed, peeled off and dried to obtain metal titanium.
- an electrolytic device 500 is provided with a nickel cage BK in which a TiAlO conductive material as an anode 520 is placed, a titanium cathode 530, and a titanium bipolar electrode 540 in the center. do.
- the titanium bipolar electrode 540 is illustrated as being thick in FIG. 5A, the titanium bipolar electrode 540 may be thin.
- Molten salt electrolysis is performed by a control mechanism supplying current to the anode 520 and the cathode 530 via the conductive line EL connected to the cage BK and the cathode 530 .
- a control mechanism supplying current to the anode 520 and the cathode 530 via the conductive line EL connected to the cage BK and the cathode 530 .
- the anode 520 is consumed, and the titanium-containing electrodeposit TC with reduced impurity content is deposited on the surface of the bipolar electrode 540. Formed on top. Formation of the titanium-containing electrodeposit TC on this bipolar electrode 540 corresponds to the rough electrodeposition step.
- FIG. 5C shows that the cathode 530 side of the bipolar electrode 540 is eluted.
- the bipolar electrode 540 will first elute titanium from the bipolar electrode 540 and then the titanium-containing electrodeposit TC.
- the bipolar electrode 540 and the titanium-containing electrodeposit TC are consumed, and a metal titanium electrodeposit TP with a reduced impurity content is formed on the surface of the cathode 530. (refining electrodeposition step).
- a titanium bipolar electrode is arranged, but instead of the bipolar electrode, for example, a titanium-containing electrodeposit TC obtained by subjecting a TiAlO conductive material to molten salt electrolysis is arranged. This may be a double pole.
- the titanium-containing electrodeposit TC is formed on the surface of the double electrode 540 on the anode 520 side, a hook (not shown) attached to the upper end of the double electrode 540 is hooked with a hanging rod or the like to should be rotated 180 degrees. By doing so, the titanium-containing electrodeposit TC faces the cathode 530 .
- the bipolar electrode and the cathode are described as being made of titanium, but the material can be appropriately changed as long as the electrodeposit can be deposited.
- the bipolar electrode must have conductivity. Therefore, non-conductive materials such as ceramics cannot be used for the bipolar electrodes.
- the bipolar poles may be non-movable or movable as described above.
- electrodeposition and elution can occur simultaneously in the case of a non-movable bipolar electrode, it is preferable to have a large number of holes opening to the anode side and the cathode side.
- electrodeposition and elution can proceed separately, so such holes as described above are unnecessary. Rather, by eliminating the pores, it is possible to avoid a situation in which the electrodeposits enter the pores and require a long time for elution.
- a plurality of crude electrodeposition steps and refinement electrodeposition steps have been described. These can be carried out in combination as appropriate. For example, after carrying out the crude electrodeposition step of the embodiment shown in FIGS. It is also possible to carry out a purification electrodeposition step of
- the metallic titanium electrodeposit according to the present invention can be produced by the method for producing metallic titanium described above, and has a reduced impurity content.
- the metal titanium electrodeposit has a low impurity content, for example, the total impurity content is 3000 ppm by mass or less.
- the metal titanium electrodeposit has an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less, and the balance is titanium and unavoidable It has a composition consisting of impurities. These unavoidable impurities are often ore-derived impurities and chloride bath-derived components.
- the content of each of the above components can also be within the range described above in "Composition of metallic titanium".
- the above-described unavoidable impurities and the like may be specified more specifically. That is, the nitrogen content in the metal titanium electrodeposit is 0.001% by mass or more and 0.03% by mass or less, and the carbon content is 0.0004% by mass or more and 0.01% by mass or less, The iron content is 0.010% by mass or less, the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, and the chromium content is 0.005% by mass or less.
- the silicon content may be 0.001% by mass or less, the manganese content may be 0.05% by mass or less, and the tin content may be 0.01% by mass or less.
- the content of each of the above components can also be within the range described above in "Composition of metallic titanium".
- the method for measuring the impurity content of each component of the metal titanium electrodeposit is the same as the method for measuring the impurity content of each component of the TiAlO conductive material described above.
- the particle size distribution of the metal titanium electrodeposit is not particularly limited, but the proportion of the metal titanium electrodeposits that are above the sieve when sieved through a 300 ⁇ m mesh sieve is, on a mass basis, a lower limit of, for example, 60% or more. Yes, and for example 70% or more.
- the upper limit of the ratio of the metal titanium electrodeposits to be on the sieve is, for example, 90% or less, for example, 85% or less.
- the metal titanium electrodeposit is pulverized to such an extent that it does not crush or pulverize, and is sieved using a sieve with an opening of 300 ⁇ m.
- the TiAlO conductive material used in Examples and Comparative Examples to be described later is a chemical blend containing titanium ore containing titanium oxide, aluminum, and calcium fluoride as a separating agent. After heat treatment under the conditions shown below. , was prepared by post-treatment according to a known method (extraction step). In the extraction process, the amount of titanium ore, aluminum and separating agent charged was adjusted so that the molar ratio of titanium oxide:aluminum:separating agent was within the range of 3:4-7:2-6.
- a measurement sample collected from the TiAlO conductive material was subjected to ICP emission spectrometry (PS3520UVDDII, manufactured by HITACHI) for metal components, inert gas fusion-infrared absorption method (TC-436AR, manufactured by LECO) for oxygen, and The impurity content of each component was measured by an inert gas fusion-thermal conductivity method (TC-436AR, manufactured by LECO) and a combustion-infrared absorption method for carbon (EMIA-920V2, manufactured by Horiba, Ltd.). This method of measuring the content of the component is also applied to titanium-containing electrodeposits, metal titanium, and metal titanium electrodeposits.
- ICP emission spectrometry PS3520UVDDII, manufactured by HITACHI
- TC-436AR inert gas fusion-infrared absorption method
- EMIA-920V2 combustion-infrared absorption method for carbon
- Example 1> (Crude electrodeposition) An electrolytic device 600 having the configuration shown in FIGS. 6A and 7 was used. The dimensions and shape of the bath portion of the electrolytic cell 610 of the electrolyzer 600 were 300 mm ⁇ 570 mm deep. Next, 30 kg of magnesium chloride (see Table 3) was put into the electrolytic bath 610 of the electrolyzer 600 and dissolved to obtain a chloride bath Bf. Next, an annular nickel cage BK in which an anode 620 made of 5000 g of TiAlO conductive material was placed was placed. A titanium round bar with a diameter of 50 mm ⁇ 300 mm was prepared as the cathode 630 . The anode 620 and the cathode 630 were arranged such that the height direction of the anode 620 and the cathode 630 was substantially parallel to the depth direction of the chloride bath.
- a control mechanism supplied electric current to the anode 620 and the cathode 630 through a conductive line EL connected to the anode 620 and the cathode 630 to perform molten salt electrolysis in the chloride bath Bf. Seven hours after the start of the current supply, the control mechanism stopped the current supply. Incidentally, as shown in FIG. 6(B), a titanium-containing electrodeposit TC deposited over the entire surface of the cathode 630 was obtained.
- the cathode 630 was pulled up from the electrolytic bath 610, and the cathode 630 and the titanium-containing electrodeposit TC were washed with water to remove adhering molten salt.
- a titanium-containing electrodeposit TC containing metallic titanium was peeled off from the cathode 630 with a cutting tool and recovered. Moisture was evaporated from the titanium-containing electrodeposit TC by vacuum separation.
- a control mechanism supplied electric current to the anode 622 and the cathode 630 via a conductive line EL connected to the anode 622 and the cathode 630 to perform molten salt electrolysis in the chloride bath Bf. Two hours after the start of the current supply, the control mechanism stopped the current supply. In addition, as shown in FIG. 6(D), a metal titanium electrodeposit TP deposited over the entire surface of the cathode 130 was obtained.
- the cathode 130 was pulled up from the electrolytic cell 110, and the cathode 130 and the metal titanium electrodeposit TP were pickled and then washed with water to remove the adhering molten salt.
- the metal titanium electrodeposit TP was peeled off from the cathode 130 with a cutting tool and collected. Moisture was evaporated from the metal titanium electrodeposit TP by vacuum separation.
- Example 2 to 6 and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1, except that the chloride bath shown in Table 3 was used. Note that only Example 6 was subjected to the refinement electrodeposition step twice. After the electrodeposits prepared in each step were washed with water and vacuum-dried in the same manner as in Example 1, the content of impurities and the percentage of sieved deposits were measured. The results are shown in Tables 4 and 5, respectively.
- the metal titanium electrodeposit TP finally obtained by molten salt electrolysis using a TiAlO conductive material having an aluminum content of 11.6 mass% and an oxygen content of 10.3 mass%
- the aluminum content was below 100 ppm by weight and the oxygen content could be reduced to below 500 ppm by weight. That is, it was confirmed that at least one of the chloride bath used for crude electrodeposition and the chloride bath used for refined electrodeposition contained 30 mol % or more of magnesium chloride. . Therefore, it is presumed that high-purity titanium metal can be produced by using such a titanium metal electrodeposit.
- Example 1 the chloride bath used in crude electrodeposition and the chloride bath used in refined electrodeposition contained 100 mol% magnesium chloride, so that It is speculated that the aluminum content and oxygen content could be reduced more reliably. In addition, it is presumed that the aluminum content and the oxygen content in the metal titanium electrodeposit TP could be more reliably reduced by performing the refinement electrodeposition multiple times in Example 6. On the other hand, in Comparative Examples 1 to 3, neither the chloride bath used for crude electrodeposition nor the chloride bath used for refined electrodeposition contained 30 mol % or more of magnesium chloride. Therefore, in Comparative Examples 1 to 3, it is presumed that the aluminum content could not be reduced satisfactorily.
- a method for producing metallic titanium comprising a refining step of refining a TiAlO conductive material containing titanium, aluminum, and oxygen,
- the refining step includes a crude electrodeposition step of obtaining a titanium-containing electrodeposit by performing molten salt electrolysis using an electrode containing the TiAlO conductive material in a chloride bath; After the rough electrodeposition step, one or more refinement electrodeposition steps of performing molten salt electrolysis using an electrode containing the titanium-containing electrodeposit in a chloride bath,
- a method for producing metallic titanium wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refined electrodeposition step contains 30 mol % or more of magnesium chloride.
- a metal titanium electrodeposit A metal titanium electrodeposit having an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less.
- Nitrogen content is 0.001% by mass or more and 0.03% by mass or less
- carbon content is 0.0004% by mass or more and 0.01% by mass or less
- iron content is 0.010% by mass or less wherein the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, the chromium content is 0.005% by mass or less, and the silicon content is 0.001% by mass % or less, a manganese content of 0.05% by mass or less, and a tin content of 0.01% by mass or less, the metal titanium electrodeposit according to [10].
Abstract
Provided is a metal titanium production method for producing metal titanium through molten salt electrolysis by using a conductive material containing titanium, aluminum, and oxygen. In this metal titanium production method, a refinement process comprises: a crude electrodeposition step for obtaining a titanium-containing electrodeposit TC by performing, in a chloride bath Bf, molten salt electrolysis using an electrode that contains a TiAlO conductive material; and at least one round of a refined electrodeposition step for performing, in a chloride bath Bf, molten salt electrolysis using an electrode that contains a titanium-containing electrodeposit TC. Regarding the chloride bath Bf used in the crude electrodeposition step and the chloride bath Bf used in the refined electrodeposition step, at least one of the chloride baths Bf contains 30 mol% or more of magnesium chloride.
Description
本発明は、金属チタンの製造方法及び金属チタン電析物に関する。
The present invention relates to a method for producing metallic titanium and a metallic titanium electrodeposit.
一般的に、金属チタンの製造はクロール法により実施されている。しかしながら、当該製造は多くの工程が関与する。
In general, the production of titanium metal is carried out by the Kroll method. However, the production involves many steps.
ところで、従来から、主にチタン合金を溶融塩電解で製造する技術が知られている。例えば、特許文献１には、チタン鉱石とアルミニウムとを含む原料を加熱処理し、得られた素材に対してその後溶融塩電解することでチタン合金を製造する方法が開示されている。
By the way, conventionally, a technique for manufacturing titanium alloys mainly by molten salt electrolysis has been known. For example, Patent Literature 1 discloses a method of producing a titanium alloy by heat-treating a raw material containing titanium ore and aluminum and then subjecting the obtained raw material to molten salt electrolysis.
上記特許文献１に記載の製造方法においては、塩化ナトリウム及び塩化カリウムからなる塩化物浴を用いてチタン合金の精錬を行っている。この精錬では、所定のアルミニウム含有量及び酸素含有量の精錬チタン生産物が得られている（特許文献１の表３参照）。そのような精錬チタン生産物は少なくともアルミニウム含有量が多いため、アルミニウムを含有するチタン合金製品の原料とはなるものの、その他のチタン合金製品や金属チタン製品の製造には不適切である。
In the manufacturing method described in Patent Document 1 above, a chloride bath composed of sodium chloride and potassium chloride is used to refine the titanium alloy. In this refining, a refined titanium product with a predetermined aluminum content and oxygen content is obtained (see Table 3 of Patent Document 1). Such refined titanium products have at least a high aluminum content, which makes them unsuitable for the production of other titanium alloy products and titanium metal products, although they can be used as raw materials for aluminum-containing titanium alloy products.
そこで、本発明は一実施形態において、チタンと、アルミニウムと、酸素およびその他不純物とを含む導電材を使用し、溶融塩電解で金属チタンを製造する方法を提供することを目的とする。
Therefore, in one embodiment, an object of the present invention is to provide a method for producing metallic titanium by molten salt electrolysis using a conductive material containing titanium, aluminum, oxygen and other impurities.
本発明者等は、例えば特許文献１に開示の発明のようにチタン合金を得る溶融塩電解により不純物含有量（特に、酸素含有量）を低減するべく種々検討を行ったところ、意外にも、溶融塩電解時に用いる塩化物浴の組成によっては酸素含有量のみでなくアルミニウム含有量も低減できるという知見を得るに至った。
The inventors of the present invention conducted various studies to reduce the impurity content (especially the oxygen content) by molten salt electrolysis to obtain a titanium alloy as disclosed in Patent Document 1, for example. It has been found that not only the oxygen content but also the aluminum content can be reduced depending on the composition of the chloride bath used in the molten salt electrolysis.
例えば、溶融塩電解は金属や合金の精製を目的として実施されることがある。チタン母合金の組成を維持しながら酸素含有量を低減させることを鋭意検討した結果、所定量の塩化マグネシウムを含有する塩化物浴を使用して溶融塩電解を実施した場合、酸素やアルミニウム以外の不純物含有量のみでなくアルミニウム含有量も低減できることを見出した。他方、例えば上記特許文献１に記載の製造方法のように塩化ナトリウムと塩化カリウムからなる塩化物浴で溶融塩電解を実施した場合、アルミニウム含有量を十分に低減させることができない。
For example, molten salt electrolysis is sometimes carried out for the purpose of refining metals and alloys. As a result of intensive studies on how to reduce the oxygen content while maintaining the composition of the titanium master alloy, it was found that when molten salt electrolysis was performed using a chloride bath containing a predetermined amount of magnesium chloride, oxygen and aluminum other than It has been found that not only the impurity content but also the aluminum content can be reduced. On the other hand, when molten salt electrolysis is performed in a chloride bath containing sodium chloride and potassium chloride, as in the production method described in Patent Document 1, the aluminum content cannot be sufficiently reduced.
これにより、例えばクロール法を実施せずにチタン鉱石から金属チタンを製造することも可能になる。また、この金属チタンを使用して、アルミニウムを含まないチタン合金製品を製造することも可能になる。
This makes it possible, for example, to produce metallic titanium from titanium ore without implementing the Kroll method. It also becomes possible to use this metallic titanium to produce titanium alloy products that do not contain aluminum.
すなわち、本発明は一側面において、チタンと、アルミニウムと、酸素とを含むＴｉＡｌＯ導電材を精錬する精錬工程を含む金属チタンの製造方法であって、前記精錬工程は、塩化物浴で前記ＴｉＡｌＯ導電材を含む電極を用いて溶融塩電解することでチタン含有電析物を得る粗電析ステップと、該粗電析ステップ後、塩化物浴で前記チタン含有電析物を含む電極を用いて溶融塩電解する１回以上の精製電析ステップとを有し、前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムを含有する、金属チタンの製造方法である。
That is, in one aspect of the present invention, there is provided a method for producing titanium metal, including a refining step of refining a TiAlO conductive material containing titanium, aluminum, and oxygen, wherein the refining step includes the TiAlO conductive material in a chloride bath. A crude electrodeposition step of obtaining a titanium-containing electrodeposit by performing molten salt electrolysis using an electrode containing a material, and after the crude electrodeposition step, melting using the electrode containing the titanium-containing electrodeposit in a chloride bath and one or more refinement electrodeposition steps of salt electrolysis, wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step is 30 mol. % or more of magnesium chloride, a method for producing metallic titanium.
本発明に係る金属チタンの製造方法の一実施形態において、前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムを含有する。
In one embodiment of the method for producing metallic titanium according to the present invention, at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refined electrodeposition step contains 50 mol % of the chloride bath. Contains more than magnesium chloride.
本発明に係る金属チタンの製造方法の一実施形態において、前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する。
In one embodiment of the method for producing metallic titanium according to the present invention, the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refined electrodeposition step are magnesium chloride containing 30 mol % or more of magnesium chloride. respectively.
本発明に係る金属チタンの製造方法の一実施形態において、前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する。
In one embodiment of the method for producing metallic titanium according to the present invention, the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refined electrodeposition step are magnesium chloride containing 50 mol % or more of magnesium chloride. respectively.
本発明に係る金属チタンの製造方法の一実施形態において、前記精錬工程前に、酸化チタンを含むチタン鉱石と、アルミニウムと、分離剤とを含む化学ブレンドを加熱処理して前記ＴｉＡｌＯ導電材を得る抽出工程を更に含む。
In one embodiment of the method for producing metallic titanium according to the present invention, the TiAlO conductive material is obtained by heat-treating a chemical blend containing a titanium ore containing titanium oxide, aluminum, and a separating agent before the refining step. Further includes an extraction step.
本発明に係る金属チタンの製造方法の一実施形態において、前記化学ブレンドに含まれる酸化チタンとアルミニウムと分離剤とのモル比は、３：４～７：２～６である。
In one embodiment of the method for producing metallic titanium according to the present invention, the molar ratio of titanium oxide, aluminum and separating agent contained in the chemical blend is 3:4-7:2-6.
本発明に係る金属チタンの製造方法の一実施形態において、前記分離剤が、フッ化カルシウム、酸化カルシウム及びフッ化ナトリウムから選ばれる１種以上を含有する。
In one embodiment of the method for producing metallic titanium according to the present invention, the separating agent contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride.
本発明に係る金属チタンの製造方法の一実施形態において、前記金属チタン中の、アルミニウム含有量が１００質量ｐｐｍ以下であり、酸素含有量が５００質量ｐｐｍ以下である。
In one embodiment of the method for producing metallic titanium according to the present invention, the metallic titanium has an aluminum content of 100 mass ppm or less and an oxygen content of 500 mass ppm or less.
本発明に係る金属チタンの製造方法の一実施形態において、前記金属チタン中の、窒素含有量が０．０３質量％以下であり、炭素含有量が０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である。
In one embodiment of the method for producing metallic titanium according to the present invention, the metallic titanium has a nitrogen content of 0.03% by mass or less, a carbon content of 0.01% by mass or less, and an iron content of is 0.010% by mass or less, the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, the chromium content is 0.005% by mass or less, and silicon The content is 0.001% by mass or less, the manganese content is 0.05% by mass or less, and the tin content is 0.01% by mass or less.
また、別の側面において、金属チタン電析物であって、アルミニウム含有量が５質量ｐｐｍ以上かつ１００質量ｐｐｍ以下であり、且つ酸素含有量が１００質量ｐｐｍ以上かつ５００質量ｐｐｍ以下である、金属チタン電析物である。
In another aspect, a metal titanium electrodeposit having an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less It is a titanium electrodeposit.
本発明に係る金属チタン電析物の一実施形態において、窒素含有量が０．００１質量％以上かつ０．０３質量％以下であり、炭素含有量が０．０００４質量％以上かつ０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である。
In one embodiment of the metal titanium electrodeposit according to the present invention, the nitrogen content is 0.001% by mass or more and 0.03% by mass or less, and the carbon content is 0.0004% by mass or more and 0.01% by mass. % or less, the iron content is 0.010 mass % or less, the magnesium content is 0.05 mass % or less, the nickel content is 0.01 mass % or less, and the chromium content is 0.01 mass % or less. 005% by mass or less, a silicon content of 0.001% by mass or less, a manganese content of 0.05% by mass or less, and a tin content of 0.01% by mass or less.
本発明の一実施形態によれば、チタンと、アルミニウムと、酸素とを含む導電材を使用し、溶融塩電解で金属チタンを製造する方法を提供することができる。
According to one embodiment of the present invention, it is possible to provide a method for producing metallic titanium by molten salt electrolysis using a conductive material containing titanium, aluminum, and oxygen.
本発明は以下に説明する各実施形態に限定されるものではなく、その要旨を逸脱しない範囲で構成要素を変形して具体化できる。また、各実施形態に開示されている複数の構成要素の適宜な組み合わせにより、種々の発明を形成できる。例えば、実施形態に示される全構成要素からいくつかの構成要素を削除して発明を形成してもよい。なお、図面では、発明に含まれる実施形態等の理解を助けるため概略として示す部材もあり、図示された大きさや位置関係等については必ずしも正確でない場合がある。
本明細書において、「金属チタン電析物」は、外観目視で概略粒状であり、ミクロな形状を観察すると樹枝状や多面体状の微細粒が連なった立体的形状を有することが多い（図９（Ｂ）参照）。 The present invention is not limited to the embodiments described below, and can be embodied by modifying the constituent elements without departing from the spirit of the present invention. Moreover, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in each embodiment. For example, the invention may be formed by omitting some components from all the components shown in the embodiments. In addition, in the drawings, some members are shown schematically in order to facilitate understanding of the embodiments included in the invention, and the illustrated sizes, positional relationships, etc. may not necessarily be accurate.
In this specification, the "metallic titanium electrodeposit" is generally granular in appearance, and when microscopically observed, it often has a three-dimensional shape in which dendritic or polyhedral fine grains are linked (Fig. 9). (B)).
本明細書において、「金属チタン電析物」は、外観目視で概略粒状であり、ミクロな形状を観察すると樹枝状や多面体状の微細粒が連なった立体的形状を有することが多い（図９（Ｂ）参照）。 The present invention is not limited to the embodiments described below, and can be embodied by modifying the constituent elements without departing from the spirit of the present invention. Moreover, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in each embodiment. For example, the invention may be formed by omitting some components from all the components shown in the embodiments. In addition, in the drawings, some members are shown schematically in order to facilitate understanding of the embodiments included in the invention, and the illustrated sizes, positional relationships, etc. may not necessarily be accurate.
In this specification, the "metallic titanium electrodeposit" is generally granular in appearance, and when microscopically observed, it often has a three-dimensional shape in which dendritic or polyhedral fine grains are linked (Fig. 9). (B)).
［１．金属チタンの製造方法］
本発明に係る金属チタンの製造方法の一実施形態においては、不純物含有量を低減する精錬工程を含む。なお、精錬工程前に、抽出工程を更に含んでよい。
以下、各工程の一例を説明する。 [1. Method for producing metallic titanium]
One embodiment of the method for producing titanium metal according to the present invention includes a refining step to reduce the impurity content. Note that an extraction step may be further included before the refining step.
An example of each step will be described below.
本発明に係る金属チタンの製造方法の一実施形態においては、不純物含有量を低減する精錬工程を含む。なお、精錬工程前に、抽出工程を更に含んでよい。
以下、各工程の一例を説明する。 [1. Method for producing metallic titanium]
One embodiment of the method for producing titanium metal according to the present invention includes a refining step to reduce the impurity content. Note that an extraction step may be further included before the refining step.
An example of each step will be described below.
＜抽出工程＞
抽出工程は、例えば酸化チタンを含有するチタン鉱石と、アルミニウムと、分離剤とを含む化学ブレンドを加熱処理してＴｉＡｌＯ導電材を得る。当該加熱処理により以下の反応が利用されると考えられる。すなわち、当該抽出工程においては、アルミニウムで金属酸化物である酸化チタンの還元を行うテルミット反応を利用している。化学ブレンドとは、ＴｉＡｌＯ導電材を得るための原料混合物である。チタン鉱石中の酸化チタンは、導電性が低いことから溶融塩電解に適さない。そのため、チタン鉱石を用いて当該抽出工程を行い、ＴｉＡｌＯ導電材を作製することができる。ＴｉＡｌＯ導電材は比較的高い導電性を有するので、金属チタンを製造するための後述する精錬工程に用いることができる。なお、当該抽出工程においては、上記特許文献１（特表２０１５－５０７６９６号公報）等に記載された公知の方法を適宜参照してＴｉＡｌＯ導電材を作製すればよい。 <Extraction process>
The extraction step heat-treats a chemical blend containing, for example, a titanium ore containing titanium oxide, aluminum, and a separating agent to obtain a TiAlO conductive material. It is considered that the following reactions are utilized by the heat treatment. That is, in the extraction step, a thermite reaction is used to reduce titanium oxide, which is a metal oxide, with aluminum. A chemical blend is a raw material mixture for obtaining a TiAlO conductive material. Titanium oxide in titanium ore is not suitable for molten salt electrolysis due to its low electrical conductivity. Therefore, the TiAlO conductive material can be produced by performing the extraction step using titanium ore. Since the TiAlO conductive material has a relatively high electrical conductivity, it can be used in the later-described refining process for producing metallic titanium. In the extraction step, the TiAlO conductive material may be produced by appropriately referring to the known method described in Patent Document 1 (Japanese Patent Publication No. 2015-507696) or the like.
抽出工程は、例えば酸化チタンを含有するチタン鉱石と、アルミニウムと、分離剤とを含む化学ブレンドを加熱処理してＴｉＡｌＯ導電材を得る。当該加熱処理により以下の反応が利用されると考えられる。すなわち、当該抽出工程においては、アルミニウムで金属酸化物である酸化チタンの還元を行うテルミット反応を利用している。化学ブレンドとは、ＴｉＡｌＯ導電材を得るための原料混合物である。チタン鉱石中の酸化チタンは、導電性が低いことから溶融塩電解に適さない。そのため、チタン鉱石を用いて当該抽出工程を行い、ＴｉＡｌＯ導電材を作製することができる。ＴｉＡｌＯ導電材は比較的高い導電性を有するので、金属チタンを製造するための後述する精錬工程に用いることができる。なお、当該抽出工程においては、上記特許文献１（特表２０１５－５０７６９６号公報）等に記載された公知の方法を適宜参照してＴｉＡｌＯ導電材を作製すればよい。 <Extraction process>
The extraction step heat-treats a chemical blend containing, for example, a titanium ore containing titanium oxide, aluminum, and a separating agent to obtain a TiAlO conductive material. It is considered that the following reactions are utilized by the heat treatment. That is, in the extraction step, a thermite reaction is used to reduce titanium oxide, which is a metal oxide, with aluminum. A chemical blend is a raw material mixture for obtaining a TiAlO conductive material. Titanium oxide in titanium ore is not suitable for molten salt electrolysis due to its low electrical conductivity. Therefore, the TiAlO conductive material can be produced by performing the extraction step using titanium ore. Since the TiAlO conductive material has a relatively high electrical conductivity, it can be used in the later-described refining process for producing metallic titanium. In the extraction step, the TiAlO conductive material may be produced by appropriately referring to the known method described in Patent Document 1 (Japanese Patent Publication No. 2015-507696) or the like.
（チタン鉱石）
チタン鉱石中の酸化チタン含有量は限定されないが、例えば５０質量％以上であり、例えば８０質量％以上であり、例えば９０質量％以上である。なお、チタン鉱石は、採掘により得られたもののみならず、いわゆるアップグレード処理されたものも含まれる。チタン鉱石における酸化チタン含有量が少ない場合はリーチング等適宜の処理を行って酸化チタン含有量を向上させる（すなわち、アップグレード処理する）ことがある。 (titanium ore)
The content of titanium oxide in the titanium ore is not limited, but is, for example, 50% by mass or more, for example 80% by mass or more, for example 90% by mass or more. Titanium ore includes not only those obtained by mining, but also those that have been so-called upgraded. When the titanium oxide content in the titanium ore is low, appropriate treatment such as leaching may be performed to improve the titanium oxide content (that is, upgrade treatment).
チタン鉱石中の酸化チタン含有量は限定されないが、例えば５０質量％以上であり、例えば８０質量％以上であり、例えば９０質量％以上である。なお、チタン鉱石は、採掘により得られたもののみならず、いわゆるアップグレード処理されたものも含まれる。チタン鉱石における酸化チタン含有量が少ない場合はリーチング等適宜の処理を行って酸化チタン含有量を向上させる（すなわち、アップグレード処理する）ことがある。 (titanium ore)
The content of titanium oxide in the titanium ore is not limited, but is, for example, 50% by mass or more, for example 80% by mass or more, for example 90% by mass or more. Titanium ore includes not only those obtained by mining, but also those that have been so-called upgraded. When the titanium oxide content in the titanium ore is low, appropriate treatment such as leaching may be performed to improve the titanium oxide content (that is, upgrade treatment).
（分離剤）
分離剤は、抽出工程においてＴｉＡｌＯ導電材と副生物であるスラグとを分離する目的で化学ブレンドに混合される。このような機能を有するものを分離剤として使用可能であるが、分離剤はフッ化カルシウム、酸化カルシウム及びフッ化ナトリウムから選ばれる１種以上を含むことが好ましく、その中でも加熱処理中の反応における形態の観点から、フッ化カルシウムを含有することがより好ましい。よって、分離剤はフッ化カルシウム単独であってもよい。 (Separating agent)
Separating agents are incorporated into the chemical blend for the purpose of separating TiAlO conductors and slag by-products in the extraction process. Those having such a function can be used as a separating agent, but the separating agent preferably contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride. From the viewpoint of morphology, it is more preferable to contain calcium fluoride. Therefore, the separating agent may be calcium fluoride alone.
分離剤は、抽出工程においてＴｉＡｌＯ導電材と副生物であるスラグとを分離する目的で化学ブレンドに混合される。このような機能を有するものを分離剤として使用可能であるが、分離剤はフッ化カルシウム、酸化カルシウム及びフッ化ナトリウムから選ばれる１種以上を含むことが好ましく、その中でも加熱処理中の反応における形態の観点から、フッ化カルシウムを含有することがより好ましい。よって、分離剤はフッ化カルシウム単独であってもよい。 (Separating agent)
Separating agents are incorporated into the chemical blend for the purpose of separating TiAlO conductors and slag by-products in the extraction process. Those having such a function can be used as a separating agent, but the separating agent preferably contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride. From the viewpoint of morphology, it is more preferable to contain calcium fluoride. Therefore, the separating agent may be calcium fluoride alone.
（化学ブレンド組成）
上記化学ブレンドを作製するために、チタン鉱石とアルミニウムと分離剤との投入量が、モル比で例えば酸化チタン：アルミニウム：分離剤＝３：４～７：２～６になるように調整する。これにより、化学ブレンドに含まれる酸化チタンとアルミニウムと分離剤とのモル比は、３：４～７：２～６である。 (Chemical blend composition)
In order to prepare the above chemical blend, the amounts of titanium ore, aluminum and separating agent are adjusted so that the molar ratio of titanium oxide:aluminum:separating agent=3:4-7:2-6, for example. Thus, the molar ratio of titanium oxide to aluminum to separating agent in the chemical blend is 3:4-7:2-6.
上記化学ブレンドを作製するために、チタン鉱石とアルミニウムと分離剤との投入量が、モル比で例えば酸化チタン：アルミニウム：分離剤＝３：４～７：２～６になるように調整する。これにより、化学ブレンドに含まれる酸化チタンとアルミニウムと分離剤とのモル比は、３：４～７：２～６である。 (Chemical blend composition)
In order to prepare the above chemical blend, the amounts of titanium ore, aluminum and separating agent are adjusted so that the molar ratio of titanium oxide:aluminum:separating agent=3:4-7:2-6, for example. Thus, the molar ratio of titanium oxide to aluminum to separating agent in the chemical blend is 3:4-7:2-6.
（加熱処理条件）
加熱処理条件について、不活性ガス（例えばＡｒ）雰囲気下、容器内部の温度が例えば１５００℃以上かつ１８００℃以下である。また、容器の内壁の材質としては、耐熱性等の観点から、カーボンやセラミック等が挙げられる。 (Heat treatment conditions)
Regarding the heat treatment conditions, the temperature inside the container is, for example, 1500° C. or higher and 1800° C. or lower in an inert gas (eg, Ar) atmosphere. From the viewpoint of heat resistance and the like, examples of materials for the inner wall of the container include carbon, ceramics, and the like.
加熱処理条件について、不活性ガス（例えばＡｒ）雰囲気下、容器内部の温度が例えば１５００℃以上かつ１８００℃以下である。また、容器の内壁の材質としては、耐熱性等の観点から、カーボンやセラミック等が挙げられる。 (Heat treatment conditions)
Regarding the heat treatment conditions, the temperature inside the container is, for example, 1500° C. or higher and 1800° C. or lower in an inert gas (eg, Ar) atmosphere. From the viewpoint of heat resistance and the like, examples of materials for the inner wall of the container include carbon, ceramics, and the like.
（ＴｉＡｌＯ導電材）
抽出工程で得られたＴｉＡｌＯ導電材は、例えばチタン含有量が５０質量％以上かつ８０質量％以下であり、アルミニウム含有量が３質量％以上かつ４０質量％以下であり、酸素含有量が０．２質量％以上かつ４０質量％以下である。
なお、上記チタン含有量は下限値として例えば６０質量％以上である。
また、上記アルミニウム含有量は下限値として例えば５質量％以上である。一方、上記アルミニウム含有量は上限値として例えば３０質量％以下、例えば２０質量％以下である。
また、上記酸素含有量は下限値として例えば３質量％以上、例えば５質量％以上、また例えば８質量％以上である。一方、上記酸素含有量は上限値として例えば３０質量％以下、例えば２０質量％以下である。
本発明においてはアルミニウム含有量及び酸素含有量が高いＴｉＡｌＯ導電材であっても、そのような不純物含有量が少なく純度が高い金属チタンを得ることができる。
なお、ＴｉＡｌＯ導電材の各成分の不純物含有量の測定方法については、本明細書の実施例に記載の測定方法を採用可能である。 (TiAlO conductive material)
The TiAlO conductive material obtained in the extraction step has, for example, a titanium content of 50% by mass or more and 80% by mass or less, an aluminum content of 3% by mass or more and 40% by mass or less, and an oxygen content of 0.5% by mass or more. It is 2% by mass or more and 40% by mass or less.
In addition, the said titanium content is 60 mass % or more as a lower limit.
Moreover, the said aluminum content is 5 mass % or more as a lower limit. On the other hand, the upper limit of the aluminum content is, for example, 30% by mass or less, for example, 20% by mass or less.
The lower limit of the oxygen content is, for example, 3% by mass or more, 5% by mass or more, or 8% by mass or more. On the other hand, the upper limit of the oxygen content is, for example, 30% by mass or less, for example, 20% by mass or less.
In the present invention, even with a TiAlO conductive material having a high aluminum content and a high oxygen content, it is possible to obtain metallic titanium with a low impurity content and high purity.
As for the method for measuring the impurity content of each component of the TiAlO conductive material, the measuring method described in the examples of this specification can be adopted.
抽出工程で得られたＴｉＡｌＯ導電材は、例えばチタン含有量が５０質量％以上かつ８０質量％以下であり、アルミニウム含有量が３質量％以上かつ４０質量％以下であり、酸素含有量が０．２質量％以上かつ４０質量％以下である。
なお、上記チタン含有量は下限値として例えば６０質量％以上である。
また、上記アルミニウム含有量は下限値として例えば５質量％以上である。一方、上記アルミニウム含有量は上限値として例えば３０質量％以下、例えば２０質量％以下である。
また、上記酸素含有量は下限値として例えば３質量％以上、例えば５質量％以上、また例えば８質量％以上である。一方、上記酸素含有量は上限値として例えば３０質量％以下、例えば２０質量％以下である。
本発明においてはアルミニウム含有量及び酸素含有量が高いＴｉＡｌＯ導電材であっても、そのような不純物含有量が少なく純度が高い金属チタンを得ることができる。
なお、ＴｉＡｌＯ導電材の各成分の不純物含有量の測定方法については、本明細書の実施例に記載の測定方法を採用可能である。 (TiAlO conductive material)
The TiAlO conductive material obtained in the extraction step has, for example, a titanium content of 50% by mass or more and 80% by mass or less, an aluminum content of 3% by mass or more and 40% by mass or less, and an oxygen content of 0.5% by mass or more. It is 2% by mass or more and 40% by mass or less.
In addition, the said titanium content is 60 mass % or more as a lower limit.
Moreover, the said aluminum content is 5 mass % or more as a lower limit. On the other hand, the upper limit of the aluminum content is, for example, 30% by mass or less, for example, 20% by mass or less.
The lower limit of the oxygen content is, for example, 3% by mass or more, 5% by mass or more, or 8% by mass or more. On the other hand, the upper limit of the oxygen content is, for example, 30% by mass or less, for example, 20% by mass or less.
In the present invention, even with a TiAlO conductive material having a high aluminum content and a high oxygen content, it is possible to obtain metallic titanium with a low impurity content and high purity.
As for the method for measuring the impurity content of each component of the TiAlO conductive material, the measuring method described in the examples of this specification can be adopted.
（比抵抗）
当該ＴｉＡｌＯ導電材の比抵抗は、金属チタンを製造するための後述する精錬工程において溶融塩電解を効率良く実施する観点から、上限値として例えば１×１０-4Ω・ｍ以下であってよい。また、当該ＴｉＡｌＯ導電材は適度に通電可能であればよいので、比抵抗の下限値は例えば１×１０-8Ω・ｍ以上であってよい。上記比抵抗は、下限値として例えば１×１０-7Ω・ｍ以上であってよく、例えば５×１０-7Ω・ｍ以上であってよい。
なお、ＴｉＡｌＯ導電材の比抵抗の測定方法については、本明細書の実施例に記載の測定方法を採用可能である。 (Resistivity)
The upper limit of the specific resistance of the TiAlO conductive material may be, for example, 1×10 −4 Ω·m or less from the viewpoint of efficiently performing molten salt electrolysis in the refining process described later for producing metallic titanium. Moreover, since the TiAlO conductive material should be moderately conductive, the lower limit of the specific resistance may be, for example, 1×10 −8 Ω·m or more. The lower limit of the specific resistance may be, for example, 1×10 −7 Ω·m or more, for example, 5×10 −7 Ω·m or more.
As for the method for measuring the resistivity of the TiAlO conductive material, the measuring method described in the examples of this specification can be adopted.
当該ＴｉＡｌＯ導電材の比抵抗は、金属チタンを製造するための後述する精錬工程において溶融塩電解を効率良く実施する観点から、上限値として例えば１×１０-4Ω・ｍ以下であってよい。また、当該ＴｉＡｌＯ導電材は適度に通電可能であればよいので、比抵抗の下限値は例えば１×１０-8Ω・ｍ以上であってよい。上記比抵抗は、下限値として例えば１×１０-7Ω・ｍ以上であってよく、例えば５×１０-7Ω・ｍ以上であってよい。
なお、ＴｉＡｌＯ導電材の比抵抗の測定方法については、本明細書の実施例に記載の測定方法を採用可能である。 (Resistivity)
The upper limit of the specific resistance of the TiAlO conductive material may be, for example, 1×10 −4 Ω·m or less from the viewpoint of efficiently performing molten salt electrolysis in the refining process described later for producing metallic titanium. Moreover, since the TiAlO conductive material should be moderately conductive, the lower limit of the specific resistance may be, for example, 1×10 −8 Ω·m or more. The lower limit of the specific resistance may be, for example, 1×10 −7 Ω·m or more, for example, 5×10 −7 Ω·m or more.
As for the method for measuring the resistivity of the TiAlO conductive material, the measuring method described in the examples of this specification can be adopted.
＜精錬工程＞
精錬工程は、不純物含有量を低減するため、電解装置を用いてＴｉＡｌＯ導電材を精錬する。すなわち、当該精錬工程では、ＴｉＡｌＯ導電材中の主にアルミニウムおよび酸素、さらにはその他の鉱石由来元素等の含有量を低減することで、純度の高い金属チタンを得る。当該精錬工程は、粗電析ステップと、粗電析ステップで得られたチタン含有電析物を含む電極を用いて溶融塩電解する１回以上の精製電析ステップとを有する。 <Smelting process>
The refining process uses an electrolytic device to refine the TiAlO conductive material in order to reduce the impurity content. That is, in the refining process, metallic titanium with high purity is obtained by reducing the contents of mainly aluminum and oxygen in the TiAlO conductive material, as well as other ore-derived elements. The refining process includes a crude electrodeposition step and one or more refinement electrodeposition steps in which molten salt electrolysis is performed using an electrode containing the titanium-containing electrodeposit obtained in the crude electrodeposition step.
精錬工程は、不純物含有量を低減するため、電解装置を用いてＴｉＡｌＯ導電材を精錬する。すなわち、当該精錬工程では、ＴｉＡｌＯ導電材中の主にアルミニウムおよび酸素、さらにはその他の鉱石由来元素等の含有量を低減することで、純度の高い金属チタンを得る。当該精錬工程は、粗電析ステップと、粗電析ステップで得られたチタン含有電析物を含む電極を用いて溶融塩電解する１回以上の精製電析ステップとを有する。 <Smelting process>
The refining process uses an electrolytic device to refine the TiAlO conductive material in order to reduce the impurity content. That is, in the refining process, metallic titanium with high purity is obtained by reducing the contents of mainly aluminum and oxygen in the TiAlO conductive material, as well as other ore-derived elements. The refining process includes a crude electrodeposition step and one or more refinement electrodeposition steps in which molten salt electrolysis is performed using an electrode containing the titanium-containing electrodeposit obtained in the crude electrodeposition step.
（電解装置）
一実施形態においては、種々の電解装置を用いることができる。図１（Ａ）に示す電解装置１００の一例はバッチ式であり、塩化物浴Ｂｆを貯留する密閉容器状の電解槽１１０と、塩化物浴Ｂｆに浸漬させて配置する陽極１２０及び陰極１３０を含む電極と、陽極１２０及び陰極１３０に導電線を介して接続されて、該陽極１２０及び該陰極１３０に通電する電源（不図示）とを備えるものが挙げられる。図示は省略するが、電解装置１００は陽極および陰極を設置し、或いは、取り出す等のために通常は開閉可能の構造である。また、図示は省略するが、塩化物浴Ｂｆ上の空間を不活性ガス雰囲気とするために、電解装置１００はガスの給排気を行う開口を備える。また、図示は省略するが、電解装置１００は適宜の箇所にヒータを備え、加熱により塩化物浴Ｂｆの溶融状態を維持できる。なお、電解槽１１０の材質は耐熱性及び耐腐食性を有していれば特に限定されるものではない。また、電極には、複極を更に含むこともある。 (Electrolyzer)
In one embodiment, various electrolytic devices can be used. An example of theelectrolysis apparatus 100 shown in FIG. 1A is of a batch type, and includes an electrolytic bath 110 in the form of a sealed container that stores a chloride bath Bf, and an anode 120 and a cathode 130 that are immersed in the chloride bath Bf. and a power source (not shown) connected to the anode 120 and the cathode 130 via conductive wires to energize the anode 120 and the cathode 130 . Although illustration is omitted, the electrolytic device 100 usually has a structure that can be opened and closed in order to install or take out the anode and cathode. Although not shown, the electrolysis apparatus 100 has an opening for gas supply and exhaust in order to make the space above the chloride bath Bf an inert gas atmosphere. Although not shown, the electrolysis apparatus 100 is provided with a heater at an appropriate location so that the chloride bath Bf can be maintained in a molten state by heating. The material of the electrolytic bath 110 is not particularly limited as long as it has heat resistance and corrosion resistance. Also, the electrodes may further include a bipolar electrode.
一実施形態においては、種々の電解装置を用いることができる。図１（Ａ）に示す電解装置１００の一例はバッチ式であり、塩化物浴Ｂｆを貯留する密閉容器状の電解槽１１０と、塩化物浴Ｂｆに浸漬させて配置する陽極１２０及び陰極１３０を含む電極と、陽極１２０及び陰極１３０に導電線を介して接続されて、該陽極１２０及び該陰極１３０に通電する電源（不図示）とを備えるものが挙げられる。図示は省略するが、電解装置１００は陽極および陰極を設置し、或いは、取り出す等のために通常は開閉可能の構造である。また、図示は省略するが、塩化物浴Ｂｆ上の空間を不活性ガス雰囲気とするために、電解装置１００はガスの給排気を行う開口を備える。また、図示は省略するが、電解装置１００は適宜の箇所にヒータを備え、加熱により塩化物浴Ｂｆの溶融状態を維持できる。なお、電解槽１１０の材質は耐熱性及び耐腐食性を有していれば特に限定されるものではない。また、電極には、複極を更に含むこともある。 (Electrolyzer)
In one embodiment, various electrolytic devices can be used. An example of the
（溶融塩）
塩化物浴を構成する溶融塩は、アルカリ金属塩化物及びアルカリ土類金属塩化物を例えば７０ｍｏｌ％以上、例えば８０ｍｏｌ％以上、例えば９０ｍｏｌ％以上含有することがある。なお、本発明において、塩化物浴に替えてフッ化物浴、臭化物浴及びヨウ化物浴を使用しない理由としては、高腐食性、高環境負荷及び高コスト等が挙げられる。
粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴Ｂｆは、酸素含有量のみならずアルミニウム含有量をも低減して金属チタンを製造する観点から、３０ｍｏｌ％以上の塩化マグネシウムを含有する。塩化マグネシウム含有量が多い塩化物浴を使用することでアルミニウム含有量の低減効果が増大しうる。なお、例えば、粗電析ステップで使用される塩化物浴のみが上記所定量の塩化マグネシウムを含有してよく、又は１回以上実施される精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴のみが上記所定量の塩化マグネシウムを含有してもよい。また、粗電析ステップで使用される塩化物浴及び１回以上実施される精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴のみが上記所定量の塩化マグネシウムを含有してもよい。
また、電析物のアルミニウム含有量及び酸素含有量をより確実に低減する観点から、粗電析ステップで使用される塩化物浴及び１回以上実施される精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が、それぞれ上記所量の塩化マグネシウムを含有してもよい。
上記の所定量塩化マグネシウムを含有する塩化物浴は電析物中のアルミニウム含有量および酸素含有量の低減に有効であり、下限値として、当該塩化マグネシウム含有量は、好ましくは３０ｍｏｌ％以上であり、より好ましくは５０ｍｏｌ％以上であり、更に好ましくは８０ｍｏｌ％以上であり、更に好ましくは８５ｍｏｌ％以上であり、更に好ましくは９０ｍｏｌ％以上である。なお、上記塩化物浴には、塩化リチウム（ＬｉＣｌ）、塩化ナトリウム（ＮａＣｌ）、塩化カリウム（ＫＣｌ）、塩化ルビジウム（ＲｂＣｌ）、塩化セシウム（ＣｓＣｌ）、塩化ベリリウム（ＢｅＣｌ2）、塩化カルシウム（ＣａＣｌ2）、塩化ストロンチウム（ＳｒＣｌ2）、塩化バリウム（ＢａＣｌ2）から選択される１種以上の金属塩化物を例えば７０ｍｏｌ％以下、また例えば５０ｍｏｌ％以下、また例えば２０ｍｏｌ％以下、また例えば１５ｍｏｌ％以下、また例えば１０ｍｏｌ％以下更に含有してもよい。さらに、塩化物浴中に任意成分として低級塩化チタンを含ませてよく、該低級塩化チタンとしては二塩化チタン及び三塩化チタン等が挙げられる。なお、該低級塩化チタンの含有量は、適宜調整すればよい。
上記のような塩化物は、操業温度等を考慮して、その具体的な塩の種類や含有量を適宜決定することができる。なお、上記モル基準の含有量は、ＩＣＰ発光分析及び原子吸光分析により測定する。
ここで、上記のモル基準の含有量は以下のようにして計算する。塩化物浴から採取した溶融塩のサンプルを固化させた後、そのサンプルの成分を、ＩＣＰ発光分析及び原子吸光分析することにより、塩化物浴Ｂｆ中の各金属イオンのモル基準の含有量を算出する。仮に塩化物浴中にＭｇＣｌ2、ＮａＣｌ、ＫＣｌ、ＣａＣｌ2、ＬｉＣｌ、ＴｉＣｌ2及びＴｉＣｌ3が含まれていた場合、ＮａとＫは原子吸光分析、その他はＩＣＰ発光分析により、金属イオンの含有量の合計（Ｍｍ）は、マグネシウムイオンの含有量、ナトリウムイオンの含有量、カリウムイオンの含有量、カルシウムイオンの含有量、リチウムイオンの含有量及び、チタンイオンの含有量を足し合わせて求める。塩化物浴中に含まれる各成分のモル基準の含有量は、当該各成分の金属イオンの含有量を当該金属イオンの含有量の合計（Ｍｍ）で除して百分率で表すことにより算出することができる。以上、塩化物浴に含まれる金属イオンの含有量に基づき、塩化物の含有量を求める。 (Molten salt)
The molten salt that constitutes the chloride bath may contain, for example, 70 mol % or more, such as 80 mol % or more, such as 90 mol % or more of alkali metal chlorides and alkaline earth metal chlorides. In the present invention, reasons for not using a fluoride bath, a bromide bath and an iodide bath in place of the chloride bath include high corrosiveness, high environmental load and high cost.
At least one chloride bath Bf of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step reduces not only the oxygen content but also the aluminum content to produce metallic titanium From the viewpoint of manufacturing, it contains 30 mol% or more of magnesium chloride. Using a chloride bath with a high magnesium chloride content can increase the effect of reducing the aluminum content. It should be noted that, for example, only the chloride bath used in the crude electrodeposition step may contain the predetermined amount of magnesium chloride, or at least Only one chloride bath may contain the predetermined amount of magnesium chloride. In addition, at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step which is performed one or more times contains the predetermined amount of magnesium chloride. may
In addition, from the viewpoint of more reliably reducing the aluminum content and oxygen content of the electrodeposition, the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement step performed one or more times At least one chloride bath of the baths may each contain the amount of magnesium chloride described above.
The above chloride bath containing a predetermined amount of magnesium chloride is effective in reducing the aluminum content and oxygen content in the electrodeposit, and the lower limit of the magnesium chloride content is preferably 30 mol % or more. , more preferably 50 mol % or more, still more preferably 80 mol % or more, still more preferably 85 mol % or more, still more preferably 90 mol % or more. The chloride bath contains lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsCl), beryllium chloride (BeCl 2 ), calcium chloride (CaCl 2 ) one or more metal chlorides selected from strontium chloride (SrCl 2 ) and barium chloride (BaCl 2 ), for example 70 mol% or less, for example 50 mol% or less, for example 20 mol% or less, or for example 15 mol% or less , and may further contain, for example, 10 mol % or less. Further, the chloride bath may optionally contain lower titanium chloride, such as titanium dichloride and titanium trichloride. The content of the lower titanium chloride may be appropriately adjusted.
Regarding the above chlorides, the specific salt type and content can be appropriately determined in consideration of the operating temperature and the like. The content on a molar basis is measured by ICP emission spectrometry and atomic absorption spectrometry.
Here, the content on a molar basis is calculated as follows. After solidifying a molten salt sample collected from the chloride bath, the components of the sample are subjected to ICP emission spectrometry and atomic absorption spectrometry to calculate the content of each metal ion on a molar basis in the chloride bath Bf. do. If the chloride bath contained MgCl 2 , NaCl, KCl, CaCl 2 , LiCl, TiCl 2 and TiCl 3 , the metal ion content was determined by atomic absorption spectroscopy for Na and K and ICP emission spectroscopy for the others. (Mm) is obtained by adding the content of magnesium ions, the content of sodium ions, the content of potassium ions, the content of calcium ions, the content of lithium ions, and the content of titanium ions. The molar content of each component contained in the chloride bath is calculated by dividing the metal ion content of each component by the total metal ion content (Mm) and expressing it as a percentage. can be done. As described above, the content of chloride is determined based on the content of metal ions contained in the chloride bath.
塩化物浴を構成する溶融塩は、アルカリ金属塩化物及びアルカリ土類金属塩化物を例えば７０ｍｏｌ％以上、例えば８０ｍｏｌ％以上、例えば９０ｍｏｌ％以上含有することがある。なお、本発明において、塩化物浴に替えてフッ化物浴、臭化物浴及びヨウ化物浴を使用しない理由としては、高腐食性、高環境負荷及び高コスト等が挙げられる。
粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴Ｂｆは、酸素含有量のみならずアルミニウム含有量をも低減して金属チタンを製造する観点から、３０ｍｏｌ％以上の塩化マグネシウムを含有する。塩化マグネシウム含有量が多い塩化物浴を使用することでアルミニウム含有量の低減効果が増大しうる。なお、例えば、粗電析ステップで使用される塩化物浴のみが上記所定量の塩化マグネシウムを含有してよく、又は１回以上実施される精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴のみが上記所定量の塩化マグネシウムを含有してもよい。また、粗電析ステップで使用される塩化物浴及び１回以上実施される精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴のみが上記所定量の塩化マグネシウムを含有してもよい。
また、電析物のアルミニウム含有量及び酸素含有量をより確実に低減する観点から、粗電析ステップで使用される塩化物浴及び１回以上実施される精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が、それぞれ上記所量の塩化マグネシウムを含有してもよい。
上記の所定量塩化マグネシウムを含有する塩化物浴は電析物中のアルミニウム含有量および酸素含有量の低減に有効であり、下限値として、当該塩化マグネシウム含有量は、好ましくは３０ｍｏｌ％以上であり、より好ましくは５０ｍｏｌ％以上であり、更に好ましくは８０ｍｏｌ％以上であり、更に好ましくは８５ｍｏｌ％以上であり、更に好ましくは９０ｍｏｌ％以上である。なお、上記塩化物浴には、塩化リチウム（ＬｉＣｌ）、塩化ナトリウム（ＮａＣｌ）、塩化カリウム（ＫＣｌ）、塩化ルビジウム（ＲｂＣｌ）、塩化セシウム（ＣｓＣｌ）、塩化ベリリウム（ＢｅＣｌ2）、塩化カルシウム（ＣａＣｌ2）、塩化ストロンチウム（ＳｒＣｌ2）、塩化バリウム（ＢａＣｌ2）から選択される１種以上の金属塩化物を例えば７０ｍｏｌ％以下、また例えば５０ｍｏｌ％以下、また例えば２０ｍｏｌ％以下、また例えば１５ｍｏｌ％以下、また例えば１０ｍｏｌ％以下更に含有してもよい。さらに、塩化物浴中に任意成分として低級塩化チタンを含ませてよく、該低級塩化チタンとしては二塩化チタン及び三塩化チタン等が挙げられる。なお、該低級塩化チタンの含有量は、適宜調整すればよい。
上記のような塩化物は、操業温度等を考慮して、その具体的な塩の種類や含有量を適宜決定することができる。なお、上記モル基準の含有量は、ＩＣＰ発光分析及び原子吸光分析により測定する。
ここで、上記のモル基準の含有量は以下のようにして計算する。塩化物浴から採取した溶融塩のサンプルを固化させた後、そのサンプルの成分を、ＩＣＰ発光分析及び原子吸光分析することにより、塩化物浴Ｂｆ中の各金属イオンのモル基準の含有量を算出する。仮に塩化物浴中にＭｇＣｌ2、ＮａＣｌ、ＫＣｌ、ＣａＣｌ2、ＬｉＣｌ、ＴｉＣｌ2及びＴｉＣｌ3が含まれていた場合、ＮａとＫは原子吸光分析、その他はＩＣＰ発光分析により、金属イオンの含有量の合計（Ｍｍ）は、マグネシウムイオンの含有量、ナトリウムイオンの含有量、カリウムイオンの含有量、カルシウムイオンの含有量、リチウムイオンの含有量及び、チタンイオンの含有量を足し合わせて求める。塩化物浴中に含まれる各成分のモル基準の含有量は、当該各成分の金属イオンの含有量を当該金属イオンの含有量の合計（Ｍｍ）で除して百分率で表すことにより算出することができる。以上、塩化物浴に含まれる金属イオンの含有量に基づき、塩化物の含有量を求める。 (Molten salt)
The molten salt that constitutes the chloride bath may contain, for example, 70 mol % or more, such as 80 mol % or more, such as 90 mol % or more of alkali metal chlorides and alkaline earth metal chlorides. In the present invention, reasons for not using a fluoride bath, a bromide bath and an iodide bath in place of the chloride bath include high corrosiveness, high environmental load and high cost.
At least one chloride bath Bf of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step reduces not only the oxygen content but also the aluminum content to produce metallic titanium From the viewpoint of manufacturing, it contains 30 mol% or more of magnesium chloride. Using a chloride bath with a high magnesium chloride content can increase the effect of reducing the aluminum content. It should be noted that, for example, only the chloride bath used in the crude electrodeposition step may contain the predetermined amount of magnesium chloride, or at least Only one chloride bath may contain the predetermined amount of magnesium chloride. In addition, at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step which is performed one or more times contains the predetermined amount of magnesium chloride. may
In addition, from the viewpoint of more reliably reducing the aluminum content and oxygen content of the electrodeposition, the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement step performed one or more times At least one chloride bath of the baths may each contain the amount of magnesium chloride described above.
The above chloride bath containing a predetermined amount of magnesium chloride is effective in reducing the aluminum content and oxygen content in the electrodeposit, and the lower limit of the magnesium chloride content is preferably 30 mol % or more. , more preferably 50 mol % or more, still more preferably 80 mol % or more, still more preferably 85 mol % or more, still more preferably 90 mol % or more. The chloride bath contains lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsCl), beryllium chloride (BeCl 2 ), calcium chloride (CaCl 2 ) one or more metal chlorides selected from strontium chloride (SrCl 2 ) and barium chloride (BaCl 2 ), for example 70 mol% or less, for example 50 mol% or less, for example 20 mol% or less, or for example 15 mol% or less , and may further contain, for example, 10 mol % or less. Further, the chloride bath may optionally contain lower titanium chloride, such as titanium dichloride and titanium trichloride. The content of the lower titanium chloride may be appropriately adjusted.
Regarding the above chlorides, the specific salt type and content can be appropriately determined in consideration of the operating temperature and the like. The content on a molar basis is measured by ICP emission spectrometry and atomic absorption spectrometry.
Here, the content on a molar basis is calculated as follows. After solidifying a molten salt sample collected from the chloride bath, the components of the sample are subjected to ICP emission spectrometry and atomic absorption spectrometry to calculate the content of each metal ion on a molar basis in the chloride bath Bf. do. If the chloride bath contained MgCl 2 , NaCl, KCl, CaCl 2 , LiCl, TiCl 2 and TiCl 3 , the metal ion content was determined by atomic absorption spectroscopy for Na and K and ICP emission spectroscopy for the others. (Mm) is obtained by adding the content of magnesium ions, the content of sodium ions, the content of potassium ions, the content of calcium ions, the content of lithium ions, and the content of titanium ions. The molar content of each component contained in the chloride bath is calculated by dividing the metal ion content of each component by the total metal ion content (Mm) and expressing it as a percentage. can be done. As described above, the content of chloride is determined based on the content of metal ions contained in the chloride bath.
（陽極・陰極）
陽極１２０及び陰極１３０はそれぞれ、例えば、棒状、動かしながら使用する長尺の帯状、筒状、板状若しくは、円柱その他の柱状又は、塊状等のものとすることができる。例えば、陽極１２０としてのＴｉＡｌＯ導電材を溶解及び鋳造し陽極を形成することができる。なお、陽極１２０と陰極１３０の電極間距離を特定の範囲内に設定したい場合は、陽極１２０と陰極１３０の対向部位に対する垂直断面での形状を相似形とすることが好ましい。例えば、筒状、棒状、又は柱状の陰極１３０を使用し、その外側に陽極１２０を配置する場合、陽極１２０も筒状としてよい。この場合、筒状の陽極１２０が陰極１３０を取り囲むので電析物が生成する面積を大きくできる。また、軸位置を固定して回転可能とした棒状または柱状の陰極１３０を使用し、対向部位に断面弧状の板状陽極１２０を使用してよい。この場合でも、陽極１２０と陰極１３０の対向部分はほぼ同じ電極間距離を維持できる。
また、チタンよりイオン化傾向が小さい金属製の籠（例えばニッケル製）の中に、先述した抽出工程で得られたＴｉＡｌＯ導電材を粒状や粉状として載置して陽極１２０を構成してもよい。この場合、籠ＢＫは多数の貫通孔を有し、籠ＢＫの形状を陽極１２０の形状として取り扱い可能である。また、当該籠に導通を図ったとしても、塩化物浴Ｂｆ内に該籠ＢＫが溶出しにくく、主にＴｉＡｌＯ導電材が溶出される。図面を用いた説明では、理解容易のため、ＴｉＡｌＯ導電材等が溶出される部分に陽極の符号を付して説明することがある。
また、陰極１３０の形状としては、金属チタンが析出するその陰極１３０の表面の少なくとも一部が、曲面形状であってもよい。このような陰極１３０を使用すると該陰極１３０を回転等作動させながら金属チタンを陰極１３０の表面に電析させることができ連続生産時の装置小型化に貢献する。 (anode/cathode)
Each of theanode 120 and the cathode 130 can be, for example, rod-shaped, a long band that is used while being moved, a cylinder, a plate-shaped, a cylinder or other columnar shape, or a block-shaped shape. For example, a TiAlO conductive material as the anode 120 can be melted and cast to form the anode. If the inter-electrode distance between the anode 120 and the cathode 130 is to be set within a specific range, it is preferable that the shapes of the opposing portions of the anode 120 and the cathode 130 are similar in vertical cross section. For example, if a cylindrical, rod-shaped, or columnar cathode 130 is used and the anode 120 is placed outside it, the anode 120 may also be cylindrical. In this case, since the cylindrical anode 120 surrounds the cathode 130, the area where the electrodeposits are produced can be increased. Alternatively, a rod-shaped or column-shaped cathode 130 that is rotatable with a fixed axial position may be used, and a plate-shaped anode 120 having an arc-shaped cross section may be used at the opposed portion. Even in this case, the opposing portions of the anode 120 and the cathode 130 can maintain substantially the same inter-electrode distance.
Alternatively, theanode 120 may be formed by placing the TiAlO conductive material obtained in the above-described extraction process in the form of granules or powder in a metal basket (for example, made of nickel) having a lower ionization tendency than titanium. . In this case, the basket BK has many through holes, and the shape of the basket BK can be treated as the shape of the anode 120 . Further, even if the cage is electrically connected, the cage BK is less likely to elute into the chloride bath Bf, and mainly the TiAlO conductive material is eluted. In the description using the drawings, for ease of understanding, the portion where the TiAlO conductive material or the like is eluted is sometimes described with the symbol of anode.
As for the shape of thecathode 130, at least part of the surface of the cathode 130 on which metallic titanium is deposited may be curved. When such a cathode 130 is used, metal titanium can be electrodeposited on the surface of the cathode 130 while rotating the cathode 130, which contributes to miniaturization of the apparatus during continuous production.
陽極１２０及び陰極１３０はそれぞれ、例えば、棒状、動かしながら使用する長尺の帯状、筒状、板状若しくは、円柱その他の柱状又は、塊状等のものとすることができる。例えば、陽極１２０としてのＴｉＡｌＯ導電材を溶解及び鋳造し陽極を形成することができる。なお、陽極１２０と陰極１３０の電極間距離を特定の範囲内に設定したい場合は、陽極１２０と陰極１３０の対向部位に対する垂直断面での形状を相似形とすることが好ましい。例えば、筒状、棒状、又は柱状の陰極１３０を使用し、その外側に陽極１２０を配置する場合、陽極１２０も筒状としてよい。この場合、筒状の陽極１２０が陰極１３０を取り囲むので電析物が生成する面積を大きくできる。また、軸位置を固定して回転可能とした棒状または柱状の陰極１３０を使用し、対向部位に断面弧状の板状陽極１２０を使用してよい。この場合でも、陽極１２０と陰極１３０の対向部分はほぼ同じ電極間距離を維持できる。
また、チタンよりイオン化傾向が小さい金属製の籠（例えばニッケル製）の中に、先述した抽出工程で得られたＴｉＡｌＯ導電材を粒状や粉状として載置して陽極１２０を構成してもよい。この場合、籠ＢＫは多数の貫通孔を有し、籠ＢＫの形状を陽極１２０の形状として取り扱い可能である。また、当該籠に導通を図ったとしても、塩化物浴Ｂｆ内に該籠ＢＫが溶出しにくく、主にＴｉＡｌＯ導電材が溶出される。図面を用いた説明では、理解容易のため、ＴｉＡｌＯ導電材等が溶出される部分に陽極の符号を付して説明することがある。
また、陰極１３０の形状としては、金属チタンが析出するその陰極１３０の表面の少なくとも一部が、曲面形状であってもよい。このような陰極１３０を使用すると該陰極１３０を回転等作動させながら金属チタンを陰極１３０の表面に電析させることができ連続生産時の装置小型化に貢献する。 (anode/cathode)
Each of the
Alternatively, the
As for the shape of the
次に、粗電析ステップ及び精製電析ステップの一例について図１（Ａ）～（Ｄ）乃至図５（Ａ）～（Ｄ）を用いてそれぞれ説明する。
なお、粗電析ステップにおいて用いられる塩化物浴が先述した所定量の塩化マグネシウムを含有する浴組成である場合、精製電析ステップにおいて用いられる塩化物浴は上記所定量の塩化マグネシウムを含有する浴組成であってよく、上記所定量の塩化マグネシウムを含有しない別の浴組成でもよい。また、精製電析ステップにおいて用いられる塩化物浴が先述した所定量の塩化マグネシウムを含有する浴組成である場合、粗電析ステップにおいて用いられる塩化物浴は上記所定量の塩化マグネシウムを含有する浴組成であってよく、上記所定量の塩化マグネシウムを含有しない別の浴組成でもよい。
また、図１（Ａ）～（Ｄ）乃至図５（Ａ）～（Ｄ）に示される各導電線は、電源（不図示）にそれぞれ接続可能であり、該電源の制御機構（不図示）は、各陽極及び各陰極に応じて電流を供給する導電線を適宜切り替えることができるものとする。 Next, examples of the crude electrodeposition step and the refined electrodeposition step will be described with reference to FIGS. 1(A) to (D) to 5(A) to (D).
When the chloride bath used in the crude electrodeposition step has a bath composition containing the aforementioned predetermined amount of magnesium chloride, the chloride bath used in the refined electrodeposition step contains the above-mentioned predetermined amount of magnesium chloride. composition, or another bath composition that does not contain the predetermined amount of magnesium chloride. Further, when the chloride bath used in the refinement electrodeposition step has a bath composition containing a predetermined amount of magnesium chloride as described above, the chloride bath used in the crude electrodeposition step contains the above-mentioned predetermined amount of magnesium chloride. composition, or another bath composition that does not contain the predetermined amount of magnesium chloride.
1A to 1D to 5A to 5D can be connected to a power supply (not shown), and a control mechanism for the power supply (not shown). is capable of appropriately switching conductive lines for supplying current according to each anode and each cathode.
なお、粗電析ステップにおいて用いられる塩化物浴が先述した所定量の塩化マグネシウムを含有する浴組成である場合、精製電析ステップにおいて用いられる塩化物浴は上記所定量の塩化マグネシウムを含有する浴組成であってよく、上記所定量の塩化マグネシウムを含有しない別の浴組成でもよい。また、精製電析ステップにおいて用いられる塩化物浴が先述した所定量の塩化マグネシウムを含有する浴組成である場合、粗電析ステップにおいて用いられる塩化物浴は上記所定量の塩化マグネシウムを含有する浴組成であってよく、上記所定量の塩化マグネシウムを含有しない別の浴組成でもよい。
また、図１（Ａ）～（Ｄ）乃至図５（Ａ）～（Ｄ）に示される各導電線は、電源（不図示）にそれぞれ接続可能であり、該電源の制御機構（不図示）は、各陽極及び各陰極に応じて電流を供給する導電線を適宜切り替えることができるものとする。 Next, examples of the crude electrodeposition step and the refined electrodeposition step will be described with reference to FIGS. 1(A) to (D) to 5(A) to (D).
When the chloride bath used in the crude electrodeposition step has a bath composition containing the aforementioned predetermined amount of magnesium chloride, the chloride bath used in the refined electrodeposition step contains the above-mentioned predetermined amount of magnesium chloride. composition, or another bath composition that does not contain the predetermined amount of magnesium chloride. Further, when the chloride bath used in the refinement electrodeposition step has a bath composition containing a predetermined amount of magnesium chloride as described above, the chloride bath used in the crude electrodeposition step contains the above-mentioned predetermined amount of magnesium chloride. composition, or another bath composition that does not contain the predetermined amount of magnesium chloride.
1A to 1D to 5A to 5D can be connected to a power supply (not shown), and a control mechanism for the power supply (not shown). is capable of appropriately switching conductive lines for supplying current according to each anode and each cathode.
＜粗電析ステップ＞
粗電析ステップは、塩化物浴ＢｆでＴｉＡｌＯ導電材を含む電極を用いて溶融塩電解することでチタン含有電析物を得る。
例えば、粗電析ステップにおいて、図１（Ａ）に示すように、陽極１２０としてのＴｉＡｌＯ導電材が載置されたニッケル製籠ＢＫと、チタン製陰極１３０とを塩化物浴Ｂｆにそれぞれ配置する。次いで、制御機構が籠ＢＫ及び陰極１３０に接続された導電線ＥＬを介して該陽極１２０及び該陰極１３０に電流を供給することで、溶融塩電解を実施する。
なお、図面上、別々の籠ＢＫにそれぞれ陽極１２０を載置しているが、例えば、円環状のニッケル製籠に陽極を載置してもよい（図６（Ａ）及び図７参照）。また、籠を使用せずに、ＴｉＡｌＯ導電材を鋳造することで得られた棒状又は板状等の陽極を直接、導電線に接続してもよい。 <Crude electrodeposition step>
In the crude electrodeposition step, molten salt electrolysis is performed in a chloride bath Bf using an electrode containing a TiAlO conductive material to obtain a titanium-containing electrodeposit.
For example, in the crude electrodeposition step, as shown in FIG. 1A, a nickel cage BK in which a TiAlO conductive material as ananode 120 is placed and a titanium cathode 130 are placed in a chloride bath Bf. . The control mechanism then supplies current to the anode 120 and the cathode 130 via the conductive line EL connected to the cage BK and the cathode 130, thereby performing molten salt electrolysis.
In the drawing, theanodes 120 are placed in separate baskets BK, but the anodes may be placed in, for example, ring-shaped nickel baskets (see FIGS. 6A and 7). Alternatively, a rod-shaped or plate-shaped anode obtained by casting a TiAlO conductive material may be directly connected to the conductive wire without using a cage.
粗電析ステップは、塩化物浴ＢｆでＴｉＡｌＯ導電材を含む電極を用いて溶融塩電解することでチタン含有電析物を得る。
例えば、粗電析ステップにおいて、図１（Ａ）に示すように、陽極１２０としてのＴｉＡｌＯ導電材が載置されたニッケル製籠ＢＫと、チタン製陰極１３０とを塩化物浴Ｂｆにそれぞれ配置する。次いで、制御機構が籠ＢＫ及び陰極１３０に接続された導電線ＥＬを介して該陽極１２０及び該陰極１３０に電流を供給することで、溶融塩電解を実施する。
なお、図面上、別々の籠ＢＫにそれぞれ陽極１２０を載置しているが、例えば、円環状のニッケル製籠に陽極を載置してもよい（図６（Ａ）及び図７参照）。また、籠を使用せずに、ＴｉＡｌＯ導電材を鋳造することで得られた棒状又は板状等の陽極を直接、導電線に接続してもよい。 <Crude electrodeposition step>
In the crude electrodeposition step, molten salt electrolysis is performed in a chloride bath Bf using an electrode containing a TiAlO conductive material to obtain a titanium-containing electrodeposit.
For example, in the crude electrodeposition step, as shown in FIG. 1A, a nickel cage BK in which a TiAlO conductive material as an
In the drawing, the
（塩化物浴の温度、電流密度）
塩化物浴Ｂｆの温度は該塩化物浴Ｂｆ内の成分次第で適宜変更すればよい。すなわち、塩化物浴が溶融状態を維持できるようにする、過度の加熱によるエネルギーロスを省く、等の観点から塩化物浴Ｂｆの温度を適宜決定すればよい。この際、各金属塩化物の融点を参考として塩化物浴Ｂｆの温度を適宜決定することも可能である。塩化物浴Ｂｆの温度について、あえて具体例を挙げると、例えば４５０℃以上かつ９００℃以下の範囲内に制御される。
また、陰極１３０の電流密度は特に限定されず適宜決定すればよい。陰極１３０の電流密度は、例えば０．０１Ａ／ｃｍ2以上かつ５Ａ／ｃｍ2以下としてよい。陰極１３０の電流密度は、式：電流密度（Ａ／ｃｍ2）＝電流（Ａ）÷電解面積（ｃｍ2）により算出することができる。ここで、電解面積については、たとえば円筒状の表面を有する陰極の場合、式：電解面積（ｃｍ2）＝陰極浸漬表面積＝陰極直径（ｃｍ）×π×陰極高さ（ｃｍ）で算出する。
なお、電極に流す電流を、連続的に流すこととする他、電流値をゼロ（すなわち通電しない）にする通電停止期間が設けられて通電期間と通電停止期間が交互に繰り返されるパルス電流としてもよい。 (chloride bath temperature, current density)
The temperature of the chloride bath Bf may be appropriately changed depending on the components in the chloride bath Bf. That is, the temperature of the chloride bath Bf may be appropriately determined from the viewpoints of maintaining the molten state of the chloride bath and eliminating energy loss due to excessive heating. At this time, it is also possible to appropriately determine the temperature of the chloride bath Bf with reference to the melting point of each metal chloride. To give a specific example, the temperature of the chloride bath Bf is controlled within a range of, for example, 450° C. or higher and 900° C. or lower.
Also, the current density of thecathode 130 is not particularly limited and may be determined as appropriate. The current density of the cathode 130 may be, for example, 0.01 A/cm 2 or more and 5 A/cm 2 or less. The current density of the cathode 130 can be calculated by the formula: current density (A/cm 2 )=current (A)÷electrolysis area (cm 2 ). Here, the electrolysis area, for example, in the case of a cathode having a cylindrical surface, is calculated by the formula: electrolysis area (cm 2 )=cathode immersion surface area=cathode diameter (cm)×π×cathode height (cm).
In addition to continuously flowing the current through the electrode, a pulse current may be used in which an energization stop period is provided in which the current value is set to zero (that is, no energization), and the energization period and the energization stop period are alternately repeated. good.
塩化物浴Ｂｆの温度は該塩化物浴Ｂｆ内の成分次第で適宜変更すればよい。すなわち、塩化物浴が溶融状態を維持できるようにする、過度の加熱によるエネルギーロスを省く、等の観点から塩化物浴Ｂｆの温度を適宜決定すればよい。この際、各金属塩化物の融点を参考として塩化物浴Ｂｆの温度を適宜決定することも可能である。塩化物浴Ｂｆの温度について、あえて具体例を挙げると、例えば４５０℃以上かつ９００℃以下の範囲内に制御される。
また、陰極１３０の電流密度は特に限定されず適宜決定すればよい。陰極１３０の電流密度は、例えば０．０１Ａ／ｃｍ2以上かつ５Ａ／ｃｍ2以下としてよい。陰極１３０の電流密度は、式：電流密度（Ａ／ｃｍ2）＝電流（Ａ）÷電解面積（ｃｍ2）により算出することができる。ここで、電解面積については、たとえば円筒状の表面を有する陰極の場合、式：電解面積（ｃｍ2）＝陰極浸漬表面積＝陰極直径（ｃｍ）×π×陰極高さ（ｃｍ）で算出する。
なお、電極に流す電流を、連続的に流すこととする他、電流値をゼロ（すなわち通電しない）にする通電停止期間が設けられて通電期間と通電停止期間が交互に繰り返されるパルス電流としてもよい。 (chloride bath temperature, current density)
The temperature of the chloride bath Bf may be appropriately changed depending on the components in the chloride bath Bf. That is, the temperature of the chloride bath Bf may be appropriately determined from the viewpoints of maintaining the molten state of the chloride bath and eliminating energy loss due to excessive heating. At this time, it is also possible to appropriately determine the temperature of the chloride bath Bf with reference to the melting point of each metal chloride. To give a specific example, the temperature of the chloride bath Bf is controlled within a range of, for example, 450° C. or higher and 900° C. or lower.
Also, the current density of the
In addition to continuously flowing the current through the electrode, a pulse current may be used in which an energization stop period is provided in which the current value is set to zero (that is, no energization), and the energization period and the energization stop period are alternately repeated. good.
電解槽１１０内は、大気中の水分等が混入することでチタン含有電析物中の不純物含有量が高くなることを抑制する観点から、例えばアルゴン等の不活性雰囲気に制御される。
The inside of the electrolytic cell 110 is controlled to an inert atmosphere such as argon, for example, from the viewpoint of suppressing an increase in the content of impurities in the titanium-containing electrodeposit due to the contamination of moisture and the like in the air.
次に、図１（Ｂ）に示すように、ニッケルよりもイオン化傾向が大きいチタンを含む陽極１２０が塩化物浴Ｂｆに溶出されるにつれ陽極１２０が消耗され、陰極１３０の表面上に不純物含有量が低減されたチタン含有電析物ＴＣが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
Next, as shown in FIG. 1B, as the anode 120 containing titanium, which has a higher ionization tendency than nickel, is eluted into the chloride bath Bf, the anode 120 is consumed, and the impurity content on the surface of the cathode 130 A titanium-containing electrodeposit TC having a reduced is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
電解槽１１０から取り出した陰極１３０の表面上に形成されたチタン含有電析物ＴＣを切削工具で剥がす等して回収する。なお、チタン含有電析物ＴＣに対し、下記の洗浄や乾燥を実施してもよい。また、洗浄や乾燥は陰極１３０と共にしてもよいし、陰極１３０から回収後に実施してもよい。
一例として、電解槽１１０から陰極１３０を取り出し、その陰極１３０及びチタン含有電析物ＴＣを酸洗浄及び／又は水洗浄でそれぞれに付着した溶融塩を溶解させて除去する。次いで、陰極１３０表面からチタン含有電析物ＴＣを切削工具等で剥がす。そして、チタン含有電析物ＴＣを容器に入れて水分等を蒸発させるため真空乾燥する。 The titanium-containing electrodeposit TC formed on the surface of thecathode 130 taken out from the electrolytic cell 110 is recovered by peeling it off with a cutting tool or the like. The titanium-containing electrodeposit TC may be washed and dried as described below. Washing and drying may be performed together with the cathode 130 or may be performed after recovery from the cathode 130 .
As an example, thecathode 130 is removed from the electrolytic cell 110, and the cathode 130 and the titanium-containing electrodeposit TC are washed with an acid and/or water to dissolve and remove the molten salt adhering thereto. Next, the titanium-containing electrodeposit TC is peeled off from the surface of the cathode 130 with a cutting tool or the like. Then, the titanium-containing electrodeposit TC is placed in a container and vacuum-dried to evaporate moisture.
一例として、電解槽１１０から陰極１３０を取り出し、その陰極１３０及びチタン含有電析物ＴＣを酸洗浄及び／又は水洗浄でそれぞれに付着した溶融塩を溶解させて除去する。次いで、陰極１３０表面からチタン含有電析物ＴＣを切削工具等で剥がす。そして、チタン含有電析物ＴＣを容器に入れて水分等を蒸発させるため真空乾燥する。 The titanium-containing electrodeposit TC formed on the surface of the
As an example, the
＜精製電析ステップ＞
精製電析ステップは、粗電析ステップ後、塩化物浴Ｂｆでチタン含有電析物ＴＣを含む電極を用いて溶融塩電解する。これにより、粗電析ステップで得られたチタン含有電析物ＴＣを更に精製することで、不純物含有量が更に低減された金属チタン電析物ＴＰが得られる。精製電析ステップは１回以上実施することができ、２回目以降は、前回得られた金属チタン電析物を電極として用いる。
例えば、図１（Ｃ）に示すように、陽極１２２としてのチタン含有電析物ＴＣが載置されたニッケル製籠ＢＫと、チタン製陰極１３０とを塩化物浴Ｂｆにそれぞれ配置する。次いで、制御機構が籠ＢＫ及び陰極１３０に接続された導電線ＥＬを介して該陽極１２２及び該陰極１３０に電流を供給することで、溶融塩電解を実施する。なお、当該陰極１３０は、粗電析ステップで使用した陰極１３０と同じでもよく、新たな陰極に交換してもよい。 <Purification electrodeposition step>
In the refinement electrodeposition step, after the crude electrodeposition step, molten salt electrolysis is performed in a chloride bath Bf using an electrode containing titanium-containing electrodeposits TC. Thus, by further purifying the titanium-containing electrodeposit TC obtained in the crude electrodeposition step, a metal titanium electrodeposit TP having a further reduced impurity content can be obtained. The refining electrodeposition step can be performed one or more times, and from the second time onwards, the metallic titanium electrodeposit obtained last time is used as an electrode.
For example, as shown in FIG. 1C, a nickel cage BK in which a titanium-containing electrodeposit TC as ananode 122 is placed and a titanium cathode 130 are placed in a chloride bath Bf. Molten salt electrolysis is then performed by the control mechanism supplying current to the anode 122 and the cathode 130 via the conductive line EL connected to the cage BK and the cathode 130 . The cathode 130 may be the same as the cathode 130 used in the crude electrodeposition step, or may be replaced with a new cathode.
精製電析ステップは、粗電析ステップ後、塩化物浴Ｂｆでチタン含有電析物ＴＣを含む電極を用いて溶融塩電解する。これにより、粗電析ステップで得られたチタン含有電析物ＴＣを更に精製することで、不純物含有量が更に低減された金属チタン電析物ＴＰが得られる。精製電析ステップは１回以上実施することができ、２回目以降は、前回得られた金属チタン電析物を電極として用いる。
例えば、図１（Ｃ）に示すように、陽極１２２としてのチタン含有電析物ＴＣが載置されたニッケル製籠ＢＫと、チタン製陰極１３０とを塩化物浴Ｂｆにそれぞれ配置する。次いで、制御機構が籠ＢＫ及び陰極１３０に接続された導電線ＥＬを介して該陽極１２２及び該陰極１３０に電流を供給することで、溶融塩電解を実施する。なお、当該陰極１３０は、粗電析ステップで使用した陰極１３０と同じでもよく、新たな陰極に交換してもよい。 <Purification electrodeposition step>
In the refinement electrodeposition step, after the crude electrodeposition step, molten salt electrolysis is performed in a chloride bath Bf using an electrode containing titanium-containing electrodeposits TC. Thus, by further purifying the titanium-containing electrodeposit TC obtained in the crude electrodeposition step, a metal titanium electrodeposit TP having a further reduced impurity content can be obtained. The refining electrodeposition step can be performed one or more times, and from the second time onwards, the metallic titanium electrodeposit obtained last time is used as an electrode.
For example, as shown in FIG. 1C, a nickel cage BK in which a titanium-containing electrodeposit TC as an
精製電析ステップにおける塩化物浴Ｂｆの組成、塩化物浴の温度、電流密度については、粗電析ステップと同じであるので説明を割愛する。
The composition of the chloride bath Bf, the temperature of the chloride bath, and the current density in the refinement electrodeposition step are the same as in the crude electrodeposition step, so the explanation is omitted.
次に、図１（Ｄ）に示すように、チタンを含む陽極１２２が塩化物浴Ｂｆに溶出されるにつれ陽極１２２が消耗され、陰極１３０の表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
Next, as shown in FIG. 1(D), the titanium-containing anode 122 is exhausted as it is eluted into the chloride bath Bf, and a metallic titanium electrode having a reduced impurity content is deposited on the surface of the cathode 130 . A precipitate TP is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
電解槽１１０から取り出した陰極１３０の表面上に形成された金属チタン電析物ＴＰを切削工具で剥がす等して回収する。なお、金属チタン電析物ＴＰに対し、上記粗電析ステップで先述した洗浄や乾燥を実施してもよい。また、洗浄や乾燥は陰極１３０と共にしてもよいし、陰極１３０から回収後に実施してもよい。
これにより、アルミニウム含有量及び酸素含有量が低減された金属チタンが得られる。 The metal titanium electrodeposit TP formed on the surface of thecathode 130 taken out from the electrolytic cell 110 is recovered by peeling it off with a cutting tool or the like. The titanium metal electrodeposit TP may be subjected to the washing and drying described above in the crude electrodeposition step. Washing and drying may be performed together with the cathode 130 or may be performed after recovery from the cathode 130 .
This yields titanium metal with reduced aluminum and oxygen content.
これにより、アルミニウム含有量及び酸素含有量が低減された金属チタンが得られる。 The metal titanium electrodeposit TP formed on the surface of the
This yields titanium metal with reduced aluminum and oxygen content.
なお、図１（Ｃ）～（Ｄ）に示す実施形態において精製電析ステップを１回実施しているが、不純物含有量を更に低減させて金属チタンの純度を更に向上させるために精製電析ステップを複数回実施してよい。より具体的には、得られた金属チタン電析物ＴＰを電解槽１１０内のニッケル製籠ＢＫに載置し、制御機構が陽極としての金属チタン電析物ＴＰとチタン製陰極１３０との間に電流を供給することで、溶融塩電解を実施する。このような実施を繰り返す度にアルミニウム含有量及び酸素含有量がより確実に低減された金属チタンを回収可能となる。ただし、製造コストの観点から、繰り返す回数を適宜採択すればよい。精製電析ステップは、例えば１回以上かつ５回以下であり、また例えば、１回以上かつ３回以下である。
In the embodiment shown in FIGS. 1(C) to 1(D), the purification electrodeposition step is performed once, but in order to further reduce the impurity content and further improve the purity of metallic titanium, the purification electrodeposition step is performed. A step may be performed multiple times. More specifically, the obtained metal titanium electrodeposit TP is placed in a nickel cage BK in the electrolytic bath 110, and the control mechanism controls the flow between the metal titanium electrodeposit TP as an anode and the titanium cathode 130. Molten salt electrolysis is performed by supplying a current to . Every time such an operation is repeated, it becomes possible to recover titanium metal in which the aluminum content and the oxygen content are more reliably reduced. However, from the viewpoint of manufacturing cost, the number of repetitions may be appropriately selected. The purification electrodeposition step is, for example, one or more and five or less times, and for example, one or more and three or less times.
（金属チタンの組成）
上記精錬工程によれば、アルミニウム含有量が１００質量ｐｐｍ以下、酸素含有量が５００質量ｐｐｍ以下、残部チタン及び不可避的不純物からなる組成に制御された金属チタンを得ることができる。この不可避的不純物は、鉱石由来の不純物や、塩化物浴由来の成分であることが多い。ここでいう金属チタンは、その組成がいわゆる工業用純チタンのチタン純度に相当し、金属チタンはその不純物含有量が少なく、例えば不純物含有量の合計は３０００質量ｐｐｍ以下である。
なお、上記アルミニウム含有量は上限値として例えば５０質量ｐｐｍ以下である。一方、上記アルミニウム含有量は下限値として例えば１０質量ｐｐｍ以上、例えば２０質量ｐｐｍ以上である。
また、上記酸素含有量は上限値として例えば４５０質量ｐｐｍ以下、例えば４００質量ｐｐｍ以下である。一方、上記酸素含有量は下限値として例えば１００質量ｐｐｍ以上、例えば２００質量ｐｐｍ以上である。
また、更なる一実施形態において、上述した不可避的不純物等をさらに具体的に特定した場合、窒素含有量が０．０３質量％以下、炭素含有量が０．０１質量％以下、鉄含有量が０．０１０質量％以下、マグネシウム含有量が０．０５質量％以下、ニッケル含有量が０．０１質量％以下、クロム含有量が０．００５質量％以下、シリコン含有量が０．００１質量％以下、マンガン含有量が０．０５質量％以下、スズ含有量が０．０１質量％以下に更に制御された金属チタンを得ることもできる。
なお、上記窒素含有量は、下限値として例えば０．００２質量％以上、例えば０．００３質量％以上である。一方、上記窒素含有量は上限値として例えば０．００９質量％以下、例えば０．００８質量％以下である。
また、上記炭素含有量は、下限値として例えば０．０００６質量％以上、例えば０．０００８質量％以上である。一方、上記炭素含有量は、上限値として例えば０．００８質量％以下であり、例えば０．００４質量％以下である。
また、上記鉄含有量は、上限値として例えば０．００５質量％以下、例えば０．００３質量％以下である。一方、上記マグネシウム含有量は、下限値として例えば０．００１質量％以上、例えば０．００５質量％以上である。
また、上記ニッケル含有量は、上限値として例えば０．００８質量％以下、例えば０．００４質量％以下である。
また、上記クロム含有量は、下限値として例えば０．０００５質量％以上、例えば０．００１質量％以上である。
また、上記シリコン含有量は、上限値として例えば０．０００５質量％以下である。
また、上記マンガン含有量は、下限値として例えば０．００１質量％以上、例えば０．００５質量％以上である。一方、上記マンガン含有量は上限値として例えば０．０３質量％以下である。
また、上記スズ含有量は、上限値として例えば０．００５質量％以下、例えば０．００３質量％以下である。
なお、本発明の一実施形態により製造された金属チタンを使用すれば、種々の純チタン製品やチタン合金製品を安価に得ることができると推察される。 (Composition of metallic titanium)
According to the refining process described above, it is possible to obtain metallic titanium having an aluminum content of 100 mass ppm or less, an oxygen content of 500 mass ppm or less, and a balance of titanium and unavoidable impurities. These unavoidable impurities are often ore-derived impurities and chloride bath-derived components. The composition of metallic titanium here corresponds to the titanium purity of so-called industrial pure titanium, and metallic titanium has a low impurity content, for example, the total impurity content is 3000 mass ppm or less.
In addition, the said aluminum content is 50 mass ppm or less as an upper limit. On the other hand, the lower limit of the aluminum content is, for example, 10 mass ppm or more, for example 20 mass ppm or more.
Moreover, the upper limit of the oxygen content is, for example, 450 mass ppm or less, for example, 400 mass ppm or less. On the other hand, the lower limit of the oxygen content is, for example, 100 mass ppm or more, for example 200 mass ppm or more.
Further, in a further embodiment, when the above-mentioned unavoidable impurities and the like are more specifically specified, the nitrogen content is 0.03% by mass or less, the carbon content is 0.01% by mass or less, and the iron content is 0.010% by mass or less, magnesium content of 0.05% by mass or less, nickel content of 0.01% by mass or less, chromium content of 0.005% by mass or less, silicon content of 0.001% by mass or less It is also possible to obtain metallic titanium in which the manganese content is further controlled to 0.05% by mass or less and the tin content is controlled to 0.01% by mass or less.
The lower limit of the nitrogen content is, for example, 0.002% by mass or more, for example 0.003% by mass or more. On the other hand, the upper limit of the nitrogen content is, for example, 0.009% by mass or less, for example, 0.008% by mass or less.
In addition, the lower limit of the carbon content is, for example, 0.0006% by mass or more, for example, 0.0008% by mass or more. On the other hand, the upper limit of the carbon content is, for example, 0.008% by mass or less, for example, 0.004% by mass or less.
The upper limit of the iron content is, for example, 0.005% by mass or less, for example 0.003% by mass or less. On the other hand, the lower limit of the magnesium content is, for example, 0.001% by mass or more, for example 0.005% by mass or more.
The upper limit of the nickel content is, for example, 0.008% by mass or less, for example, 0.004% by mass or less.
Further, the chromium content is, as a lower limit, 0.0005% by mass or more, for example 0.001% by mass or more.
The upper limit of the silicon content is, for example, 0.0005% by mass or less.
Further, the manganese content is, as a lower limit, for example 0.001% by mass or more, for example 0.005% by mass or more. On the other hand, the upper limit of the manganese content is, for example, 0.03% by mass or less.
The upper limit of the tin content is, for example, 0.005% by mass or less, for example 0.003% by mass or less.
It is presumed that various pure titanium products and titanium alloy products can be obtained at low cost by using metallic titanium produced according to one embodiment of the present invention.
上記精錬工程によれば、アルミニウム含有量が１００質量ｐｐｍ以下、酸素含有量が５００質量ｐｐｍ以下、残部チタン及び不可避的不純物からなる組成に制御された金属チタンを得ることができる。この不可避的不純物は、鉱石由来の不純物や、塩化物浴由来の成分であることが多い。ここでいう金属チタンは、その組成がいわゆる工業用純チタンのチタン純度に相当し、金属チタンはその不純物含有量が少なく、例えば不純物含有量の合計は３０００質量ｐｐｍ以下である。
なお、上記アルミニウム含有量は上限値として例えば５０質量ｐｐｍ以下である。一方、上記アルミニウム含有量は下限値として例えば１０質量ｐｐｍ以上、例えば２０質量ｐｐｍ以上である。
また、上記酸素含有量は上限値として例えば４５０質量ｐｐｍ以下、例えば４００質量ｐｐｍ以下である。一方、上記酸素含有量は下限値として例えば１００質量ｐｐｍ以上、例えば２００質量ｐｐｍ以上である。
また、更なる一実施形態において、上述した不可避的不純物等をさらに具体的に特定した場合、窒素含有量が０．０３質量％以下、炭素含有量が０．０１質量％以下、鉄含有量が０．０１０質量％以下、マグネシウム含有量が０．０５質量％以下、ニッケル含有量が０．０１質量％以下、クロム含有量が０．００５質量％以下、シリコン含有量が０．００１質量％以下、マンガン含有量が０．０５質量％以下、スズ含有量が０．０１質量％以下に更に制御された金属チタンを得ることもできる。
なお、上記窒素含有量は、下限値として例えば０．００２質量％以上、例えば０．００３質量％以上である。一方、上記窒素含有量は上限値として例えば０．００９質量％以下、例えば０．００８質量％以下である。
また、上記炭素含有量は、下限値として例えば０．０００６質量％以上、例えば０．０００８質量％以上である。一方、上記炭素含有量は、上限値として例えば０．００８質量％以下であり、例えば０．００４質量％以下である。
また、上記鉄含有量は、上限値として例えば０．００５質量％以下、例えば０．００３質量％以下である。一方、上記マグネシウム含有量は、下限値として例えば０．００１質量％以上、例えば０．００５質量％以上である。
また、上記ニッケル含有量は、上限値として例えば０．００８質量％以下、例えば０．００４質量％以下である。
また、上記クロム含有量は、下限値として例えば０．０００５質量％以上、例えば０．００１質量％以上である。
また、上記シリコン含有量は、上限値として例えば０．０００５質量％以下である。
また、上記マンガン含有量は、下限値として例えば０．００１質量％以上、例えば０．００５質量％以上である。一方、上記マンガン含有量は上限値として例えば０．０３質量％以下である。
また、上記スズ含有量は、上限値として例えば０．００５質量％以下、例えば０．００３質量％以下である。
なお、本発明の一実施形態により製造された金属チタンを使用すれば、種々の純チタン製品やチタン合金製品を安価に得ることができると推察される。 (Composition of metallic titanium)
According to the refining process described above, it is possible to obtain metallic titanium having an aluminum content of 100 mass ppm or less, an oxygen content of 500 mass ppm or less, and a balance of titanium and unavoidable impurities. These unavoidable impurities are often ore-derived impurities and chloride bath-derived components. The composition of metallic titanium here corresponds to the titanium purity of so-called industrial pure titanium, and metallic titanium has a low impurity content, for example, the total impurity content is 3000 mass ppm or less.
In addition, the said aluminum content is 50 mass ppm or less as an upper limit. On the other hand, the lower limit of the aluminum content is, for example, 10 mass ppm or more, for example 20 mass ppm or more.
Moreover, the upper limit of the oxygen content is, for example, 450 mass ppm or less, for example, 400 mass ppm or less. On the other hand, the lower limit of the oxygen content is, for example, 100 mass ppm or more, for example 200 mass ppm or more.
Further, in a further embodiment, when the above-mentioned unavoidable impurities and the like are more specifically specified, the nitrogen content is 0.03% by mass or less, the carbon content is 0.01% by mass or less, and the iron content is 0.010% by mass or less, magnesium content of 0.05% by mass or less, nickel content of 0.01% by mass or less, chromium content of 0.005% by mass or less, silicon content of 0.001% by mass or less It is also possible to obtain metallic titanium in which the manganese content is further controlled to 0.05% by mass or less and the tin content is controlled to 0.01% by mass or less.
The lower limit of the nitrogen content is, for example, 0.002% by mass or more, for example 0.003% by mass or more. On the other hand, the upper limit of the nitrogen content is, for example, 0.009% by mass or less, for example, 0.008% by mass or less.
In addition, the lower limit of the carbon content is, for example, 0.0006% by mass or more, for example, 0.0008% by mass or more. On the other hand, the upper limit of the carbon content is, for example, 0.008% by mass or less, for example, 0.004% by mass or less.
The upper limit of the iron content is, for example, 0.005% by mass or less, for example 0.003% by mass or less. On the other hand, the lower limit of the magnesium content is, for example, 0.001% by mass or more, for example 0.005% by mass or more.
The upper limit of the nickel content is, for example, 0.008% by mass or less, for example, 0.004% by mass or less.
Further, the chromium content is, as a lower limit, 0.0005% by mass or more, for example 0.001% by mass or more.
The upper limit of the silicon content is, for example, 0.0005% by mass or less.
Further, the manganese content is, as a lower limit, for example 0.001% by mass or more, for example 0.005% by mass or more. On the other hand, the upper limit of the manganese content is, for example, 0.03% by mass or less.
The upper limit of the tin content is, for example, 0.005% by mass or less, for example 0.003% by mass or less.
It is presumed that various pure titanium products and titanium alloy products can be obtained at low cost by using metallic titanium produced according to one embodiment of the present invention.
（別の実施形態）
以下に、別の実施形態を説明する。以下で説明する実施形態は、上述の実施形態と相違する点について重点的に説明する。すなわち、上記実施形態で説明した構成は、適宜以下の実施形態に適用することができる。
図１（Ａ）～（Ｄ）に示す実施形態は陽極と陰極が概略同じ高さに配置されているが、陽極と陰極の配置を変更しても粗電析ステップおよび精製電析ステップは実施可能である。その一例として、陰極を上側、陽極を下側に配置する実施形態を以下に説明する。図２（Ａ）に示すように、電解装置２００に、例えば電解槽２１０の底部にニッケル製基台ＢＳ及び該基台ＢＳ上に陽極２２０としてのＴｉＡｌＯ導電材を載置し、該陽極２２０よりも高い位置にチタン製陰極２３０を配置する。次いで、制御機構が基台ＢＳ及び陰極２３０に接続された導電線ＥＬを介して該陽極２２０及び該陰極２３０に電流を供給することで、溶融塩電解を実施する（粗電析ステップ）。
次に、図２（Ｂ）に示すように、陽極２２０が塩化物浴Ｂｆに溶出されるにつれ陽極２２０が消耗され、陰極２３０の表面上に不純物含有量が低減されたチタン含有電析物ＴＣが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽２１０から取り出した陰極２３０の表面上に形成されたチタン含有電析物ＴＣを切削工具で剥がす等して回収する。なお、チタン含有電析物ＴＣに対し、先述した洗浄や乾燥を実施してもよい。
次に、図２（Ｃ）に示すように、電解槽２１０の底部にニッケル製基台ＢＳ及び該基台ＢＳ上に陽極２２２としてのチタン含有電析物ＴＣを載置し、該陽極２２２よりも高い位置にチタン製陰極２３０を配置する。次いで、制御機構が基台ＢＳ及び陰極２３０に接続された導電線ＥＬを介して該陽極２２２及び該陰極２３０に電流を供給することで、溶融塩電解を実施する（精製電析ステップ）。
次に、図２（Ｄ）に示すように、チタンを含む陽極２２２が塩化物浴Ｂｆに溶出されるにつれ陽極２２２が消耗され、陰極２３０表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽２１０から陰極２３０を取り出し、該陰極２３０の表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。 (another embodiment)
Another embodiment is described below. In the embodiments described below, the points that are different from the above-described embodiments will be mainly described. That is, the configurations described in the above embodiments can be appropriately applied to the following embodiments.
In the embodiment shown in FIGS. 1(A) to 1(D), the anode and the cathode are arranged at approximately the same height, but the crude electrodeposition step and the refinement electrodeposition step can be performed even if the arrangement of the anode and the cathode is changed. It is possible. As an example, an embodiment in which the cathode is arranged on the upper side and the anode is arranged on the lower side will be described below. As shown in FIG. 2(A), in anelectrolytic device 200, for example, a nickel base BS is placed on the bottom of an electrolytic bath 210, and a TiAlO conductive material as an anode 220 is placed on the base BS. A titanium cathode 230 is placed at a higher position. Next, the control mechanism supplies current to the anode 220 and the cathode 230 through the conductive line EL connected to the base BS and the cathode 230, thereby performing molten salt electrolysis (rough electrodeposition step).
Next, as shown in FIG. 2(B), as theanode 220 is eluted into the chloride bath Bf, the anode 220 is consumed, and a titanium-containing electrodeposit TC having a reduced impurity content is deposited on the surface of the cathode 230. is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
Next, the titanium-containing electrodeposit TC formed on the surface of thecathode 230 taken out from the electrolytic bath 210 is recovered by peeling it off with a cutting tool or the like. Note that the titanium-containing electrodeposit TC may be washed and dried as described above.
Next, as shown in FIG. 2(C), a nickel-made base BS and a titanium-containing electrodeposit TC as ananode 222 are placed on the base BS at the bottom of the electrolytic cell 210. A titanium cathode 230 is placed at a higher position. Next, the control mechanism supplies current to the anode 222 and the cathode 230 through the conductive line EL connected to the base BS and the cathode 230, thereby performing molten salt electrolysis (refining electrodeposition step).
Next, as shown in FIG. 2(D), as theanode 222 containing titanium is eluted into the chloride bath Bf, the anode 222 is exhausted, and metal titanium electrodeposition with reduced impurity content is deposited on the surface of the cathode 230. Entity TP is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
Next, thecathode 230 is taken out from the electrolytic cell 210, and the metal titanium electrodeposit TP formed on the surface of the cathode 230 is washed, peeled off and dried to obtain metal titanium.
以下に、別の実施形態を説明する。以下で説明する実施形態は、上述の実施形態と相違する点について重点的に説明する。すなわち、上記実施形態で説明した構成は、適宜以下の実施形態に適用することができる。
図１（Ａ）～（Ｄ）に示す実施形態は陽極と陰極が概略同じ高さに配置されているが、陽極と陰極の配置を変更しても粗電析ステップおよび精製電析ステップは実施可能である。その一例として、陰極を上側、陽極を下側に配置する実施形態を以下に説明する。図２（Ａ）に示すように、電解装置２００に、例えば電解槽２１０の底部にニッケル製基台ＢＳ及び該基台ＢＳ上に陽極２２０としてのＴｉＡｌＯ導電材を載置し、該陽極２２０よりも高い位置にチタン製陰極２３０を配置する。次いで、制御機構が基台ＢＳ及び陰極２３０に接続された導電線ＥＬを介して該陽極２２０及び該陰極２３０に電流を供給することで、溶融塩電解を実施する（粗電析ステップ）。
次に、図２（Ｂ）に示すように、陽極２２０が塩化物浴Ｂｆに溶出されるにつれ陽極２２０が消耗され、陰極２３０の表面上に不純物含有量が低減されたチタン含有電析物ＴＣが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽２１０から取り出した陰極２３０の表面上に形成されたチタン含有電析物ＴＣを切削工具で剥がす等して回収する。なお、チタン含有電析物ＴＣに対し、先述した洗浄や乾燥を実施してもよい。
次に、図２（Ｃ）に示すように、電解槽２１０の底部にニッケル製基台ＢＳ及び該基台ＢＳ上に陽極２２２としてのチタン含有電析物ＴＣを載置し、該陽極２２２よりも高い位置にチタン製陰極２３０を配置する。次いで、制御機構が基台ＢＳ及び陰極２３０に接続された導電線ＥＬを介して該陽極２２２及び該陰極２３０に電流を供給することで、溶融塩電解を実施する（精製電析ステップ）。
次に、図２（Ｄ）に示すように、チタンを含む陽極２２２が塩化物浴Ｂｆに溶出されるにつれ陽極２２２が消耗され、陰極２３０表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽２１０から陰極２３０を取り出し、該陰極２３０の表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。 (another embodiment)
Another embodiment is described below. In the embodiments described below, the points that are different from the above-described embodiments will be mainly described. That is, the configurations described in the above embodiments can be appropriately applied to the following embodiments.
In the embodiment shown in FIGS. 1(A) to 1(D), the anode and the cathode are arranged at approximately the same height, but the crude electrodeposition step and the refinement electrodeposition step can be performed even if the arrangement of the anode and the cathode is changed. It is possible. As an example, an embodiment in which the cathode is arranged on the upper side and the anode is arranged on the lower side will be described below. As shown in FIG. 2(A), in an
Next, as shown in FIG. 2(B), as the
Next, the titanium-containing electrodeposit TC formed on the surface of the
Next, as shown in FIG. 2(C), a nickel-made base BS and a titanium-containing electrodeposit TC as an
Next, as shown in FIG. 2(D), as the
Next, the
図３に示す実施形態は、電解槽の少なくとも一部をニッケル製とし、かつ、ニッケル製である部分を陰極として使用する実施形態である。また、チタン含有電析物ＴＣを塩化物浴Ｂｆから取り出さずに金属チタンを製造できる実施形態である。図３（Ａ）に示すように、電解装置３００に、陽極３２０としてのＴｉＡｌＯ導電材が載置されたニッケル製籠ＢＫを配置する。このとき、電解槽３１０のうち少なくとも内壁の材質をニッケル製にすることで、溶融塩電解時に当該内壁を陰極３３０にする。次いで、制御機構が籠ＢＫ及び陰極３３０に接続された導電線ＥＬを介して該陽極３２０及び該陰極３３０に電流を供給することで、溶融塩電解を実施する（粗電析ステップ）。
次に、図３（Ｂ）に示すように、陽極３２０が塩化物浴Ｂｆに溶出されるにつれ陽極３２０が消耗され、電解槽３１０の内壁上に不純物含有量が低減されたチタン含有電析物ＴＣが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、塩化物浴Ｂｆからニッケル製籠ＢＫを取り出す。
次に、図３（Ｃ）に示すように、チタン製陰極３３５を塩化物浴Ｂｆ内に配置する。このとき、ニッケル製電解槽３１０の内壁表面上に形成されたチタン含有電析物ＴＣを陽極３２２にする。次いで、制御機構が電解槽３１０の内壁及び陰極３３５に接続された導電線ＥＬを介して該陽極３２２及び該陰極３３５に電流を供給することで、溶融塩電解を実施する（精製電析ステップ）。
次に、図３（Ｄ）に示すように、陽極３２２が塩化物浴Ｂｆに溶出されるにつれ陽極３２２が消耗され、陰極３３５の表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽３１０から陰極３３５を取り出し、該陰極３３５の表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。 The embodiment shown in FIG. 3 is an embodiment in which at least part of the electrolytic cell is made of nickel and the part made of nickel is used as the cathode. In addition, it is an embodiment in which metallic titanium can be produced without taking out the titanium-containing electrodeposit TC from the chloride bath Bf. As shown in FIG. 3(A), a nickel basket BK in which a TiAlO conductive material as ananode 320 is placed is arranged in the electrolytic device 300 . At this time, by making the material of at least the inner wall of the electrolytic cell 310 nickel, the inner wall serves as the cathode 330 during the molten salt electrolysis. Next, the control mechanism supplies current to the anode 320 and the cathode 330 via the conductive wire EL connected to the cage BK and the cathode 330, thereby performing molten salt electrolysis (rough electrodeposition step).
Next, as shown in FIG. 3B, as theanode 320 is eluted into the chloride bath Bf, the anode 320 is exhausted, and a titanium-containing electrodeposit with reduced impurity content is formed on the inner wall of the electrolytic bath 310. TC is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
Next, the nickel basket BK is removed from the chloride bath Bf.
Next, as shown in FIG. 3C, atitanium cathode 335 is placed in the chloride bath Bf. At this time, the titanium-containing electrodeposit TC formed on the inner wall surface of the nickel electrolytic bath 310 is used as the anode 322 . Next, the control mechanism supplies a current to the anode 322 and the cathode 335 via the conductive wire EL connected to the inner wall of the electrolytic cell 310 and the cathode 335 to perform molten salt electrolysis (refining electrodeposition step). .
Next, as shown in FIG. 3(D), theanode 322 is consumed as the anode 322 is eluted into the chloride bath Bf, and a metallic titanium electrodeposit TP having a reduced impurity content is formed on the surface of the cathode 335. is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
Next, thecathode 335 is taken out from the electrolytic bath 310, and the metal titanium electrodeposit TP formed on the surface of the cathode 335 is washed, peeled off and dried to obtain metal titanium.
次に、図３（Ｂ）に示すように、陽極３２０が塩化物浴Ｂｆに溶出されるにつれ陽極３２０が消耗され、電解槽３１０の内壁上に不純物含有量が低減されたチタン含有電析物ＴＣが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、塩化物浴Ｂｆからニッケル製籠ＢＫを取り出す。
次に、図３（Ｃ）に示すように、チタン製陰極３３５を塩化物浴Ｂｆ内に配置する。このとき、ニッケル製電解槽３１０の内壁表面上に形成されたチタン含有電析物ＴＣを陽極３２２にする。次いで、制御機構が電解槽３１０の内壁及び陰極３３５に接続された導電線ＥＬを介して該陽極３２２及び該陰極３３５に電流を供給することで、溶融塩電解を実施する（精製電析ステップ）。
次に、図３（Ｄ）に示すように、陽極３２２が塩化物浴Ｂｆに溶出されるにつれ陽極３２２が消耗され、陰極３３５の表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽３１０から陰極３３５を取り出し、該陰極３３５の表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。 The embodiment shown in FIG. 3 is an embodiment in which at least part of the electrolytic cell is made of nickel and the part made of nickel is used as the cathode. In addition, it is an embodiment in which metallic titanium can be produced without taking out the titanium-containing electrodeposit TC from the chloride bath Bf. As shown in FIG. 3(A), a nickel basket BK in which a TiAlO conductive material as an
Next, as shown in FIG. 3B, as the
Next, the nickel basket BK is removed from the chloride bath Bf.
Next, as shown in FIG. 3C, a
Next, as shown in FIG. 3(D), the
Next, the
チタン含有電析物ＴＣを塩化物浴Ｂｆから取り出さずに金属チタンを製造できる更なる別の実施形態を説明する。図４（Ａ）に示すように、電解装置４００に、陽極４２０としてのＴｉＡｌＯ導電材が載置されたニッケル製籠ＢＫを配置する。次いで、籠ＢＫが配置された位置よりも中央部に向かって２枚のチタン製陰極４３０、チタン製陰極４３５を並べて配置する。この実施形態では、電析の効率化の観点から、チタン製陰極４３０は陽極４２０側とチタン製陰極４３５側とに開口を有する孔を多数備えることが好ましい。この孔の形状は特段限定されず、断面が直線状の貫通孔でもよいし、多孔体が有するような複雑な形状の孔でもよい。次いで、制御機構が接続された籠ＢＫ及び陰極４３０に導電線ＥＬを介して該陽極４２０及び該陰極４３０に電流を供給することで、溶融塩電解を実施する（粗電析ステップ）。
次に、図４（Ｂ）に示すように、陽極４２０が塩化物浴Ｂｆに溶出されるにつれ陽極４２０が消耗され、陰極４３０の表面上に不純物含有量が低減されたチタン含有電析物ＴＣが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、図４（Ｃ）に示すように、チタン含有電析物ＴＣが表面上に形成された陰極４３０（図４（Ｂ）参照。）から陽極４２４に切り替え、制御機構が切り替えられた陽極４２４及び中央部付近の陰極４３５に電流を供給することで、溶融塩電解を実施する（精製電析ステップ）。このとき、チタン含有電析物ＴＣが陽極４２２となる。
次に、図４（Ｄ）に示すように、陽極４２２、場合によりさらに陽極４２４が塩化物浴Ｂｆに溶出されるにつれ陽極が消耗され、陰極４３５の表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽４１０から陰極４３５を取り出し、該陰極４３５の表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。 Yet another embodiment is described in which metallic titanium can be produced without removing the titanium-containing electrodeposit TC from the chloride bath Bf. As shown in FIG. 4A, a nickel basket BK in which a TiAlO conductive material as ananode 420 is placed is placed in an electrolysis device 400 . Next, two titanium cathodes 430 and 435 are arranged side by side toward the center from the position where the cage BK is arranged. In this embodiment, from the viewpoint of efficiency of electrodeposition, the titanium cathode 430 preferably has a large number of holes having openings on the anode 420 side and the titanium cathode 435 side. The shape of this hole is not particularly limited, and it may be a through hole with a linear cross section, or a hole with a complicated shape such as that of a porous body. Next, molten salt electrolysis is carried out by supplying electric current to the anode 420 and the cathode 430 through the conductive wire EL to the basket BK and the cathode 430 to which the control mechanism is connected (crude electrodeposition step).
Next, as shown in FIG. 4B, as theanode 420 is eluted into the chloride bath Bf, the anode 420 is exhausted, and a titanium-containing electrodeposit TC having a reduced impurity content is deposited on the surface of the cathode 430. is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
Next, as shown in FIG. 4(C), the cathode 430 (see FIG. 4(B)) having the titanium-containing electrodeposit TC formed on the surface is switched to theanode 424, and the anode whose control mechanism has been switched. Molten salt electrolysis is performed by supplying current to 424 and cathode 435 near the center (refining electrodeposition step). At this time, the titanium-containing electrodeposit TC becomes the anode 422 .
Next, as shown in FIG. 4(D), theanode 422 and possibly also the anode 424 are depleted as they are eluted into the chloride bath Bf, leaving metal with reduced impurity content on the surface of the cathode 435. A titanium electrodeposit TP is formed. Then, the control mechanism stops the current supply to end the molten salt electrolysis.
Next, thecathode 435 is taken out from the electrolytic bath 410, and the metal titanium electrodeposit TP formed on the surface of the cathode 435 is washed, peeled off and dried to obtain metal titanium.
次に、図４（Ｂ）に示すように、陽極４２０が塩化物浴Ｂｆに溶出されるにつれ陽極４２０が消耗され、陰極４３０の表面上に不純物含有量が低減されたチタン含有電析物ＴＣが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、図４（Ｃ）に示すように、チタン含有電析物ＴＣが表面上に形成された陰極４３０（図４（Ｂ）参照。）から陽極４２４に切り替え、制御機構が切り替えられた陽極４２４及び中央部付近の陰極４３５に電流を供給することで、溶融塩電解を実施する（精製電析ステップ）。このとき、チタン含有電析物ＴＣが陽極４２２となる。
次に、図４（Ｄ）に示すように、陽極４２２、場合によりさらに陽極４２４が塩化物浴Ｂｆに溶出されるにつれ陽極が消耗され、陰極４３５の表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される。そして、溶融塩電解を終了させるために、制御機構が電流の供給を停止する。
次に、電解槽４１０から陰極４３５を取り出し、該陰極４３５の表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。 Yet another embodiment is described in which metallic titanium can be produced without removing the titanium-containing electrodeposit TC from the chloride bath Bf. As shown in FIG. 4A, a nickel basket BK in which a TiAlO conductive material as an
Next, as shown in FIG. 4B, as the
Next, as shown in FIG. 4(C), the cathode 430 (see FIG. 4(B)) having the titanium-containing electrodeposit TC formed on the surface is switched to the
Next, as shown in FIG. 4(D), the
Next, the
チタン含有電析物ＴＣを塩化物浴Ｂｆから取り出さずに、かつ、電源接続の変更を行わずに連続的に複数回の電析を行う実施形態を説明する。図５（Ａ）に示すように、電解装置５００に、陽極５２０としてのＴｉＡｌＯ導電材が載置されたニッケル製籠ＢＫと、チタン製陰極５３０と、中央部にチタン製複極５４０をそれぞれ配置する。図５（Ａ）ではチタン製複極５４０が厚いものとして図示されているが、チタン製複極５４０は薄いものであっても構わない。制御機構が籠ＢＫ及び陰極５３０に接続された導電線ＥＬを介して該陽極５２０及び該陰極５３０に電流を供給することで、溶融塩電解を実施する。
次に、図５（Ｂ）に示すように、陽極５２０が塩化物浴Ｂｆに溶出されるにつれ陽極５２０が消耗され、不純物含有量が低減されたチタン含有電析物ＴＣが複極５４０の表面上に形成される。この複極５４０へのチタン含有電析物ＴＣの生成が粗電析ステップに該当する。
なお、陽極と陰極の間に電流が流れているので、陽極の溶解と複極の溶解は同時に進行しうる。図５（Ｃ）では、複極５４０の内、陰極５３０側が溶出することを示している。この実施形態では、複極５４０は、最初は該複極５４０由来のチタンを溶出し、その後チタン含有電析物ＴＣを溶出することとなる。
次に、図５（Ｄ）に示すように、複極５４０やチタン含有電析物ＴＣが消耗され、陰極５３０の表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される（精製電析ステップ）。次に、溶融塩電解を終了させるために、電流の供給を停止する。
次に、電解槽５１０から陰極５３０を取り出し、該陰極５３０表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。
なお、図５（Ａ）においては、チタン製の複極を配置しているが、例えば複極に替えてＴｉＡｌＯ導電材を溶融塩電解することで得られたチタン含有電析物ＴＣを配置してこれを複極としてもよい。
また例えば、陽極５２０側の複極５４０の表面上にチタン含有電析物ＴＣが形成された後、該複極５４０の上端に付いたフック（不図示）に吊るし棒等を引っ掛けて複極５４０を１８０度回転すればよい。そうすることで、チタン含有電析物ＴＣが陰極５３０に向かい合う。
以上の説明において、複極および陰極はチタン製として説明したが、電析物が析出可能であればその材質は適宜変更可能である。なお、複極については導電性を有する必要がある。よって、複極はセラミック等の非導電性材料は使用できない。
複極は上述のとおり、非可動式としてもよいし、可動式としてもよい。非可動式の複極の場合は電析と溶出が同時に起こり得るため、陽極側と陰極側とに開口する孔を多数備えることが好ましい。他方、可動式の複極の場合は電析と溶出とを各々進行させることが可能であるので、上記のような孔は不要である。むしろ、孔を無くすことで孔内に電析物が入り込み溶出に時間がかかるといった事態を回避しうる。
以上のとおり、複数の粗電析ステップ、精製電析ステップを説明した。これらは適宜組合せて実施することも可能であり、例えば図１（Ａ）及び（Ｂ）に示す実施形態の粗電析ステップを実施した後、図２（Ｃ）及び（Ｄ）に示す実施形態の精製電析ステップを実施することも可能である。 An embodiment will be described in which the titanium-containing electrodeposits TC are continuously electrodeposited a plurality of times without taking them out of the chloride bath Bf and without changing the power supply connection. As shown in FIG. 5(A), anelectrolytic device 500 is provided with a nickel cage BK in which a TiAlO conductive material as an anode 520 is placed, a titanium cathode 530, and a titanium bipolar electrode 540 in the center. do. Although the titanium bipolar electrode 540 is illustrated as being thick in FIG. 5A, the titanium bipolar electrode 540 may be thin. Molten salt electrolysis is performed by a control mechanism supplying current to the anode 520 and the cathode 530 via the conductive line EL connected to the cage BK and the cathode 530 .
Next, as shown in FIG. 5B, as theanode 520 is eluted into the chloride bath Bf, the anode 520 is consumed, and the titanium-containing electrodeposit TC with reduced impurity content is deposited on the surface of the bipolar electrode 540. Formed on top. Formation of the titanium-containing electrodeposit TC on this bipolar electrode 540 corresponds to the rough electrodeposition step.
In addition, since a current is flowing between the anode and the cathode, the dissolution of the anode and the dissolution of the bipolar electrode can proceed simultaneously. FIG. 5C shows that thecathode 530 side of the bipolar electrode 540 is eluted. In this embodiment, the bipolar electrode 540 will first elute titanium from the bipolar electrode 540 and then the titanium-containing electrodeposit TC.
Next, as shown in FIG. 5(D), thebipolar electrode 540 and the titanium-containing electrodeposit TC are consumed, and a metal titanium electrodeposit TP with a reduced impurity content is formed on the surface of the cathode 530. (refining electrodeposition step). Next, the current supply is stopped in order to terminate the molten salt electrolysis.
Next, thecathode 530 is taken out from the electrolytic bath 510, and the metal titanium electrodeposit TP formed on the surface of the cathode 530 is washed, peeled off and dried to obtain metal titanium.
In FIG. 5A, a titanium bipolar electrode is arranged, but instead of the bipolar electrode, for example, a titanium-containing electrodeposit TC obtained by subjecting a TiAlO conductive material to molten salt electrolysis is arranged. This may be a double pole.
Alternatively, for example, after the titanium-containing electrodeposit TC is formed on the surface of thedouble electrode 540 on the anode 520 side, a hook (not shown) attached to the upper end of the double electrode 540 is hooked with a hanging rod or the like to should be rotated 180 degrees. By doing so, the titanium-containing electrodeposit TC faces the cathode 530 .
In the above description, the bipolar electrode and the cathode are described as being made of titanium, but the material can be appropriately changed as long as the electrodeposit can be deposited. Note that the bipolar electrode must have conductivity. Therefore, non-conductive materials such as ceramics cannot be used for the bipolar electrodes.
The bipolar poles may be non-movable or movable as described above. Since electrodeposition and elution can occur simultaneously in the case of a non-movable bipolar electrode, it is preferable to have a large number of holes opening to the anode side and the cathode side. On the other hand, in the case of a movable bipolar electrode, electrodeposition and elution can proceed separately, so such holes as described above are unnecessary. Rather, by eliminating the pores, it is possible to avoid a situation in which the electrodeposits enter the pores and require a long time for elution.
As described above, a plurality of crude electrodeposition steps and refinement electrodeposition steps have been described. These can be carried out in combination as appropriate. For example, after carrying out the crude electrodeposition step of the embodiment shown in FIGS. It is also possible to carry out a purification electrodeposition step of
次に、図５（Ｂ）に示すように、陽極５２０が塩化物浴Ｂｆに溶出されるにつれ陽極５２０が消耗され、不純物含有量が低減されたチタン含有電析物ＴＣが複極５４０の表面上に形成される。この複極５４０へのチタン含有電析物ＴＣの生成が粗電析ステップに該当する。
なお、陽極と陰極の間に電流が流れているので、陽極の溶解と複極の溶解は同時に進行しうる。図５（Ｃ）では、複極５４０の内、陰極５３０側が溶出することを示している。この実施形態では、複極５４０は、最初は該複極５４０由来のチタンを溶出し、その後チタン含有電析物ＴＣを溶出することとなる。
次に、図５（Ｄ）に示すように、複極５４０やチタン含有電析物ＴＣが消耗され、陰極５３０の表面上に不純物含有量が低減された金属チタン電析物ＴＰが形成される（精製電析ステップ）。次に、溶融塩電解を終了させるために、電流の供給を停止する。
次に、電解槽５１０から陰極５３０を取り出し、該陰極５３０表面上に形成された金属チタン電析物ＴＰを洗浄、剥離、乾燥を行い、金属チタンを得る。
なお、図５（Ａ）においては、チタン製の複極を配置しているが、例えば複極に替えてＴｉＡｌＯ導電材を溶融塩電解することで得られたチタン含有電析物ＴＣを配置してこれを複極としてもよい。
また例えば、陽極５２０側の複極５４０の表面上にチタン含有電析物ＴＣが形成された後、該複極５４０の上端に付いたフック（不図示）に吊るし棒等を引っ掛けて複極５４０を１８０度回転すればよい。そうすることで、チタン含有電析物ＴＣが陰極５３０に向かい合う。
以上の説明において、複極および陰極はチタン製として説明したが、電析物が析出可能であればその材質は適宜変更可能である。なお、複極については導電性を有する必要がある。よって、複極はセラミック等の非導電性材料は使用できない。
複極は上述のとおり、非可動式としてもよいし、可動式としてもよい。非可動式の複極の場合は電析と溶出が同時に起こり得るため、陽極側と陰極側とに開口する孔を多数備えることが好ましい。他方、可動式の複極の場合は電析と溶出とを各々進行させることが可能であるので、上記のような孔は不要である。むしろ、孔を無くすことで孔内に電析物が入り込み溶出に時間がかかるといった事態を回避しうる。
以上のとおり、複数の粗電析ステップ、精製電析ステップを説明した。これらは適宜組合せて実施することも可能であり、例えば図１（Ａ）及び（Ｂ）に示す実施形態の粗電析ステップを実施した後、図２（Ｃ）及び（Ｄ）に示す実施形態の精製電析ステップを実施することも可能である。 An embodiment will be described in which the titanium-containing electrodeposits TC are continuously electrodeposited a plurality of times without taking them out of the chloride bath Bf and without changing the power supply connection. As shown in FIG. 5(A), an
Next, as shown in FIG. 5B, as the
In addition, since a current is flowing between the anode and the cathode, the dissolution of the anode and the dissolution of the bipolar electrode can proceed simultaneously. FIG. 5C shows that the
Next, as shown in FIG. 5(D), the
Next, the
In FIG. 5A, a titanium bipolar electrode is arranged, but instead of the bipolar electrode, for example, a titanium-containing electrodeposit TC obtained by subjecting a TiAlO conductive material to molten salt electrolysis is arranged. This may be a double pole.
Alternatively, for example, after the titanium-containing electrodeposit TC is formed on the surface of the
In the above description, the bipolar electrode and the cathode are described as being made of titanium, but the material can be appropriately changed as long as the electrodeposit can be deposited. Note that the bipolar electrode must have conductivity. Therefore, non-conductive materials such as ceramics cannot be used for the bipolar electrodes.
The bipolar poles may be non-movable or movable as described above. Since electrodeposition and elution can occur simultaneously in the case of a non-movable bipolar electrode, it is preferable to have a large number of holes opening to the anode side and the cathode side. On the other hand, in the case of a movable bipolar electrode, electrodeposition and elution can proceed separately, so such holes as described above are unnecessary. Rather, by eliminating the pores, it is possible to avoid a situation in which the electrodeposits enter the pores and require a long time for elution.
As described above, a plurality of crude electrodeposition steps and refinement electrodeposition steps have been described. These can be carried out in combination as appropriate. For example, after carrying out the crude electrodeposition step of the embodiment shown in FIGS. It is also possible to carry out a purification electrodeposition step of
［２．金属チタン電析物］
本発明に係る金属チタン電析物は、先述した金属チタンの製造方法により製造可能であり、不純物含有量が低減されている。金属チタン電析物はその不純物含有量が少なく、例えば不純物含有量の合計は３０００質量ｐｐｍ以下である。一実施形態において、当該金属チタン電析物は、アルミニウム含有量が５質量ｐｐｍ以上かつ１００質量ｐｐｍ以下であり且つ酸素含有量が１００質量ｐｐｍ以上かつ５００質量ｐｐｍ以下であり、残部チタン及び不可避的不純物からなる組成を有する。この不可避的不純物は、鉱石由来の不純物や、塩化物浴由来の成分であることが多い。上記各成分の含有量は、さらに、「金属チタンの組成」にて上述した範囲とすることもできる。 [2. Titanium Electrodeposit]
The metallic titanium electrodeposit according to the present invention can be produced by the method for producing metallic titanium described above, and has a reduced impurity content. The metal titanium electrodeposit has a low impurity content, for example, the total impurity content is 3000 ppm by mass or less. In one embodiment, the metal titanium electrodeposit has an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less, and the balance is titanium and unavoidable It has a composition consisting of impurities. These unavoidable impurities are often ore-derived impurities and chloride bath-derived components. The content of each of the above components can also be within the range described above in "Composition of metallic titanium".
本発明に係る金属チタン電析物は、先述した金属チタンの製造方法により製造可能であり、不純物含有量が低減されている。金属チタン電析物はその不純物含有量が少なく、例えば不純物含有量の合計は３０００質量ｐｐｍ以下である。一実施形態において、当該金属チタン電析物は、アルミニウム含有量が５質量ｐｐｍ以上かつ１００質量ｐｐｍ以下であり且つ酸素含有量が１００質量ｐｐｍ以上かつ５００質量ｐｐｍ以下であり、残部チタン及び不可避的不純物からなる組成を有する。この不可避的不純物は、鉱石由来の不純物や、塩化物浴由来の成分であることが多い。上記各成分の含有量は、さらに、「金属チタンの組成」にて上述した範囲とすることもできる。 [2. Titanium Electrodeposit]
The metallic titanium electrodeposit according to the present invention can be produced by the method for producing metallic titanium described above, and has a reduced impurity content. The metal titanium electrodeposit has a low impurity content, for example, the total impurity content is 3000 ppm by mass or less. In one embodiment, the metal titanium electrodeposit has an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less, and the balance is titanium and unavoidable It has a composition consisting of impurities. These unavoidable impurities are often ore-derived impurities and chloride bath-derived components. The content of each of the above components can also be within the range described above in "Composition of metallic titanium".
また一実施形態において、上述した不可避的不純物等をさらに具体的に特定することもありうる。すなわち、当該金属チタン電析物中の窒素含有量が０．００１質量％以上かつ０．０３質量％以下であり、炭素含有量が０．０００４質量％以上かつ０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下であってよい。上記各成分の含有量は、さらに、「金属チタンの組成」にて上述した範囲とすることもできる。
なお、金属チタン電析物の各成分の不純物含有量の測定方法については、先述したＴｉＡｌＯ導電材の各成分の不純物含有量の測定方法と同様である。 Moreover, in one embodiment, the above-described unavoidable impurities and the like may be specified more specifically. That is, the nitrogen content in the metal titanium electrodeposit is 0.001% by mass or more and 0.03% by mass or less, and the carbon content is 0.0004% by mass or more and 0.01% by mass or less, The iron content is 0.010% by mass or less, the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, and the chromium content is 0.005% by mass or less. The silicon content may be 0.001% by mass or less, the manganese content may be 0.05% by mass or less, and the tin content may be 0.01% by mass or less. The content of each of the above components can also be within the range described above in "Composition of metallic titanium".
The method for measuring the impurity content of each component of the metal titanium electrodeposit is the same as the method for measuring the impurity content of each component of the TiAlO conductive material described above.
なお、金属チタン電析物の各成分の不純物含有量の測定方法については、先述したＴｉＡｌＯ導電材の各成分の不純物含有量の測定方法と同様である。 Moreover, in one embodiment, the above-described unavoidable impurities and the like may be specified more specifically. That is, the nitrogen content in the metal titanium electrodeposit is 0.001% by mass or more and 0.03% by mass or less, and the carbon content is 0.0004% by mass or more and 0.01% by mass or less, The iron content is 0.010% by mass or less, the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, and the chromium content is 0.005% by mass or less. The silicon content may be 0.001% by mass or less, the manganese content may be 0.05% by mass or less, and the tin content may be 0.01% by mass or less. The content of each of the above components can also be within the range described above in "Composition of metallic titanium".
The method for measuring the impurity content of each component of the metal titanium electrodeposit is the same as the method for measuring the impurity content of each component of the TiAlO conductive material described above.
（篩別）
更なる実施形態において、当該金属チタン電析物の粒度分布は特に限定されないが、３００μｍ目の篩で篩別した際の篩上となる割合が、質量基準で、下限値として例えば６０％以上であり、また例えば７０％以上である。また、当該金属チタン電析物の前記篩上となる割合は上限値として例えば９０％以下であり、例えば８５％以下である。
以下、篩別による粒度分布の測定方法の一例を示す。
酸素濃度５体積％以下のアルゴン雰囲気のグローブボックス内で、金属チタン電析物を破砕や粉砕しない程度に解砕し、目開き３００μｍの篩を用いて篩別する。下記式（１）に示すように、目開き３００μｍの篩上の金属チタン電析物の質量（Ａ1）を、篩に投入した全質量（Ａtotal）で除し、割合（α）を百分率で算出する。
α（％）＝Ａ1（ｇ）／Ａ（total）×１００ (Sieving)
In a further embodiment, the particle size distribution of the metal titanium electrodeposit is not particularly limited, but the proportion of the metal titanium electrodeposits that are above the sieve when sieved through a 300 μm mesh sieve is, on a mass basis, a lower limit of, for example, 60% or more. Yes, and for example 70% or more. In addition, the upper limit of the ratio of the metal titanium electrodeposits to be on the sieve is, for example, 90% or less, for example, 85% or less.
An example of the method for measuring the particle size distribution by sieving is shown below.
In a glove box in an argon atmosphere with an oxygen concentration of 5% by volume or less, the metal titanium electrodeposit is pulverized to such an extent that it does not crush or pulverize, and is sieved using a sieve with an opening of 300 μm. As shown in the following formula (1), the mass (A 1 ) of the metal titanium electrodeposit on the sieve with an opening of 300 μm is divided by the total mass (A total ) put into the sieve, and the ratio (α) is expressed as a percentage. Calculated by
α (%) = A1 (g)/ A ( total ) x 100
更なる実施形態において、当該金属チタン電析物の粒度分布は特に限定されないが、３００μｍ目の篩で篩別した際の篩上となる割合が、質量基準で、下限値として例えば６０％以上であり、また例えば７０％以上である。また、当該金属チタン電析物の前記篩上となる割合は上限値として例えば９０％以下であり、例えば８５％以下である。
以下、篩別による粒度分布の測定方法の一例を示す。
酸素濃度５体積％以下のアルゴン雰囲気のグローブボックス内で、金属チタン電析物を破砕や粉砕しない程度に解砕し、目開き３００μｍの篩を用いて篩別する。下記式（１）に示すように、目開き３００μｍの篩上の金属チタン電析物の質量（Ａ1）を、篩に投入した全質量（Ａtotal）で除し、割合（α）を百分率で算出する。
α（％）＝Ａ1（ｇ）／Ａ（total）×１００ (Sieving)
In a further embodiment, the particle size distribution of the metal titanium electrodeposit is not particularly limited, but the proportion of the metal titanium electrodeposits that are above the sieve when sieved through a 300 μm mesh sieve is, on a mass basis, a lower limit of, for example, 60% or more. Yes, and for example 70% or more. In addition, the upper limit of the ratio of the metal titanium electrodeposits to be on the sieve is, for example, 90% or less, for example, 85% or less.
An example of the method for measuring the particle size distribution by sieving is shown below.
In a glove box in an argon atmosphere with an oxygen concentration of 5% by volume or less, the metal titanium electrodeposit is pulverized to such an extent that it does not crush or pulverize, and is sieved using a sieve with an opening of 300 μm. As shown in the following formula (1), the mass (A 1 ) of the metal titanium electrodeposit on the sieve with an opening of 300 μm is divided by the total mass (A total ) put into the sieve, and the ratio (α) is expressed as a percentage. Calculated by
α (%) = A1 (g)/ A ( total ) x 100
本発明を実施例及び比較例に基づいて具体的に説明する。以下の実施例及び比較例の記載は、あくまで本発明の技術的内容の理解を容易とするための試験的な具体例であり、本発明の技術的範囲はこれらの具体例によって制限されるものではない。
The present invention will be specifically described based on examples and comparative examples. The descriptions of the following examples and comparative examples are merely experimental specific examples for facilitating the understanding of the technical content of the present invention, and the technical scope of the present invention is limited by these specific examples. is not.
［ＴｉＡｌＯ導電材の評価］
まず、後述する実施例および比較例で用いるＴｉＡｌＯ導電材を、酸化チタンを含むチタン鉱石と、アルミニウムと、分離剤としてのフッ化カルシウムとを含む化学ブレンドを下記に示す条件下で加熱処理した後、公知の方法に基づき後処理をして準備した（抽出工程）。当該抽出工程では、チタン鉱石とアルミニウムと分離剤との投入量が、モル比で酸化チタン：アルミニウム：分離剤＝３：４～７：２～６の範囲内になるように調整した。当該ＴｉＡｌＯ導電材から採取された測定用試料を、金属成分はＩＣＰ発光分析法（ＰＳ３５２０ＵＶＤＤＩＩ、ＨＩＴＡＣＨＩ社製）、酸素は不活性ガス融解－赤外線吸収法（ＴＣ－４３６ＡＲ、ＬＥＣＯ社製）、窒素は不活性ガス融解－熱伝導度法（ＴＣ－４３６ＡＲ、ＬＥＣＯ社製）、炭素は燃焼－赤外線吸収法（ＥＭＩＡ－９２０Ｖ２、堀場製作所社製）により各成分の不純物含有量を測定した。なお、この成分含有量の測定方法は、チタン含有電析物、金属チタン、金属チタン電析物にも適用する。また、１０ｍｍ角のブロック形状として採取された別途の測定用試料を２端子測定法（低抵抗計３５６６－ＲＹ、鶴賀電機株式会社製）により比抵抗を測定した。これらの結果を表１に示す。
＜ＴｉＡｌＯ導電材の製造条件＞
チタン鉱石：酸化チタン含有量９５質量％
不活性ガス：アルゴンガス
加熱温度：１５００℃～１８００℃ [Evaluation of TiAlO conductive material]
First, the TiAlO conductive material used in Examples and Comparative Examples to be described later is a chemical blend containing titanium ore containing titanium oxide, aluminum, and calcium fluoride as a separating agent. After heat treatment under the conditions shown below. , was prepared by post-treatment according to a known method (extraction step). In the extraction process, the amount of titanium ore, aluminum and separating agent charged was adjusted so that the molar ratio of titanium oxide:aluminum:separating agent was within the range of 3:4-7:2-6. A measurement sample collected from the TiAlO conductive material was subjected to ICP emission spectrometry (PS3520UVDDII, manufactured by HITACHI) for metal components, inert gas fusion-infrared absorption method (TC-436AR, manufactured by LECO) for oxygen, and The impurity content of each component was measured by an inert gas fusion-thermal conductivity method (TC-436AR, manufactured by LECO) and a combustion-infrared absorption method for carbon (EMIA-920V2, manufactured by Horiba, Ltd.). This method of measuring the content of the component is also applied to titanium-containing electrodeposits, metal titanium, and metal titanium electrodeposits. Further, the specific resistance of a separate measurement sample collected in the form of a 10 mm square block was measured by a two-terminal measurement method (low resistance meter 3566-RY, manufactured by Tsuruga Electric Co., Ltd.). These results are shown in Table 1.
<Conditions for manufacturing TiAlO conductive material>
Titanium ore: Titanium oxide content 95% by mass
Inert gas: Argon gas Heating temperature: 1500°C to 1800°C
まず、後述する実施例および比較例で用いるＴｉＡｌＯ導電材を、酸化チタンを含むチタン鉱石と、アルミニウムと、分離剤としてのフッ化カルシウムとを含む化学ブレンドを下記に示す条件下で加熱処理した後、公知の方法に基づき後処理をして準備した（抽出工程）。当該抽出工程では、チタン鉱石とアルミニウムと分離剤との投入量が、モル比で酸化チタン：アルミニウム：分離剤＝３：４～７：２～６の範囲内になるように調整した。当該ＴｉＡｌＯ導電材から採取された測定用試料を、金属成分はＩＣＰ発光分析法（ＰＳ３５２０ＵＶＤＤＩＩ、ＨＩＴＡＣＨＩ社製）、酸素は不活性ガス融解－赤外線吸収法（ＴＣ－４３６ＡＲ、ＬＥＣＯ社製）、窒素は不活性ガス融解－熱伝導度法（ＴＣ－４３６ＡＲ、ＬＥＣＯ社製）、炭素は燃焼－赤外線吸収法（ＥＭＩＡ－９２０Ｖ２、堀場製作所社製）により各成分の不純物含有量を測定した。なお、この成分含有量の測定方法は、チタン含有電析物、金属チタン、金属チタン電析物にも適用する。また、１０ｍｍ角のブロック形状として採取された別途の測定用試料を２端子測定法（低抵抗計３５６６－ＲＹ、鶴賀電機株式会社製）により比抵抗を測定した。これらの結果を表１に示す。
＜ＴｉＡｌＯ導電材の製造条件＞
チタン鉱石：酸化チタン含有量９５質量％
不活性ガス：アルゴンガス
加熱温度：１５００℃～１８００℃ [Evaluation of TiAlO conductive material]
First, the TiAlO conductive material used in Examples and Comparative Examples to be described later is a chemical blend containing titanium ore containing titanium oxide, aluminum, and calcium fluoride as a separating agent. After heat treatment under the conditions shown below. , was prepared by post-treatment according to a known method (extraction step). In the extraction process, the amount of titanium ore, aluminum and separating agent charged was adjusted so that the molar ratio of titanium oxide:aluminum:separating agent was within the range of 3:4-7:2-6. A measurement sample collected from the TiAlO conductive material was subjected to ICP emission spectrometry (PS3520UVDDII, manufactured by HITACHI) for metal components, inert gas fusion-infrared absorption method (TC-436AR, manufactured by LECO) for oxygen, and The impurity content of each component was measured by an inert gas fusion-thermal conductivity method (TC-436AR, manufactured by LECO) and a combustion-infrared absorption method for carbon (EMIA-920V2, manufactured by Horiba, Ltd.). This method of measuring the content of the component is also applied to titanium-containing electrodeposits, metal titanium, and metal titanium electrodeposits. Further, the specific resistance of a separate measurement sample collected in the form of a 10 mm square block was measured by a two-terminal measurement method (low resistance meter 3566-RY, manufactured by Tsuruga Electric Co., Ltd.). These results are shown in Table 1.
<Conditions for manufacturing TiAlO conductive material>
Titanium ore: Titanium oxide content 95% by mass
Inert gas: Argon gas Heating temperature: 1500°C to 1800°C
［金属チタンの製造］
＜実施例１＞
（粗電析）
図６（Ａ）及び図７に示した構成を備える電解装置６００を使用した。電解装置６００の電解槽６１０の浴部分の寸法形状は、３００ｍｍΦ×５７０ｍｍ深さとした。次に、電解装置６００の電解槽６１０内に３０ｋｇの塩化マグネシウム（表３参照。）を投入して、これを溶解させて塩化物浴Ｂｆとした。次に、５０００ｇのＴｉＡｌＯ導電材からなる陽極６２０が載置された円環状のニッケル製籠ＢＫを配置した。また、陰極６３０としては、径５０ｍｍ×３００ｍｍのチタン丸棒を準備した。なお、陽極６２０及び陰極６３０の高さ方向が塩化物浴の深さ方向とほぼ平行になるように、陽極６２０及び陰極６３０を配置した。 [Manufacturing of metallic titanium]
<Example 1>
(Crude electrodeposition)
Anelectrolytic device 600 having the configuration shown in FIGS. 6A and 7 was used. The dimensions and shape of the bath portion of the electrolytic cell 610 of the electrolyzer 600 were 300 mmφ×570 mm deep. Next, 30 kg of magnesium chloride (see Table 3) was put into the electrolytic bath 610 of the electrolyzer 600 and dissolved to obtain a chloride bath Bf. Next, an annular nickel cage BK in which an anode 620 made of 5000 g of TiAlO conductive material was placed was placed. A titanium round bar with a diameter of 50 mm×300 mm was prepared as the cathode 630 . The anode 620 and the cathode 630 were arranged such that the height direction of the anode 620 and the cathode 630 was substantially parallel to the depth direction of the chloride bath.
＜実施例１＞
（粗電析）
図６（Ａ）及び図７に示した構成を備える電解装置６００を使用した。電解装置６００の電解槽６１０の浴部分の寸法形状は、３００ｍｍΦ×５７０ｍｍ深さとした。次に、電解装置６００の電解槽６１０内に３０ｋｇの塩化マグネシウム（表３参照。）を投入して、これを溶解させて塩化物浴Ｂｆとした。次に、５０００ｇのＴｉＡｌＯ導電材からなる陽極６２０が載置された円環状のニッケル製籠ＢＫを配置した。また、陰極６３０としては、径５０ｍｍ×３００ｍｍのチタン丸棒を準備した。なお、陽極６２０及び陰極６３０の高さ方向が塩化物浴の深さ方向とほぼ平行になるように、陽極６２０及び陰極６３０を配置した。 [Manufacturing of metallic titanium]
<Example 1>
(Crude electrodeposition)
An
制御機構が陽極６２０及び陰極６３０に連結された導電線ＥＬを介して該陽極６２０及び該陰極６３０に電流を供給して、塩化物浴Ｂｆ中にて溶融塩電解を行った。電流の供給開始時から７時間経過後、制御機構が電流の供給を停止した。なお、図６（Ｂ）に示すように、その陰極６３０の表面全体に亘って析出されたチタン含有電析物ＴＣが得られた。
＜電解条件＞
電解槽内：Ａｒガス雰囲気
塩化物浴の温度：８５０℃
電流密度：０．５Ａ／ｃｍ2 A control mechanism supplied electric current to theanode 620 and the cathode 630 through a conductive line EL connected to the anode 620 and the cathode 630 to perform molten salt electrolysis in the chloride bath Bf. Seven hours after the start of the current supply, the control mechanism stopped the current supply. Incidentally, as shown in FIG. 6(B), a titanium-containing electrodeposit TC deposited over the entire surface of the cathode 630 was obtained.
<Electrolysis conditions>
Inside the electrolytic cell: Ar gas atmosphere Chloride bath temperature: 850°C
Current density: 0.5 A/cm 2
＜電解条件＞
電解槽内：Ａｒガス雰囲気
塩化物浴の温度：８５０℃
電流密度：０．５Ａ／ｃｍ2 A control mechanism supplied electric current to the
<Electrolysis conditions>
Inside the electrolytic cell: Ar gas atmosphere Chloride bath temperature: 850°C
Current density: 0.5 A/cm 2
電流の供給停止後、電解槽６１０から陰極６３０を引き上げて、該陰極６３０及びチタン含有電析物ＴＣを水洗し、それぞれ付着していた溶融塩を除去した。当該陰極６３０から金属チタンを含有するチタン含有電析物ＴＣを切削工具で剥がし回収した。当該チタン含有電析物ＴＣを真空分離で水分を蒸発させた。
After the current supply was stopped, the cathode 630 was pulled up from the electrolytic bath 610, and the cathode 630 and the titanium-containing electrodeposit TC were washed with water to remove adhering molten salt. A titanium-containing electrodeposit TC containing metallic titanium was peeled off from the cathode 630 with a cutting tool and recovered. Moisture was evaporated from the titanium-containing electrodeposit TC by vacuum separation.
粗電析で得られたチタン含有電析物ＴＣから採取された測定用試料を、先述の方法により各成分の不純物含有量を測定した。この結果を表４に示す。
また、篩別法（目開き３００μｍの篩を使用）によりチタン含有電析物ＴＣにおける篩上となる割合を測定した。
さらに、チタン含有電析物ＴＣの形状確認のため、カメラで撮影した。また、チタン含有電析物ＴＣの形状確認のため、下記測定条件にてＳＥＭ観察した。これらの結果を図８（Ａ）及び図８（Ｂ）に示す。
＜ＳＥＭ測定条件＞
ＳＥＭ：型式ＪＳＭ－７８００Ｆ、ＪＥＯＬ社製
加速電圧：１０ｋＶ
倍率：６０～１０００倍の範囲内 A sample for measurement taken from the titanium-containing electrodeposit TC obtained by crude electrodeposition was measured for the impurity content of each component by the method described above. The results are shown in Table 4.
In addition, the percentage of the titanium-containing electrodeposits TC that were on the sieve was measured by a sieving method (using a sieve with an opening of 300 μm).
Further, a photograph was taken with a camera to confirm the shape of the titanium-containing electrodeposit TC. In order to confirm the shape of the titanium-containing electrodeposit TC, SEM observation was performed under the following measurement conditions. These results are shown in FIGS. 8(A) and 8(B).
<SEM measurement conditions>
SEM: Model JSM-7800F, manufactured by JEOL Accelerating voltage: 10 kV
Magnification: within the range of 60 to 1000 times
また、篩別法（目開き３００μｍの篩を使用）によりチタン含有電析物ＴＣにおける篩上となる割合を測定した。
さらに、チタン含有電析物ＴＣの形状確認のため、カメラで撮影した。また、チタン含有電析物ＴＣの形状確認のため、下記測定条件にてＳＥＭ観察した。これらの結果を図８（Ａ）及び図８（Ｂ）に示す。
＜ＳＥＭ測定条件＞
ＳＥＭ：型式ＪＳＭ－７８００Ｆ、ＪＥＯＬ社製
加速電圧：１０ｋＶ
倍率：６０～１０００倍の範囲内 A sample for measurement taken from the titanium-containing electrodeposit TC obtained by crude electrodeposition was measured for the impurity content of each component by the method described above. The results are shown in Table 4.
In addition, the percentage of the titanium-containing electrodeposits TC that were on the sieve was measured by a sieving method (using a sieve with an opening of 300 μm).
Further, a photograph was taken with a camera to confirm the shape of the titanium-containing electrodeposit TC. In order to confirm the shape of the titanium-containing electrodeposit TC, SEM observation was performed under the following measurement conditions. These results are shown in FIGS. 8(A) and 8(B).
<SEM measurement conditions>
SEM: Model JSM-7800F, manufactured by JEOL Accelerating voltage: 10 kV
Magnification: within the range of 60 to 1000 times
（精製電析）
図６（Ｃ）に示すように、電解装置６００の電解槽６１０内に３０ｋｇの塩化マグネシウム（表３参照。）を投入して、これを溶解させて塩化物浴Ｂｆとした。次に、５００ｇのチタン含有電析物ＴＣからなる陽極６２２が載置された円環状のニッケル製籠ＢＫを配置した。また、陰極６３０としては、径５０ｍｍ×３００ｍｍのチタン丸棒を準備した。なお、陽極６２２及び陰極６３０の高さ方向が塩化物浴の深さ方向とほぼ平行になるように、陽極６２２及び陰極６３０を配置した。 (refining electrodeposition)
As shown in FIG. 6(C), 30 kg of magnesium chloride (see Table 3) was put into theelectrolytic bath 610 of the electrolyzer 600 and dissolved to form a chloride bath Bf. Next, a ring-shaped nickel basket BK in which an anode 622 made of 500 g of titanium-containing electrodeposit TC was placed was placed. A titanium round bar with a diameter of 50 mm×300 mm was prepared as the cathode 630 . The anode 622 and the cathode 630 were arranged such that the height direction of the anode 622 and the cathode 630 was substantially parallel to the depth direction of the chloride bath.
図６（Ｃ）に示すように、電解装置６００の電解槽６１０内に３０ｋｇの塩化マグネシウム（表３参照。）を投入して、これを溶解させて塩化物浴Ｂｆとした。次に、５００ｇのチタン含有電析物ＴＣからなる陽極６２２が載置された円環状のニッケル製籠ＢＫを配置した。また、陰極６３０としては、径５０ｍｍ×３００ｍｍのチタン丸棒を準備した。なお、陽極６２２及び陰極６３０の高さ方向が塩化物浴の深さ方向とほぼ平行になるように、陽極６２２及び陰極６３０を配置した。 (refining electrodeposition)
As shown in FIG. 6(C), 30 kg of magnesium chloride (see Table 3) was put into the
制御機構が陽極６２２及び陰極６３０に連結された導電線ＥＬを介して該陽極６２２及び該陰極６３０に電流を供給して、塩化物浴Ｂｆ中にて溶融塩電解を行った。電流の供給開始時から２時間経過後、制御機構が電流の供給を停止した。なお、図６（Ｄ）に示すように、その陰極１３０の表面全体に亘って析出された金属チタン電析物ＴＰが得られた。
＜電解条件＞
電解槽内：Ａｒガス雰囲気
塩化物浴の温度：８５０℃
電流密度：０．５Ａ／ｃｍ2 A control mechanism supplied electric current to theanode 622 and the cathode 630 via a conductive line EL connected to the anode 622 and the cathode 630 to perform molten salt electrolysis in the chloride bath Bf. Two hours after the start of the current supply, the control mechanism stopped the current supply. In addition, as shown in FIG. 6(D), a metal titanium electrodeposit TP deposited over the entire surface of the cathode 130 was obtained.
<Electrolysis conditions>
Inside the electrolytic cell: Ar gas atmosphere Chloride bath temperature: 850°C
Current density: 0.5 A/cm 2
＜電解条件＞
電解槽内：Ａｒガス雰囲気
塩化物浴の温度：８５０℃
電流密度：０．５Ａ／ｃｍ2 A control mechanism supplied electric current to the
<Electrolysis conditions>
Inside the electrolytic cell: Ar gas atmosphere Chloride bath temperature: 850°C
Current density: 0.5 A/cm 2
電流の供給停止後、電解槽１１０から陰極１３０を引き上げて、該陰極１３０及び金属チタン電析物ＴＰを酸洗し、さらに水洗し、それぞれ付着していた溶融塩を除去した。当該陰極１３０から金属チタン電析物ＴＰを切削工具で剥がし回収した。当該金属チタン電析物ＴＰを真空分離で水分を蒸発させた。
After the supply of current was stopped, the cathode 130 was pulled up from the electrolytic cell 110, and the cathode 130 and the metal titanium electrodeposit TP were pickled and then washed with water to remove the adhering molten salt. The metal titanium electrodeposit TP was peeled off from the cathode 130 with a cutting tool and collected. Moisture was evaporated from the metal titanium electrodeposit TP by vacuum separation.
精製電析で得られた金属チタン電析物ＴＰから採取された測定用試料を、先述の方法により各成分の不純物含有量を測定した。この結果を表４に示す。
また、篩別法（目開き３００μｍの篩を使用）により金属チタン電析物ＴＰにおける篩上となる割合を測定した。これらの結果を表５に示す。
さらに、金属チタン電析物ＴＰの形状確認のため、カメラで撮影した。また、金属チタン電析物ＴＰの形状確認のため、下記測定条件にてＳＥＭ観察した。これらの結果を図９（Ａ）及び図９（Ｂ）に示す。
＜ＳＥＭ測定条件＞
ＳＥＭ：型式ＪＳＭ－７８００Ｆ、ＪＥＯＬ社製
加速電圧：１０ｋＶ
倍率：６０～１０００倍の範囲内 A sample for measurement taken from the metal titanium electrodeposit TP obtained by the refinement electrodeposition was measured for the impurity content of each component by the method described above. The results are shown in Table 4.
In addition, the proportion of the metal titanium electrodeposits TP that were above the sieve was measured by a sieving method (using a sieve with an opening of 300 μm). These results are shown in Table 5.
Further, a photograph was taken with a camera to confirm the shape of the titanium metal electrodeposit TP. In order to confirm the shape of the metal titanium electrodeposit TP, SEM observation was performed under the following measurement conditions. These results are shown in FIGS. 9(A) and 9(B).
<SEM measurement conditions>
SEM: Model JSM-7800F, manufactured by JEOL Accelerating voltage: 10 kV
Magnification: within the range of 60 to 1000 times
また、篩別法（目開き３００μｍの篩を使用）により金属チタン電析物ＴＰにおける篩上となる割合を測定した。これらの結果を表５に示す。
さらに、金属チタン電析物ＴＰの形状確認のため、カメラで撮影した。また、金属チタン電析物ＴＰの形状確認のため、下記測定条件にてＳＥＭ観察した。これらの結果を図９（Ａ）及び図９（Ｂ）に示す。
＜ＳＥＭ測定条件＞
ＳＥＭ：型式ＪＳＭ－７８００Ｆ、ＪＥＯＬ社製
加速電圧：１０ｋＶ
倍率：６０～１０００倍の範囲内 A sample for measurement taken from the metal titanium electrodeposit TP obtained by the refinement electrodeposition was measured for the impurity content of each component by the method described above. The results are shown in Table 4.
In addition, the proportion of the metal titanium electrodeposits TP that were above the sieve was measured by a sieving method (using a sieve with an opening of 300 μm). These results are shown in Table 5.
Further, a photograph was taken with a camera to confirm the shape of the titanium metal electrodeposit TP. In order to confirm the shape of the metal titanium electrodeposit TP, SEM observation was performed under the following measurement conditions. These results are shown in FIGS. 9(A) and 9(B).
<SEM measurement conditions>
SEM: Model JSM-7800F, manufactured by JEOL Accelerating voltage: 10 kV
Magnification: within the range of 60 to 1000 times
＜実施例２～６、比較例１～３＞
実施例２～６、比較例１～３においては、表３に示す塩化物浴に変更した点を除き、実施例１と同様にそれぞれ実施した。なお、実施例６のみは精製電析ステップを２回実施した。各ステップで作製した電析物を実施例１と同様に水洗浄及び真空乾燥後、不純物含有量及び篩上となる割合を測定した。その結果を表４及び表５にそれぞれ示す。 <Examples 2 to 6, Comparative Examples 1 to 3>
Examples 2 to 6 and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1, except that the chloride bath shown in Table 3 was used. Note that only Example 6 was subjected to the refinement electrodeposition step twice. After the electrodeposits prepared in each step were washed with water and vacuum-dried in the same manner as in Example 1, the content of impurities and the percentage of sieved deposits were measured. The results are shown in Tables 4 and 5, respectively.
実施例２～６、比較例１～３においては、表３に示す塩化物浴に変更した点を除き、実施例１と同様にそれぞれ実施した。なお、実施例６のみは精製電析ステップを２回実施した。各ステップで作製した電析物を実施例１と同様に水洗浄及び真空乾燥後、不純物含有量及び篩上となる割合を測定した。その結果を表４及び表５にそれぞれ示す。 <Examples 2 to 6, Comparative Examples 1 to 3>
Examples 2 to 6 and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1, except that the chloride bath shown in Table 3 was used. Note that only Example 6 was subjected to the refinement electrodeposition step twice. After the electrodeposits prepared in each step were washed with water and vacuum-dried in the same manner as in Example 1, the content of impurities and the percentage of sieved deposits were measured. The results are shown in Tables 4 and 5, respectively.
（実施例による考察）
実施例１～６において、アルミニウム含有量１１．６質量％及び酸素含有量１０．３質量％のＴｉＡｌＯ導電材を用いた溶融塩電解により、最終的に得られた金属チタン電析物ＴＰ中のアルミニウム含有量は１００質量ｐｐｍ以下であり、且つ酸素含有量は５００質量ｐｐｍ以下まで低減することができた。すなわち、粗電析で使用される塩化物浴及び精製電析で使用される塩化物浴のうち少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムを含有することが有用であることを確認した。したがって、このような金属チタン電析物を用いれば、純度の高い金属チタンを製造することが可能であると推察される。
特に、実施例１において、粗電析で使用される塩化物浴及び精製電析で使用される塩化物浴が１００ｍｏｌ％の塩化マグネシウムを含有していたことで、金属チタン電析物ＴＰ中のアルミニウム含有量及び酸素含有量をより確実に低減させることができたと推察される。
また、実施例６において、精製電析を複数回実施したことで、金属チタン電析物ＴＰ中のアルミニウム含有量及び酸素含有量をより確実に低減させることができたと推察される。
一方、比較例１～３においては、粗電析で使用される塩化物浴及び精製電析で使用される塩化物浴のいずれも３０ｍｏｌ％以上の塩化マグネシウムを含有していなかった。そのため、比較例１～３においては、アルミニウム含有量を良好に低減させることができなかったと推察される。 (Consideration by Example)
In Examples 1 to 6, the metal titanium electrodeposit TP finally obtained by molten salt electrolysis using a TiAlO conductive material having an aluminum content of 11.6 mass% and an oxygen content of 10.3 mass% The aluminum content was below 100 ppm by weight and the oxygen content could be reduced to below 500 ppm by weight. That is, it was confirmed that at least one of the chloride bath used for crude electrodeposition and the chloride bath used for refined electrodeposition contained 30 mol % or more of magnesium chloride. . Therefore, it is presumed that high-purity titanium metal can be produced by using such a titanium metal electrodeposit.
In particular, in Example 1, the chloride bath used in crude electrodeposition and the chloride bath used in refined electrodeposition contained 100 mol% magnesium chloride, so that It is speculated that the aluminum content and oxygen content could be reduced more reliably.
In addition, it is presumed that the aluminum content and the oxygen content in the metal titanium electrodeposit TP could be more reliably reduced by performing the refinement electrodeposition multiple times in Example 6.
On the other hand, in Comparative Examples 1 to 3, neither the chloride bath used for crude electrodeposition nor the chloride bath used for refined electrodeposition contained 30 mol % or more of magnesium chloride. Therefore, in Comparative Examples 1 to 3, it is presumed that the aluminum content could not be reduced satisfactorily.
実施例１～６において、アルミニウム含有量１１．６質量％及び酸素含有量１０．３質量％のＴｉＡｌＯ導電材を用いた溶融塩電解により、最終的に得られた金属チタン電析物ＴＰ中のアルミニウム含有量は１００質量ｐｐｍ以下であり、且つ酸素含有量は５００質量ｐｐｍ以下まで低減することができた。すなわち、粗電析で使用される塩化物浴及び精製電析で使用される塩化物浴のうち少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムを含有することが有用であることを確認した。したがって、このような金属チタン電析物を用いれば、純度の高い金属チタンを製造することが可能であると推察される。
特に、実施例１において、粗電析で使用される塩化物浴及び精製電析で使用される塩化物浴が１００ｍｏｌ％の塩化マグネシウムを含有していたことで、金属チタン電析物ＴＰ中のアルミニウム含有量及び酸素含有量をより確実に低減させることができたと推察される。
また、実施例６において、精製電析を複数回実施したことで、金属チタン電析物ＴＰ中のアルミニウム含有量及び酸素含有量をより確実に低減させることができたと推察される。
一方、比較例１～３においては、粗電析で使用される塩化物浴及び精製電析で使用される塩化物浴のいずれも３０ｍｏｌ％以上の塩化マグネシウムを含有していなかった。そのため、比較例１～３においては、アルミニウム含有量を良好に低減させることができなかったと推察される。 (Consideration by Example)
In Examples 1 to 6, the metal titanium electrodeposit TP finally obtained by molten salt electrolysis using a TiAlO conductive material having an aluminum content of 11.6 mass% and an oxygen content of 10.3 mass% The aluminum content was below 100 ppm by weight and the oxygen content could be reduced to below 500 ppm by weight. That is, it was confirmed that at least one of the chloride bath used for crude electrodeposition and the chloride bath used for refined electrodeposition contained 30 mol % or more of magnesium chloride. . Therefore, it is presumed that high-purity titanium metal can be produced by using such a titanium metal electrodeposit.
In particular, in Example 1, the chloride bath used in crude electrodeposition and the chloride bath used in refined electrodeposition contained 100 mol% magnesium chloride, so that It is speculated that the aluminum content and oxygen content could be reduced more reliably.
In addition, it is presumed that the aluminum content and the oxygen content in the metal titanium electrodeposit TP could be more reliably reduced by performing the refinement electrodeposition multiple times in Example 6.
On the other hand, in Comparative Examples 1 to 3, neither the chloride bath used for crude electrodeposition nor the chloride bath used for refined electrodeposition contained 30 mol % or more of magnesium chloride. Therefore, in Comparative Examples 1 to 3, it is presumed that the aluminum content could not be reduced satisfactorily.
１００、２００、３００、４００、５００、６００ 電解装置
１１０、２１０、３１０、４１０、５１０、６１０ 電解槽
１２０、１２２、２２０、２２２、３２０、３２２、４２０、４２２、４２４、５２０、６２０、６２２ 陽極
１３０、２３０、３３０、３３５、４３０、４３５、５３０、６３０ 陰極
５４０ 複極
Ｂｆ 塩化物浴
ＢＫ 籠
ＢＳ 基台
ＥＬ 導電線
ＴＣ チタン含有電析物
ＴＰ 金属チタン電析物 100, 200, 300, 400, 500, 600 electrolyzer 110, 210, 310, 410, 510, 610 electrolytic cell 120, 122, 220, 222, 320, 322, 420, 422, 424, 520, 620, 622 anode 130, 230, 330, 335, 430, 435, 530, 630 Cathode 540 Bipolar Bf Chloride bath BK Basket BS Base EL Conductive wire TC Titanium-containing electrodeposit TP Metal titanium electrodeposit
１１０、２１０、３１０、４１０、５１０、６１０ 電解槽
１２０、１２２、２２０、２２２、３２０、３２２、４２０、４２２、４２４、５２０、６２０、６２２ 陽極
１３０、２３０、３３０、３３５、４３０、４３５、５３０、６３０ 陰極
５４０ 複極
Ｂｆ 塩化物浴
ＢＫ 籠
ＢＳ 基台
ＥＬ 導電線
ＴＣ チタン含有電析物
ＴＰ 金属チタン電析物 100, 200, 300, 400, 500, 600
なお、本発明は以下の発明も包含するものとする。
［１］
チタンと、アルミニウムと、酸素とを含むＴｉＡｌＯ導電材を精錬する精錬工程を含む金属チタンの製造方法であって、
前記精錬工程は、塩化物浴で前記ＴｉＡｌＯ導電材を含む電極を用いて溶融塩電解することでチタン含有電析物を得る粗電析ステップと、
該粗電析ステップ後、塩化物浴で前記チタン含有電析物を含む電極を用いて溶融塩電解する１回以上の精製電析ステップとを有し、
前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムを含有する、金属チタンの製造方法。
［２］
前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムを含有する、［１］に記載の金属チタンの製造方法。
［３］
前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する、［１］に記載の金属チタンの製造方法。
［４］
前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する、［１］に記載の金属チタンの製造方法。
［５］
前記精錬工程前に、酸化チタンを含むチタン鉱石と、アルミニウムと、分離剤とを含む化学ブレンドを加熱処理して前記ＴｉＡｌＯ導電材を得る抽出工程を更に含む、［１］～［４］のいずれか一つに記載の金属チタンの製造方法。
［６］
前記化学ブレンドに含まれる酸化チタンとアルミニウムと分離剤とのモル比は、３：４～７：２～６である、［５］に記載の金属チタンの製造方法。
［７］
前記分離剤が、フッ化カルシウム、酸化カルシウム及びフッ化ナトリウムから選ばれる１種以上を含有する、［５］又は［６］に記載の金属チタンの製造方法。
［８］
前記金属チタン中の、アルミニウム含有量が１００質量ｐｐｍ以下であり、酸素含有量が５００質量ｐｐｍ以下である、［１］～［７］のいずれか一つに記載の金属チタンの製造方法。
［９］
前記金属チタン中の、窒素含有量が０．０３質量％以下であり、炭素含有量が０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である、［８］に記載の金属チタンの製造方法。
［１０］
金属チタン電析物であって、
アルミニウム含有量が５質量ｐｐｍ以上かつ１００質量ｐｐｍ以下であり、且つ酸素含有量が１００質量ｐｐｍ以上かつ５００質量ｐｐｍ以下である、金属チタン電析物。
［１１］
窒素含有量が０．００１質量％以上かつ０．０３質量％以下であり、炭素含有量が０．０００４質量％以上かつ０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である、［１０］に記載の金属チタン電析物。 It should be noted that the present invention also includes the following inventions.
[1]
A method for producing metallic titanium, comprising a refining step of refining a TiAlO conductive material containing titanium, aluminum, and oxygen,
The refining step includes a crude electrodeposition step of obtaining a titanium-containing electrodeposit by performing molten salt electrolysis using an electrode containing the TiAlO conductive material in a chloride bath;
After the rough electrodeposition step, one or more refinement electrodeposition steps of performing molten salt electrolysis using an electrode containing the titanium-containing electrodeposit in a chloride bath,
A method for producing metallic titanium, wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refined electrodeposition step contains 30 mol % or more of magnesium chloride.
[2]
The metal according to [1], wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step contains 50 mol% or more of magnesium chloride. A method of manufacturing titanium.
[3]
Production of metallic titanium according to [1], wherein the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refinement electrodeposition step each contain 30 mol % or more of magnesium chloride. Method.
[4]
Production of metallic titanium according to [1], wherein the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refinement electrodeposition step each contain 50 mol% or more of magnesium chloride. Method.
[5]
Any of [1] to [4], further comprising an extraction step of obtaining the TiAlO conductive material by heat-treating a chemical blend containing titanium ore containing titanium oxide, aluminum, and a separating agent before the refining step. A method for producing metallic titanium according to any one of the above.
[6]
The method for producing metallic titanium according to [5], wherein the molar ratio of titanium oxide, aluminum and separating agent contained in the chemical blend is 3:4 to 7:2 to 6.
[7]
The method for producing metallic titanium according to [5] or [6], wherein the separating agent contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride.
[8]
The method for producing metallic titanium according to any one of [1] to [7], wherein the metallic titanium has an aluminum content of 100 mass ppm or less and an oxygen content of 500 mass ppm or less.
[9]
The nitrogen content in the metal titanium is 0.03% by mass or less, the carbon content is 0.01% by mass or less, the iron content is 0.010% by mass or less, and the magnesium content is 0. 0.05% by mass or less, a nickel content of 0.01% by mass or less, a chromium content of 0.005% by mass or less, a silicon content of 0.001% by mass or less, and a manganese content is 0.05% by mass or less, and the tin content is 0.01% by mass or less.
[10]
A metal titanium electrodeposit,
A metal titanium electrodeposit having an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less.
[11]
Nitrogen content is 0.001% by mass or more and 0.03% by mass or less, carbon content is 0.0004% by mass or more and 0.01% by mass or less, and iron content is 0.010% by mass or less wherein the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, the chromium content is 0.005% by mass or less, and the silicon content is 0.001% by mass % or less, a manganese content of 0.05% by mass or less, and a tin content of 0.01% by mass or less, the metal titanium electrodeposit according to [10].
［１］
チタンと、アルミニウムと、酸素とを含むＴｉＡｌＯ導電材を精錬する精錬工程を含む金属チタンの製造方法であって、
前記精錬工程は、塩化物浴で前記ＴｉＡｌＯ導電材を含む電極を用いて溶融塩電解することでチタン含有電析物を得る粗電析ステップと、
該粗電析ステップ後、塩化物浴で前記チタン含有電析物を含む電極を用いて溶融塩電解する１回以上の精製電析ステップとを有し、
前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムを含有する、金属チタンの製造方法。
［２］
前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムを含有する、［１］に記載の金属チタンの製造方法。
［３］
前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する、［１］に記載の金属チタンの製造方法。
［４］
前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する、［１］に記載の金属チタンの製造方法。
［５］
前記精錬工程前に、酸化チタンを含むチタン鉱石と、アルミニウムと、分離剤とを含む化学ブレンドを加熱処理して前記ＴｉＡｌＯ導電材を得る抽出工程を更に含む、［１］～［４］のいずれか一つに記載の金属チタンの製造方法。
［６］
前記化学ブレンドに含まれる酸化チタンとアルミニウムと分離剤とのモル比は、３：４～７：２～６である、［５］に記載の金属チタンの製造方法。
［７］
前記分離剤が、フッ化カルシウム、酸化カルシウム及びフッ化ナトリウムから選ばれる１種以上を含有する、［５］又は［６］に記載の金属チタンの製造方法。
［８］
前記金属チタン中の、アルミニウム含有量が１００質量ｐｐｍ以下であり、酸素含有量が５００質量ｐｐｍ以下である、［１］～［７］のいずれか一つに記載の金属チタンの製造方法。
［９］
前記金属チタン中の、窒素含有量が０．０３質量％以下であり、炭素含有量が０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である、［８］に記載の金属チタンの製造方法。
［１０］
金属チタン電析物であって、
アルミニウム含有量が５質量ｐｐｍ以上かつ１００質量ｐｐｍ以下であり、且つ酸素含有量が１００質量ｐｐｍ以上かつ５００質量ｐｐｍ以下である、金属チタン電析物。
［１１］
窒素含有量が０．００１質量％以上かつ０．０３質量％以下であり、炭素含有量が０．０００４質量％以上かつ０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である、［１０］に記載の金属チタン電析物。 It should be noted that the present invention also includes the following inventions.
[1]
A method for producing metallic titanium, comprising a refining step of refining a TiAlO conductive material containing titanium, aluminum, and oxygen,
The refining step includes a crude electrodeposition step of obtaining a titanium-containing electrodeposit by performing molten salt electrolysis using an electrode containing the TiAlO conductive material in a chloride bath;
After the rough electrodeposition step, one or more refinement electrodeposition steps of performing molten salt electrolysis using an electrode containing the titanium-containing electrodeposit in a chloride bath,
A method for producing metallic titanium, wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refined electrodeposition step contains 30 mol % or more of magnesium chloride.
[2]
The metal according to [1], wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step contains 50 mol% or more of magnesium chloride. A method of manufacturing titanium.
[3]
Production of metallic titanium according to [1], wherein the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refinement electrodeposition step each contain 30 mol % or more of magnesium chloride. Method.
[4]
Production of metallic titanium according to [1], wherein the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refinement electrodeposition step each contain 50 mol% or more of magnesium chloride. Method.
[5]
Any of [1] to [4], further comprising an extraction step of obtaining the TiAlO conductive material by heat-treating a chemical blend containing titanium ore containing titanium oxide, aluminum, and a separating agent before the refining step. A method for producing metallic titanium according to any one of the above.
[6]
The method for producing metallic titanium according to [5], wherein the molar ratio of titanium oxide, aluminum and separating agent contained in the chemical blend is 3:4 to 7:2 to 6.
[7]
The method for producing metallic titanium according to [5] or [6], wherein the separating agent contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride.
[8]
The method for producing metallic titanium according to any one of [1] to [7], wherein the metallic titanium has an aluminum content of 100 mass ppm or less and an oxygen content of 500 mass ppm or less.
[9]
The nitrogen content in the metal titanium is 0.03% by mass or less, the carbon content is 0.01% by mass or less, the iron content is 0.010% by mass or less, and the magnesium content is 0. 0.05% by mass or less, a nickel content of 0.01% by mass or less, a chromium content of 0.005% by mass or less, a silicon content of 0.001% by mass or less, and a manganese content is 0.05% by mass or less, and the tin content is 0.01% by mass or less.
[10]
A metal titanium electrodeposit,
A metal titanium electrodeposit having an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less.
[11]
Nitrogen content is 0.001% by mass or more and 0.03% by mass or less, carbon content is 0.0004% by mass or more and 0.01% by mass or less, and iron content is 0.010% by mass or less wherein the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, the chromium content is 0.005% by mass or less, and the silicon content is 0.001% by mass % or less, a manganese content of 0.05% by mass or less, and a tin content of 0.01% by mass or less, the metal titanium electrodeposit according to [10].
Claims (11)
- チタンと、アルミニウムと、酸素とを含むＴｉＡｌＯ導電材を精錬する精錬工程を含む金属チタンの製造方法であって、
前記精錬工程は、塩化物浴で前記ＴｉＡｌＯ導電材を含む電極を用いて溶融塩電解することでチタン含有電析物を得る粗電析ステップと、
該粗電析ステップ後、塩化物浴で前記チタン含有電析物を含む電極を用いて溶融塩電解する１回以上の精製電析ステップとを有し、
前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムを含有する、金属チタンの製造方法。 A method for producing metallic titanium, comprising a refining step of refining a TiAlO conductive material containing titanium, aluminum, and oxygen,
The refining step includes a crude electrodeposition step of obtaining a titanium-containing electrodeposit by performing molten salt electrolysis using an electrode containing the TiAlO conductive material in a chloride bath;
After the rough electrodeposition step, one or more refinement electrodeposition steps of performing molten salt electrolysis using an electrode containing the titanium-containing electrodeposit in a chloride bath,
A method for producing metallic titanium, wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refined electrodeposition step contains 30 mol % or more of magnesium chloride. - 前記粗電析ステップで使用される塩化物浴及び精製電析ステップで使用される塩化物浴のうち少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムを含有する、請求項１に記載の金属チタンの製造方法。 2. The metal according to claim 1, wherein at least one of the chloride bath used in the crude electrodeposition step and the chloride bath used in the refinement electrodeposition step contains 50 mol % or more of magnesium chloride. A method of manufacturing titanium.
- 前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が３０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する、請求項１に記載の金属チタンの製造方法。 The production of metallic titanium according to claim 1, wherein the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refinement electrodeposition step each contain 30 mol% or more of magnesium chloride. Method.
- 前記粗電析ステップで使用される塩化物浴及び前記精製電析ステップで使用される少なくとも１つの塩化物浴が５０ｍｏｌ％以上の塩化マグネシウムをそれぞれ含有する、請求項１に記載の金属チタンの製造方法。 2. The production of metallic titanium according to claim 1, wherein the chloride bath used in the crude electrodeposition step and at least one chloride bath used in the refinement electrodeposition step each contain 50 mol % or more of magnesium chloride. Method.
- 前記精錬工程前に、酸化チタンを含むチタン鉱石と、アルミニウムと、分離剤とを含む化学ブレンドを加熱処理して前記ＴｉＡｌＯ導電材を得る抽出工程を更に含む、請求項１～４のいずれか一項に記載の金属チタンの製造方法。 5. The method according to any one of claims 1 to 4, further comprising an extraction step of heat-treating a chemical blend containing a titanium ore containing titanium oxide, aluminum, and a separating agent to obtain the TiAlO conductive material before the refining step. 10. A method for producing metallic titanium according to claim 1.
- 前記化学ブレンドに含まれる酸化チタンとアルミニウムと分離剤とのモル比は、３：４～７：２～６である、請求項５に記載の金属チタンの製造方法。 The method for producing metallic titanium according to claim 5, wherein the molar ratio of titanium oxide, aluminum and separating agent contained in the chemical blend is 3:4-7:2-6.
- 前記分離剤が、フッ化カルシウム、酸化カルシウム及びフッ化ナトリウムから選ばれる１種以上を含有する、請求項５又は６に記載の金属チタンの製造方法。 The method for producing metallic titanium according to claim 5 or 6, wherein the separating agent contains one or more selected from calcium fluoride, calcium oxide and sodium fluoride.
- 前記金属チタン中の、アルミニウム含有量が１００質量ｐｐｍ以下であり、酸素含有量が５００質量ｐｐｍ以下である、請求項１～７のいずれか一項に記載の金属チタンの製造方法。 The method for producing metallic titanium according to any one of claims 1 to 7, wherein the metallic titanium has an aluminum content of 100 mass ppm or less and an oxygen content of 500 mass ppm or less.
- 前記金属チタン中の、窒素含有量が０．０３質量％以下であり、炭素含有量が０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である、請求項８に記載の金属チタンの製造方法。 The nitrogen content in the metal titanium is 0.03% by mass or less, the carbon content is 0.01% by mass or less, the iron content is 0.010% by mass or less, and the magnesium content is 0. 0.05% by mass or less, a nickel content of 0.01% by mass or less, a chromium content of 0.005% by mass or less, a silicon content of 0.001% by mass or less, and a manganese content is 0.05% by mass or less, and the tin content is 0.01% by mass or less.
- 金属チタン電析物であって、
アルミニウム含有量が５質量ｐｐｍ以上かつ１００質量ｐｐｍ以下であり、且つ酸素含有量が１００質量ｐｐｍ以上かつ５００質量ｐｐｍ以下である、金属チタン電析物。 A metal titanium electrodeposit,
A metal titanium electrodeposit having an aluminum content of 5 mass ppm or more and 100 mass ppm or less and an oxygen content of 100 mass ppm or more and 500 mass ppm or less. - 窒素含有量が０．００１質量％以上かつ０．０３質量％以下であり、炭素含有量が０．０００４質量％以上かつ０．０１質量％以下であり、鉄含有量が０．０１０質量％以下であり、マグネシウム含有量が０．０５質量％以下であり、ニッケル含有量が０．０１質量％以下であり、クロム含有量が０．００５質量％以下であり、シリコン含有量が０．００１質量％以下であり、マンガン含有量が０．０５質量％以下であり、スズ含有量が０．０１質量％以下である、請求項１０に記載の金属チタン電析物。 Nitrogen content is 0.001% by mass or more and 0.03% by mass or less, carbon content is 0.0004% by mass or more and 0.01% by mass or less, and iron content is 0.010% by mass or less wherein the magnesium content is 0.05% by mass or less, the nickel content is 0.01% by mass or less, the chromium content is 0.005% by mass or less, and the silicon content is 0.001% by mass % or less, the manganese content is 0.05 mass % or less, and the tin content is 0.01 mass % or less.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06173065A (en) * | 1992-12-09 | 1994-06-21 | Japan Energy Corp | Method for refining ti |
| JP2015507696A (en) | 2011-12-22 | 2015-03-12 | ユニヴァーサル テクニカル リソース サービシーズ インコーポレイテッド | Apparatus and method for titanium extraction and refining |
| WO2018159774A1 (en) * | 2017-03-01 | 2018-09-07 | 国立大学法人京都大学 | Method for producing titanium foil or titanium plate, and cathode electrode |
| WO2020044841A1 (en) * | 2018-08-31 | 2020-03-05 | 東邦チタニウム株式会社 | Method for producing metal titanium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06173065A (en) * | 1992-12-09 | 1994-06-21 | Japan Energy Corp | Method for refining ti |
| JP2015507696A (en) | 2011-12-22 | 2015-03-12 | ユニヴァーサル テクニカル リソース サービシーズ インコーポレイテッド | Apparatus and method for titanium extraction and refining |
| WO2018159774A1 (en) * | 2017-03-01 | 2018-09-07 | 国立大学法人京都大学 | Method for producing titanium foil or titanium plate, and cathode electrode |
| WO2020044841A1 (en) * | 2018-08-31 | 2020-03-05 | 東邦チタニウム株式会社 | Method for producing metal titanium |
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